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Dual‐Metal Sites Drive Tandem Electrocatalytic CO<sub>2</sub> to C<sub>2+</sub> Products

Guixian Xie, Weiwei Guo, Zijian Fang, Zongxia Duan, Xianzhen Lang, Doudou Liu, Guoliang Mei, Yanling Zhai, Xiaofu Sun, Xiaoquan Lu

2024Angewandte Chemie International Edition66 citationsDOIOpen Access PDF

Abstract

Abstract The electrochemical conversion of CO 2 into valuable chemicals is a promising route for renowable energy storage and the mitigation of greenhouse gas emission, and production of multicarbon (C 2+ ) products is highly desired. Here, we report a 1.4 %Pd−Cu@CuPz 2 comprising of dispersive CuO x and PdO dual nanoclusters embedded in the MOF CuPz 2 (Pz=Pyrazole), which achieves a high C 2+ Faradaic efficiency (FE C2+ ) of 81.9 % and C 2+ alcohol FE of 47.5 % with remarkable stability when using 0.1 M KCl aqueous solution as electrolyte in a typical H‐cell. Particularly, the FE of alcohol is obviously improved on 1.4 %Pd−Cu@CuPz 2 compared to Cu@CuPz 2 . Theoretical calculations have revealed that the enhanced interfacial electron transfer facilitates the adsorption of *CO intermediate and *CO−*CO dimerization on the Cu−Pd dual sites bridged by Cu nodes of CuPz 2 . Additionally, the oxophilicity of Pd can stabilize the key intermediate *CH 2 CHO and promote subsequent proton‐coupled electron transfer more efficiently, confirming that the formation pathway is skew towards *C 2 H 5 OH. Consequently, the Cu−Pd dual sites play a synergistic tandem role in cooperatively improving the selectivity of alcohol and accelerating reductive conversion of CO 2 to C 2+ .

Topics & Concepts

TandemFaraday efficiencyNanoclustersElectrochemistryChemistryElectron transferMetalAqueous solutionAdsorptionSelectivityCatalysisInorganic chemistryMaterials sciencePhotochemistryElectrodePhysical chemistryOrganic chemistryComposite materialCO2 Reduction Techniques and CatalystsIonic liquids properties and applicationsAdvanced Photocatalysis Techniques
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