Versatile Nature of Oxygen Vacancies in Bismuth Vanadate Bulk and (001) Surface

被引：38

作者：

Hegner, Franziska Simone ^{[1
]}

Forrer, Daniel ^{[2
,3
]}

Galan-Mascaros, Jose Ramon ^{[1
,4
]}

Lopez, Nuria ^{[1
]}

Selloni, Annabella ^{[5
]}

机构：

[1] BIST, Inst Chem Res Catalonia ICIQ, Avinguda Paisos Catalans 16, Tarragona 43007, Spain

[2] CNR, ICMATE, Via F Marzolo 1, I-35131 Padua, Italy

[3] INSTM, Via F Marzolo 1, I-35131 Padua, Italy

[4] ICREA, Passeig Lluis Co 23, Barcelona 08010, Spain

[5] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2019年 / 10卷 / 21期

关键词：

BIVO4; PHOTOANODES; WATER OXIDATION; DOPED BIVO4; THIN-FILM; EVOLUTION; TRANSPORT; DYNAMICS;

D O I：

10.1021/acs.jpclett.9b02552

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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 (VO3)-O-IV and (BiO7)-O-II subunits or a V-IV-O-V-IV/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 similar to 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.

引用

页码：6672 / 6678

页数：13

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