2026-04-13T01:41:33Zhttps://recercat.cat/oai/request

oai:recercat.cat:2072/3685982024-12-20T18:53:41Zcom_2072_300912com_2072_4427col_2072_301309

2020-10-11T02:45:07Z urn:hdl:2072/368598 Versatile Nature of Oxygen Vacancies in Bismuth Vanadate Bulk and (001) Surface Hegner, Franziska Simone Forrer, Daniel Galán-Mascarós, José Ramón López, Núria Selloni, Annabella Bismuth vanadate (BiVO4) has emerged as one of the most promising photoanode materials for solar fuel production. Oxygen vacancies play a pivotal role in the photoelectrochemical efficiency, yet their electronic nature and contribution to n-type conductivity are still under debate. Using first-principles calculations, we show that oxygen vacancies in BiVO4 have two distinguishable geometric configurations characterized by either undercoordinated, reduced VIVO3 and BiIIO7 subunits or a VIV−O−VIV/V bridge (split vacancy), quenching the oxygen vacancy site. While both configurations have similar energies in the bulk, the (001) subsurface acts like an energetic sink that stabilizes the split oxygen vacancy by ∼1 eV. The barrierless creation of a bridging V2O7 unit allows for partial electron delocalization throughout the near-surface region, consistent with recent experimental observations indicating that BiVO4(001) is an electron-rich surface. 2020-01-21T16:02:31Z 2024-04-23T10:19:13Z 2020-10-11T02:45:07Z 2024-04-23T10:19:13Z 2019-10-12 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion http://hdl.handle.net/2072/368598 https://doi.org/10.1021/acs.jpclett.9b02552 eng A-LEAF (Grant Agreement No. 732840) RTI2018-101394-BI00 DoE-BES Division of Chemical Sciences, Geosciences and Biosciences under Award DE-SC0007347 info:eu-repo/semantics/openAccess L'accés als continguts d'aquest document queda condicionat a l'acceptació de les condicions d'ús establertes per la següent llicència Creative Commons:http://creativecommons.org/licenses/by-nc-nd/4.0/ RECERCAT (Dipòsit de la Recerca de Catalunya)