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This work builds upon existing academic studies by utilizing industrially relevant proton exchange membrane catalyst-coated membrane electrode assemblies in an applicable cell design. To overcome challenges in spectral analysis, a methodology for spectral deconvolution with a focus on stability and validity was developed and verified by two-dimensional correlation analysis. Based on\n                    <jats:italic>in operando<\/jats:italic>\n                    studies during potential-dependent electrolysis and catalyst relaxation at open circuit potential, the oxygen evolution reaction pathway on iridium-based catalyst-coated membrane electrode assemblies was found to involve a concerted redox reaction of both iridium and oxygen. Formation of the active species occurs from iridium oxo-hydroxides and crystalline IrO\n                    <jats:sub>2<\/jats:sub>\n                    via oxidative charging. Enhanced proton conduction due to ionomer presence in application-oriented systems promotes deprotonation, causing oxidative charging of the catalyst well before the oxygen evolution reaction onset.\n                  <\/jats:p>","DOI":"10.1038\/s42004-026-02162-9","type":"journal-article","created":{"date-parts":[[2026,8,6]],"date-time":"2026-08-06T16:06:34Z","timestamp":1786032394000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Insights into the Ir-O redox dynamics of an operating PEM water electrolyzer using in operando Raman spectroscopy"],"prefix":"10.1038","volume":"9","author":[{"given":"Sebastian","family":"Speer","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1227-4936","authenticated-orcid":false,"given":"Sven","family":"Jovanovic","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0009-7819-0768","authenticated-orcid":false,"given":"Christina","family":"Oe\u00df","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2289-5987","authenticated-orcid":false,"given":"Andr\u00e9","family":"Karl","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0004-8214-2981","authenticated-orcid":false,"given":"Eva","family":"Jodat","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0013-6325","authenticated-orcid":false,"given":"R\u00fcdiger-A.","family":"Eichel","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2026,8,6]]},"reference":[{"key":"2162_CR1","doi-asserted-by":"publisher","first-page":"16977","DOI":"10.1021\/ja407115p","volume":"135","author":"CCL McCrory","year":"2013","unstructured":"McCrory, C. 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