Andrey Tarasov

The Mechanism of CO and CO2 Hydrogenation to Methanol over Cu-Based Catalysts

Methanol, an important chemical, fuel additive, and precursor for clean fuels, is produced by hydrogenation of carbon oxides over Cu‐based catalysts. Despite the technological maturity of this process, the understanding of this apparently simple reaction is still incomplete with regard to the reaction mechanism and the active sites. Regarding the latter, recent progress has shown that stepped and ZnOx‐decorated Cu surfaces are crucial for the performance of industrial catalysts. Herein, we integrate this insight with additional experiments into a full microkinetic description of methanol synthesis. In particular, we show how the presence or absence of the Zn promoter dramatically changes not only the activity, but unexpectedly the reaction mechanism itself. The Janus‐faced character of Cu with two different sites for methanol synthesis, Zn‐promoted and unpromoted, resolves the long‐standing controversy regarding the Cu/Zn synergy and adds methanol synthesis to the few major industrial catalytic processes that are described on an atomic level.

Stable Performance of Ni-Catalysts in Dry Reforming of Methane at High Temperatures for an Efficient CO2-Conversion into Syngas

The catalytic performance of a Ni/MgAlOx catalyst was investigated in the high temperature CO2 reforming of CH4. The catalyst was developed using a Ni, Mg, Al hydrotalcite‐like precursor obtained by co‐precipitation. Despite the high Ni loading of 55 wt%, the synthesized Ni/MgAlOx catalyst possessed a thermally stable microstructure up to 900 °C with Ni nanoparticles of 9 nm. This stability is attributed to the embedding nature of the oxide matrix, and allows increasing the reaction temperature without losing active Ni surface area. To evaluate the effect of the reaction temperature on the reforming performance and the coking behavior, two different reaction temperatures (800 and 900 °C) were investigated. At both temperatures the prepared catalyst showed high rates of CH4 consumption. The higher temperature promotes the stability of the catalyst performance due to mitigation of the carbon formation.

Synthesis and Characterisation of a Highly Active Cu/ZnO:Al Catalyst

We report the application of an optimised synthesis protocol of a Cu/ZnO:Al catalyst. The different stages of synthesis are all well‐characterised by using various methods with regard to the (micro‐)structural, textural, solid‐state kinetic, defect and surface properties. The low amount of the Al promoter (3 %) influences but does not generally change the phase evolution known for binary Cu/ZnO catalysts. Its main function seems to be the introduction of defect sites in ZnO by doping. These sites as well as the large Cu surface area are responsible for the large N2O chemisorption capacity. Under reducing conditions, the Al promoter, just as Zn, is found enriched at the surface suggesting an active role in the strong metal–support interaction between Cu and ZnO:Al. The different stages of the synthesis are comprehensively analysed and found to be highly reproducible in the 100 g scale. The resulting catalyst is characterised by a uniform elemental distribution, small Cu particles (8 nm), a porous texture (pore size of approximately 25 nm), high specific surface area (approximately 120 m2 g−1), a high amount of defects in the Cu phase and synergetic Cu–ZnO interaction. A high and stable performance was found in methanol synthesis. We wish to establish this complex but well‐studied material as a benchmark system for Cu‐based catalysts.

Microwave Assisted Synthesis of Stable and Highly Active Ir-oxohydroxides for Electrochemical Oxidation of Water

Water splitting for hydrogen production in acidic media has been limited by the poor stability of the anodic electrocatalyst devoted to the oxygen evolution reaction (OER). To help circumvent this problem we have synthesized a class of novel Ir oxohydroxides by rapid microwave-asisted hydrothermal synthesis, which bridges the gap between electrodeposited amorphous IrOx films and crystalline IrO2 electrocatalysts prepared by calcination routes. For electrode loadings two orders of magnitude below current standards, the synthesized compounds present an unrivalled combination of high activity and stability under commercially relevant OER conditions in comparison to reported benchmarks, without need for pretreatment. The best compound achieved a lifetime 33 times longer than the best commercial Ir benchmark. Thus, the reported efficient synthesis of an Ir oxohydroxide phase with superior intrinsic OER performance constitutes a major step towards the targeted design of cost-efficient Ir based OER electrocatalysts for acidic media.

High-Performance Supported Iridium Oxohydroxide Water Oxidation Electrocatalysts

The synthesis of a highly active and yet stable electrocatalyst for the anodic oxygen evolution reaction (OER) remains a major challenge for acidic water splitting on an industrial scale. To address this challenge, we obtained an outstanding high-performance OER catalyst by loading Ir on conductive antimony-doped tin oxide (ATO)-nanoparticles by a microwave (MW)-assisted hydrothermal route. The obtained Ir phase was identified by using XRD as amorphous (XRD-amorphous), highly hydrated IrIII/IV oxohydroxide. To identify chemical and structural features responsible for the high activity and exceptional stability under acidic OER conditions with loadings as low as 20 μgIr  cm-2 , we used stepwise thermal treatment to gradually alter the XRD-amorphous Ir phase by dehydroxylation and crystallization of IrO2 . This resulted in dramatic depletion of OER performance, indicating that the outstanding electrocatalytic properties of the MW-produced IrIII/IV oxohydroxide are prominently linked to the nature of the produced Ir phase. This finding is in contrast with the often reported stable but poor OER performance of crystalline IrO2 -based compounds produced through more classical calcination routes. Our investigation demonstrates the immense potential of Ir oxohydroxide-based OER electrocatalysts for stable high-current water electrolysis under acidic conditions.

Atomic scale insight on the increased stability of tungsten modified platinum/carbon fuel cell catalysts

The limited stability of carbon‐supported Pt catalysts for the oxygen reduction reaction is a key obstacle for their commercial application in fuel cells. Here we report on the properties of a tungsten‐modified Pt/C catalyst that shows enhanced stability under potential cycling conditions compared to a reference Pt/C catalyst. Although routine structural investigation by XRD and TEM show an inhomogeneous distribution of tungsten species on the modified catalyst surface, X‐ray photoelectron spectroscopy points to an overall changed catalytic behavior of Pt nanoparticles. Aberration‐corrected atomic‐scale imaging reveals the presence of homogeneously dispersed tungsten atomic species that decorate the surface of the carbon support and the Pt nanoparticles. The presented results demonstrate that detailed and localized imaging at the atomic scale is essential for the identification of the relevant species amongst spectator phases and thus, for the understanding of the improved integral behavior of a modified catalyst.