In Situ Raman Study of Potential‐Dependent Surface Adsorbed Carbonate, CO, OH, and C Species on Cu Electrodes During Electrochemical Reduction of CO<sub>2</sub>

Moradzaman, Mozhgan; Mul, Guido

doi:10.1002/celc.202001598

Cited by 91 publications

(91 citation statements)

References 45 publications

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“…This was reported to be from adsorbed OH ads on the Cu surface, originating from the high local pH near the catalyst surface due to the consumption of protons by CO 2 RR and HER. [48] After removing the potential, no intermediate peaks were detected, but a new broad peak indicative of cuprous oxide appeared at 610-625 cm -1 . [45] Thus, we can conclude that metallic copper is the active site for CO 2 RR, and is responsible for adsorbing the key reaction intermediate, CO, for C 2+ products.…”

Section: Investigation Into the Mechanism Of C 2+ Enhancementmentioning

confidence: 95%

Enhanced Electrocatalytic CO₂ Reduction to C₂₊ Products by Adjusting the Local Reaction Environment with Polymer Binders

Pham

Zhang

et al. 2022

Advanced Energy Materials

109

108

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sequestrated. Recently, electrochemical CO 2 reduction reactions (CO 2 RR) enabled by renewable energy have been suggested as a promising strategy to solve these problems, sequestrating discharged CO 2 into chemical feedstocks, and downscaling the use of fossil fuels in the chemical production industry. In addition, CO 2 RR is an efficient way to store electricity generated from intermittent renewable energies in the form of liquid fuels for transport and other applications. [3][4][5] Copper-based materials are the most investigated class of catalysts for CO 2 RR due to their unique ability to reduce CO 2 molecules to carbonaceous compounds containing more than two carbon atoms (C 2+ products). However, the high overpotential required and the low product selectivity over the pristine Cu surface have motivated researchers to develop more efficient strategies to overcome these challenges. Most previous publications have focused on engineering the properties of Cu-based catalysts, such as optimizing the size and shape of Cu nanomaterials, [6][7][8][9][10] introducing grain boundaries, [11] and creating alloys with other metals [12][13][14][15] to increase the number of active sites and/or to improve the intrinsic catalytic activities of Cu toward the desired products. Despite the tremendous progress that has been made, CO 2 RR is still not viable at an industrial scale.The activity and selectivity of the electrochemical CO 2 reduction reaction (CO 2 RR) are often hindered by the limited access of CO 2 to the catalyst surface and overtaken by the competing hydrogen evolution reaction. Herein, it is revealed that polymers used as catalyst binders can effectively modulate the accessibility of CO 2 relative to H 2 O at the vicinity of the catalyst and thus the performance of CO 2 RR. Three polymers with different hydrophilicities (i.e., polyacrylic acid (PAA), Nafion, and fluorinated ethylene propylene (FEP)) are selected as binders for Cu catalysts. At a thickness of only ≈1.2 nm, these binders strongly affect the activity and selectivity toward multi-carbon (C 2+ ) products. The FEP coated catalyst exhibits a C 2+ partial current density of over 600 mA cm −2 with ≈77% faradaic efficiency at −0.76 V versus RHE. This high performance is attributed to the hydrophobic (aerophilic) properties of FEP, which reduces the local concentration of H 2 O and enhances that of the reactant (i.e., CO 2 ) and the reaction intermediates (i.e., CO). These findings suggest that tuning the hydrophobicity of electrocatalysts with polymer binders can be a promising way to regulate the performance of electrochemical reactions involving gas-solid-liquid interfaces.

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Section: Investigation Into the Mechanism Of C 2+ Enhancementmentioning

confidence: 95%

Enhanced Electrocatalytic CO₂ Reduction to C₂₊ Products by Adjusting the Local Reaction Environment with Polymer Binders

Pham

Zhang

et al. 2022

Advanced Energy Materials

109

108

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“…The interpretation of carboxylate adsorption was questioned, with evidence that this assignment was instead attributed to adsorbed mono‐ and bi‐dentate carbonates that were found in addition to a Cu‐C species, a difficult to reduce Cu(OH) x species and adsorbed carbon monoxide 46. Bi‐dentate carbonate adsorbed on the copper cathode at the lowest onset potential and was desorbed as the magnitude of the cathodic potential increased.…”

Section: Direct Electrochemical Reduction Of Carbon Dioxide To Ethylenementioning

confidence: 99%

Process Parameters in the Electrochemical Reduction of Carbon Dioxide to Ethylene

Sturman

Oelgemöller

2021

ChemBioEng Reviews

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Ethylene is one of the most widely used chemical compounds. It is readily transformed to a variety of useful products that can replace those derived from fossil sources. Further, the ability to produce ethylene from atmospheric carbon dioxide would significantly assist in the urgent need to stabilize, and ultimately to reduce, the concentration of greenhouse gases in the atmosphere. This review covers the electrochemical reduction of carbon dioxide at copper‐based cathodes. The direct production of ethylene is the focus of the review, but it is also relevant to include the important ethylene precursor and intermediate in the carbon dioxide reduction reaction, carbon monoxide. Carbon monoxide can be reduced to ethylene on a copper cathode under similar conditions to carbon dioxide. Ethanol is another potential product of the reduction of carbon dioxide at a copper cathode. It can be readily dehydrated to ethylene, further enhancing the overall yield of ethylene. The aim of the review is to show that there are many interacting parameters that influence the effectiveness and efficiency of the electrochemical reduction of carbon dioxide at copper‐based cathodes.

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“…For SERS experiments, polycrystalline rough Cu electrodes were prepared according to the procedure described elsewhere 27 . In brief, Cu discs were mechanically polished followed by anodic treatment in 85% phosphoric acid (3 V for 2.5 min), sonication in MiliQ water and drying in an Ar stream.…”

Section: Electrode Preparationmentioning

confidence: 99%

“…on a polycrystalline, rough Cu electrodes during simultaneous reduction of CO 2 and NO 3 -. SERS is a suitable technique to detect reaction intermediates and it was already used to monitor electrochemical reduction of CO 2 on Cu surfaces26,27 . Moreover, Electrochemical Mass Spectrometry (EC-MS) was used to study potential dependent desorption of products from the electrode surface, which in combination with…”

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confidence: 99%

Carbon-Nitrogen bond formation on Cu electrodes during CO2 reduction in NO3- solution

Krzywda¹,

Rodríguez²,

Benes³

et al. 2021

Preprint

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In performing electrochemical reduction of CO2 over Cu electrodes, the anions present in solution typically do not participate in the formation of reaction products. NO3- is an exception, and previous reports indicate the formation of urea in certain process conditions. Here we demonstrate by use of Surface Enhanced Raman Spectroscopy and Electrochemical Mass spectrometry that simultaneous reduction of NO3- and CO2 on Cu surfaces forms carbon-nitrogen bonds in the form of cyanide. The Raman peak position of C≡N is dependent on the oxidation state of the Cu surface, and Cu-C≡N can be oxidized by anodic polarization yielding NO. More importantly, Cyanide likely forms soluble Cu-C≡N complexes, which cause catalyst surface instability. The implications of this observation for practical application of a process for electrochemical formation of urea, are discussed.

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In Situ Raman Study of Potential‐Dependent Surface Adsorbed Carbonate, CO, OH, and C Species on Cu Electrodes During Electrochemical Reduction of CO₂

Cited by 91 publications

References 45 publications

Enhanced Electrocatalytic CO₂ Reduction to C₂₊ Products by Adjusting the Local Reaction Environment with Polymer Binders

Enhanced Electrocatalytic CO₂ Reduction to C₂₊ Products by Adjusting the Local Reaction Environment with Polymer Binders

Process Parameters in the Electrochemical Reduction of Carbon Dioxide to Ethylene

Carbon-Nitrogen bond formation on Cu electrodes during CO2 reduction in NO3- solution

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In Situ Raman Study of Potential‐Dependent Surface Adsorbed Carbonate, CO, OH, and C Species on Cu Electrodes During Electrochemical Reduction of CO2

Cited by 91 publications

References 45 publications

Enhanced Electrocatalytic CO2 Reduction to C2+ Products by Adjusting the Local Reaction Environment with Polymer Binders

Enhanced Electrocatalytic CO2 Reduction to C2+ Products by Adjusting the Local Reaction Environment with Polymer Binders

Process Parameters in the Electrochemical Reduction of Carbon Dioxide to Ethylene

Carbon-Nitrogen bond formation on Cu electrodes during CO2 reduction in NO3- solution

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In Situ Raman Study of Potential‐Dependent Surface Adsorbed Carbonate, CO, OH, and C Species on Cu Electrodes During Electrochemical Reduction of CO₂

Enhanced Electrocatalytic CO₂ Reduction to C₂₊ Products by Adjusting the Local Reaction Environment with Polymer Binders

Enhanced Electrocatalytic CO₂ Reduction to C₂₊ Products by Adjusting the Local Reaction Environment with Polymer Binders