{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T06:04:09Z","timestamp":1789625049173,"version":"build-2803163510"},"reference-count":30,"publisher":"Wiley","license":[{"start":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T00:00:00Z","timestamp":1789516800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T00:00:00Z","timestamp":1789516800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/100016714","name":"University of Sharjah","doi-asserted-by":"publisher","award":["25021440180"],"award-info":[{"award-number":["25021440180"]}],"id":[{"id":"10.13039\/100016714","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["advanced.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Advanced Science"],"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Counter\u2010cations play a key role in modulating the redox chemistry and phase behavior of polyoxometalates (POMs). In this study, we report a potential\u2010controlled, ammonium\u2010assisted electrodeposition of POMs from nonaqueous electrolytes. Owing to its tetrahedral geometry and hydrogen\u2010bonding capability, NH\n                    <jats:sub>4<\/jats:sub>\n                    <jats:sup>+<\/jats:sup>\n                    uniquely stabilizes reduced POM clusters at the electrode interface, enabling reversible solid\u2010to\u2010solution transitions. Using the mixed\u2010valence vanadium cluster [V\n                    <jats:sub>18<\/jats:sub>\n                    O\n                    <jats:sub>46<\/jats:sub>\n                    (NO\n                    <jats:sub>3<\/jats:sub>\n                    )]\n                    <jats:sup>5\u2212<\/jats:sup>\n                    and Keggin\u2010type POM cluster, [PMo\n                    <jats:sub>12<\/jats:sub>\n                    O\n                    <jats:sub>40<\/jats:sub>\n                    ]\n                    <jats:sup>3\u2212<\/jats:sup>\n                    as model systems, we demonstrate controlled reversible charge\u2010transfer dynamics, including effective mass deposition under reductive potentials and complete dissolution upon oxidation, as confirmed by cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM) measurements. Microscopic and spectroscopic investigations reveal that electrodeposition at low potentials involves partial reduction of redox\u2010active metal centers within the POM framework, accompanied by NH\n                    <jats:sub>4<\/jats:sub>\n                    <jats:sup>+<\/jats:sup>\n                    incorporation via hydrogen\u2010bonded networks, forming NH\n                    <jats:sub>4<\/jats:sub>\n                    <jats:sup>+<\/jats:sup>\n                    \u2010coupled POM\u2010derived deposits, which exhibit a significantly different pathway from the classic metal electrodeposition (metal plating). Leveraging this reversible behavior, we propose the design of POM electrodeposition\u2010based hybrid redox flow battery (RFB), where NH\n                    <jats:sub>4<\/jats:sub>\n                    <jats:sup>+<\/jats:sup>\n                    \u2010driven POM electrodeposition\/dissolution in the negative half\u2010cell enables electron storage\/release during charge\/discharge processes, and validate the design through proof\u2010of\u2010concept battery demonstrations. These findings provide important initial insights into NH\n                    <jats:sub>4<\/jats:sub>\n                    <jats:sup>+<\/jats:sup>\n                    \u2010driven reversible POM electrodeposition and highlight its potential in advancing electrochemical energy storage technologies.\n                  <\/jats:p>","DOI":"10.1002\/advs.77673","type":"journal-article","created":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T05:37:14Z","timestamp":1789623434000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Potential\u2010Controlled Ammonium\u2010Assisted Reversible Electrodeposition of Polyoxometalates for Hybrid Redox Flow Batteries"],"prefix":"10.1002","author":[{"given":"Ke","family":"Wang","sequence":"first","affiliation":[{"name":"Institute of Inorganic Chemistry I Ulm University  Ulm Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5795-4639","authenticated-orcid":false,"given":"Nikhil","family":"Arya","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry I Ulm University  Ulm Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sadia","family":"Shahid","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry I Ulm University  Ulm Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9197-4526","authenticated-orcid":false,"given":"Montaha","family":"Anjass","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry I Ulm University  Ulm Germany"},{"name":"Department of Chemistry University of Sharjah  Sharjah UAE"},{"name":"CELEST Green Energy Lab Ulm Ulm University  Ulm Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,16]]},"reference":[{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200902483"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cs35190k"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201905600"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c10584"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3EE00569K"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jechem.2020.03.009"},{"key":"e_1_2_9_8_1","doi-asserted-by":"crossref","first-page":"9857","DOI":"10.1021\/acs.iecr.6b02316","article-title":"Electrochemical Properties of Keggin\u2010Structure Polyoxometalates in Acetonitrile: Effects of Countercation, Heteroatom, and Framework Metal Exchange","volume":"55","author":"Chen J.\u2010J. J.","year":"2016","journal-title":"Industrial and Engineering Chemistry Research"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsaem.9b02239"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202306170"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2TA00486K"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1557\/JMR.2003.0349"},{"key":"e_1_2_9_13_1","doi-asserted-by":"crossref","DOI":"10.1002\/anie.202115046","article-title":"The Emergence of Aqueous Ammonium\u2010Ion Batteries","volume":"61","author":"Han J.","year":"2022","journal-title":"Angewandte Chemie International Edition"},{"key":"e_1_2_9_14_1","doi-asserted-by":"crossref","DOI":"10.1002\/adfm.202112179","article-title":"Research Development on Aqueous Ammonium\u2010Ion Batteries","volume":"32","author":"Zhang R.","year":"2022","journal-title":"Advanced Functional Materials"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1007\/s10800\u2010019\u201001381\u20104"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3EE02030D"},{"key":"e_1_2_9_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202415545"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201907934"},{"key":"e_1_2_9_19_1","doi-asserted-by":"crossref","DOI":"10.1002\/anie.202301629","article-title":"Ammonium Ion Batteries: Material, Electrochemistry and Strategy","volume":"62","author":"Zheng R.","year":"2023","journal-title":"Angewandte Chemie International Edition"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202114548"},{"key":"e_1_2_9_21_1","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2008.578"},{"key":"e_1_2_9_22_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0jm03011b"},{"key":"e_1_2_9_23_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022\u20100728(02)00901\u20104"},{"key":"e_1_2_9_24_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022\u20100728(00)00094\u20102"},{"key":"e_1_2_9_25_1","doi-asserted-by":"crossref","first-page":"3881","DOI":"10.1021\/acs.inorgchem.8b03508","article-title":"A. Sol\u00e9\u2010Daura and Colleagues Investigates The Influence Of The Redox State On The Collective Behavior In Solution Of Polyoxovanadates Using the [I@V18O42]q\u2212 system","volume":"58","author":"Sol\u00e9\u2010Daura A.","year":"2019","journal-title":"Inorganic Chemical"},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.porgcoat.2017.02.001"},{"key":"e_1_2_9_27_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cattod.2011.10.018"},{"key":"e_1_2_9_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.201907802"},{"key":"e_1_2_9_29_1","doi-asserted-by":"crossref","first-page":"574","DOI":"10.3390\/electrochem5040037","article-title":"Electrochemical Characterization of Recast Nafion\u00ae Film\u2010Modified Electrodes in Acetonitrile with Various Electrolytes","volume":"5","author":"Claire A. F.","year":"2024","journal-title":"Electrochem"},{"key":"e_1_2_9_30_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.est.2017.07.017"},{"key":"e_1_2_9_31_1","doi-asserted-by":"publisher","DOI":"10.1038\/451652a"}],"container-title":["Advanced Science"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/advanced.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/advs.77673","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/advanced.onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/advs.77673","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/advanced.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/advs.77673","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T05:37:16Z","timestamp":1789623436000},"score":1,"resource":{"primary":{"URL":"https:\/\/advanced.onlinelibrary.wiley.com\/doi\/10.1002\/advs.77673"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,16]]},"references-count":30,"alternative-id":["10.1002\/advs.77673"],"URL":"https:\/\/doi.org\/10.1002\/advs.77673","archive":["Portico"],"relation":{},"ISSN":["2198-3844","2198-3844"],"issn-type":[{"value":"2198-3844","type":"print"},{"value":"2198-3844","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,16]]},"assertion":[{"value":"2026-05-25","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-08-28","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-09-16","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e77673"}}