To date, copper is the only heterogeneous catalyst that has shown a propensity to produce valuable hydrocarbons and alcohols, such as ethylene and ethanol, from electrochemical CO2 reduction (CO2R). There are variety of factors that impact CO2R activity and selectivity, including the catalyst surface structure, morphology, composition, the choice of electrolyte ions and pH, and the electrochemical cell design. Many of these factors are often intertwined, which can complicate catalyst discovery and design efforts. Here we take a broad and historical view of these different aspects and their complex interplay in CO2R catalysis on Cu, with the purpose of providing new insights, critical evaluations, and guidance to the field with regard to research directions and best practices. First, we describe the various experimental probes and complementary theoretical methods that have been used to discern the mechanisms by which products are formed, and next we present our current understanding of the complex reaction networks for CO2R on Cu. We then analyze two key methods that have been used in attempts to alter the activity and selectivity of Cu: nanostructuring and the formation of bimetallic electrodes. Finally, we offer some perspectives on the future outlook for electrochemical CO2R.

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Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte

This Critical Review provides an overview of the recent developments in the synthesis and characterization of bimetallic nanoparticles. Initially the review follows a materials science perspective on preparing bimetallic nanoparticles with designer morphologies, after which the emphasis shifts towards recent developments in using these bimetallic particles for catalysing either oxidation or reduction. In the final part of this review we present an overview of the utilization of bimetallic catalyst systems for the transformation of bio-renewable substrates and reactions related to the realization of a bio-refinery. Because of the sheer number of examples of transformations in this area, a few key examples, namely selective oxidation, hydrogenation/hydrogenolysis and reforming of biomass derived molecules, have been chosen for this review. Reports of bimetallic catalysts being used for the aforementioned transformations are critically analysed and the potential for exploiting such bimetallic catalysts have also been highlighted. A specific objective of this review article is to motivate researchers to synthesize some of the “designer” bimetallic catalysts with specific nanostructures, inspired from recent advances in the area of materials chemistry, and to utilize them for the transformation of biomass derived materials that are very complex and pose different challenges compared to those of simple organic molecules. We consider that supported bimetallic nanoparticles have an important role to play as catalysts in our quest for a more green and sustainable society.

Designing bimetallic catalysts for a green and sustainable future

Solid Oxide Fuel Cells (SOFCs) are one of the most promising technologies for future efficient conversion of the chemical energy stored in fuels to electrical energy. One of the primary advantages of SOFCs is the potential to operate with a wide variety of fuels. While H2 is the fuel of choice for most fuel cells, operation with fossil-derived and bio-derived hydrocarbon fuels would bypass the costly requirement of a new H2 infrastructure, and accelerate adoption of fuel cell technology. This is feasible as SOFCs transport oxygen anions from the air electrode (cathode) to the fuel electrode (anode). The primary barrier to the realization of fuel flexible SOFCs is the anode material set. Traditional SOFC anodes are based on Ni composites. While these are very efficient for H2 and CO fuels, Ni catalyzes graphite formation from dry hydrocarbons, leading to rapid degradation of cell performance and possible mechanical failure. This motivates the development of new anode materials and composites. The principle requirements of an anode are oxygen anion conductivity, electronic conductivity, and electrocatalytic activity toward the desired reaction. This entry reviews the primary issues in direct hydrocarbon anode development and discusses the new materials and composites that have been developed to meet this challenge.

Direct hydrocarbon solid oxide fuel cells.

Binary alloy surface compositions from bulk alloy thermodynamic data

Platinum nanoparticles in the size range of 1.7-7.1 nm were produced by alcohol reduction methods. A polymer (poly(vinylpyrrolidone), PVP) was used to stabilize the particles by capping them in aqueous solution. The particles were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). TEM investigations demonstrate that the particles have a narrow size distribution. Mesoporous SBA-15 silica with 9-nm pores was synthesized by a hydrothermal process and used as a catalyst support. After incorporation into mesoporous SBA-15 silica using low-power sonication, the catalysts were calcined to remove the stabilizing polymer from the nanoparticle surface and reduced by H2. Pt particle sizes determined from selective gas adsorption measurements are larger than those determined by bulk techniques such as XRD and TEM. Roomtemperature ethylene hydrogenation was chosen as a model reaction to probe the activity of the Pt/SBA-15 materials. The reaction was shown to be structure insensitive over a series of Pt/SBA-15 materials with particle sizes between 1.7 and 3.6 nm. The hydrogenolysis of ethane on Pt particles from 1.7 to 7.1 nm was weakly structure sensitive with smaller particles demonstrating higher specific activity. Turnover rates for ethane hydrogenolysis increased monotonically with increasing metal dispersion, suggesting that coordinatively unsaturated metal atoms present in small particles are more active for C 2H6 hydrogenolysis than the low index planes that dominate in large particles. An explanation for the structure sensitivity is suggested, and the potential applications of these novel supported nanocatalysts for further studies of structure -activity and structure-selectivity relationships are discussed.

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J.L. Carter

Papers

Catalytic hydrogenolysis and dehydrogenation over copper-nickel alloys

Hydrogenolysis of n-heptane over unsupported metals

The paramagnetic susceptibility of supported nickel