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They were subsequently explored as bifunctional electrocatalysts for oxygen electrodes, i.e., oxygen reduction (ORR) and evolution (OER) reaction, for aqueous rechargeable metal-air batteries in alkaline media. The lowest Tafel slope (85 mV dec\u22121) value and the highest OER current density of 93.8 mA cm\u22122 were obtained for the Fe-POM electrocatalyst. Similar OER electrochemical catalytic activity was noticed for the Co-POM electrocatalyst. This behavior was confirmed by electrochemical impedance spectroscopy, where Fe-POM gave the lowest charge transfer resistance of 3.35 \u03a9, followed by Co-POM with Rct of 15.04 \u03a9, during the OER. Additionally, Tafel slope values of 85 and 109 mV dec\u22121 were calculated for Fe-POM and Co-POM, respectively, during the ORR. The ORR at Fe-POM proceeded by mixed two- and four-electron pathways, while ORR at Co-POM proceeded exclusively by the four-electron pathway. Finally, capacitance studies were conducted on the synthesized POMs.<\/jats:p>","DOI":"10.3390\/batteries10060197","type":"journal-article","created":{"date-parts":[[2024,6,3]],"date-time":"2024-06-03T12:19:46Z","timestamp":1717417186000},"page":"197","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Transition Metal-Based Polyoxometalates for Oxygen Electrode Bifunctional Electrocatalysis"],"prefix":"10.3390","volume":"10","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2266-6738","authenticated-orcid":false,"given":"Jadranka","family":"Miliki\u0107","sequence":"first","affiliation":[{"name":"Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12\u201316, 11158 Belgrade, Serbia"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1494-1453","authenticated-orcid":false,"given":"Filipe","family":"Gusm\u00e3o","sequence":"additional","affiliation":[{"name":"Center of Physics and Engineering of Advanced Materials, Laboratory for Physics of Materials and Emerging Technologies, Chemical Engineering Department, Instituto Superior T\u00e9cnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1861-1128","authenticated-orcid":false,"given":"Sara","family":"Kne\u017eevi\u0107","sequence":"additional","affiliation":[{"name":"CNRS, Bordeaux INP, Institut des Sciences Mol\u00e9culaires, University of Bordeaux, UMR 5255, 33607 Pessac, France"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2886-1868","authenticated-orcid":false,"given":"Nemanja","family":"Gavrilov","sequence":"additional","affiliation":[{"name":"Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12\u201316, 11158 Belgrade, Serbia"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1596-0675","authenticated-orcid":false,"given":"Anup","family":"Paul","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7920-2638","authenticated-orcid":false,"given":"Diogo M. F.","family":"Santos","sequence":"additional","affiliation":[{"name":"Center of Physics and Engineering of Advanced Materials, Laboratory for Physics of Materials and Emerging Technologies, Chemical Engineering Department, Instituto Superior T\u00e9cnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal"}]},{"given":"Biljana","family":"\u0160ljuki\u0107","sequence":"additional","affiliation":[{"name":"Center of Physics and Engineering of Advanced Materials, Laboratory for Physics of Materials and Emerging Technologies, Chemical Engineering Department, Instituto Superior T\u00e9cnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2024,6,3]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"2006855","DOI":"10.1002\/adfm.202006855","article-title":"Intrinsic Structure Modification of Electrode Materials for Aqueous Metal-Ion and Metal-Air Batteries","volume":"31","author":"Ling","year":"2021","journal-title":"Adv. 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