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Structural evolution and strain generation of derived-Cu catalysts during CO₂ electroreduction.

ABSTRACT: Copper (Cu)-based catalysts generally exhibit high C₂₊ selectivity during the electrochemical CO₂ reduction reaction (CO₂RR). However, the origin of this selectivity and the influence of catalyst precursors on it are not fully understood. We combine operando X-ray diffraction and operando Raman spectroscopy to monitor the structural and compositional evolution of three Cu precursors during the CO₂RR. The results indicate that despite different kinetics, all three precursors are completely reduced to Cu(0) with similar grain sizes (~11 nm), and that oxidized Cu species are not involved in the CO₂RR. Furthermore, Cu(OH)₂- and Cu₂(OH)₂CO₃-derived Cu exhibit considerable tensile strain (0.43%~0.55%), whereas CuO-derived Cu does not. Theoretical calculations suggest that the tensile strain in Cu lattice is conducive to promoting CO₂RR, which is consistent with experimental observations. The high CO₂RR performance of some derived Cu catalysts is attributed to the combined effect of the small grain size and lattice strain, both originating from the in situ electroreduction of precursors. These findings establish correlations between Cu precursors, lattice strains, and catalytic behaviors, demonstrating the unique ability of operando characterization in studying electrochemical processes.

SUBMITTER: Lei Q

PROVIDER: S-EPMC9388520 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature

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Structural evolution and strain generation of derived-Cu catalysts during CO2 electroreduction.

Lei Qiong Q Huang Liang L Yin Jun J Davaasuren Bambar B Yuan Youyou Y Dong Xinglong X Wu Zhi-Peng ZP Wang Xiaoqian X Yao Ke Xin KX Lu Xu X Han Yu Y

Nature communications 20220818 1

Copper (Cu)-based catalysts generally exhibit high C2+ selectivity during the electrochemical CO2 reduction reaction (CO2RR). However, the origin of this selectivity and the influence of catalyst precursors on it are not fully understood. We combine operando X-ray diffraction and operando Raman spectroscopy to monitor the structural and compositional evolution of three Cu precursors during the CO2RR. The results indicate that despite different kinetics ...[more]

PMID: 35982055

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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.

Dataset Information

Structural evolution and strain generation of derived-Cu catalysts during CO₂ electroreduction.

Publications

Structural evolution and strain generation of derived-Cu catalysts during CO<sub>2</sub> electroreduction.

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