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Here, we show that this assumption fails when metal nuclearity and support hydroxyl chemistry are considered. Using a well\u2010defined set of Pt single\u2010atom and nanoparticle catalysts supported on hydroxyl\u2010rich CeO\n                    <jats:sub>2<\/jats:sub>\n                    and hydroxyl\u2010poor Al\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3<\/jats:sub>\n                    , we uncover a striking, size\u2010dependent inversion of water effects. On CeO\n                    <jats:sub>2<\/jats:sub>\n                    \u2010supported Pt nanoparticles, water activation generates surface hydroxyls that withdraw electron density from Pt, weaken CO adsorption and alleviate CO poisoning, thereby enhancing activity. In contrast, the same hydroxyl species inhibit methanol conversion on single\u2010atom Pt by competing for adsorption sites and stabilizing kinetically trapped formate intermediates. These opposing effects vanish on Al\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3<\/jats:sub>\n                    , where water activation is limited. This size\u2010dependent inversion extends to other single\u2010atom catalysts and reducible supports (e.g., Pd\n                    <jats:sub>1<\/jats:sub>\n                    \/CeO\n                    <jats:sub>2<\/jats:sub>\n                    , Rh\n                    <jats:sub>1<\/jats:sub>\n                    \/CeO\n                    <jats:sub>2<\/jats:sub>\n                    ), confirming its generality and establishing a predictive framework for understanding and controlling water effects in reforming catalysis.\n                  <\/jats:p>","DOI":"10.1002\/anie.1134406","type":"journal-article","created":{"date-parts":[[2026,7,26]],"date-time":"2026-07-26T17:56:51Z","timestamp":1785088611000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Water Is Not Universally Promotional: Size\u2010Dependent Inversion of Water Effects in Methanol Steam Reforming"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8287-6799","authenticated-orcid":false,"given":"Shipan","family":"Liang","sequence":"first","affiliation":[{"name":"Advanced Materials and Catalysis Group Zhejiang Key Laboratory of Low\u2010Carbon Synthesis of Value\u2010Added Chemicals State Key Laboratory of Clean Energy Utilization Institute of Catalysis Department of Chemistry Zhejiang University  Hangzhou P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9955-6249","authenticated-orcid":false,"given":"Bing","family":"Lu","sequence":"additional","affiliation":[{"name":"Advanced Materials and Catalysis Group Zhejiang Key Laboratory of Low\u2010Carbon Synthesis of Value\u2010Added Chemicals State Key Laboratory of Clean Energy Utilization Institute of Catalysis Department of Chemistry Zhejiang University  Hangzhou P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hao","family":"Wang","sequence":"additional","affiliation":[{"name":"Advanced Materials and Catalysis Group Zhejiang Key Laboratory of Low\u2010Carbon Synthesis of Value\u2010Added Chemicals State Key Laboratory of Clean Energy Utilization Institute of Catalysis Department of Chemistry Zhejiang University  Hangzhou P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhenzhen","family":"Wang","sequence":"additional","affiliation":[{"name":"Advanced Materials and Catalysis Group Zhejiang Key Laboratory of Low\u2010Carbon Synthesis of Value\u2010Added Chemicals State Key Laboratory of Clean Energy Utilization Institute of Catalysis Department of Chemistry Zhejiang University  Hangzhou P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2047-3465","authenticated-orcid":false,"given":"Shanjun","family":"Mao","sequence":"additional","affiliation":[{"name":"Advanced Materials and Catalysis Group Zhejiang Key Laboratory of Low\u2010Carbon Synthesis of Value\u2010Added Chemicals State Key Laboratory of Clean Energy Utilization Institute of Catalysis Department of Chemistry Zhejiang University  Hangzhou P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jinqi","family":"Xiong","sequence":"additional","affiliation":[{"name":"Advanced Materials and Catalysis Group Zhejiang Key Laboratory of Low\u2010Carbon Synthesis of Value\u2010Added Chemicals State Key Laboratory of Clean Energy Utilization Institute of Catalysis Department of Chemistry Zhejiang University  Hangzhou P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8043-5757","authenticated-orcid":false,"given":"Yong","family":"Wang","sequence":"additional","affiliation":[{"name":"Advanced Materials and Catalysis Group Zhejiang Key Laboratory of Low\u2010Carbon Synthesis of Value\u2010Added Chemicals State Key Laboratory of Clean Energy Utilization Institute of Catalysis Department of Chemistry Zhejiang University  Hangzhou P. R. 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