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Herein, we report a bismuth-based paired electrosynthesis system (Bi NSs\/CF || Bi\/NF-20) for the simultaneous coproduction of high value formate at both electrodes via cathodic CO2 reduction (CO2RR) and anodic methanol oxidation (MOR). Crucially, these self-supported electrodes are rationally constructed through a spontaneous galvanic replacement strategy, offering a sustainable alternative to conventional energy intensive fabrication. Consequently, the integrated two-electrode electrolyzer operates stably at 3 V for 50 h, yielding a combined FE exceeding 185% and impressive production capacities of more than 400 g kWh\u20131. Combined in situ Raman spectroscopy and theoretical calculations reveal that the intrinsic electronic properties of the Bi NSs\/CF facilitate the rate-determining step by lowering the *OCHO formation barrier, and elucidate the dynamic evolution of active sites during the MOR. This study offers a compelling strategy for designing integrated electrolyzers toward CO2 valorization with high atom economy.<\/jats:p>","DOI":"10.1021\/acs.inorgchem.6c03633","type":"journal-article","created":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T12:01:59Z","timestamp":1789473719000},"page":"22688-22697","source":"Crossref","is-referenced-by-count":0,"title":["Galvanic Replacement\nDerived Bi-Based Catalysts for\nFormate Coproduction via Coupled CO2RR and Methanol Oxidation"],"prefix":"10.1021","volume":"65","author":[{"given":"Jialuo","family":"Li","sequence":"first","affiliation":[{"name":"Dalian University of Technology , , ,","place":["Dalian, China, 116024"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guojie","family":"Gao","sequence":"additional","affiliation":[{"name":"Dalian University of Technology , , ,","place":["Dalian, China, 116024"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yu","family":"Wei","sequence":"additional","affiliation":[{"name":"Dalian University of Technology , , ,","place":["Dalian, China, 116024"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0003-6139-2116","authenticated-orcid":true,"given":"Taolue","family":"Liu","sequence":"additional","affiliation":[{"name":"Dalian University of Technology , , ,","place":["Dalian, China, 116024"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hanwen","family":"Xu","sequence":"additional","affiliation":[{"name":"Dalian University of Technology , , ,","place":["Dalian, China, 116024"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mingxia","family":"Guo","sequence":"additional","affiliation":[{"name":"Dalian University of Technology , , ,","place":["Dalian, China, 116024"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2429-7147","authenticated-orcid":true,"given":"Xin","family":"Ding","sequence":"additional","affiliation":[{"name":"Qingdao University , , , ,","place":["Qingdao, Shandong, China, 266071"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9895-4088","authenticated-orcid":true,"given":"Yan","family":"Gao","sequence":"additional","affiliation":[{"name":"Dalian University of Technology , , ,","place":["Dalian, China, 116024"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,15]]},"reference":[{"issue":"1","key":"2026092809230099100_cit1","doi-asserted-by":"publisher","first-page":"188","DOI":"10.1021\/acsenergylett.6b00574","article-title":"Formic Acid as a Hydrogen Energy Carrier","volume":"2","author":"Eppinger","year":"2017","journal-title":"ACS Energy Lett."},{"issue":"15","key":"2026092809230099100_cit2","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.202103799","article-title":"Formic Acid to Power towards Low-Carbon\nEconomy","volume":"12","author":"Dutta","year":"2022","journal-title":"Adv. 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