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Revealing the CO Coverage-Driven C-C Coupling Mechanism for Electrochemical CO₂ Reduction on Cu₂O Nanocubes via Operando Raman Spectroscopy.

ABSTRACT: Electrochemical reduction of carbon dioxide (CO₂RR) is an attractive route to close the carbon cycle and potentially turn CO₂ into valuable chemicals and fuels. However, the highly selective generation of multicarbon products remains a challenge, suffering from poor mechanistic understanding. Herein, we used operando Raman spectroscopy to track the potential-dependent reduction of Cu₂O nanocubes and the surface coverage of reaction intermediates. In particular, we discovered that the potential-dependent intensity ratio of the Cu-CO stretching band to the CO rotation band follows a volcano trend similar to the CO₂RR Faradaic efficiency for multicarbon products. By combining operando spectroscopic insights with Density Functional Theory, we proved that this ratio is determined by the CO coverage and that a direct correlation exists between the potential-dependent CO coverage, the preferred C-C coupling configuration, and the selectivity to C₂₊ products. Thus, operando Raman spectroscopy can serve as an effective method to quantify the coverage of surface intermediates during an electrocatalytic reaction.

SUBMITTER: Zhan C

PROVIDER: S-EPMC8256421 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:To address the challenge of selectivity toward single products in Cu-catalyzed electrochemical CO2 reduction, one strategy is to incorporate a second metal with the goal of tuning catalytic activity via synergy effects. In particular, catalysts based on Cu modified with post-transition metals (Sn or In) are known to reduce CO2 selectively to either CO or HCOO- depending on their composition. However, it remains unclear exactly which factors induce this switch in reaction pathways and whether these two related bimetal combinations follow similar general structure-activity trends. To investigate these questions systematically, Cu-In and Cu-Sn bimetallic catalysts were synthesized across a range of composition ratios and studied in detail. Compositional and morphological control was achieved via a simple electrochemical synthesis approach. A combination of operando and quasi-in situ spectroscopic techniques, including X-ray photoelectron, X-ray absorption, and Raman spectroscopy, was used to observe the dynamic behaviors of the catalysts' surface structure, composition, speciation, and local environment during CO2 electrolysis. The two systems exhibited similar selectivity dependency on their surface composition. Cu-rich catalysts produce mainly CO, while Cu-poor catalysts were found to mainly produce HCOO-. Despite these similarities, the speciation of Sn and In at the surface differed from each other and was found to be strongly dependent on the applied potential and the catalyst composition. For Cu-rich compositions optimized for CO production (Cu85In15 and Cu85Sn15), indium was present predominantly in the reduced metallic form (In0), whereas tin mainly existed as an oxidized species (Sn2/4+). Meanwhile, for the HCOO--selective compositions (Cu25In75 and Cu40Sn60), the indium exclusively exhibited In0 regardless of the applied potential, while the tin was reduced to metallic (Sn0) only at the most negative applied potential, which corresponds to the best HCOO- selectivity. Furthermore, while Cu40Sn60 enhances HCOO- selectivity by inhibiting H2 evolution, Cu25In75 improves the HCOO- selectivity at the expense of CO production. Due to these differences, we contend that identical mechanisms cannot be used to explain the behavior of these two bimetallic systems (Cu-In and Cu-Sn). Operando surface-enhanced Raman spectroscopy measurements provide direct evidence of the local alkalization and its impact on the dynamic transformation of oxidized Cu surface species (Cu2O/CuO) into a mixture of Cu(OH)2 and basic Cu carbonates [Cux(OH)y(CO3)y] rather than metallic Cu under CO2 electrolysis. This study provides unique insights into the origin of the switch in selectivity between CO and HCOO- pathways at Cu bimetallic catalysts and the nature of surface-active sites and key intermediates for both pathways.

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Revealing the CO Coverage-Driven C-C Coupling Mechanism for Electrochemical CO₂ Reduction on Cu₂O Nanocubes via Operando Raman Spectroscopy.

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Revealing the CO Coverage-Driven C-C Coupling Mechanism for Electrochemical CO2 Reduction on Cu2O Nanocubes via Operando Raman Spectroscopy.

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OmicsDI is part of the ELIXIR infrastructure

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Revealing the CO Coverage-Driven C-C Coupling Mechanism for Electrochemical CO₂ Reduction on Cu₂O Nanocubes via Operando Raman Spectroscopy.