New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces

Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N.; Jaramillo, Thomas F.

doi:10.1039/c2ee21234j

Cited by 2,682 publications

(3,134 citation statements)

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“…(19) The working electrode compartment and counter electrode compartment, which each had an electrolyte volume of 5 mL and a gas headspace of ∼1 mL, were separated by a Selemion membrane (AMV, AGC Engineering). A Ag/AgCl reference electrode (BASi, RE-6), which was stored in saturated KCl when not in use, was used; all measured potentials were converted to the RHE scale.…”

Section: Electrochemical Methodsmentioning

confidence: 99%

“…(18,19) The highest Faradaic efficiencies for methane reported to date are 64% on a (210) copper single crystal (18,20) and 73% on an electrodeposited copper electrode. (21) Although studies conducted on high-purity foils, single crystals, and electrodeposited materials have served as useful benchmarks and provide fundamental insights into how copper catalyzes the reduction of CO 2 , these model materials are impractical for electrolyzers as they have low surface areas, cannot be incorporated into the membrane electrode assemblies (22) that are needed to achieve high current densities with low ionic resistances, or are expensive.…”

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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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Section: Electrochemical Methodsmentioning

confidence: 99%

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confidence: 99%

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

2014

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“…Thus, we predict that acetylene is not formed under these conditions, which is consistent with experiment. 6 Sequential hydrogenation of H 2 CC ad with H ad (2q-2r-2s) leads to CH 3 CH 2,ad . Surprisingly, the last step is nonelectrochemical β-elimination (2t with ΔG ⧧ = 0.59 eV) that delivers the final ethylene product, leading to very fast kinetics, with a turn over frequency (TOF) of 7 × 10 2 s −1 , based on the Eyring−Polanyi equation.…”

Section: Journal Of the American Chemical Societymentioning

confidence: 99%

Atomistic Mechanisms Underlying Selectivities in C₁ and C₂ Products from Electrochemical Reduction of CO on Cu(111)

2016

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Practical environmental and energy applications of the electrochemical reduction of CO 2 to chemicals and fuels require far more efficient and selective electrocatalysts beyond the only working material Cu, but the wealth of experimental data on Cu can serve to validate any proposed mechanisms. To provide design guidelines, we use quantum mechanics to predict the detailed atomistic mechanisms responsible for C 1 and C 2 products on Cu. Thus, we report the pH dependent routes to the major products, methane and ethylene, and identify the key intermediates where branches to methanol, ketene, ethanol, acetylene, and ethane are kinetically blocked. We discovered that surface water on Cu plays a key role in the selectivity for hydrocarbon products over the oxygencontaining alcohol products by serving as a strong proton donor for electrochemical dehydration reductions. We suggest new experiments to validate our predicted mechanisms.

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“…Reports of C 2 H 5 OH production from CO 2 RR is almoste xclusive to Cu-based electrocatalysts, which are shown to produce small amounts of C 2 H 5 OH (Table 3). [88,93,201] Typically,p olycrystalline Cu foil can generate very minute quantities of C 2 H 5 OH, as outlined in the works of Kuhl et al [149] AlthoughH ori et al attained aF E C 2 H 5 OH value of around 22 % with pristine Cu foil at an applied potentialo fÀ1. 48 www.chemsuschem.org based catalysts.…”

Section: Ethanolmentioning

confidence: 99%

Liquid Hydrocarbon Production from CO₂: Recent Development in Metal‐Based Electrocatalysis

Daiyan

et al. 2017

ChemSusChem

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Rising levels of CO2 accumulation in the atmosphere have attracted considerable interest in technologies capable of CO2 capture, storage and conversion. The electrochemical reduction of CO2 into high‐value liquid organic products could be of vital importance to mitigate this issue. The conversion of CO2 into liquid fuels by using photovoltaic cells, which can readily be integrated in the current infrastructure, will help realize the creation of a sustainable cycle of carbon‐based fuel that will promote zero net CO2 emissions. Despite promising findings, significant challenges still persist that must be circumvented to make the technology profitable for large‐scale utilization. With such possibilities, this Minireview presents the current high‐performing catalysts for the electrochemical reduction of CO2 to liquid hydrocarbons, address the limitations and unify the current understanding of the different reaction mechanisms. The Minireview also explores current research directions to improve process efficiencies and production rate and discusses the scope of using photo‐assisted electrochemical reduction systems to find stable, highly efficient catalysts that can harvest solar energy directly to convert CO2 into liquid hydrocarbons.

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New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces

Cited by 2,682 publications

References 40 publications

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

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

Atomistic Mechanisms Underlying Selectivities in C₁ and C₂ Products from Electrochemical Reduction of CO on Cu(111)

Liquid Hydrocarbon Production from CO₂: Recent Development in Metal‐Based Electrocatalysis

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New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces

Cited by 2,682 publications

References 40 publications

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

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

Atomistic Mechanisms Underlying Selectivities in C1 and C2 Products from Electrochemical Reduction of CO on Cu(111)

Liquid Hydrocarbon Production from CO2: Recent Development in Metal‐Based Electrocatalysis

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Atomistic Mechanisms Underlying Selectivities in C₁ and C₂ Products from Electrochemical Reduction of CO on Cu(111)

Liquid Hydrocarbon Production from CO₂: Recent Development in Metal‐Based Electrocatalysis