2026-04-13T01:52:04Zhttps://recercat.cat/oai/request

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

00925njm 22002777a 4500 dc Hegner, Franziska Simone author Forrer, Daniel author Galán-Mascarós, José Ramón author López, Núria author Selloni, Annabella author 2019-10-12 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. http://hdl.handle.net/2072/368598 https://doi.org/10.1021/acs.jpclett.9b02552 Versatile Nature of Oxygen Vacancies in Bismuth Vanadate Bulk and (001) Surface