Activity Descriptors for CO<sub>2</sub> Electroreduction to Methane on Transition-Metal Catalysts

Peterson, Andrew A.; Nørskov, Jens K.

doi:10.1021/jz201461p

Cited by 1,345 publications

(1,723 citation statements)

References 64 publications

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“…Renewable chemical fuels such as hydrocarbons, methanol, hydrogen and ammonia may be synthesized from CO 2 , H 2 O and N 2 by solar-driven photochemical [1,2], electrocatalytic [3,4] or thermochemical processes [5]. The latter approach uses the entire spectrum of concentrated solar energy as the source of high-temperature process heat, and as such provides a thermodynamically favourable path to solar fuels and materials production with high energy conversion efficiencies.…”

Section: Introductionmentioning

confidence: 99%

“…These studies were motivated by the temporary formation of NH 3 at low pressures from an iron nitride contamination of the catalyst that Ostwald used [20]. The NH 3 formation ceased quickly, because the spent iron nitride could not be regenerated with N 2 at low pressure and the work spurred the development of the Haber-Bosch process, in which NH 3 is formed at high pressure to shift the thermodynamic equilibrium [19].…”

Section: Introductionmentioning

confidence: 99%

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Rational design of metal nitride redox materials for solar-driven ammonia synthesis

2015

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Fixed nitrogen is an essential chemical building block for plant and animal protein, which makes ammonia (NH 3 ) a central component of synthetic fertilizer for the global production of food and biofuels. A global project on artificial photosynthesis may foster the development of production technologies for renewable NH 3 fertilizer, hydrogen carrier and combustion fuel. This article presents an alternative path for the production of NH 3 from nitrogen, water and solar energy. The process is based on a thermochemical redox cycle driven by concentrated solar process heat at 700–1200°C that yields NH 3 via the oxidation of a metal nitride with water. The metal nitride is recycled via solar-driven reduction of the oxidized redox material with nitrogen at atmospheric pressure. We employ electronic structure theory for the rational high-throughput design of novel metal nitride redox materials and to show how transition-metal doping controls the formation and consumption of nitrogen vacancies in metal nitrides. We confirm experimentally that iron doping of manganese nitride increases the concentration of nitrogen vacancies compared with no doping. The experiments are rationalized through the average energy of the dopant d-states, a descriptor for the theory-based design of advanced metal nitride redox materials to produce sustainable solar thermochemical ammonia.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Rational design of metal nitride redox materials for solar-driven ammonia synthesis

2015

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“…1,2 Among all pure metals, copper is the only one that gives a rich gamut of single-and multi-carbon products, [3][4][5] which can be explained by an optimal binding energy of CO to the surface. 6,7 However, the explanation becomes more complicated when dealing with nanostructured copper materials derived from oxidized precursors, which show both higher activity and greatly enhanced selectivity towards multicarbon products. [8][9][10][11][12][13][14][15][16] It has been hypothesized that this could be related for instance to an increase of local pH, [17][18][19] grain boundaries, 20 undercoordinated sites, 21 or residual oxides.…”

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confidence: 99%

Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction

Eilert

Cavalca

Roberts

et al. 2016

J. Phys. Chem. Lett.

367

384

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Copper electrocatalysts derived from an oxide have shown extraordinary electrochemical properties for the carbon dioxide reduction reaction (CO 2 RR). Using in situ Ambient Pressure Xray Photoelectron Spectroscopy (APXPS) and quasi in situ Electron Energy Loss Spectroscopy (EELS) in a Transmission Electron Microscope (TEM), we show that there is a substantial amount of residual oxygen in nanostructured, oxide-derived copper electrocatalysts, but no residual copper oxide. Based on these findings in combination with Density Functional Theory (DFT) simulations, we propose that residual subsurface oxygen changes the electronic structure of the catalyst and creates sites with higher carbon monoxide binding energy. If such sites are stable under the strongly reducing conditions found in CO 2 RR, these findings would explain the high efficiencies of oxide-derived copper in reducing carbon dioxide to multi-carbon compounds such as ethylene.

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“…Copper is attractive in comparison, as it produces more reduced hydrocarbon products. (8,(15)(16)(17) One of the hydrocarbon products formed on copper electrocatalysts is methane, which forms through the following half-reaction:…”

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confidence: 99%

Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst

2014

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Although the vast majority of hydrocarbon fuels and products are presently derived from petroleum, there is much interest in the development of routes for synthesizing these same products by hydrogenating CO 2 . The simplest hydrocarbon target is methane, which can utilize existing infrastructure for natural gas storage, distribution, and consumption. Electrochemical methods for methanizing CO 2 currently suffer from a combination of low activities and poor selectivities. We demonstrate that copper nanoparticles supported on glassy carbon (n-Cu/C) achieve up to 4 times greater methanation current densities compared to high-purity copper foil electrodes. The n-Cu/ C electrocatalyst also exhibits an average Faradaic efficiency for methanation of 80% during extended electrolysis, the highest Faradaic efficiency for room-temperature methanation reported to date. We find that the level of copper catalyst loading on the glassy carbon support has an enormous impact on the morphology of the copper under catalytic conditions and the resulting Faradaic efficiency for methane. The improved activity and Faradaic efficiency for methanation involves a mechanism that is distinct from what is generally thought to occur on copper foils. Electrochemical data indicate that the early steps of methanation on n-Cu/C involve a pre-equilibrium one-electron transfer to CO 2 to form an adsorbed radical, followed by a rate-limiting nonelectrochemical step in which the adsorbed CO 2 radical reacts with a second CO 2 molecule from solution. These nanoscale copper electrocatalysts represent a first step toward the preparation of practical methanation catalysts that can be incorporated into membrane-electrode assemblies in electrolyzers.

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Activity Descriptors for CO₂ Electroreduction to Methane on Transition-Metal Catalysts

Cited by 1,345 publications

References 64 publications

Rational design of metal nitride redox materials for solar-driven ammonia synthesis

Rational design of metal nitride redox materials for solar-driven ammonia synthesis

Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction

Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst

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Activity Descriptors for CO2 Electroreduction to Methane on Transition-Metal Catalysts

Cited by 1,345 publications

References 64 publications

Rational design of metal nitride redox materials for solar-driven ammonia synthesis

Rational design of metal nitride redox materials for solar-driven ammonia synthesis

Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction

Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst

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Activity Descriptors for CO₂ Electroreduction to Methane on Transition-Metal Catalysts