{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T00:56:05Z","timestamp":1760316965268,"version":"build-2065373602"},"reference-count":59,"publisher":"Wiley","issue":"15","license":[{"start":{"date-parts":[[2025,6,12]],"date-time":"2025-06-12T00:00:00Z","timestamp":1749686400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["PTDC\/BTA\u2010BTA\/0935\/2020"],"award-info":[{"award-number":["PTDC\/BTA\u2010BTA\/0935\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemElectroChem"],"published-print":{"date-parts":[[2025,7,24]]},"abstract":"<jats:p>The electrocatalytic reduction of carbon dioxide (CO<jats:sub>2<\/jats:sub>) to formate by the enzyme formate dehydrogenase (FDH) makes use of the enzyme's observed reversibility, offering a promising strategy for the mitigation of CO<jats:sub>2<\/jats:sub> and the production of value\u2010added compounds. To enhance the catalytic potential of <jats:italic>Desulfovibrio desulfuricans<\/jats:italic> FDH (<jats:italic>Dd<\/jats:italic>FDH), a range of artificial and natural redox cofactors is investigated using electrochemical methods. These studies included direct (nonmediated) conditions and mediated conditions employing viologens (methyl and benzyl viologens), and small heme proteins (cytochromes). Methyl viologen acts as an efficient mediator for CO<jats:sub>2<\/jats:sub> reduction, achieving a very high current density of 216\u2009\u03bcA\u2009cm<jats:sup>\u22122<\/jats:sup>. The studies of the different small proteins, namely cytochrome split\u2010soret (<jats:italic>cyt<\/jats:italic> SS), cytochrome <jats:italic>c<\/jats:italic><jats:sub>3<\/jats:sub> (<jats:italic>cyt<\/jats:italic> <jats:italic>c<\/jats:italic><jats:sub>3<\/jats:sub>), and cytochrome <jats:italic>c<\/jats:italic><jats:sub>552<\/jats:sub> (<jats:italic>cyt<\/jats:italic> <jats:italic>c<\/jats:italic><jats:sub>552<\/jats:sub>), allow the identification of the potential natural physiological partners. These isolated cytochromes, from the same organism, are electrochemically characterized, from which detailed redox processes are determined and later used as mediators to explore <jats:italic>Dd<\/jats:italic>FDH catalytic activity in both formate oxidation and CO<jats:sub>2<\/jats:sub> reduction. Best results are attained with cytochrome <jats:italic>cyt<\/jats:italic> SS and <jats:italic>cyt<\/jats:italic> <jats:italic>c<\/jats:italic><jats:sub>3,<\/jats:sub> increasing the electrocatalytic activity for formate oxidation by 7.5 times and 5.8 times, respectively.<\/jats:p>","DOI":"10.1002\/celc.202500100","type":"journal-article","created":{"date-parts":[[2025,6,29]],"date-time":"2025-06-29T10:20:24Z","timestamp":1751192424000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Electroenzymatic CO<sub>2<\/sub> Reduction Using Formate Dehydrogenase: Direct and Mediated Catalysis"],"prefix":"10.1002","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8570-4768","authenticated-orcid":false,"given":"Navendu","family":"Paul","sequence":"first","affiliation":[{"name":"LAQV, REQUIMTE (Associated Laboratory for Green Chemistry) NOVA School of Science and Technology NOVA FCT  2829\u2010516 Caparica Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0971-4977","authenticated-orcid":false,"given":"Isabel","family":"Moura","sequence":"additional","affiliation":[{"name":"LAQV, REQUIMTE (Associated Laboratory for Green Chemistry) NOVA School of Science and Technology NOVA FCT  2829\u2010516 Caparica Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6901-6591","authenticated-orcid":false,"given":"Lu\u00edsa B.","family":"Maia","sequence":"additional","affiliation":[{"name":"LAQV, REQUIMTE (Associated Laboratory for Green Chemistry) NOVA School of Science and Technology NOVA FCT  2829\u2010516 Caparica Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7892-8955","authenticated-orcid":false,"given":"Cristina M.","family":"Cordas","sequence":"additional","affiliation":[{"name":"LAQV, REQUIMTE (Associated Laboratory for Green Chemistry) NOVA School of Science and Technology NOVA FCT  2829\u2010516 Caparica Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4726-2388","authenticated-orcid":false,"given":"Jose J. G.","family":"Moura","sequence":"additional","affiliation":[{"name":"LAQV, REQUIMTE (Associated Laboratory for Green Chemistry) NOVA School of Science and Technology NOVA FCT  2829\u2010516 Caparica Portugal"}]}],"member":"311","published-online":{"date-parts":[[2025,6,12]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.5194\/essd-15-5301-2023"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41558-018-0190-1"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr300463y"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr4002758"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.joule.2017.09.003"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-0-387-49489-0_3"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35360A"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-030-58315-6_2"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202102702"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1093\/bbb\/zbab197"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0680639"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/pro.3498"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00775-014-1218-2"},{"key":"e_1_2_7_15_1","first-page":"1","volume-title":"Molybdenum and Tungsten Enzymes: Biochemistry","author":"Maia L. B.","year":"2017"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-030-58315-6_3"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1042\/bj3010625"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.biochem.6b00181"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1080\/07388551.2021.1981820"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0NJ01183E"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0958-1669(03)00094-6"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/acssuschemeng.1c07260"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.molcatb.2014.01.007"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chemosphere.2021.133117"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.seppur.2022.123090"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1007\/s10529-020-02937-7"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41598-023-49021-4"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.8b00551"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.langmuir.4c01444"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0801290105"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c04529"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.0c21932"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.electacta.2017.01.112"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201814419"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1002\/cey2.304"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b00127"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.elecom.2016.02.006"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201803397"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsenergylett.9b02436"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcb.3c04652"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.3390\/catal8050192"},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b03941"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2019.110694"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1007\/s007750050125"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2007.04.011"},{"key":"e_1_2_7_46_1","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.M115.688457"},{"key":"e_1_2_7_47_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CC01541B"},{"key":"e_1_2_7_48_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0680742"},{"key":"e_1_2_7_49_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201800750"},{"key":"e_1_2_7_50_1","doi-asserted-by":"publisher","DOI":"10.1002\/celc.201801256"},{"key":"e_1_2_7_51_1","doi-asserted-by":"publisher","DOI":"10.1007\/s007750000159"},{"key":"e_1_2_7_52_1","doi-asserted-by":"publisher","DOI":"10.1111\/j.1432-1033.1997.00445.x"},{"key":"e_1_2_7_53_1","doi-asserted-by":"publisher","DOI":"10.1111\/j.1432-1033.1987.tb10674.x"},{"key":"e_1_2_7_54_1","unstructured":"C.Costa PhD Thesis Universidade NOVA De Lisboa (PT)1994."},{"key":"e_1_2_7_55_1","doi-asserted-by":"publisher","DOI":"10.1039\/D4SC02431A"},{"key":"e_1_2_7_56_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0005-2728(05)80270-1"},{"key":"e_1_2_7_57_1","doi-asserted-by":"publisher","DOI":"10.1016\/0005-2795(71)90078-X"},{"key":"e_1_2_7_58_1","doi-asserted-by":"publisher","DOI":"10.1111\/j.1432-1033.1989.tb15168.x"},{"key":"e_1_2_7_59_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0300-9084(78)80828-1"},{"key":"e_1_2_7_60_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41586-021-03819-2"}],"container-title":["ChemElectroChem"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/celc.202500100","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T20:20:29Z","timestamp":1760300429000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/celc.202500100"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,6,12]]},"references-count":59,"journal-issue":{"issue":"15","published-print":{"date-parts":[[2025,7,24]]}},"alternative-id":["10.1002\/celc.202500100"],"URL":"https:\/\/doi.org\/10.1002\/celc.202500100","archive":["Portico"],"relation":{},"ISSN":["2196-0216","2196-0216"],"issn-type":[{"type":"print","value":"2196-0216"},{"type":"electronic","value":"2196-0216"}],"subject":[],"published":{"date-parts":[[2025,6,12]]},"assertion":[{"value":"2025-03-25","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-06-12","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202500100"}}