Dong Gu

Controllable Synthesis of Mesoporous Peapod‐like Co3O4@Carbon Nanotube Arrays for High‐Performance Lithium‐Ion Batteries

Transition metal oxides are regarded as promising anode materials for lithium-ion batteries because of their high theoretical capacities compared with commercial graphite. Unfortunately, the implementation of such novel anodes is hampered by their large volume changes during the Li(+) insertion and extraction process and their low electric conductivities. Herein, we report a specifically designed anode architecture to overcome such problems, that is, mesoporous peapod-like Co3O4@carbon nanotube arrays, which are constructed through a controllable nanocasting process. Co3O4 nanoparticles are confined exclusively in the intratubular pores of the nanotube arrays. The pores between the nanotubes are open, and thus render the Co3O4 nanoparticles accessible for effective electrolyte diffusion. Moreover, the carbon nanotubes act as a conductive network. As a result, the peapod-like Co3O4 @carbon nanotube electrode shows a high specific capacity, excellent rate capacity, and very good cycling performance.

Highly Ordered Mesoporous Cobalt-Containing Oxides: Structure, Catalytic Properties, and Active Sites in Oxidation of Carbon Monoxide

Co3O4 with a spinel structure is a very active oxide catalyst for the oxidation of CO. In such catalysts, octahedrally coordinated Co(3+) is considered to be the active site, while tetrahedrally coordinated Co(2+) is assumed to be basically inactive. In this study, a highly ordered mesoporous CoO has been prepared by H2 reduction of nanocast Co3O4 at low temperature (250 °C). The as-prepared CoO material, which has a rock-salt structure with a single Co(2+) octahedrally coordinated by lattice oxygen in Fm3̅m symmetry, exhibited unexpectedly high activity for CO oxidation. Careful investigation of the catalytic behavior of mesoporous CoO catalyst led to the conclusion that the oxidation of surface Co(2+) to Co(3+) causes the high activity. Other mesoporous spinels (CuCo2O4, CoCr2O4, and CoFe2O4) with different Co species substituted with non/low-active metal ions were also synthesized to investigate the catalytically active site of cobalt-based catalysts. The results show that not only is the octahedrally coordinated Co(3+) highly active but also the octahedrally coordinated Co(2+) species in CoFe2O4 with an inverse spinel structure shows some activity. These results suggest that the octahedrally coordinated Co(2+) species is easily oxidized and shows high catalytic activity for CO oxidation.

Gold on Different Manganese Oxides: Ultra-Low-Temperature CO Oxidation over Colloidal Gold Supported on Bulk-MnO2 Nanomaterials

Nanoscopic gold particles have gained very high interest because of their promising catalytic activity for various chemicals reactions. Among these reactions, low-temperature CO oxidation is the most extensively studied one due to its practical relevance in environmental applications and the fundamental problems associated with its very high activity at low temperatures. Gold nanoparticles supported on manganese oxide belong to the most active gold catalysts for CO oxidation. Among a variety of manganese oxides, Mn2O3 is considered to be the most favorable support for gold nanoparticles with respect to catalytic activity. Gold on MnO2 has been shown to be significantly less active than gold on Mn2O3 in previous work. In contrast to these previous studies, in a comprehensive study of gold nanoparticles on different manganese oxides, we developed a gold catalyst on MnO2 nanostructures with extremely high activity. Nanosized gold particles (2-3 nm) were supported on α-MnO2 nanowires and mesoporous β-MnO2 nanowire arrays. The materials were extremely active at very low temperature (-80 °C) and also highly stable at 25 °C (70 h) under normal conditions for CO oxidation. The specific reaction rate of 2.8 molCO·h(-1)·gAu(-1) at a temperature as low as -85 °C is almost 30 times higher than that of the most active Au/Mn2O3 catalyst.

Co3O4 Nanoparticles Supported on Mesoporous Carbon for Selective Transfer Hydrogenation of α,β-Unsaturated Aldehydes

A simple and scalable method for synthesizing Co3 O4 nanoparticles supported on the framework of mesoporous carbon (MC) was developed. Benefiting from an ion-exchange process during the preparation, the cobalt precursor is introduced into a mesostructured polymer framework that results in Co3 O4 nanoparticles (ca. 3 nm) supported on MC (Co3 O4 /MC) with narrow particle size distribution and homogeneous dispersion after simple reduction/pyrolysis and mild oxidation steps. The as-obtained Co3 O4 /MC is a highly efficient catalyst for transfer hydrogenation of α,β-unsaturated aldehydes. Selectivities towards unsaturated alcohols are always higher than 95 % at full conversion. In addition, the Co3 O4 /MC shows high stability under the reaction conditions, it can be recycled at least six times without loss of activity.

Surface Casting Synthesis of Mesoporous Zirconia with a CMK-5-like Structure and High Surface Area

About 15 years ago, the Ryoo group described the synthesis of CMK-5, a material consisting of a hexagonal arrangement of carbon nanotubes. Extension of the surface casting synthesis to oxide compositions, however, was not possible so far, in spite of many attempts. Here it is demonstrated, that crystalline mesoporous hollow zirconia materials with very high surface areas up to 400 m2  g-1 , and in selected cases in the form of CMK-5-like, are indeed accessible via such a surface casting process. The key for the successful synthesis is an increased interaction between the silica hard template surface and the zirconia precursor species by using silanol group-rich mesoporous silica as a hard template. The surface areas of the obtained zirconias exceed those of conventionally hard-templated ones by a factor of two to three. The surface casting process seems to be applicable also to other oxide materials.

Avoiding Self‐Poisoning: A Key Feature for the High Activity of Au/Mg(OH)2 Catalysts in Continuous Low‐Temperature CO Oxidation

Au/Mg(OH)2 catalysts have been reported to be far more active in the catalytic low-temperature CO oxidation (below 0 °C) than the thoroughly investigated Au/TiO2 catalysts. Based on kinetic and in situ infrared spectroscopy (DRIFTS) measurements, we demonstrate that the comparatively weak interaction of Au/Mg(OH)2 with CO2 formed during the low-temperature reaction is the main reason for the superior catalyst performance. This feature enables rapid product desorption and hence continuous CO oxidation at temperatures well below 0 °C. At these temperatures, Au/TiO2 also catalyzes CO2 formation, but does not allow for CO2 desorption, which results in self-poisoning. At higher temperatures (above 0 °C), however, CO2 formation is rate-limiting, which results in a much higher activity for Au/TiO2 under these reaction conditions.

High activity and negative apparent activation energy in low-temperature CO oxidation – present on Au/Mg(OH)2, absent on Au/TiO2

Aiming at a better understanding of the unusual low-temperature CO oxidation reaction behavior on Au/Mg(OH)2 catalysts, we investigated this reaction mainly by combined kinetic and in situ IR spectroscopy measurements over a wide range of temperatures, from −90 °C to 200 °C. Catalysts with a very narrow Au particle size distribution were prepared by colloidal deposition. Kinetic measurements, performed under differential, dry reaction conditions at different constant temperatures, enabled the separation of thermal and deactivation effects. They revealed that the distinct reaction behavior, with an exceptionally high activity at temperatures below 0 °C and decreasing CO oxidation rates in the range between −50 °C and 30 °C, equivalent to a negative apparent activation energy, does not result from either deactivation effects or H2O trace impurities, but is an intrinsic feature of the reaction. An unusual temperature dependence was also observed for the tendency for deactivation, with a pronounced maximum at −20 °C, which mainly results from an accumulation of surface carbonate species blocking active reaction sites or access of adsorbed reactants to them. Similar measurements on Au/TiO2 catalysts revealed that the high activity of Au/Mg(OH)2 in the low-temperature range compared to Au/TiO2 is first of all due to the weaker interactions of Mg(OH)2 with CO2 compared to TiO2. This leads to an increasing tendency of CO2 product molecules to adsorb on the latter catalyst at reaction temperatures below 0 °C and hence to rapid ‘self-poisoning’ with CO2 desorption as the rate-limiting step. For Au/Mg(OH)2, CO2 desorption is much faster, allowing much higher rates in the continuous CO oxidation. Based on temporal analysis of products (TAP) reactor measurements, the decay of the reaction rates in the range −50 °C to +50 °C is tentatively attributed to a decreasing steady-state coverage of weakly bound molecularly adsorbed O2 with increasing temperature, while stable adsorbed active surface oxygen is negligible over the entire range of reaction temperatures investigated. The implications of these and earlier findings for the mechanistic understanding of the low-temperature CO oxidation on Au/Mg(OH)2 and support effects therein are discussed.

Tracking the Active Catalyst for Iron-Based Ammonia Decomposition by In Situ Synchrotron Diffraction Studies

Iron‐based catalysts for NH3 decomposition have been studied by a combination of catalytic tests and in situ synchrotron diffraction experiments performed in an inert sapphire plug‐flow cell. In contrast to steel‐based reaction cells, sapphire or quartz glass cells show no blind activity. Starting from iron oxide precursors, iron nitrides form during the activation cycle. Nitrides remain as main crystalline phases and govern the conversion of NH3 decomposition in the subsequent cycles. In this work structural and compositional changes of the nitrides were monitored in situ during heating and cooling cycles. The state of the catalyst under reaction conditions was analyzed by high resolution in situ synchrotron diffraction experiments. The analyses enable establishing reaction pathways and correlation of structural features with catalytic conversions. The most active phases are iron nitrides with high mobility and solubility for nitrogen atoms, such as Fe3Nx. Phase changes from Fe3Nx to γ‐FeNx were observed above 700 °C. The formation of γ‐FeNx seems to suppress the catalytic conversion. Moreover, the positive influence of a mesostructured support/catalyst composite on the catalytic conversion and catalyst stability were studied in detail.