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Thermocatalytic WGSR achieves high product purity but requires energy\u2010intensive gas separation, while room\u2010temperature electrocatalysis is limited by low current densities due to mass transfer constraints. Here, we report a high\u2010temperature polymer electrolyte membrane electrolyzer (HT\u2010PEME) operating at 120\u00b0C\u2013200\u00b0C that combines the advantages of both approaches. The HT\u2010PEME utilizes a RuIr\/C catalyst, with Ir sites enhancing the balance of *OH\u2010 and CO\u2010adsorption on Ru, accelerating WGSR kinetics and lowering overpotential. Operating above the boiling point of water, the system shifts to a gas\u2013solid reaction interface, overcoming mass transfer limitations. This setup delivers a steady\u2010state current density of 1179 mA cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    at 0.6 V, producing hydrogen at \u2265\u00a099.99% purity without external separation processes. Furthermore, this high performance has been successfully scaled up to an electrolyzer stack comprising five 45 cm\n                    <jats:sup>2<\/jats:sup>\n                    membrane electrode assemblies (MEAs). This design offers a scalable, efficient solution for high\u2010purity hydrogen production through electrochemical WGSR.\n                  <\/jats:p>","DOI":"10.1002\/anie.6581557","type":"journal-article","created":{"date-parts":[[2026,10,8]],"date-time":"2026-10-08T09:56:45Z","timestamp":1791453405000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["High\u2010Purity Hydrogen Production From Water\u2013Gas Shift Reaction in a High\u2010Temperature Polymer Electrolyte Membrane Electrolyzer"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0005-8633-139X","authenticated-orcid":false,"given":"Zuyao","family":"Jiang","sequence":"first","affiliation":[{"name":"State Key Laboratory of Chemo\/Bio\u2010Sensing and Chemometrics, College of Chemistry and Chemical Engineering Hunan University  Changsha China"},{"name":"Greater Bay Area Institute for Innovation Hunan University  Guangzhou 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