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Modulating catalyst microstructures to accelerate protonation has thus emerged as a promising strategy to boost from CO\n                    <jats:sub>2<\/jats:sub>\n                    to CO selectivity. Here, we report ultrasmall Ni nanocluster catalysts (denoted as Ni\n                    <jats:sub>3<\/jats:sub>\n                    \u2500N\u2500C) prepared via one\u2010step pyrolysis of Ni\u2010containing precursors under H\n                    <jats:sub>2<\/jats:sub>\n                    atmosphere. Compared to conventional Ni\u2500N\u2500C with symmetric Ni\u2500N\n                    <jats:sub>4<\/jats:sub>\n                    motifs, Ni\n                    <jats:sub>3<\/jats:sub>\n                    \u2500N\u2500C displays similar physicochemical characteristics\u2014Ni loading, defect density, surface area\u2014yet exhibits distinct local Ni coordination environments. These sub\u2010nanoclusters markedly enhance CO\n                    <jats:sub>2<\/jats:sub>\n                    RR performance, delivering\u00a0&gt;\u00a090% CO Faradaic efficiency (FE\n                    <jats:sub>CO<\/jats:sub>\n                    ) across \u22120.6 to \u22121.0\u00a0V versus RHE, with a peak FE\n                    <jats:sub>CO<\/jats:sub>\n                    of \u223c95% at \u22120.8\u00a0V. Density functional theory calculations reveal that Ni\n                    <jats:sub>3<\/jats:sub>\n                    \u2500N\u2500C substantially lowers the energy barrier for *COOH formation owing to altered adsorption configurations, thereby facilitating the rate\u2010limiting protonation step. In situ FTIR measurements further confirm the accelerated *COOH formation on Ni\n                    <jats:sub>3<\/jats:sub>\n                    \u2500N\u2500C surfaces. This work highlights the critical role of Ni sub\u2010nanoclusters in PCET modulation and establishes a rational design principle for nanocluster\u2010based catalysts in CO\n                    <jats:sub>2<\/jats:sub>\n                    RR.\n                  <\/jats:p>","DOI":"10.1002\/anie.202518107","type":"journal-article","created":{"date-parts":[[2025,11,3]],"date-time":"2025-11-03T08:03:54Z","timestamp":1762157034000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Ultrasmall Nickel Nanoclusters Accelerating Protonation for Efficient CO\n                    <sub>2<\/sub>\n                    Electroreduction towards CO"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7067-6917","authenticated-orcid":false,"given":"Jun","family":"Wu","sequence":"first","affiliation":[{"name":"School of Metallurgy and Environment Central South University  Changsha 410083 China"},{"name":"State Key Laboratory of Advanced Metallurgy for Non\u2010ferrous Metals  Changsha 410083 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wuyi","family":"Zhang","sequence":"additional","affiliation":[{"name":"School of Metallurgy and Environment Central South University  Changsha 410083 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lin","family":"Wu","sequence":"additional","affiliation":[{"name":"School of Metallurgy and Environment Central South University  Changsha 410083 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xinlei","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Metallurgy and Environment Central South University  Changsha 410083 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jing","family":"Yuan","sequence":"additional","affiliation":[{"name":"School of Metallurgy and Environment Central South University  Changsha 410083 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kailong","family":"Xu","sequence":"additional","affiliation":[{"name":"School of Metallurgy and Environment Central South University  Changsha 410083 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yani","family":"Hua","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering and Technology Xi\u2019 an Jiaotong University  Xi\u2019 an 710049 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhan","family":"Gao","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering and Technology Xi\u2019 an Jiaotong University  Xi\u2019 an 710049 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hui","family":"Liu","sequence":"additional","affiliation":[{"name":"School of Metallurgy and Environment Central South University  Changsha 410083 China"},{"name":"State Key Laboratory of Advanced Metallurgy for Non\u2010ferrous Metals  Changsha 410083 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9007-4817","authenticated-orcid":false,"given":"Min","family":"Liu","sequence":"additional","affiliation":[{"name":"School of Metallurgy and Environment Central South University  Changsha 410083 China"},{"name":"Hunan Joint International Research Center for Carbon Dioxide Resource Utilization, School of Physics Central South University  Changsha 410083 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