In this work, a novel in situ auto-reduction strategy was developed to encapsulate uniformly dispersed Pd clusters/nanoparticles in MIL-125-NH2. It is demonstrated that the amino groups in MIL-125-NH2 can react with formaldehyde to form novel reducing groups (-NH[sbnd]CH2OH), which can in situ auto-reduce the encapsulated Pd2+ ions to metallic Pd clusters/nanoparticles. As no additional reductants are required, the strategy limits the aggregation and migration of Pd clusters and the formation of large Pd nanoparticles via controlling the amount of Pd2+ precursor. When applied as catalysts in the hydrogenation of phenol in the aqueous phase, the obtained Pd(1.5)/MIL-125-NH-CH2OH catalyst with highly dispersed Pd clusters/nanoparticles with the size of around 2 nm exhibited 100% of phenol conversion and 100% of cyclohexanone selectivity at 70 °C after 5 h, as well as remarkable reusability for at least five cycles due to the large MOF surface area, the highly dispersed Pd clusters/nanoparticles and their excellent stability within the MIL-125-NH-CH2OH framework. © 2021

Selective photocatalytic oxidation of alcohols into value-added aldehydes or ketones is a promising alternative for alcohol oxidation concerning the mild reaction conditions and the controllable selectivity. To increase the activity, defective Bi2WO6 with abundant oxygen vacancies (OVs) was synthesized via substitution of W by Ta. The resulting Ta-doped Bi2WO6 loaded with Pt nanoparticles as co-catalyst efficiently converted aromatic and aliphatic alcohols into the corresponding carbonyl compounds with high selectivity (>99%) in aqueous solution under visible-light irradiation and anaerobic conditions, with equivalent H2 as a coupled product. The optimal amount of benzyl alcohol converted by the Ta-doped catalyst was two times higher than that of the undoped catalyst. Surface OVs were found to favor the dissociative adsorption of the alcohols and to prolong the life time of the charge carriers. More importantly, isotopic labelling experiments confirmed that over Pt-loaded pristine undoped Bi2WO6, the coupled H2 product results from water reduction, while over Pt-loaded Ta-doped Bi2WO6, the produced H2 originates from benzyl alcohol, implying that benzyl alcohol can be photo-oxidized via a complete dehydrogenation pathway. Thus, enriched surface OVs in photocatalysts can activate α-C-H bonds in alcohols, boosting the photocatalytic oxidation performance. © 2021 Elsevier B.V.

NaNbO3 enriched with oxygen vacancies by Ni doping was successfully synthesized via a polymerized complex method and applied as a photocatalyst in the oxidation of cinnamyl alcohol (CA) to cinnamaldehyde in air. Reaction rates as high as 45 μmol h-1 were achieved under visible light with a high apparent quantum efficiency of 67.2% and excellent chemoselectivity larger than 99%. UV-vis, electron paramagnetic resonance, and attenuated total reflectance infrared spectroscopy results indicate that the CA molecules preferentially adsorb at the oxygen vacancies, thus enabling electron transfer between coordinatively bound CA and NaNbO3 under visible light, inducing CA oxidation. The photocatalytic aerobic oxidation of CA is assumed to proceed via the one-photon pathway with H2O2 as the coupled product. The photodeposited Pt nanoparticles on the surface not only enhanced the oxidation rate but also improved the selectivity to cinnamaldehyde substantially because of the fast decomposition of formed H2O2, in this way avoiding its consecutive oxidation by H2O2. The oxygen vacancies on the surface generated by Ni doping are identified to play a decisive role in the chemisorption of cinnamyl alcohol and the interface charge transfer. © 2021 American Chemical Society. All rights reserved.

CO2 methanation using nickel-based catalysts has attracted large interest as a promising power-to-gas route. Ni nanoparticles supported on nitrogen-doped CNTs with Ni loadings in the range from 10 wt% to 50 wt% were synthesized by impregnation, calcination and reduction and characterized by elemental analysis, X-ray powder diffraction, H2 temperature-programmed reduction, CO pulse chemisorption and transmission electron microscopy. The Ni/NCNT catalysts were highly active in CO2 methanation at atmospheric pressure, reaching over 50% CO2 conversion and over 95% CH4 selectivity at 340 °C and a GHSV of 50,000 mL g−1 h−1 under kinetically controlled conditions. The small Ni particle sizes below 10 nm despite the high Ni loading is ascribed to the efficient anchoring on the N-doped CNTs. The optimum loading of 30 wt%–40 wt% Ni was found to result in the highest Ni surface area, the highest degree of conversion and the highest selectivity to methane. A constant TOF of 0.3 s−1 was obtained indicating similar catalytic properties of the Ni nanoparticles in the range from 10 wt% to 50 wt% Ni loading. Long-term experiments showed that the Ni/NCNT catalyst with 30 wt% Ni was highly stable for 100 h time on stream. © 2020 Science Press

SrTiO3 was prepared by a polymeric precursor method and applied in the photocatalytic aerobic oxidation of HCl in a flat-plate reactor equipped with a UV LED array (368 nm). Reaction rates up to 240 mmol h−1 m−2 and apparent quantum yields up to 33 % using an illuminated area of 60 cm−2 were achieved with highly crystalline SrTiO3 calcined at 750 °C, outperforming commercially available SrTiO3 by a factor of almost 2. A gradual catalyst deactivation was observed, which was due to the formation of crystalline SrCl2×2 H2O on the surface confirmed by X-ray diffraction, electron microscopy and X-ray photoelectron spectroscopy (XPS). Increasing the HCl partial pressure accelerated both Cl2 formation and catalyst deactivation. XP spectra revealed an intrinsic surface segregation of Sr and the presence of several Sr- or O-containing surface species. High Cl2 yields up to 42 % obtained with an illuminated area of 120 cm−2 encourage further research on a photocatalytic Deacon process for improved HCl recycling. © 2021 The Authors. ChemPhotoChem published by Wiley-VCH GmbH

Highly selective one-step hydrogenation of phenol to cyclohexanone, an important intermediate in the production of nylon 6 and nylon 66, is desirable but remains a challenge. Pd nanoparticles supported on nitrogen- and oxygen-functionalized carbon nanotubes (NCNTs, OCNTs) were prepared, characterized, and applied in the hydrogenation of phenol to cyclohexanone to study the effect of N-doping. Almost full conversion of phenol with high selectivity to cyclohexanone was achieved over Pd/NCNT under mild reaction conditions using either H2 or formic acid (FA) as a hydrogen source. The effects of reaction temperature and FA/phenol ratio and the reusability were investigated. Separate FA decomposition experiments without and with the addition of phenol were performed to investigate the reaction mechanism, especially the deactivation behavior. Deactivation was observed for both catalysts during the FA decomposition, while only Pd/OCNT rather than Pd/NCNT was deactivated in the transfer hydrogenation with FA and the FA decomposition in the presence of phenol, indicating the unique role of N-doping. Therefore, we assume that deactivation is caused by the strongly bound formates on the active Pd sites, suppressing further FA decomposition and/or transfer hydrogenation on Pd. The nonplanar adsorption of phenol on NCNTs via weak O−H⋅⋅⋅N interactions enables the occurrence of the subsequent hydrogenation by adsorbed formate on Pd. © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH

The elimination of waste and by-product generation and reduced dependence on hazardous chemicals are the key steps towards environmentally sustainable chemical transformations. Heterogeneously catalysed oxidation of cyclohexene with environmentally friendly oxidizing agents such as O2, H2O2 and tert-butyl hydroperoxide (TBHP) has great potential to replace existing processes using stoichiometric oxidants. A series of spray-flame synthesised nanoparticulate LaCo1-xFexO3 catalysts was employed for cyclohexene oxidation, and the comparative results showed that TBHP led to the highest initial activity and allylic selectivity, but O2 resulted in higher conversion for longer reaction times. Furthermore, the influence of Fe substitution was studied, which did not show any beneficial synergistic effects. LaCoO3 was found to be the optimum catalyst for cyclohexene oxidation with O2, following first-order reaction kinetics with an apparent activation energy of 57 kJ mol-1. The catalyst showed good reusability due to its highly stable particle size, morphology and perovskite structure. 7-Oxabicyclo[4.1.0]heptan-2-one was identified to be formed by the oxidation of 2-cyclohexene-1-one with 2-cyclohexene-1-hydroperoxide. © 2020 The Royal Society of Chemistry.

Monometallic Mo and W carbides as well as highly mixed (Mo,W) carbides with various Mo/W ratios were synthesized directly on oxygen-functionalized carbon nanotubes (OCNTs), and used as noble-metal-free electrocatalysts in the hydrogen evolution reaction (HER) under both acidic and alkaline conditions. A purely orthorhombic structure was found in both monometallic and mixed carbide samples by X-ray diffraction. Transmission electron microscopy images showed that the carbide particles were highly dispersed on the OCNTs with well-controlled particle size. The homogeneous distribution of Mo and W in the carbides was confirmed by elemental mapping. (Mo,W)2C/OCNT with a Mo/W ratio of 3 : 1 showed the lowest overpotential to reach a current density of 10 mA/cm2 (87 mV in 0.1 M KOH and 92 mV in 0.5 M H2SO4), and the smallest Tafel slope of 34 mV/dec. Long-term stability under both alkaline and acidic conditions was demonstrated for 24 h. Our results revealed that an optimal amount of W in the mixed carbide can significantly improve its performance in the HER following the Tafel reaction pathway, most likely due to the weakened Mo−Hads bond. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

The design of efficient oxygen electrocatalysts is extremely important and urgent for much energy storage and conversion equipment. Among these, the high energy densities of lithium-oxygen batteries (LOBs) have driven us to explore bifunctional catalysts. Compared with non-aqueous LOBs, which have been blamed for poor cycling stability due to their undesirable side reaction, hybrid LOBs have been considered an alternative solution due to their high electrochemical reversibility and safeness. Here, one-dimensional hierarchical mesoporous/macroporous LaMn0.7Co0.3O3-x nanotubes were synthesized through an electrospinning method combined with an annealing treatment. With the suitable heat treatment and rational doping with elemental Co, the LMCO-800 sample shows a well-designed hierarchical porous nanotube structure and possess great bifunctional electrocatalytic performance. The linear sweep voltammetry (LSV) curves show that the half-wave potential (E1/2) of the LMCO-800 sample is 0.72 V (vs. RHE) and the average electron transfer number (n) is calculated to be 3.8. Moreover, the successful doping of elemental Co into the LMCO-800 nanotubes can shorten the average distance of the Mn-Mn atoms and promote the formation of O-O bonds, contributing to the enhanced OER performance. The high specific surface area and one-dimensional nanotubes can greatly benefit oxygen diffusion, facilitate electrolyte infiltration and improve electron transfer. Consequently, the as-assembled hybrid lithium-oxygen batteries with an LMCO-800 cathode exhibit superior cycling stability. © 2018 The Royal Society of Chemistry.

Spillover hydrogen species were generated by dissociative H2 adsorption on Pt nanoparticles supported on nitrogen-doped mesoporous carbon. The spillover hydrogen species on the support can migrate back to the Pt nanoparticles and hydrogenate subsequently adsorbed nitrobenzene to aniline at 80 °C, which was detected during temperature-programmed desorption experiments from 80 to 300 °C in pure He. The amount of spillover hydrogen can be tuned mainly by the pre-reduction temperature rather than by other parameters. The absence of aniline formation during nitrobenzene desorption experiments in the presence of CO indicates that hydrogenation occurs exclusively on Pt and that the spillover hydrogen species are present on the carbon support in a chemically inactive state. Most likely, spillover hydrogen is reversibly stored on the carbon support as adsorbed protons on the surface and as electrons in the bulk. These findings provide a new perspective on Pt/C-based hydrogen storage materials and fuel cell catalysts. © 2018

The oxidation and stability of multi-walled carbon nanotubes (CNTs) have been investigated by exposing CNTs in 30% w/v H2O2 solution at room temperature (RT) for up to 8 weeks and at 80 °C for up to 8 h. H2O2 oxidation not only generated surface oxygen-containing groups, but also created surface defects, as disclosed by results of temperature-programmed desorption and X-ray Photoelectron Spectroscopy. The total surface oxygen content was found to be correlated to the final H2O2 concentration. The higher the total surface oxygen content on CNTs, the lower the final H2O2 concentration. Meanwhile, the carbon oxidation and simultaneous H2O2 decomposition were observed and confirmed by an online analysis of evolved gases during the oxidation stepwise heated from room temperature to 80 °C. Raman study showed that the D/G and D'/G ratios of the CNTs oxidized at RT first decreased with an oxidation time of 4 weeks and then increased when prolonging the oxidation time up to 8 weeks. Similar trend was also observed on the CNTs oxidized at 80 °C. The size of CNTs was gradually reduced with increasing oxidation time as shown by SEM studies. Our work reveals the critical changes in the surface oxygen groups as well as the changes in morphology at two distinct stages of hydrogen peroxide treatment, purification and then functionalization. CNTs can withstand 30% w/v H2O2 oxidation for only a certain time, while they may be damaged or consumed eventually in long-term applications. Our study contributes to filling in the knowledge gap about CNT surface oxidation and structural changes with H2O2 treatment under industrial conditions. © 2018 Elsevier B.V.

Nitrogen-doped carbon nanotubes (NCNTs) were used as a support for iron (Fe) nanoparticles applied in carbon dioxide (CO2) hydrogenation at 633 K and 25 bar (1 bar = 105 Pa). The Fe/NCNT catalyst promoted with both potassium (K) and manganese (Mn) showed high performance in CO2 hydrogenation, reaching 34.9% conversion with a gas hourly space velocity (GHSV) of 3.1 L·(g·h)−1. Product selectivities were high for olefin products and low for short-chain alkanes for the K-promoted catalysts. When Fe/NCNT catalyst was promoted with both K and Mn, the catalytic activity was stable for 60 h of reaction time. The structural effect of the Mn promoter was demonstrated by X-ray diffraction (XRD), temperature-programmed reduction (TPR) with molecular hydrogen (H2), and in situ X-ray absorption near-edge structure (XANES) analysis. The Mn promoter stabilized wüstite (FeO) as an intermediate and lowered the TPR onset temperature. Catalytic ammonia (NH3) decomposition was used as an additional probe reaction for characterizing the promoter effects. The Fe/NCNT catalyst promoted with both K and Mn had the highest catalytic activity, and the Mn-promoted Fe/NCNT catalysts had the highest thermal stability under reducing conditions. © 2017 THE AUTHORS

By doping the TiO2 support with nitrogen, strong metal-support interactions (SMSI) in Pd/TiO2 catalysts can be tailored to obtain high-performance supported Pd nanoparticles (NPs) in nitrobenzene (NB) hydrogenation catalysis. According to the comparative studies by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), and diffuse reflectance CO FTIR (CO-DRIFTS), N-doping induced a structural promoting effect, which is beneficial for the dispersion of Pd species on TiO2. High-angle annular dark-field scanning transmission electron microscopy study of Pd on N-doped TiO2 confirmed a predominant presence of sub-2 nm Pd NPs, which are stable under the applied hydrogenation conditions. XPS and CO-DRIFTS revealed the formation of strongly coupled Pd-N species in Pd/TiO2 with N-doped TiO2 as support. Density functional theory (DFT) calculations over model systems with Pdn (n = 1, 5, or 10) clusters deposited on TiO2(101) surface were performed to verify and supplement the experimental observations. In hydrogenation catalysis using NB as a model molecule, Pd NPs on N-doped TiO2 outperformed those on N-free TiO2 in terms of both catalytic activity and stability, which can be attributed to the presence of highly dispersed Pd NPs providing more active sites, and to the formation of Pd-N species favoring the dissociative adsorption of the reactant NB and the easier desorption of the product aniline. (Figure Presented). © 2016 American Chemical Society.

Metal oxides and carbon-based materials are the most promising electrode materials for a wide range of low-cost and highly efficient energy storage and conversion devices. Creating unique nanostructures of metal oxides and carbon materials is imperative to the development of a new generation of electrodes with high energy and power density. Here we report our findings in the development of a novel graphene aerogel assisted method for preparation of metal oxide nanoparticles (NPs) derived from bulk MOFs (Co-based MOF, Co(mIM)2 (mIM = 2-methylimidazole). The presence of cobalt oxide (CoOx) hollow NPs with a uniform size of 35 nm monodispersed in N-doped graphene aerogels (NG-A) was confirmed by microscopic analyses. The evolved structure (denoted as CoOx/NG-A) served as a robust Pt-free electrocatalyst with excellent activity for the oxygen reduction reaction (ORR) in an alkaline electrolyte solution. In addition, when Co was removed, the resulting nitrogen-rich porous carbon-graphene composite electrode (denoted as C/NG-A) displayed exceptional capacitance and rate capability in a supercapacitor. Further, this method is readily applicable to creation of functional metal oxide hollow nanoparticles on the surface of other carbon materials such as graphene and carbon nanotubes, providing a good opportunity to tune their physical or chemical activities. © 2017 American Chemical Society.

We report metallic NiPS3@NiOOH core shell heterostructures as an efficient and durable electrocatalyst for the oxygen evolution reaction, exhibiting a low onset potential of 1.48 V (vs RHE) and stable performance for over 160 h. The atomically thin NiPS3 nanosheets are obtained by exfoliation of bulk NiPS3 in the presence of an ionic surfactant. The OER mechanism was studied by a combination of SECM, in situ Raman spectroscopy, SEM, and XPS measurements, which enabled direct observation of the formation of a NiPS3@NiOOH core shell heterostructure at the electrode interface. Hence, the active form of the catalyst is represented as NiPS3@NiOOH core shell structure. Moreover, DFT calculations indicate an intrinsic metallic character of the NiPS3 nanosheets with densities of states (DOS) similar to the bulk material. The high OER activity of the NiPS3 nanosheets is attributed to a high density of accessible active metallic-edge and defect sites due to structural disorder, a unique NiPS3@NiOOH core shell heterostructure, where the presence of P and S modulates the rface electronic structure of Ni in NiPS3, thus providing excellent conductive pathway for efficient electron-transport to the NiOOH shell. These findings suggest that good size control during liquid exfoliation may be advantageously used for the formation of electrically conductive NiPS3@ NiOOH core shell electrode materials for the electrochemical water oxidation.

The growth of metal–organic framework (ZIF-67) nanocrystals on nickel foam (NF), followed by carbonization in diluted H2, leads to a nitrogen-doped carbon-nanotube-grafted cobalt/carbon polyhedra film on NF. The obtained material serves as a highly active binder-free electrocatalyst for both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), enabling high-performance alkaline (0.1 m KOH) water electrolysis with potentials of 1.62 and 0.24 V, respectively, at OER and HER current densities of 10 mA cm−2. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Cobalt oxide nanoparticles were deposited on nitrogen-doped carbon nanotubes (NCNTs) through impregnation by using cobalt nitrate as a precursor and subsequent drying and calcination. Co loadings were prepared in the range from 4 to 40 wt%, and hydrogen and ammonia were applied in the thermal post-treatment of the CoOx/NCNT samples. The Co3O4 spinel structure was detected in all samples, while the thermal treatment in ammonia and hydrogen led to the formation of CoO and metallic Co in addition. Treatment in ammonia resulted in the partial reduction of Co3O4 to CoO and nitrogen doping of the oxides, leading to excellent electrocatalytic activity in the oxygen evolution reaction (OER) and stability despite of the lower Co oxidation states compared with the sample calcined in air. In contrast, the sample reduced in hydrogen showed a lower activity and stability in the OER. The high activity of the ammonia-treated sample can be assigned to improved conductivity, favorable surface properties with surface nitrogen improving the hydrophilicity of the catalysts, and the more facile transformation to the OER-active layered cobalt oxyhydroxide phase under anodic conditions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Co-based layered double hydroxide (LDH) catalysts with Fe and Al contents in the range of 15 to 45 at % were synthesized by an efficient coprecipitation method. In these catalysts, Fe3+ or Al3+ ions play an essential role as trivalent species to stabilize the LDH structure. The obtained catalysts were characterized by a comprehensive combination of surface- and bulk-sensitive techniques and were evaluated for the oxygen evolution reaction (OER) on rotating disk electrodes. The OER activity decreased upon increasing the Al content for the Co- and Al-based LDH catalysts, whereas a synergistic effect in Co- and Fe-based LDHs was observed, which resulted in an optimal Fe content of 35 at %. This catalyst was spray-coated on Ni foam electrodes and showed very good stability in a flow-through cell with a potential of approximately 1.53 V at 10 mA cm−2 in 1 m KOH for at least 48 h. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Surface functionalization of carbon nanotubes (CNTs) was achieved by a thermal treatment in the presence of pre-adsorbed potassium hydroxide and steam at 350–550 °C. The generated oxygen-containing functional groups were more basic and thermally stable compared with conventional acid-generated groups. The influence of the KOH-steam co-treatment conditions on the functionalization of CNTs was systematically investigated. Residual K species were found to intercalate in the inner graphene layers of the CNTs providing additional Brønsted basicity. Owing to the favorable basic properties and high thermal stability of the generated functional groups, Pd nanoparticles supported on the co-treated CNTs were found to be strongly anchored leading to a high degree of Pd dispersion and a high resistance to sintering. The Pd nanoparticles on the co-treated CNT support produced at 450 °C and 550 °C showed the highest activity and yields of acetic acid in the aerobic oxidation of aqueous ethanol reaching almost full conversion after 5 h in the absence of additional base. In addition, the KOH-steam co-treatment was found to enhance the recyclability of the Pd/CNT catalysts. © 2017 Elsevier Ltd

Manganese oxides are promising electrocatalysts for the oxygen evolution reaction due to their versatile redox properties. Manganese oxide (MnOx) nanoparticles were synthesized on oxygen- and nitrogen-functionalized carbon nanotubes (OCNTs and NCNTs) by calcination in air of Mn-impregnated CNTs with a loading of 10 wt% Mn. The calcined samples were exposed to reducing conditions by thermal treatment in H2 or NH3, and to strongly oxidizing conditions using HNO3 vapor, which enabled us to flexibly tune the oxidation state of Mn from 2+ in MnO to 4+ in MnO2. The samples were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscopy and temperature-programmed reduction. The oxidation state of Mn was more easily changed in the MnOx/NCNTs samples compared with the MnOx/OCNTs samples. Furthermore, the reduction of MnO2 to MnO occurred in one-step on NCNTs, whereas Mn2O3 intermediate states were observed for OCNTs. STEM and TEM images revealed a smaller and uniform dispersion of the MnOx nanoparticles on NCNTs as compared to OCNTs. Electrocatalytic oxygen evolution tests in 0.1 M KOH showed that Mn in high oxidation states, specifically 4+ as in MnO2 generated by HNO3 vapor treatment, is more active than Mn in lower oxidation states, using the potential at 10 mA cm-2 and the Tafel slopes as the performance metrics. © the Owner Societies 2017.

To accelerate the large-scale commercialization of electrochemical energy storage and conversion technologies through water splitting and regeneration in reversible fuel cells, cost-effective, highly efficient, and durable reversible oxygen electrodes are required. We report a comparatively simple approach to modify a group of oxygen-evolving perovskites based on lanthanum cobaltite into effective bifunctional systems through partial atom substitution, which, upon intermixing with nitrogen-doped carbon nanotubes, achieve remarkably low round-trip overvoltage of <850mV in the electrocatalysis of oxygen reduction and oxygen evolution in an alkaline electrolyte, KOH (0.1m). Besides the bifunctional electrocatalytic performance, the composite systems with a low Fe content possessed promising long-term stability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

It is demonstrated that amorphous cobalt boride (Co2B) prepared by the chemical reduction of CoCl2 using NaBH4 is an exceptionally efficient electrocatalyst for the oxygen evolution reaction (OER) in alkaline electrolytes and is simultaneously active for catalyzing the hydrogen evolution reaction (HER). The catalyst achieves a current density of 10 mA cm(-2) at 1.61 V on an inert support and at 1.59 V when impregnated with nitrogen-doped graphene. Stable performance is maintained at 10 mA cm(-2) for at least 60 h. The optimized catalyst, Co2B annealed at 500 degrees C (Co2B-500) evolves oxygen more efficiently than RuO2 and IrO2, and its performance matches the best cobalt-based catalysts reported to date. Co2B is irreversibly oxidized at OER conditions to form a CoOOH surface layer. The active form of the catalyst is therefore represented as CoOOH/Co2B. EXAFS observations indicate that boron induces lattice strain in the crystal structure of the metal, which potentially diminishes the thermodynamic and kinetic barrier of the hydroxylation reaction, formation of the OOH* intermediate, a key limiting step in the OER.

Efficient reversible oxygen electrodes for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are vitally important for various energy conversion devices, such as regenerative fuel cells and metal-air batteries. However, realization of such electrodes is impeded by insufficient activity and instability of electrocatalysts for both water splitting and oxygen reduction. We report highly active bifunctional electrocatalysts for oxygen electrodes comprising core-shell Co@Co3O4 nanoparticles embedded in CNT-grafted N-doped carbon-polyhedra obtained by the pyrolysis of cobalt metal-organic framework (ZIF-67) in a reductive H2 atmosphere and subsequent controlled oxidative calcination. The catalysts afford 0.85 V reversible overvoltage in 0.1 m KOH, surpassing Pt/C, IrO2, and RuO2 and thus ranking them among one of the best non-precious-metal electrocatalysts for reversible oxygen electrodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The synthesis and characterization of gas phase oxygen-and nitrogen-functionalized multi-walled carbon nanotubes (OMWCNTs and NMWCNTs) and the dispersibility of these tubes in organic solvents were investigated. Recently, carbon nanotubes have shown supreme capacity to effectively enhance the efficiency of organic solar cells (OSCs). A critical challenge is to individualize tubes from their bundles in order to provide homogenous nano-domains in the active layer of OSCs. OMWCNTs and NMWCNTs were synthesized via HNO3 vapor and NH3 treatments, respectively. Surface functional groups and the structure of the tubes were analyzed by temperature-programmed desorption, Fourier transform infrared spectroscopy, transmission electron microscopy, and Raman spectroscopy which confirmed the formation of functional groups on the tube surface and the enhancement of surface defects. Elemental analysis demonstrated that the oxygen and nitrogen content increased with increasing treatment time of the multi-walled carbon nanotube (MWCNT) in HNO3 vapor. According to ultra-violet visible spectroscopy, modification of the MWCNT increased the extinction coefficients of the tubes owing to enhanced compatibility of the functionalized tubes with organic matrices.

Metal-organic frameworks (MOFs) feature a great possibility for a broad spectrum of applications. Hollow MOF structures with tunable porosity and multifunctionality at the nanoscale with beneficial properties are desired as hosts for catalytically active species. Herein, we demonstrate the formation of well-defined hollow Zn/Co-based zeolitic imidazolate frameworks (ZIFs) by use of epitaxial growth of Zn-MOF (ZIF-8) on preformed Co-MOF (ZIF-67) nanocrystals that involve in situ self-sacrifice/excavation of the Co-MOF. Moreover, any type of metal nanoparticles can be accommodated in Zn/Co-ZIF shells to generate yolk-shell metal@ZIF structures. Transmission electron microscopy and tomography studies revealed the inclusion of these nanoparticles within hollow Zn/Co-ZIF with dominance of the Zn-MOF as shell. Our findings lead to a generalization of such hollow systems that are working effectively to other types of ZIFs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitrogen-functionalized carbon nanotubes are promising materials in catalysis due to their versatile surface properties involving nitrogen groups, oxygen groups, surface defects and metal impurities. These factors can be used to tune the dispersion, morphology, crystal structure, electronic structure, mobility/stability and finally the catalytic performance of supported metal nanoparticles. This review focuses on selected examples aiming at understanding the interactions between surface groups, defects, and metal species and their impact on the catalytic properties in electrocatalysis and gas-phase redox catalysis. © 2016 The Royal Society of Chemistry.

Non-noble metal based materials efficiently catalyzing the hydrogen evolution reaction (HER) are reported based on a novel strategy where electrocatalytically active ultrathin molybdenum sulphoselenide sheets are incorporated into electrically conducting reduced graphene oxide sheets via a self-assembly approach. By taking advantage of the electrostatic attraction between the two oppositely charged nanosheets, MoSSe@rGO composite materials are obtained exhibiting superior electrocatalytic activity and stability for the HER allowing a current density of 5 mA cm−2 at a low overpotential of only 135 mV. These findings pave the way to novel electrocatalysts based on composites of MoSSe and reduced graphene oxide towards the design of ultra-light, mechanically robust and electrically conductive electrode materials for electrocatalytic water splitting. © 2016 Elsevier Ltd

Low-cost electrocatalysts based on highly dispersed molybdenum carbide supported on carbon nanotubes (CNTs) were developed for the hydrogen evolution reaction (HER). The synthesis of MoxC/CNT was achieved by impregnation using ammonium heptamolybdate followed by a thermal treatment at 700 °C in CH4/H2, H2 or N2. The composites were characterized by X-ray diffraction, N2 physisorption, and X-ray photoelectron spectroscopy. β-Mo2C was the main Mo carbide phase generated in N2 or H2, whereas α-MoC was the dominant phase formed in CH4/H2. All the MoxC/CNT composites were catalytically active in the HER under alkaline conditions. The catalyst pretreated in pure H2 exhibited the highest HER activity, which was found to correlate with a higher amount of Mo2C, a higher total Mo content and a higher Mo surface concentration compared with the other two less active samples. Amorphous carbon on the surface seems to play an important role in limiting the HER performance of the Mo carbide catalysts, and the treatment in H2 removed it most effectively leading to high HER activity. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Nitrogen-doped mesoporous hollow carbon spheres (NHCS) consisting of hybridized amorphous and graphitic carbon were synthesized by chemical vapor deposition with pitch as raw material. Treatment with HNO3 vapor was performed to incorporate oxygen-containing groups on NHCS, and the resulting NHCS-O showed excellent rate capacity, high reversible capacity, and excellent cycling stability when tested as the anode material in lithium-ion batteries. The NHCS-O electrode maintained a reversible specific capacity of 616 mAh g-1 after 250 cycles at a current rate of 500 mA g-1, which is an increase of 113 % compared to the pristine hollow carbon spheres. In addition, the NHCS-O electrode exhibited a reversible capacity of 503 mAh g-1 at a high current density of 1.5 A g-1. The superior electrochemical performance of NHCS-O can be attributed to the hybrid structure, high N and O contents, and rich surface defects. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The role of the stability of surface functional groups in oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (CNTs) applied as support for iron catalysts in high-temperature Fischer-Tropsch synthesis was studied in a fixed-bed U-tube reactor at 340°C and 25 bar with a H2:CO ratio of 1. Iron oxide nanoparticles supported on untreated oxygen-functionalized CNTs (OCNTs) and nitrogen-functionalized CNTs (NCNTs) as well as thermally treated OCNTs were synthesized by the dry impregnation method using ammonium ferric citrate as iron precursor. The properties of all catalysts were examined using X-ray diffraction, temperature-programmed reduction in H2, X-ray photoelectron spectroscopy and temperature-programmed oxidation in O2. The activity loss for iron nanoparticles supported on untreated OCNTs was found to originate from severe sintering and carbon encapsulation of the iron carbide nanoparticles under reaction conditions. Conversely, the sintering of the iron carbide nanoparticles on thermally treated OCNTs and untreated NCNTs during reaction was far less pronounced. The presence of more stable surface functional groups in both thermally treated OCNTs and untreated NCNTs is assumed to be responsible for the less severe sintering of the iron carbide nanoparticles during reaction. As a result, no activity loss for iron nanoparticles supported on thermally treated OCNTs and untreated NCNTs was observed, which even became gradually more active under reaction conditions. © 2015 Published by Elsevier B.V.

This article describes a facile one-pot solvothermal method to prepare Fe2O3/graphene composite as high performance electrode material for supercapacitor. The morphology and structure of the samples were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Xray photoelectron spectroscopy, Raman spectra and nitrogen isothermal adsorption-desorption. The results reveal that the efficient loading of quasi-hexagonal alpha-Fe2O3 nanoplates and the reduction of graphene oxide were simultaneously realized. The electrochemical measurement demonstrates that Fe2O3/rGO composite shows a specific capacitance as high as 1083 F g(-1) at a discharge current density of 2 A g(-1). Even at the current density of 10 A g(-1), the specific capacitance is still as high as 517 F g(-1). After 1000 cycles, the capacity retention is still maintained at 75%. The electrochemical performances of the composites are superior to the pure samples owing to the synergistic effect of Fe2O3 and rGO. (C) 2016 Elsevier Ltd. All rights reserved.

Pd nanoparticles supported on carbon nanotubes were applied in the selective oxidation of ethanol in the liquid phase. The characterization of the surface and bulk properties combined with the catalytic tests indicated the dissolution and redeposition of Pd under the reaction conditions. A dynamic interplay within the Pd life cycle was identified to be responsible for the overall reactivity. Nitrogen-doped carbon nanotubes were found to act as an excellent support for the Pd catalyst system by efficiently stabilizing and recapturing the Pd species, which resulted in high activity and selectivity to acetic acid. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Large scale commercialization of direct ethanol fuel cells is hampered by the high cost and scarcity of noble metal electrocatalysts employed at both the anode and cathode. We demonstrate improved utilization of palladium as anode catalyst for ethanol oxidation by exploiting the strong interaction between Pd nanoparticles and nitrogen-doped carbon nanotubes (NCNTs) as support. 0.85 wt% Pd supported on NCNTs achieved a specific current density of 517 A gPd - 1 compared with 421 A gPd - 1 for 0.86 wt% Pd on oxygen-functionalized carbon nanotubes. The electrocatalytic performance deteriorated only gradually and catalysis was sustained for at least 80 h. © 2015 Elsevier B.V. All rights reserved.

Preparing a stable suspension is a main step towards the electrophoretically depositing of homogeneous and dense composite coatings on NiTi for its biomedical application. In the present study, different composite suspensions of hydroxyapatite, silicon and multi-walled carbon nano-tubes were prepared using n-butanol and triethanolamine as media and dispersing agent, respectively. Multi-walled carbon nanotubes were first functionalized in the nitric acid vapor for 15 h at 175 °C, and then mixed into suspensions. Thermal desorption spectroscopy profiles indicate the formation of functional groups on multi-walled carbon nano-tubes. An excellent suspension stability can be achieved for different amounts of triethanolamine. The amount of triethanolamine can be increased by adding a second component to a stable hydroxyapatite suspension due to an electrostatic interaction between components in suspension. The stability of composite suspension is less than that of the hydroxyapatite suspension, due to density differences, which under the gravitational force promote the demixing. The scanning electron microscopy images of the coatings surface show that more dense coatings are developed on NiTi substrate using electrophoretic deposition and sintering at 850 °C in the simultaneous presence of silicon and multi-walled carbon nanotubes in the hydroxyapatite coatings. The atomic force microscopy results of the coatings surface represent that composite coatings of hydroxyapatite-20 wt.% silicon and hydroxyapatite-20 wt.% silicon-1 wt.% multi-walled carbon nano-tubes with low zeta potential have rougher surfaces. © 2016 Elsevier B.V. All rights reserved.

RuO2 nanoparticles supported on multi-walled carbon nanotubes (CNTs) functionalized with oxygen (OCNTs) and nitrogen (NCNTs) were employed for the oxygen evolution reaction (OER) in 0.1 M KOH. The catalysts were synthesized by metal-organic chemical vapor deposition using ruthenium carbonyl (Ru3(CO)12) as Ru precursor. The obtained RuO2/OCNT and RuO2/NCNT composites were characterized using TEM, H2-TPR, XRD and XPS in order probe structure-activity correlations, particularly, the effect of the different surface functional groups on the electrochemical OER performance. The electrocatalytic activity and stability of the catalysts with mean RuO2 particle sizes of 13-14 nm was evaluated by linear sweep voltammetry, cyclic voltammetry, and chronopotentiometry, showing that the generation of nitrogen-containing functional groups on CNTs was beneficial for both OER activity and stability. In the presence of RuO2, carbon corrosion was found to be significantly less severe. © 2016 Science Press and Dalian Institute of Chemical Physics. All rights reserved.

TiO2 quantum dots embedded in bamboo-like porous carbon nanotubes have been constructed through the pyrolysis of sulfonated polymer nanotubes and TiO2 hybrids. The TiO2 quantum dots are formed during the pyrolysis, due to the space confinement within the highly cross-linked copolymer networks. The sulfonation degree of the polymer nanotubes is a critical factor to ensure the formation of the unique interpenetrating structure. The nanocomposites exhibit high reversible capacity of 523 mAh g-1 at 100 mA g-1 after 200 cycles, excellent rate capability and superior long-term cycling stability at high current density, which could attain a high discharge capacity of 189 mAh g-1 at 2000 mA g-1 for up to 2000 cycles. The enhanced electrochemical performance of the nanocomposites benefit from the uniform distribution of TiO2 quantum dots, high electronic conductivity of porous carbons and unique interpenetrating structure, which simultaneously solved the major problems of TiO2 anode facing the pulverization, loss of electrical contact and particle aggregation. © 2016 Elsevier B.V. All rights reserved.

Nitrogen-doped carbon nanotubes (NCNTs) were synthesized by chemical vapor deposition using cobalt-based oxides as catalyst and ethylenediamine (EDA) as carbon/nitrogen precursor. The influence of growth time, EDA concentration and growth temperature on the morphology, yield, composition, graphitization and oxidation resistance of the NCNTs was systematically investigated by using Raman spectroscopy, temperature-programmed oxidation and other techniques. The NCNT growth from ethylenediamine with a high N/C ratio involves several processes including mainly (1) catalytic growth of NCNTs, (2) homogeneous gas-phase decomposition of EDA, (3) non-catalytic deposition of pyrolytic carbon/nitrogen species and (4) surface etching of amorphous carbon or carbon at defect sites through gasification. At a later growth stage the etching process appears to be dominating, leading to the thinning of nanotubes and the decrease of yield. Moreover, the surface etching through carbon gasification strongly influences the structure and degree of graphitization of NCNTs. © 2015 Science Press and Dalian Institute of Chemical Physics. All rights reserved.

An efficient two-step gas-phase method was developed for the synthesis of Co<inf>3</inf>O<inf>4</inf>-MnO<inf>2</inf>-CNT hybrids used as electrocatalysts in the oxygen evolution reaction (OER). Spinel Co-Mn oxide was used for the catalytic growth of multiwalled carbon nanotubes (CNTs) and the amount of metal species remaining in the CNTs was adjusted by varying the growth time. Gas-phase treatment in HNO<inf>3</inf> vapor at 200 °C was performed to 1)open the CNTs, 2)oxidize encapsulated Co nanoparticles to Co<inf>3</inf>O<inf>4</inf> as well as MnO nanoparticles to MnO<inf>2</inf>, and 3)to create oxygen functional groups on carbon. The hybrid demonstrated excellent OER activity and stability up to 37.5h under alkaline conditions, with longer exposure to HNO<inf>3</inf> vapor up to 72h beneficial for improved electrocatalytic properties. The excellent OER performance can be assigned to the high oxidation states of the oxide nanoparticles, the strong electrical coupling between these oxides and the CNTs as well as favorable surface properties rendering the hybrids a promising alternative to noble metal based OER catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The co-doping of graphene with nitrogen and sulfur was investigated aiming at understanding their interactions with the presence of oxygen in graphene. The co-doped graphene (NS-G) was synthesized via a one-pot hydrothermal route using graphene oxide as starting material and L-cysteine, an amino acid containing both N and S, as the doping agent. The obtained NS-G with a three-dimensional hierarchical structure containing both macropores and mesopores exhibited excellent mechanical stabilities under both wet and dry conditions. As compared to N or S singly doped graphene, the co-doped sample contains significantly higher concentrations of N and S species especially pyrollic N groups. The co-doped sample considerably outperformed the singly doped samples when used as free-standing electrode in supercapacitors due to enhanced pseudocapacitance. The simultaneous incorporation of S and N species with the presence of oxygen significantly modified the surface chemistry of carbon leading to considerably higher doping levels, although directly bonding between N and S is neither likely nor detected. Hence, the synergetic effect between N and S occurred through carbon atoms in neighboring hexagonal rings in a graphene sheet.

The notion of metal-free catalysts is used to refer to carbon materials modified with nonmetallic elements. However, some claimed metal-free catalysts are prepared using metal-containing precursors. It is highly contested that metal residues in nitrogen-doped carbon (NC) catalysts play a crucial role in the oxygen reduction reaction (ORR). In an attempt to reconcile divergent views, a definition for truly metal-free catalysts is proposed and the differences between NC and M-N<inf>x</inf>/C catalysts are discussed. Metal impurities at levels usually undetectable by techniques such as XPS, XRD, and EDX significantly promote the ORR. Poisoning tests to mask the metal ions reveal the involvement of metal residues as active sites or as modifiers of the electronic structure of the active sites in NC. The unique merits of both M-N<inf>x</inf>/C and NC catalysts are discussed to inspire the development of more advanced nonprecious-metal catalysts for the ORR. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An eggshell Mo2C catalyst which is designed from the rapid combination of molybdate with melamine is described. In contrast to Pd-based catalysts, the eggshell Mo2C operates effectively with a wide-concentration window in high-temperature gas phase hydrogenation of phenylacetylene, thus, an economical and energy-efficient front-end purification of styrene monomers might be possible. (c) 2015 American Institute of Chemical Engineers AIChE J, 61: 2522-2531, 2015

Electrochemical corrosion is a major problem for carbon materials used in electrocatalysis. Highly dispersed TiO<inf>2</inf> was deposited on O-functionalized and N-doped carbon nanotubes by chemical vapour deposition to tackle the carbon corrosion problem. Very low Ti loadings of about 1 wt% were applied to minimize the negative influence of TiO<inf>2</inf> as a semiconductor on the high conductivity of carbon materials. Both N doping and TiO<inf>2</inf> coating facilitate strong metal-support interactions and favour the formation of small Pt particles. N doping improved the intrinsic catalytic activity of the carbon support and enhanced the conductivity due to the removal of surface oxygen groups, while the negative effect of TiO<inf>2</inf> on conductivity is counterbalanced by its promoting effect on metal-support interactions leading to enhanced overall catalytic performance. Pt/TiO<inf>2</inf>/NCNTs showed the highest ORR activity, and significantly outperformed Pt/NCNTs in electrochemical stability tests. © the Owner Societies 2015.

Hydrogenation of CO2 to hydrocarbons over iron nanoparticles supported on oxygen-functionalized multi-walled carbon nanotubes was studied in a fixed-bed U-tube reactor at 25 bar with a H2:CO2 ratio of 3. Conversion of CO2 was approximately 35% yielding C 1-C5 products at 360°C with methane and CO as major products. The CO2 equilibrium conversion for temperatures in the range of 320° to 420°C was analysed by using CHEMCAD simulation software. Comparison between experimental and simulated degrees of CO 2 conversion shows that reverse water gas shift equilibrium had been achieved in the investigated temperature range and that less than 47% of CO 2 can be converted to CO at 420°C. © 2014 Indian Academy of Sciences.

Coal based nanofibers were prepared by electrospinning a mixture of polyacrylonitrile and acid treated coal. Coal based activated carbon fibers were further obtained by carbonization and steam activation. The effects of acid treatment on raw coal were studied to explain the enhanced solubility in various solvents. The solubility of coal was as high as 6.6 wt% in N,N- dimethylformamide. The electrochemical performance of supercapacitor electrodes using coal based activated carbon fiber mats was then studied. This binder-free electrode showed a specific capacitance of 230 F g-1 at a current density of 1 A g-1 and an excellent capacity retention of 97% after 1000 cycles. © 2014 the Partner Organisations.

CO2 hydrogenation to short-chain hydrocarbons was investigated over iron catalysts supported on oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (CNTs) and on silica, which were synthesized by the dry impregnation method using ammonium ferric citrate as precursor. The reduction of the calcined catalysts was examined in detail using temperature-programmed reduction in H2 and in situ X-ray absorption near-edge structure (XANES) analysis. The XANES results revealed that the mixture of hematite and magnetite was gradually transformed into wustite and metallic iron during heating in H2. Iron oxide nanoparticles supported on nitrogen-functionalized CNTs were easier to reduce compared to those on oxygen-functionalized CNTs indicating a promoting effect of the nitrogen functional groups. The interaction between iron oxide and silica was found to be much stronger inhibiting the reduction to metallic iron. As a result, the catalytic activity of iron nanoparticles supported on CNTs in CO2 hydrogenation at 360 °C, 25 bar and a H2:CO 2 ratio of 3 was almost twofold higher compared with iron supported on silica. CO2 was converted into C1-C5 hydrocarbons with CO and methane as major products over all catalysts. The Fe/NCNT catalyst achieved the highest olefin selectivity of 11% in the hydrocarbons range of C2-C5. In contrast, mostly paraffins were formed over the Fe/SiO2 catalyst. © 2014 Elsevier B.V.

A one-pot hydrothermal route was developed for the preparation of nitrogen-doped graphene (NG) hydrogels using graphene oxide (GO) as a raw material and nine amino acids with different acidities (acidic, neutral and basic) as doping agents. The morphology, structure and composition of the prepared NG using three amino acids (dl-aspartic acid, acidic; l-glycine, neutral; l-arginine, basic) were characterized by SEM, nitrogen physisorption, Raman and XPS spectroscopy. Acidic amino acids yielded NG with a cross-linked 3D network with a large specific surface area of 367.1 m2 g -1, while NG arising from the use of basic amino acids showed a tightly stacked structure with a much smaller surface area of 10.5 m2 g-1. The charged amino acids, and the ensuing electrostatic interactions between the amino acid and GO, affect the morphology of NG, and ultimately affect its electrochemical performance. The samples prepared using acidic amino acids, with the lowest surface N content (1.0%) but the largest surface area, displayed high specific capacitance of 246 F g-1 at 3 A g-1. The microstructure, surface area and effective nitrogen content, mainly the pyridinic nitrogen group related to pseudocapacitance, play important roles in the capacitive performance of the NG samples. © 2014 the Partner Organisations.

The type and the amount of functional groups on the surface of carbon nanotubes (CNTs) were tuned to improve the activity of supported Co nanoparticles in hydrogenation catalysis. Surface nitrogen species on CNTs significantly promoted the decomposition of the cobalt precursor and the reduction of cobalt oxide, and improved the resistance of metallic Co against oxidation in ambient atmosphere. In the selective hydrogenation of nitrobenzene in the gas phase, Co supported on CNTs with the highest surface nitrogen content showed the highest activity, which is ascribed to the higher reducibility and the lower oxidation state of the Co nanoparticles under reaction conditions. For Co nanoparticles supported on CNTs with a smaller amount of surface nitrogen groups, a repeated reduction at 350 °C was essential to achieve a comparable high catalytic activity reaching 90% conversion at 250 °C, pointing to the importance of nitrogen species for the supported Co nanoparticles in nitrobenzene hydrogenation. © 2014 American Chemical Society.

For practical solid-state hydrogen storage, reversibility under mild conditions is crucial. Complex metal hydrides such as NaAlH4 and LiBH4 have attractive hydrogen contents. However, hydrogen release and especially uptake after desorption are sluggish and require high temperatures and pressures. Kinetics can be greatly enhanced by nanostructuring, for instance by confining metal hydrides in a porous carbon scaffold. We present for a detailed study of the impact of the nature of the carbon-metal hydride interface on the hydrogen storage properties. Nanostructures were prepared by melt infiltration of either NaAlH4 or LiBH4 into a carbon scaffold, of which the surface had been modified, varying from H-terminated to oxidized (up to 4.4 O/nm2). It has been suggested that the chemical and electronic properties of the carbon/metal hydride interface can have a large influence on hydrogen storage properties. However, no significant impact on the first H2 release temperatures was found. In contrast, the surface properties of the carbon played a major role in determining the reversible hydrogen storage capacity. Only a part of the oxygen-containing groups reacted with hydrides during melt infiltration, but further reaction during cycling led to significant losses, with reversible hydrogen storage capacity loss up to 40% for surface oxidized carbon. However, if the carbon surface had been hydrogen terminated, ∼6 wt% with respect to the NaAlH4 weight was released in the second cycle, corresponding to 95% reversibility. This clearly shows that control over the nature and amount of surface groups offers a strategy to achieve fully reversible hydrogen storage in complex metal hydride-carbon nanocomposites. © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

There are several strategies to improve the electrochemical performance of TiO2 as negative electrode material for Li-ion batteries. Introducing oxygen vacancies through hydrogen reduction leads to an enhancement in electrical conductivity. However, this strategy does not improve the low lithium-ion mobility. Herein, we show that by decreasing the temperature of hydrogen annealing the improved lithium-ion mobility of high-surface-area TiO2 and β-TiO2 can be combined with the enhanced electrical conductivity of oxygen deficiencies. Annealing at only 275–300 °C in pure hydrogen atmosphere successfully creates oxygen vacancies in TiO2, as confirmed by UV/Vis spectroscopy, whereas the temperature is low enough to maintain a high specific surface area and prevent β-to-anatase phase transformation. The hydrogen reduction of high-surface-area anatase or anatase/β-TiO2 at these temperatures leads to improvements in the performance, achieving charge capacities of 142 or 152 mAh g−1 at 10C, respectively. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Metal-free nitrogen modified carbon catalysts (NC) are very closely related to MNC catalysts which contain a transition metal(s) (M), usually Fe or Co as an essential constituent. We investigated the influence of metal inclusions on the activity of nitrogen-doped carbon black in the electrocatalysis of the oxygen reduction reaction (ORR). A reference metal-free NC catalyst was prepared by pyrolysis of a polypyrrole/Vulcan XC72 composite at 800 °C for 2 h under helium. Controlled amounts of Co, Fe, Mn and Ni in low concentrations were then introduced into NC by impregnating it with the corresponding meso-tetra(4-pyridyl) porphyrin metal complex followed by further pyrolysis at 650 °C for 2 h under helium. The resulting catalysts were investigated for ORR using rotating disk electrode and rotating-ring disk electrode voltammetry in 0.1 M KOH. Additionally, the rate of decomposition of hydrogen peroxide by the different catalysts was determined in order to probe the influence of the metal inclusions on the mechanism and selectivity of the ORR. The results show that Fe, Co and Mn inclusions cause a substantial decrease of the overpotential of the reaction and enhance the catalytic current, whereas the presence of Ni has a poisoning effect on ORR. In the presence of Fe, the catalysts apparently reduce oxygen selectively to OH- in a direct four electron transfer process as opposed to the two-step, two electron pathway involving hydrogen peroxide as an intermediate for the case of the NC catalyst. © 2013 Elsevier Ltd.

Reversible interconversion of water into H2 and O2, and the recombination of H2 and O2 to H2O thereby harnessing the energy of the reaction provides a completely green cycle for sustainable energy conversion and storage. The realization of this goal is however hampered by the lack of efficient catalysts for water splitting and oxygen reduction. We report exceptionally active bifunctional catalysts for oxygen electrodes comprising Mn3O4 and Co 3O4 nanoparticles embedded in nitrogen-doped carbon, obtained by selective pyrolysis and subsequent mild calcination of manganese and cobalt N4 macrocyclic complexes. Intimate interaction was observed between the metals and nitrogen suggesting residual M-Nx coordination in the catalysts. The catalysts afford remarkably lower reversible overpotentials in KOH (0.1M) than those for RuO2, IrO2, Pt, NiO, Mn3O4, and Co3O4, thus placing them among the best non-precious-metal catalysts for reversible oxygen electrodes reported to date. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Insufficient electrochemical stability is a major challenge for carbon materials in oxygen reduction reaction (ORR) due to carbon corrosion and insufficient metal-support interactions. In this work, titania is explored as an alternative support for Pt catalysts. Oxygen deficient titania samples including TiO<inf>2-x</inf> and TiO<inf>2-x</inf>N<inf>y</inf> were obtained by thermal treatment of anatase TiO<inf>2</inf> under flowing H<inf>2</inf> and NH<inf>3</inf>, respectively. Pt nanoparticles were deposited on the titania by a modified ethylene glycol method. The samples were characterized by N<inf>2</inf>-physisorption, X-ray diffraction and X-ray photoelectron spectroscopy. The ORR activity and long-term stability of supported Pt catalysts were evaluated using linear sweep voltammetry and chronoamperometry in 0.1 mol/L HClO<inf>4</inf>. Pt/TiO<inf>2-x</inf> and Pt/TiO<inf>2-x</inf>N<inf>y</inf> showed higher ORR activities than Pt/TiO<inf>2</inf> as indicated by higher onset potentials. Oxygen deficiency in TiO<inf>2-x</inf> and TiO<inf>2-x</inf>N<inf>y</inf> contributed to the high ORR activity due to enhanced charge transfer, as disclosed by electrochemical impedance spectroscopy studies. Electrochemical stability studies revealed that Pt/TiO<inf>2-x</inf> exhibited a higher stability with a lower current decay rate than commercial Pt/C, which can be attributed to the stable oxide support and strong interaction between Pt nanoparticles and the oxygen-deficient TiO<inf>2-x</inf> support. © 2014 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

The notorious instability of non-precious-metal catalysts for oxygen reduction and evolution is by far the single unresolved impediment for their practical applications. We have designed highly stable and active bifunctional catalysts for reversible oxygen electrodes by oxidative thermal scission, where we concurrently rupture nitrogen-doped carbon nanotubes and oxidize Co and Mn nanoparticles buried inside them to form spinel Mn-Co oxide nanoparticles partially embedded in the nanotubes. Impressively high dual activity for oxygen reduction and evolution is achieved using these catalysts, surpassing those of Pt/C, RuO2, and IrO2 and thus raising the prospect of functional low-cost, non-precious-metal bifunctional catalysts in metal-air batteries and reversible fuel cells, among others, for a sustainable and green energy future. © 2014 American Chemical Society.

CNT growth experiments on a cobalt-based catalyst were conducted in a tubular fixed bed reactor at different temperatures and ethene concentrations. The measured kinetic data were analyzed with an isothermal, dynamic reactor model taking into account pore and film diffusion as well as the size of CNT agglomerates as a function of time. Based on previously published results it was found that the CNT agglomerates are enlarged by an average factor of 6.5 compared to the original diameter of the catalyst particle. Under these conditions, the development of the agglomerate diameter with time can be described with a single parameter which is independent of the reaction conditions. The rate of the CNT growth was determined to be first order in the ethene concentration with an activation energy of 107. kJ/mol. The catalyst deactivation by cumulative encapsulation of active sites was found to be second order with respect to the consumed amount of ethene with a rate constant independent of the temperature. Nevertheless, deactivation takes place faster at higher temperatures and/or ethene concentrations, since the deactivation process is directly coupled to the rate of CNT synthesis. © 2014 Elsevier B.V.

Nitrogen-doped carbon nanotubes (NCNTs) are highly active electrocatalysts in the oxygen reduction reaction (ORR) at alkaline conditions. However, the initial activation and stabilization of NCNTs have rarely been investigated at industrially relevant conditions. Three types of NCNTs were synthesized by catalytic growth (NCNT-growth) or posttreatment of oxygen-functionalized CNTs with NH3 (NCNT-NH3) or aniline (NCNT-aniline). The obtained NCNTs were treated in 10 M KOH at 80 C for 5 h, and the formation of oxygen groups by alkaline treatment and their interaction with existing nitrogen groups was analyzed. X-ray photoelectron spectroscopy showed that the concentrations of pyridinic and quaternary nitrogen increased in NCNT-growth due to the KOH treatment accompanied by the decrease of pyrrolic nitrogen, whereas the nitrogen groups changed differently in NCNT-NH3 and NCNT-aniline. NCNT-NH3 showed the highest ORR activity before alkaline treatment. After the treatment, the activity of NCNT-growth was higher, whereas those of NCNT-NH3 and NCNT-aniline were lower. These results were found to be correlated with changes in the nitrogen groups caused by alkaline treatment. Furthermore, NCNTs showed different C=O/C-O ratios after alkaline treatment as compared to a strong increase of C-O in CNTs, indicating that the presence of nitrogen in NCNTs influences the formation of oxygen groups on carbon and surface oxidation. © 2013 American Chemical Society.

Improving the chemical diffusion of Li ions in anatase TiO2 is essential to enhance its rate capability as a negative electrode for Li-ion batteries. Ammonia annealing has been used to improve the rate capability of Li4Ti5O12. Similarly, ammonia annealing improves the Li-ion storage performance of anatase TiO2 in terms of the stability upon cycling and the Crate capability. In order to distinguish whether N doping or oxygen deficiencies, both introduced upon ammonia annealing, are more relevant for the observed improvement, a systematic electrochemical study was performed. The results suggest that the creation of oxygen vacancies upon ammonia annealing is the main reason for the improvement of the stability and C-rate capability. © 2013 Wiley-VCH Verlag GmbH & Co. KGaA.

Carbon nanotubes (CNTs) grown on carbon cloth substantially increased the surface area of the electrodes. Carbon cloths were pretreated with HNO3 vapor before CNTs growth and electrochemically oxidized afterwards. The CNT-modified carbon cloths were characterized using scanning electron microscopy, Raman spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Biofuel cells based on these CNT-modified electrode materials using Laccase from Trametes hirsuta and cellobiose dehydrogenase from Myriococcum thermophilium entrapped in specifically designed Os-complex modified redox polymers showed a power density of 5.87μW/cm2 which is 125 fold enhanced as compared with electrodes prepared on untreated carbon cloth. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A direct strategy for the creation of defects on carbon nanofibers (CNFs) has been developed by steam treatment. Nitrogen physisorption, XRD, Raman spectra, SEM and TEM analyses proved the existence of the new defects on CNFs. BET surface area of CNFs after steam treatment was enhanced from 20 to 378 m2/g. Pd catalysts supported on CNFs were also prepared by colloidal deposition method. The different activity of Pd/CNFs catalysts in the partial hydrogenation of phenylacetylene further demonstrated the diverse surfaces of CNFs could be formed by steam treatment. © 2013 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences. Published by Elsevier B.V.

The influence of support polarity on Pd/CNF for the deoxygenation of fatty acids was studied. Catalysts with a low (O/C = 3.5 × 10-2 at/at from X-ray photoelectron spectroscopy (XPS)) and a high (O/C = 5.9 × 10-2 at/at from XPS) amount of oxygen containing groups on the support were prepared. The latter were introduced via a HNO3 gas phase oxidation treatment on Pd loaded supports. The presence of oxygen containing groups was beneficial for the activity of Pd for the deoxygenation of the amphiphilic stearic acid. This is attributed to a favorable mode of adsorption of the reactant via the carboxylic acid group on the more polar support in the vicinity of the catalytically active Pd nanoparticles. © 2013 American Chemical Society.

Water-assisted growth of multiwalled carbon nanotubes (CNTs) was studied over a Co-based catalyst under plug-flow conditions. The influence of water concentration and temperature on the growth kinetics within the first 300 s was analyzed by measuring the conversion of ethylene. Feeding 200 ppm H2O vapor at 650 C accelerated the initial growth rate and extended the mean lifetime of the catalytically active sites. Higher water concentrations of up to 500 ppm led to lower growth rates and lower CNT yields. Water of 200 ppm showed a promoting effect at 650 C, but an inhibiting effect at 550 C. The CO generated by steam gasification of deposited carbon was monitored online indicating coking of the catalyst. The results demonstrate that water plays a dual role: the removal of amorphous carbon on the catalyst by gasification and partial oxidation of the metallic Co catalyst. Water also influenced the diameter distribution of the CNTs. © 2013 American Chemical Society.

A white Mo(VI)-melamine hybrid solid precipitated immediately when aqueous solutions of (NH4)6Mo7O24 and melamine were mixed. This hybrid proved to be an efficient single-source precursor for single-phase β-Mo2C. Treating the precursor at 650 C in either Ar or H2 resulted in molybdenum carbides, with H 2 being the optimal choice from the perspective of achieving a high-purity carbide. This single-source route successfully inverted the direction of carbon diffusion, thus alleviating the polymerization of carbon species on the carbide surface, which will provide several advantages in catalytic applications. As in the hydrogenation of naphthalene, an ultrahigh selectivity to tetralin was achieved over the resultant β-Mo2C, and its highly purified surface facilitated a steady state with high conversion. With the characteristics of low cost and nontoxicity, the Mo(VI)-melamine hybrid could serve as a green starting material for obtaining highly crystallized β-Mo2C with high purity. © 2013 American Chemical Society.

Nitrogen-doped carbon materials were synthesized and used as metal-free electrocatalysts for the oxygen reduction reaction (ORR) under alkaline conditions. The synthesis was achieved by thermal treatment of nitrogen-containing polymers diluted in different carbon materials. Polypyrrole, polyaniline and polyacrylonitrile were used as N precursors. Carbon black and two types of commercial carbon nanotubes were used as carbon matrices. The obtained N contents were in the range of 1-1.8 wt.%. Different N species including pyridinic, pyrrolic and quaternary N were quantitatively determined by X-ray photoelectron spectroscopy. The ORR activities were evaluated in 0.1 M KOH. Rotating disc electrode studies revealed the presence of multiple active centers in all the samples. The sample obtained using polypyrrole and small diameter nanotubes (ca. 15 nm) had the highest onset potential at -0.07 V vs. Ag/AgCl/3 M KCl, which also showed a significantly higher electrochemical stability than the sample from carbon black and polypyrrole. The ORR activity was not correlated to the total nitrogen amount, but to the amount of pyridinic and quaternary N species. For the onset potential and the (Npyridinic + Nquaternary)/Ntotal ratio a quasi-linear relation was found, which points to the substantial role of pyridinic- and quaternary-N species in ORR catalysis. © 2013 Elsevier Ltd. All rights reserved.

Tailoring the morphology and structure of graphene can result in novel properties for advanced applications. Here, we demonstrate the fabrication of nanostructured few-layer graphene through a mild etching process via catalytic steam gasification of carbon by Fe nanoparticles (NPs). Controlling the reaction temperature, steam concentration, and the loading density of the NPs enables the fine-tuning of the etching level of graphene. Well-defined nanotrenches with a width of less than 25 nm were formed by channeling of the catalytic NPs. Etching caves and quasi-semicircular etched edges were observed as well. The nonlinear optical properties of the resulting nanostructured graphene were studied under a 532 nm nanosecond pulse laser through an open-aperture apparatus. At the same level of the linear extinction coefficient, it exhibits superior optical limiting performance in comparison with pristine graphene and C60, showing a large potential in nanophotonic devices. This enhancement is ascribed to the defects formed by etching resulting in a finite band gap in nanostructured graphene. © 2013 American Chemical Society.

A setup for optically monitoring the agglomerate growth of multiwalled carbon nanotubes (MWCNTs) by catalytic chemical vapor deposition on single Co-Mn-Al-Mg oxide catalyst particles with ethene as carbon precursor has been developed. Ethene concentrations and temperatures were varied between 5. -75. Vol.% and 550-770. °C, respectively. It could be shown that the agglomerate growth is rapid and the final diameter is reached after a few ten seconds to about 3. min depending on the reaction conditions. The average enlargement factor of the agglomerates over all experiments was found to be 6.5. ±. 1.2 compared to the original diameter of the catalyst particle. The growth rate is enhanced by both, reaction temperature and ethene concentration. Hence it is concluded that the agglomerate growth rate is associated with the reaction rate of MWCNT synthesis. Short time experiments and analysis of the resulting agglomerates have confirmed an earlier proposed growth mechanism. © 2013 Elsevier B.V.

Oxygen- and nitrogen-functionalized carbon nanotubes (OCNTs and NCNTs) were applied as metal-free catalysts in selective olefin hydrogenation. A series of NCNTs was synthesized by NH3 post-treatment of OCNTs. Temperature-programmed desorption, N2 physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 °C led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis. Copyright © 2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.

The initial growth kinetics of multi-walled carbon nanotubes (CNTs) was investigated using a highly active Co-based mixed-oxide catalyst in a tubular fixed-bed reactor under plug-flow conditions with ethene as carbon source. The growth temperature and the ethene concentration were systematically varied in the range from 758 to 923 K and from 5 to 45 vol.%, respectively. The carbon mass accumulation was derived from the ethene conversion and analyzed by a kinetic model, from which the initial CNT growth rate and the mean lifetime of the active sites were derived permitting the prediction of the maximum theoretical CNT yield. With increasing growth temperatures up to 923 K both the initial growth rate and the mean lifetime of active sites increased strongly with a significantly prolonged lifetime above 848 K. The initial growth rate was slow at lower ethene concentrations, but the mean life time was very high. Increasing the ethene concentration up to 45 vol.% led to a much higher initial growth rate, but shortened the mean lifetime strongly. Due to the fast deactivation at high ethene concentrations, the predicted maximum yield decreased considerably approaching the yield obtained after 5 min of time on stream. © 2013 Elsevier Ltd. All rights reserved.

The influence of the residual growth catalyst on the reducibility and catalytic activity of Pt nanoparticles supported on oxygen- and nitrogen-functionalized CNTs (OCNTs and NCNTs) was systematically investigated. It was found that the presence of the residual growth catalyst significantly influenced the oxygen and nitrogen functionalization of CNTs, which consequently altered the reducibility of the supported Pt nanoparticles. Pt nanoparticles on NCNTs showed a higher stability against sintering in reducing atmosphere at 200 C and 400 C than those on OCNTs. On NCNTs, Pt was in a higher oxidation state and was not as easily reducible as on OCNTs. In hydrogenation catalysis, removing the residual growth catalyst is essential for the supported Pt catalyst to achieve a better performance. Compared with Pt on OCNTs, Pt on NCNTs was less active, but more selective in olefin hydrogenation due to the poisoning effect of the surface nitrogen species. © 2013 Elsevier Inc. All rights reserved.

A high-performance Pd catalyst for selective olefin hydrogenation was synthesized by supporting Pd nanoparticles on nitrogen-doped carbon nanotubes (NCNTs). X-ray diffraction, hydrogen chemisorption, transmission electron microscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize Pd supported on NCNTs and nitrogen-free oxygen-functionalized CNTs (OCNTs). The Pd nanoparticles were stabilized on NCNTs with narrower size distribution compared with OCNTs. The XPS analysis revealed that the nitrogen functional groups favor the reduction of Pd on CNTs suggesting an electronic promoter effect. The Pd/NCNT catalyst showed extraordinary catalytic performance in terms of activity, selectivity and stability in the selective hydrogenation of cyclooctadiene, which is related to the structural and electronic promoting effect of the NCNT support. © 2013 The Royal Society of Chemistry.

The power of spray-dried TiO2 in LIBs: TiO2(B)/ anatase is synthesized by spray drying and investigated as negative electrode material in Li-ion batteries. It exhibits excellent Li-ion storage performances, especially at high charge/discharge rates. The presence of the β phase of TiO2 improves Li-ion diffusivity. Additionally, the scalable synthesis method also allows for Nb-doping, which assists in the maintenance of the electronic conductivity as the thickness of film increases. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

We show in this study that the presence of trace metal residues in some supposedly metal-free catalysts for oxygen reduction, at concentrations which are difficult to detect using conventional methods such as XPS and EDX, can profoundly promote the ORR activity of the catalysts. © 2013 Elsevier B.V. All rights reserved.

The selective hydrogenation of naphthalene to tetralin has been conducted on Mo2C/AC prepared by microwave irradiation, and achieved a lasting high conversion with 100% selectivity up to 60 hours. The choice of activated carbon as a support is critical in gaining an ideal balance between high activity and good stability of the catalyst. © 2012 The Royal Society of Chemistry.

A CNTs-TiO 2-δ composite consisting of carbon nanotubes (CNTs) grown by catalytic chemical vapor deposition on oxygen-deficient titanium dioxide (TiO 2-δ) nanoparticles was synthesized and investigated as high-rate negative electrode material for Li-ion batteries. An initial reversible capacity of 185 mAhg - 1 was obtained at C/2, with an initial irreversible loss of 15%. The composite showed a high stability upon cycling, with 92% retention of the capacity after 37 cycles, and good high rate capability, with a capacity of 102 mAhg - 1 at 10C. The performance of the CNTs-TiO 2-δ composite was compared to that of pristine commercial TiO 2 and to that of oxygen-deficient TiO 2 - δwith the aim of identifying the source of the improvement. Both TiO 2-δ and CNTs network were found to contribute to the enhanced electrochemical performance of CNTs-TiO 2-δ composite. © 2012 Elsevier B.V.

Cheers for titania: An N-doped composite of carbon nanotubes (CNTs) and mesoporous TiO 2 is used as support for Pt nanoparticles applied in the oxygen reduction reaction. The composite Pt/N-TiO 2-CNT shows a higher stability than Pt particles on carbon black or N-doped CNTs, as indicated by accelerated stress tests of up to 2000 cycles. The enhanced stability is attributed to strong interactions between TiO 2 and Pt and a higher corrosion resistance of TiO 2 as well as CNTs. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen containing groups were introduced, onto carbon nanofibers (CNFs) that were previously loaded with palladium, using HNO 3 vapor. Using traditional liquid-phase oxidations this is not possible due to severe metal leaching. For the samples oxidized using HNO 3 vapor temperature programmed desorption and X-ray photoelectron spectroscopy revealed the presence of two major classes of oxygen containing groups, i.e. carboxylic acid groups which are thermally stable up to 300 °C and less acidic (e.g. phenol) and basic groups which were stable up to 700 °C. The amount of acidic oxygen containing groups introduced by this gas-phase treatment ranged from 0.1 to 0.3 mmol/g, as determined by titration. The latter amount is comparable to that introduced by traditional liquid-phase treatment in 65% HNO 3 on bare CNFs. Transmission electron microscopy and H 2-chemisorption measurements show a gradual increase of the average metal particle size from 2.1 nm for the starting Pd/CNF to 4.5 nm for Pd/CNF treated for 75 h in HNO 3 vapor indicating that the extent of sintering with gas-phase treatment is limited. Elemental analysis showed that no leaching occurred upon gas-phase oxidation, whereas 90% of the metal was lost with a liquid-phase reflux HNO 3 treatment. © 2012 Elsevier Ltd. All rights reserved.

Concerted efforts: A high-potential biocathode based on co-immobilization of glucose oxidase (GOx) and horseradish peroxidase (HRP) onto a carbon nanotube/carbon microfiber modified graphite rod electrode (CNT/CMF/GR) is described (see figure). The GOx/HRP biocathode shows a remarkable biocatalytic activity in the presence of glucose and oxygen. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Commercial carbon cloth made of PAN-based carbon fibres was used as free-standing anode for lithium intercalation. The role of surface functional groups on the specific irreversible charge loss and reversible charge during the intercalation and de-intercalation of lithium ions into carbon cloth has been investigated. Oxygen groups have been introduced by nitric acid vapour treatment and subsequently gradually removed by thermal treatment at different temperatures in He or H 2 atmosphere as confirmed by X-ray photoelectron spectroscopy. A clear correlation between the amount of surface-bound oxygen groups and the irreversible specific charge was observed. Three irreversible processes were distinguished during the first cathodic scan: (i) reduction of oxygen groups, (ii) formation of the solid electrolyte interphase (SEI) and (iii) presumably exfoliation. The latter one was only observed for samples with low surface oxygen concentration, and its contribution to the irreversible capacity was small due to the low graphitization degree of the samples. An increased specific reversible charge upon increasing the amount of oxygen-containing groups was observed with the main improvement above 1.5 V. © 2012 Elsevier Ltd. All rights reserved.

High-temperature Fischer-Tropsch synthesis for the production of short-chain olefins over iron catalysts supported on multiwalled carbon nanotubes (CNTs) was investigated under industrially relevant conditions (340°C, 25bar, H 2/CO=1) to elucidate the influence of nitrogen and oxygen functionalization of the CNTs on the activity, selectivity, and long-term stability. Surface functionalization of the CNTs was achieved by means of a gas-phase treatment using nitric acid vapor at 200°C for oxygen functionalization (O-CNTs) and ammonia at 400°C for the subsequent nitrogen doping (N-CNTs). Ammonium iron citrate impregnation followed by calcination was applied for the deposition of iron nanoparticles with particle sizes below 9nm. Subsequent to reduction in pure H 2 at 380°C, the Fe/N-CNT and Fe/O-CNT catalysts were applied in Fischer-Tropsch synthesis, in which they showed comparable initial conversion values with an excellent olefin selectivity [S(C 3-C 6)&gt;85%] and low chain growth probability (α≤0.5). TEM analysis of the used catalysts detected particle sizes of 23 and 26nm on O-CNTs and N-CNTs, respectively, and Fe 5C 2 was identified as the major phase by using XRD, with only traces of Fe 3O 4. After 50h time on stream under steady-state conditions, an almost twofold higher activity compared to the Fe/O-CNT catalysts had been maintained by the Fe/N-CNT catalysts, which are considered excellent Fischer-Tropsch catalysts for the production of short-chain olefins owing to their high activity, high selectivity to olefins, low chain growth probability, and superior long-term stability. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The gasification of carbon with CO 2 was applied to examine the role of the residual iron growth catalyst in multi-walled carbon nanotubes (CNTs), which were pre-treated either by refluxing in nitric acid at 120 °C or by nitric acid vapor at 200 °C. Temperature-programmed desorption (TPD) and surface reaction (TPSR) experiments were performed in He and CO 2, respectively. The Fe nanoparticles were retained after the treatment in HNO 3 vapor, whereas the liquid HNO 3 treatment was able to remove the accessible residual Fe catalyst. The exposed Fe nanoparticles were found to catalyze the gasification of CNTs with CO 2 according to the reverse Boudouard reaction C + CO 2 = 2CO. In case of the CNTs pretreated in HNO 3 vapor, evolving CO 2 formed due to the decomposition of oxygen-containing functional groups during the TPD experiments was fully converted above 750 °C into desorbing CO, and the addition of 2000 ppm CO 2 in the feed gas during the TPSR experiments resulted in full conversion at 1000 °C. X-ray photoelectron spectroscopy studies show that the treatment in HNO 3 vapor at 200 °C favors the formation of oxygen species doubly bound to carbon (CO groups). During the TPSR experiments, CO 2 as a weak oxidant partially oxidized the CNTs leading to the formation of CO groups, and a much higher amount of these groups was detected on HNO 3 vapor-treated CNTs with residual Fe catalyst. Their presence suggests that CO groups are reaction intermediates of the CNT gasification with CO 2, which is considered an effective test reaction for the presence of residual catalytically active nanoparticles. © 2012 Elsevier B.V.

Gas-phase methods were applied for the oxygen and nitrogen functionalization of multiwalled carbon nanotubes (CNTs). The oxygen functionalization was performed by HNO 3 vapor treatment at temperatures from 200 to 250 °C for 12 h up to 120 h. The oxygen-functionalized CNTs were used as the starting material for nitrogen functionalization through thermal treatment under NH 3. The BET surface area increased after the treatment in HNO 3 vapor, which also caused the weight loss due to carbon corrosion. The oxygen content increased with increasing treatment time but decreased with increasing temperature, as disclosed by elemental analysis, X-ray photoelectron spectroscopy, and temperature-programmed desorption (TPD) results. The surface acidity increased with increasing treatment time as shown by TPD using NH 3 as a probe molecule. As to nitrogen functionalization, the amount of nitrogen was correlated with the oxygen amount in the starting CNTs. A higher NH 3 concentration caused a lower BET surface area due to carbon corrosion. The incorporation of both oxygen and nitrogen lowered the thermal resistance of CNTs. The nitrogen-functionalized CNTs showed only a slight decrease, in contrast to a significant decrease observed for O-functionalized CNTs. The formation or removal of coordinatively unsaturated carbon like amorphous carbon or defects was found to be involved in all of the functionalization, desorption, and oxidation processes. © 2012 American Chemical Society.

The synthesis of bimetallic nanoparticles (NPs) with well-defined morphology and a size of <5 nm remains an ongoing challenge. Here, we developed a facile and efficient approach to the design of bimetallic nanostructures by the galvanic replacement reaction facilitated by high-intensity ultrasound (100 W, 20 kHz) at low temperatures. As a model system, Pt-Cu NPs deposited on nitrogen-doped carbon nanotubes (NCNTs) were synthesized and characterized by spectroscopic and microscopic techniques. Transmission electron microscopy (TEM) inspection shows that the mean diameter of Pt-Cu NPs can be as low as ≈2.8 nm, regardless of the much larger initial Cu particle size, and that a significant increase in particle number density by a factor of 35 had occurred during the replacement process. The concentration of the Pt precursor solution as well as of the size of the seed particles were found to control the size of the bimetallic NPs. Energy dispersive X-ray spectroscopy performed in the scanning TEM mode confirmed the alloyed nature of the Pt-Cu NPs. Electrochemical oxygen reduction measurements demonstrated that the resulting Pt-Cu/NCNT catalysts exhibit an approximately 2-fold enhancement in both mass- and area-related activities compared with a commercial Pt/C catalyst. © 2012 American Chemical Society.

A hierarchical carbon-fiber composite was synthesized based on carbon cloth (CC) modified with primary carbon microfibers (CMF) and subsequently secondary carbon nanotubes (CNT), thus forming a three-dimensional hierarchical structure with high BET surface area. The primary CMFs and the secondary CNTs are grown with electrodeposited iron nanoparticles as catalysts from methane and ethylene, respectively. After deposition of Pt nanoparticles by chemical vapor deposition from (trimethyl)cyclopentadienylplatinum, the resulting hierarchical composite was used as catalyst in the electrocatalytic oxygen reduction (oxygen reduction reaction, ORR) as specific test reaction. The modification of the CC with CMFs and CNTs improved the electrochemical properties of the carbon composite as revealed by electrochemical impedance measurements evidencing a low charge transfer resistance for redox mediators at the modified CC. X-ray photoelectron spectroscopy measurements were carried out to identify the chemical state and the surface atomic concentration of the Pt catalysts deposited on the hierarchical carbon composites. The ORR activity of Pt supported on different composites was investigated using rotating disk electrode measurements and scanning electrochemical microscopy. These electrochemical studies revealed that the obtained structured catalyst support is very promising for electrochemical applications, e.g. fuel cells. © 2012 Elsevier Ltd. All rights reserved.

Multi-walled CNT were oxidised with nitric acid in liquid and gas-phase. By splitting the capacity and initial charge loss during lithium intercalation into different potential regions, it was possible to relate these values to the CNT surface oxygen groups as determined by XPS. Gas-phase oxidised CNT show a significantly lower amount of initial charge loss (172 mAh/g) compared to liquid-phase oxidised CNT (283 mAh/g). This decrease originates from less pronounced exfoliation likely caused by an increase of surface carbonyl groups. © 2011 Elsevier B.V.

The sintering of iron nanoparticles on carbon nanotubes (CNTs) under different atmospheres was investigated. CNTs were first treated with HNO3 vapor at 200°C to obtain O-functionalized CNTs (OCNTs). The OCNTs were treated in ammonia at 400°C to obtain N-doped CNTs (NCNTs). Highly dispersed FeOx nanoparticles were subsequently deposited by chemical vapor deposition from ferrocene under oxidizing conditions. The obtained FeOx/OCNT and FeOx/NCNT samples were allowed to sinter at 500°C under flowing helium, hydrogen, or ammonia. The samples were studied by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. A significant increase in particle size and a decrease in Fe surface atomic concentration were observed in all the sintered samples. The sintering on OCNTs was more severe than on NCNTs, which can be attributed to stronger metal-substrate interactions and a higher amount of surface defects on NCNTs. The applied gas atmosphere had a substantial influence on the sintering behavior of the nanoparticles: treatment in helium led to the growth of particles and a significant widening of particle size distributions, whereas treatment in hydrogen or ammonia resulted in the growth of particles, but not in the widening of particle size distributions. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thin film metal oxide material libraries were prepared by sputter deposition of nanoscale Ti/Nb precursor multilayers followed by ex situ oxidation. The metal composition was varied from 6 at.% Nb to 27 at.% Nb. Additionally, thin wedge-type layers of Pt with a nominal thickness gradient from 0 to 5 nm were sputter-deposited on top of the oxides. The materials libraries were characterized with respect to metallic film composition, oxide thickness, phases, electrical conductivity, Pt thickness, and electrochemical activity for the oxygen reduction reaction (ORR). Electrochemical investigations were carried out by cyclic voltammetry using an automated scanning droplet cell. For a nominal Pt thickness >1 nm, no significant dependence of the ORR activity on the Pt thickness or the substrate composition was observed. However, below that critical thickness, a strong decrease of the surface-normalized activity in terms of reduction currents and potentials was observed. For such thin Pt layers, the conductivity of the substrate seems to have a substantial impact on the catalytic activity. Results from X-ray photoelectron spectroscopy (XPS) measurements suggest that the critical Pt thickness coincides with the transition from a continuous Pt film into isolated particles at decreasing nominal Pt thickness. In the case of isolated Pt particles, the activity of Pt decisively depends on its ability to exchange electrons with the oxide layer, and hence, a dependence on the substrate conductivity is rationalized. © 2011 American Chemical Society.

A straight-forward method for the synthesis of metal-free catalysts for oxygen reduction by thermal treatment of a mixture of poly(3,5-pyridine) with carbon black in helium is reported. The catalyst was characterized by X-ray diffraction and photoelectron spectroscopy, cyclic voltammetry and rotating disk electrode measurements. The new catalyst exhibited remarkable activity similar to Pt-based catalysts in alkaline media. © 2011 Elsevier B.V. All Rights Reserved.

MoO 3/γ-Al 2O 3 composites are synthesized by CVD under atmospheric pressure using Mo(CO) 6 as the precursor and porous γ-Al 2O 3 particles in a horizontal, rotating, hot-wall reactor, which is also used for calcination in air. The composites are characterized by N 2 physisorption, atomic absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM), and laser Raman spectroscopy (LRS). The synthesized samples exhibit excellent porosity, even at high Mo loadings. A much higher Mo yield is achieved when applying sublimation-adsorption in static air instead of using flowing N 2. A high degree of Mo dispersion on alumina is confirmed by XRD, LRS, and TEM; with a Mo surface density as high as 5.2 atoms nm -2, the sample is X-ray amorphous, there are no polymeric molybdate species detectable by LRS, and the island size of the molybdate species is about 1 nm according to TEM. The XPS analysis shows that exclusively Mo VI species are present on all synthesized samples. Thus, the applied rotating, hot-wall reactor achieves efficient mixing and homogeneous deposition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An industrially applicable cobalt-based catalyst was optimized for the production of multiwalled carbon nanotubes (CNTs) from ethene in a hot-wall reactor. A series of highly active Co-Mn-Al-Mg spinel-type oxides with systematically varied Co: Mn ratios was synthesized by precipitation and calcined at different temperatures. The addition of Mn drastically enhanced the catalytic activity of the Co nanoparticles resulting in an extraordinarily high CNTyield of up to 249 g CNT/gcat. All quaternary catalysts possessed an excellent selectivity towards the growth of CNTs. The detailed characterization of the obtained CNTs by electron microscopy, Raman spectroscopy and thermogravimetry demonstrated that a higher Mn content results in a narrower CNT diameter distribution, while the morphology of the CNTs and their oxidation resistance remains rather similar. The temperature- programmed reduction of the calcined precursors as well as in situ X-ray absorption spectroscopy investigations during the growth revealed that the remarkable promoting effect of the Mn is due to the presence of monovalent Mn (II) oxide in the working catalyst, which enhances the catalytic activity of the metallic Co nanoparticles by strong metal-oxide interactions. The observed correlations between the added Mn promoter and the catalytic performance are of high relevance for the production of CNTs on an industrial scale. © 2011 Elsevier Ltd. All rights reserved.

Rhodium Drive: Carbon nanotube-supported rhodium sulfide electrocatalysts are prepared by sequential chemical vapor deposition of iron, controlled vapor phase polymerization of thiophene, and finally impregnation of the rhodium precursor and pyrolysis. The electrocatalysts are applied in the oxygen reduction reaction under HCl electrolysis conditions. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nb-doped TiO2 nanoparticles were prepared by a continuous spray drying process using ammonium niobate (V) oxalate and titanium oxysulfate as water-soluble precursors. The structural and electronic properties were investigated using thermogravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. Nb was found to be mainly incorporated as Nb5+ into the TiO2 lattice resulting in a charge compensation by Ti vacancies. The characterization results indicate that Nb was homogeneously distributed within the titania lattice, and that the surface segregation of Nb, which is commonly observed for Nb-doped TiO 2, was significantly less pronounced. The high homogeneity and the lower extent of surface segregation originate from the efficient atomization of homogeneous precursor solutions and the fast evaporation of the solvent in the spray drying process. As a result, the ion mobility is diminished and spheres of well-mixed precursor materials are formed. Using the continuous spray drying process followed by a controlled heat treatment, the phase composition, the crystal size and the surface area of the Nb-doped TiO2 nanoparticles are easily adjustable. © The Royal Society of Chemistry 2011.

TiO 2 was deposited on high surface area porous silica gel (400 m 2g -1) in a fluidized bed reactor. Chemical vapor deposition was employed for the coating under vacuum conditions with TiCl 4 as precursor. Nitrogen physisorption, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis spectroscopy were applied to characterize the obtained TiO 2-SiO 2 composites with different Ti loadings up to 5 wt%. Only a slight decrease in the specific surface area was detected at low Ti loadings. At a Ti loading of 2 wt%, TiO 2 was found to be highly dispersed on the SiO 2 surface likely in form of a thin film. At higher Ti loadings, two weak reflections corresponding to anatase TiO 2 were observed in the diffraction patterns indicating the presence of crystalline bulk TiO 2. High resolution XPS clearly distinguished two types of Ti species, i.e., Ti-O-Si at the interface and Ti-O-Ti in bulk TiO 2. The presence of polymeric TiOx species at low Ti loadings was confirmed by a blue shift in the UV-vis spectra as compared to bulk TiO 2. All these results point to a strong interaction between the TiO 2 deposit and the porous SiO 2 substrate especially at low Ti loadings. Copyright © 2011 American Scientific Publishers All rights reserved.

Surface defects were created on carbon nanotubes (CNTs) by catalytic steam gasification or catalytic etching with iron as catalysts. The structure and morphology of the etched CNTs were studied by transmission electron microscopy (TEM) and scanning tunneling microscopy (STM). The electronic structure of the etched CNTs was investigated by ultraviolet photoelectron spectroscopy (UPS). The etched CNTs were treated by nitric acid to obtain oxygen-containing functional groups. The amount and the thermal stability of these groups were studied by temperature-resolved X-ray photoelectron spectroscopy (XPS). Temperature-programmed desorption with ammonia as a probe molecule (NH 3-TPD) was employed to investigate the interaction of the surface defects with foreign molecules in gas phase. TEM and STM studies disclosed the presence of surface defects especially edge planes on the etched CNTs. Etching of CNTs led to a less pronounced p-π band than the as-is CNTs, as evidenced by UPS studies. The XPS and NH 3-TPD studies demonstrated that the defects on the CNTs enhanced the reactivity of the exposed surfaces allowing obtaining a higher degree of oxygen functionalization and more active adsorption sites. © 2010 Elsevier Ltd. All rights reserved.

Carbon nanotube (CNT) supported sulfided Rh catalysts were prepared applying three different routes: deposition-precipitation (DP), grafting of colloidal Rh nanoparticles, and polythiophene-assisted synthesis. The catalysts (1.4-1.8 wt%) prepared by DP were synthesized on CNTs from RhCl3 using hydrogen peroxide and subsequent exposure to on-line generated H 2S followed by heat treatment. The Rh particles were found to be highly dispersed on the CNT surface. Alternatively, RhSx/Rh nanoparticles with four different loadings (4.3-21.9 wt%) grafted on carbon nanotubes were prepared through a functionalization of CNTs with short chain thiols and subsequent binding of colloidal Rh nanoparticles onto the thiolated CNTs. All steps of the synthesis were monitored by XPS. Finally, polythiophene/CNT composites were prepared and employed in the preparation of Rh17S15/Rh nanoparticles supported on CNTs. The CNTs with the highest polythiophene loading yielded the highest amount of Rh 17S15 after Rh deposition and thermal treatment. The activity and stability of the prepared catalysts were studied towards the oxygen reduction reaction. © 2010 Elsevier B.V. All rights reserved.

Binding of gold nanoparticles (Au-NP) at amine-functionalised multi-walled carbon nanotubes (MWNTs) is proposed. The MWNTs are functionalised with acylchloride groups, which further react with ethylenediamine to form amine-functionalised MWCNTs. These amines are able to bind preformed colloidal Au-NPs. The Au/MWNT composite material facilitates electron-transfer reactions with free-diffusing redox compounds. © 2010 Elsevier B.V. All rights reserved.

Despite the advances in high throughput experimentation in recent years the synthesis of realistic catalyst libraries especially gradient catalyst libraries remains as a challenge in material science. Recently, we have developed a method for the synthesis of gradient catalyst libraries consisting of nanoparticles supported on high surface area porous substrates. Chemical vapor deposition (CVD) was employed as a gas-phase method for the synthesis. The method made use of the lateral concentration profile of the precursor-loaded carrier gas stream during CVD, resulting in concentration profile of the deposits on porous substrates. In this report, high surface area materials of both powders (e.g., silica) and bulk composites (e.g., hierarchical carbon structures) were successfully employed as substrates for the deposition of single metal or bimetallic catalyst libraries. The synthesis was achieved by controlling the flow behavior of the effluent precursor stream. The resulting effusion cone led to a radial deposition gradient on the substrate. Different from thin film-type model catalyst libraries, the obtained catalysts can be tested under realistic reaction conditions. Methanol oxidation was studied as a test reaction using scanning mass spectrometry. Copyright © 2010 American Scientific Publishers.

Nitrogen doping of multi-walled carbon nanotubes (CNTs) was achieved by the carbonization of a polyaniline (PANI) coating. First, the CNTs were partially oxidized with KMnO4 to obtain oxygen-containing functional groups. Depending on the KMnO4 loading, thin layers of birnessite-type MnO2 (10 wt% and 30 wt%) were obtained by subsequent thermal decomposition. CNT-supported MnO2 was then used for the oxidative polymerization of aniline in acidic solution, and the resulting PANI-coated CNTs were finally heated at 550 °C and 850 °C in inert gas. The samples were characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. A thin layer of carbonized PANI was observed on the CNT surface, and the surface nitrogen concentration of samples prepared from 30% MnO 2 was found to amount to 7.6 at% and 3.8 at% after carbonization at 550 °C and 850 °C, respectively. These CNTs with nitrogen-containing shell were further studied by electrochemical impedance spectroscopy and used as catalysts for the oxygen reduction reaction. The sample synthesized from 30 wt% MnO2 followed by carbonization at 850 °C showed the best electrochemical performance indicating efficient nitrogen doping. © 2010 The Royal Society of Chemistry.

Rhodium-rhodium sulfide nanoparticles supported on multi-walled carbon nanotubes (CNTs) were synthesized via a multi-step colloid route. The CNTs were first exposed to nitric acid to generate oxygen-containing functional groups, and then treated with thionyl chloride to generate acyl chloride groups. The grafting of thiol groups was subsequently carried out by reaction with 4-aminothiophenol. Colloidal rhodium nanoparticles were synthesized using rhodium chloride as metal source, sodium citrate as stabilizer, and sodium borohydride as reducing agent. The immobilization of the generated colloidal rhodium nanoparticles was achieved by adding the thiolated CNTs to the colloidal suspension. All these steps were monitored by X-ray photoelectron spectroscopy, which disclosed the presence of rhodium sulfide, whereas metallic rhodium was detected by X-ray diffraction, suggesting that the nanoparticles probably consist of a metallic Rh core covered by a sulfide layer. Scanning and transmission electron microscopy studies showed that the diameter of the catalyst particles was about 7 nm even at high Rh loadings. Rotating disc electrode measurements and cyclic voltammetry were employed to test the electrocatalytic activity in the oxygen reduction reaction in hydrochloric acid. Among all the synthesized catalysts with different rhodium loadings (4.3-21.9%), the 16.1% rhodium catalyst was found to be the most active catalyst. In comparison to the commercial E-TEK Pt/C catalyst, the 16.1% catalyst displayed a higher electrochemical stability in the highly corrosive electrolyte, as determined by stability tests with frequent current interruptions. © 2010 The Royal Society of Chemistry.

Nitrogen-containing functional groups were generated on the surface of partially oxidized multi-walled carbon nanotubes (CNTs) via post-treatment in ammonia. The treatment temperature was varied in order to tune the amount and type of nitrogen- and oxygen-containing functional groups, which were studied using high-resolution X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD). The surface defects on CNTs due to the incorporation of nitrogen were investigated by Raman spectroscopy. Deconvoluted XP N1s spectra were used for the quantification of different nitrogen-containing functional groups, and TPD studies were performed in inert and ammonia atmosphere to investigate the surface reactions occurring on the oxidized CNT surfaces quantitatively. Nitrile, lactam, imide and amine-type functional groups were formed in the presence of ammonia below 300 °C. When the OCNTs were treated in the medium temperature range between 300 °C to 500 °C, mainly pyridine-type nitrogen groups were generated, whereas pyridinic, pyrrolic and quaternary-type nitrogen groups were the dominating species present on the CNT surface when treated above 500 °C. It was found that about 38% of the oxygen functional groups react with ammonia below 500 °C. © 2010 the Owner Societies.

Adsorption of horseradish peroxidase (HRP) on graphite rod electrodes sequentially modified with carbon microfibers (CMF) carrying carbon nanotubes in a hierarchically structured arrangement and finally pyrene hexanoic acid (PHA) for improving hydrophilicity of the electrode surface is the basis for the direct bioelectrocatalytic reduction of H 2O 2 at potentials as high as about +600 mV. The high-potential direct bioelectrocatalytic reduction of H 2O 2 is implying a direct bioelectrochemical communication between the Fe IVO,P + redox state known as compound I. The HRP loading was optimized leading to a current of 800 μA at a potential of 300 mV. © 2010 the Owner Societies.