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Among them, CuGa<jats:sub>2<\/jats:sub> selectively converts CO<jats:sub>2<\/jats:sub> to methanol with remarkable Faradaic efficiency of 77.26% at an extremely low potential of \u22120.3\u00a0V vs RHE. The high performance of CuGa<jats:sub>2<\/jats:sub> compared to Cu<jats:sub>9<\/jats:sub>Ga<jats:sub>4<\/jats:sub> is driven by its unique 2D structure, which retains surface and subsurface oxide species (Ga<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>) even in the reduction atmosphere. The Ga<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> species is mapped by X\u2010ray photoelectron spectroscopy (XPS) and X\u2010ray absorption fine structure (XAFS) techniques and electrochemical measurements. The eCO<jats:sub>2<\/jats:sub>RR selectivity to methanol are decreased at higher potential due to the lattice expansion caused by the reduction of the Ga<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>, which is probed by in situ XAFS, quasi in situ powder X\u2010ray diffraction, and ex situ XPS measurements. The mechanism of the formation of methanol is visualized by in situ infrared (IR) spectroscopy and the source of the carbon of methanol at the molecular level is confirmed from the isotope\u2010labeling experiments in presence of <jats:sup>13<\/jats:sup>CO<jats:sub>2<\/jats:sub>. Finally, to minimize the mass transport limitations and improve the overall eCO<jats:sub>2<\/jats:sub>RR performance, a poly(tetrafluoroethylene)\u2010based gas diffusion electrode is used in the flow cell configuration.<\/jats:p>","DOI":"10.1002\/adma.202109426","type":"journal-article","created":{"date-parts":[[2022,3,12]],"date-time":"2022-03-12T09:23:25Z","timestamp":1647077005000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":190,"title":["Structure\u2010Tailored Surface Oxide on Cu\u2013Ga Intermetallics Enhances CO<sub>2<\/sub> Reduction Selectivity to Methanol at Ultralow Potential"],"prefix":"10.1002","volume":"34","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9922-2073","authenticated-orcid":false,"given":"Debabrata","family":"Bagchi","sequence":"first","affiliation":[{"name":"New Chemistry Unit Jawaharlal Nehru Centre for Advanced Scientific Research  Jakkur Bangalore 560064 India"},{"name":"School of Advanced Materials Jawaharlal Nehru Centre for Advanced Scientific Research  Jakkur Bangalore 560064 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jithu","family":"Raj","sequence":"additional","affiliation":[{"name":"New Chemistry Unit Jawaharlal Nehru Centre for Advanced Scientific Research  Jakkur Bangalore 560064 India"},{"name":"School of Advanced Materials Jawaharlal Nehru Centre for Advanced Scientific Research  Jakkur Bangalore 560064 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2491-3678","authenticated-orcid":false,"given":"Ashutosh Kumar","family":"Singh","sequence":"additional","affiliation":[{"name":"School of Advanced Materials Jawaharlal Nehru Centre for Advanced Scientific Research  Jakkur Bangalore 560064 India"},{"name":"Chemistry and Physics of Materials Unit Jawaharlal Nehru Centre for Advanced Scientific Research  Jakkur Bangalore 560064 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1649-0123","authenticated-orcid":false,"given":"Arjun","family":"Cherevotan","sequence":"additional","affiliation":[{"name":"New Chemistry Unit Jawaharlal Nehru Centre for Advanced Scientific Research  Jakkur Bangalore 560064 India"},{"name":"School of Advanced Materials Jawaharlal Nehru Centre for Advanced Scientific Research  Jakkur Bangalore 560064 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3540-1341","authenticated-orcid":false,"given":"Soumyabrata","family":"Roy","sequence":"additional","affiliation":[{"name":"New Chemistry Unit Jawaharlal Nehru Centre for Advanced Scientific Research  Jakkur Bangalore 560064 India"},{"name":"School of Advanced Materials Jawaharlal Nehru Centre for Advanced Scientific Research  Jakkur Bangalore 560064 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kaja Sai","family":"Manoj","sequence":"additional","affiliation":[{"name":"New Chemistry Unit Jawaharlal Nehru Centre for Advanced Scientific Research  Jakkur Bangalore 560064 India"},{"name":"School of Advanced Materials Jawaharlal Nehru Centre for Advanced Scientific Research  Jakkur Bangalore 560064 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9857-4907","authenticated-orcid":false,"given":"C. 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