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Photothermal catalysis, in which hot electrons participate in catalytic reaction, offers a promising pathway for low\u2010temperature MSR. Herein, a Cu\/CeZrO\n                    <jats:italic>\n                      <jats:sub>x<\/jats:sub>\n                    <\/jats:italic>\n                    photothermal catalyst (denoted as CuCZ) was prepared through a coprecipitation\u2013calcination\u2013reduction strategy. The optimized CuCZ achieves a hydrogen production rate of 180.9\u00a0\u00b5mol g\n                    <jats:sup>\u22121<\/jats:sup>\n                    s\n                    <jats:sup>\u22121<\/jats:sup>\n                    under full\u2010spectrum irradiation at 199\u00b0C, which is 26.2 times larger than that obtained with thermocatalytic mode, while maintaining a CO selectivity below 0.2%. A comprehensive structural characterization reveals the formation of Cu\n                    <jats:italic>\n                      <jats:sup>\u03b4<\/jats:sup>\n                    <\/jats:italic>\n                    <jats:sup>+<\/jats:sup>\n                    \u2212O\n                    <jats:italic>\n                      <jats:sub>v<\/jats:sub>\n                    <\/jats:italic>\n                    \u2013CeZrO\n                    <jats:italic>\n                      <jats:sub>x<\/jats:sub>\n                    <\/jats:italic>\n                    interfacial sites with pronounced light\u2010induced interfacial reconstruction. In situ spectroscopic studies, kinetic analyses, and density functional theory calculations substantiate a photo\u2010assisted thermocatalytic mechanism, in which photoexcitation drives hot electron injection and interfacial electron transfer, triggering a dynamic evolution of the Cu\n                    <jats:sup>0<\/jats:sup>\n                    \/Cu\n                    <jats:sup>+<\/jats:sup>\n                    \u2013[O*\u21cbO\n                    <jats:sub>v<\/jats:sub>\n                    ]\u2013Ce\n                    <jats:sup>3+<\/jats:sup>\n                    \/Ce\n                    <jats:sup>4+<\/jats:sup>\n                    interfacial structure. This dynamic interface enables the synergistic coupling of methanol dissociation, H\n                    <jats:sub>2<\/jats:sub>\n                    O activation, and lattice oxygen regeneration, which boosts the kinetically relevant step (HCOO* conversion) by five times and delivers a 21.8% reduction in the kinetic isotope effect. This photo\u2010assisted thermocatalysis overcomes the inherent kinetic limitations of low\u2010temperature MSR, accounting for significantly promoted reaction efficiency.\n                  <\/jats:p>","DOI":"10.1002\/anie.4099867","type":"journal-article","created":{"date-parts":[[2026,10,13]],"date-time":"2026-10-13T07:26:52Z","timestamp":1791876412000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Photo\u2010Promoted Thermocatalysis: Low\u2010Temperature Methanol Steam Reforming Toward Hydrogen Production"],"prefix":"10.1002","author":[{"given":"Shaoteng","family":"Yuan","sequence":"first","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing P. R. China"},{"name":"Quzhou Institute for Innovation in Resource Chemical Engineering  Quzhou P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0624-3241","authenticated-orcid":false,"given":"Yusen","family":"Yang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing P. R. China"},{"name":"Quzhou Institute for Innovation in Resource Chemical Engineering  Quzhou P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongbo","family":"Bao","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaohui","family":"Yang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wenxin","family":"Guo","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bin","family":"Wang","sequence":"additional","affiliation":[{"name":"Beijing Research Institute of Chemical Industry Sinopec Group  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lirong","family":"Zheng","sequence":"additional","affiliation":[{"name":"Institute of High Energy Physics Chinese Academy of Sciences  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8532-3348","authenticated-orcid":false,"given":"Song","family":"Hong","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3559-2096","authenticated-orcid":false,"given":"Xin","family":"Zhang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lei","family":"Wang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing P. R. China"},{"name":"Quzhou Institute for Innovation in Resource Chemical Engineering  Quzhou P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6494-0825","authenticated-orcid":false,"given":"Hao","family":"Meng","sequence":"additional","affiliation":[{"name":"Department of Chemistry The Hong Kong Polytechnic University  Kowloon, Hong Kong S.A.R. P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5257-790X","authenticated-orcid":false,"given":"Min","family":"Wei","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing P. R. China"},{"name":"Quzhou Institute for Innovation in Resource Chemical Engineering  Quzhou P. R. 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