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Herein, methanol oxidation reaction (MOR) is used to replace OER, coupling CO<jats:sub>2<\/jats:sub>RR to achieve co\u2010production of formate. Through enhancing OCHO* adsorption by oxygen vacancies engineering and synergistic effect by heteroatom doping, Bi\/Bi<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> and Ni\u2500Bi(OH)<jats:sub>3<\/jats:sub> are synthesized for efficient production of formate via simultaneous CO<jats:sub>2<\/jats:sub>RR and methanol oxidation reaction (MOR), achieving that the coupling of CO<jats:sub>2<\/jats:sub>RR\/\/MOR only required 7.26\u00a0kWh\u00a0g<jats:sub>formate<\/jats:sub><jats:sup>\u22121<\/jats:sup> power input, much lower than that of CO<jats:sub>2<\/jats:sub>RR\/\/OER (13.67\u00a0kWh\u00a0g<jats:sub>formate<\/jats:sub><jats:sup>\u22121<\/jats:sup>). Bi\/Bi<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> exhibits excellent electrocatalytic CO<jats:sub>2<\/jats:sub>RR performance, achieving FE<jats:sub>formate<\/jats:sub> &gt;80% in a wide potential range from \u22120.7 to \u22121.2\u00a0V (vs RHE). For MOR, Ni\u2500Bi(OH)<jats:sub>3<\/jats:sub> exhibits efficient MOR catalytic performance with the FE<jats:sub>formate<\/jats:sub> &gt;98% in the potential range of 1.35\u20131.6\u00a0V (vs RHE). Not only demonstrates the two\u2010electrode systems exceptional stability, working continuously for over 250\u00a0h under a cell voltage of 3.0\u00a0V, but the cathode and anode can maintain a FE of over 80%. DFT calculation results reveal that the oxygen vacancies of Bi\/Bi<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> enhance the adsorption of OCHO* intermediate, and Ni\u2500Bi(OH)<jats:sub>3<\/jats:sub> reduce the energy barrier for the rate determining step, leading to high catalytic activity.<\/jats:p>","DOI":"10.1002\/smll.202307741","type":"journal-article","created":{"date-parts":[[2023,12,14]],"date-time":"2023-12-14T14:19:45Z","timestamp":1702563585000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":42,"title":["Bismuth\u2010Based Electrocatalysts for Identical Value\u2010Added Formic Acid Through Coupling CO<sub>2<\/sub> Reduction and Methanol Oxidation"],"prefix":"10.1002","volume":"20","author":[{"given":"Shengjie","family":"Hao","sequence":"first","affiliation":[{"name":"State Key Laboratory of Fine Chemicals School of Chemical Engineering Dalian University of Technology  Dalian Liaoning 116024 P. R. 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