Screening Surface Structure–Electrochemical Activity Relationships of Copper Electrodes under CO2 Electroreduction Conditions
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ABSTRACT:
SUBMITTER: Wahab O
PROVIDER: S-EPMC9171721 | biostudies-literature | 2022 May
REPOSITORIES: biostudies-literature
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Project description:Electrocatalytic CO2 reduction to value-added hydrocarbon products using metallic copper (Cu) catalysts is a potentially sustainable approach to facilitate carbon neutrality. However, Cu metal suffers from unavoidable and uncontrollable surface reconstruction during electrocatalysis, which can have either adverse or beneficial effects on its electrocatalytic performance. In a break from the current catalyst design path, we propose a strategy guiding the reconstruction process in a favorable direction to improve the performance. Typically, the controlled surface reconstruction is facilely realized using an electrolyte additive, ethylenediamine tetramethylenephosphonic acid, to substantially promote CO2 electroreduction to CH4 for commercial polycrystalline Cu. As a result, a stable CH4 Faradaic efficiency of 64% with a partial current density of 192 mA cm-2, thus enabling an impressive CO2-to-CH4 conversion rate of 0.25 µmol cm-2 s-1, is achieved in an alkaline flow cell. We believe our study will promote the exploration of electrochemical reconstruction and provide a promising route for the discovery of high-performance electrocatalysts.
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Project description:The electrochemical reduction of CO2 (CO2RR) is a sustainable alternative for producing fuels and chemicals, although the production of highly desired hydrocarbons is still a challenge due to the higher overpotential requirement in combination with the competitive hydrogen evolution reaction (HER). Tailoring the electrolyte composition is a possible strategy to favor the CO2RR over the HER. In this work we studied the solvent effect on the CO2RR on a nanostructured Cu electrode in acetonitrile solvent with different amounts of water. Similar to what has been observed for aqueous media, our online gas chromatography results showed that CO2RR in acetonitrile solvent is also structure-dependent, since nanocube-covered copper (CuNC) was the only surface (in comparison to polycrystalline Cu) capable of producing a detectable amount of ethylene (10% FE), provided there is enough water present in the electrolyte (>500 mM). In situ Fourier Transform Infrared (FTIR) spectroscopy showed that in acetonitrile solvent the presence of CO2 strongly inhibits HER by driving away water from the interface. CO is by far the main product of CO2RR in acetonitrile (>85% Faradaic efficiency), but adsorbed CO is not detected. This suggests that in acetonitrile media CO adsorption is inhibited compared to aqueous media. Remarkably, the addition of water to acetonitrile has little quantitative and almost no qualitative effect on the activity and selectivity of the CO2RR. This indicates that water is not strongly involved in the rate-determining step of the CO2RR in acetonitrile. Only at the highest water concentrations and at the CuNC surface, the CO coverage becomes high enough that a small amount of C2+ product is formed.
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Project description:Copper-based materials are known for converting CO2 into deep reduction products via electrochemical reduction reaction (CO2 RR). As the major multicarbon products (C2+ ), ethanol (C2 H5 OH) and ethylene (C2 H4 ) are believed to share a common oxygenic intermediate according to theoretical studies, while the key factors that bifurcate C2 H5 OH and C2 H4 pathways on Cu-based catalysts are not fully understood. Here, a surface oxophilicity regulation strategy to enhance C2 H5 OH production in CO2 RR is proposed, demonstrated by a Cu-Sn bimetallic system. Compared with bare Cu catalyst, the Cu-Sn bimetallic catalysts show improved C2 H5 OH but suppressed C2 H4 selectivity. The experimental results and theoretical calculations demonstrate that the surface oxophilicity of Cu-Sn catalysts plays an important role in steering the protonation of the key oxygenic intermediate and guides the reaction pathways to C2 H5 OH. This study provides new insights into the electrocatalyst design for enhanced production of oxygenic products from CO2 RR by engineering the surface oxophilicity of copper-based catalysts.
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Project description:Copper electrodes are especially effective in catalysis of C2 and further multi-carbon products in the CO2 reduction reaction (CO2 RR) and therefore of major technological interest. The reasons for the unparalleled Cu performance in CO2 RR are insufficiently understood. Here, the electrode-electrolyte interface was highlighted as a dynamic physical-chemical system and determinant of catalytic events. Exploiting the intrinsic surface-enhanced Raman effect of previously characterized Cu foam electrodes, operando Raman experiments were used to interrogate structures and molecular interactions at the electrode-electrolyte interface at subcatalytic and catalytic potentials. Formation of a copper carbonate hydroxide (CuCarHyd) was detected, which resembles the mineral malachite. Its carbonate ions could be directly converted to CO at low overpotential. These and further experiments suggested a basic mode of CO2 /carbonate reduction at Cu electrodes interfaces that contrasted previous mechanistic models: the starting point in carbon reduction was not CO2 but carbonate ions bound to the metallic Cu electrode in form of CuCarHyd structures. It was hypothesized that Cu oxides residues could enhance CO2 RR indirectly by supporting formation of CuCarHyd motifs. The presence of CuCarHyd patches at catalytic potentials might result from alkalization in conjunction with local electrical potential gradients, enabling the formation of metastable CuCarHyd motifs over a large range of potentials.
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Project description:Developing active and selective catalysts that convert CO2 into valuable products remains a critical challenge for further application of the electrochemical CO2 reduction reaction (CO2RR). Catalytic tuning with organic additives/films has emerged as a promising strategy to tune CO2RR activity and selectivity. Herein, we report a facile method to significantly change CO2RR selectivity and activity of copper and gold electrodes. We found improved selectivity toward HCOOH at low overpotentials on both polycrystalline Cu and Au electrodes after chemical modification with a poly(4-vinylpyridine) (P4VP) layer. In situ attenuated total reflection surface-enhanced infrared reflection-adsorption spectroscopy and contact angle measurements indicate that the hydrophobic nature of the P4VP layer limits mass transport of HCO3- and H2O, whereas it has little influence on CO2 mass transport. Moreover, the early onset of HCOOH formation and the enhanced formation of HCOOH over CO suggest that P4VP modification promotes a surface hydride mechanism for HCOOH formation on both electrodes.
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Project description:Non-noble metal molecular catalysts mediating the electrocatalytic reduction of carbon dioxide are still scarce. This work reports the electrochemical reduction of CO2 to formate catalyzed by the bimetallic complex [(bdt)MoVI(O)S2CuICN]2- (bdt = benzenedithiolate), a mimic of the active site of the Mo-Cu carbon monoxide dehydrogenase enzyme (CODH2). Infrared spectroelectrochemical (IR-SEC) studies coupled with density functional theory (DFT) computations revealed that the complex is only a pre-catalyst, the active catalyst being generated upon reduction in the presence of CO2. We found that the two-electron reduction of [(bdt)MoVI(O)S2CuICN]2- triggers the transfer of the oxo moiety to CO2 forming CO3 2- and the complex [(bdt)MoIVS2CuICN]2- and that a further one-electron reduction is needed to generate the active catalyst. Its protonation yields a reactive MoVH hydride intermediate which reacts with CO2 to produce formate. These findings are particularly relevant to the design of catalysts from metal oxo precursors.
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Project description:In this work, four different 4 cm2-sized nanostructured Cu-based electrocatalysts have been designed by a one-step electrodeposition process of Cu metal on a three-dimensional carbonaceous membrane. One consisted of Cu0, and the other three were obtained by further simple oxidative treatments. Morphological, structural, and electrochemical investigations on the four materials were carried out by scanning electron microscopy, Raman spectroscopy, X-ray diffraction, linear sweep voltammetry, and potential-controlled electrolysis. All the electrocatalysts showed promising catalytic activities toward CO2 electroreduction in liquid phase, with a remarkable selectivity toward acetic acid achieved when using the oxidized materials. In particular, the best electrocatalytic activity was observed for the Cu2O-Cu0 catalyst, working at a relatively low potential (-0.4 V vs RHE), which exhibited a stable and low current density of 0.46 mA cm-2 and a productivity of 308 μmol gcat-1 h-1. These results were attributed to the nanostructured morphology that is characterized by many void spaces and by a high surface area, which should guarantee a large number of CuI and Cu0 catalytic active sites. Moreover, kinetic analyses and preliminary studies about catalyst regeneration highlighted the stability of the best-performing catalyst.
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Project description:The electrocatalytic carbon dioxide (CO2 ) reduction reaction (CO2 RR) into hydrocarbons is a promising approach for greenhouse gas mitigation, but many details of this dynamic reaction remain elusive. Here, time-resolved surface-enhanced Raman spectroscopy (TR-SERS) is employed to successfully monitor the dynamics of CO2 RR intermediates and Cu surfaces with sub-second time resolution. Anodic treatment at 1.55 V vs. RHE and subsequent surface oxide reduction (below -0.4 V vs. RHE) induced roughening of the Cu electrode surface, which resulted in hotspots for TR-SERS, enhanced time resolution (down to ≈0.7 s) and fourfold improved CO2 RR efficiency toward ethylene. With TR-SERS, the initial restructuring of the Cu surface was followed (<7 s), after which a stable surface surrounded by increased local alkalinity was formed. Our measurements revealed that a highly dynamic CO intermediate, with a characteristic vibration below 2060 cm-1 , is related to C-C coupling and ethylene production (-0.9 V vs. RHE), whereas lower cathodic bias (-0.7 V vs. RHE) resulted in gaseous CO production from isolated and static CO surface species with a distinct vibration at 2092 cm-1 .
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