Direct Evidence of Surface Reduction in Monoclinic BiVO4

被引：83

作者：

Rossell, Marta D. ^{[1
]}

Agrawal, Piyush ^{[1
,2
]}

Borgschulte, Andreas ^{[3
]}

Hebert, Cecile ^{[4
]}

Passerone, Daniele ^{[2
]}

Erni, Rolf ^{[1
]}

机构：

[1] Empa, Swiss Fed Labs Mat Sci & Technol, Electron Microscopy Ctr, CH-8600 Dubendorf, Switzerland

[2] Empa, Swiss Fed Labs Mat Sci & Technol, Nanotech Surfaces Lab, CH-8600 Dubendorf, Switzerland

[3] Empa, Swiss Fed Labs Mat Sci & Technol, Adv Analyt Technol, CH-8600 Dubendorf, Switzerland

[4] Ecole Polytech Fed Lausanne, Ctr Interdisciplinaire Microscopie Elect, CH-1015 Lausanne, Switzerland

来源：

CHEMISTRY OF MATERIALS | 2015年 / 27卷 / 10期

基金：

瑞士国家科学基金会;

关键词：

VISIBLE-LIGHT; BISMUTH; DEGRADATION; WATER; DECOMPOSITION; SEPARATION; EVOLUTION; OXIDES; O-2;

D O I：

10.1021/cm504248d

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：

Local measurements of the oxidation state of vanadium in monoclinic BiVO4 particles by means of electron energy-loss spectroscopy in scanning transmission electron microscopy reveal a pronounced surface reduction: within a 5-nm-thick shell, the oxidation state of vanadium is reduced from +5 to about +4. Thus, charge neutrality near the surface demands for similar to 15% oxygen vacancies. Our results provide direct evidence for the segregation of oxygen vacancies at the surface of BiVO4. This observation is confirmed by X-ray photoelectron spectroscopy. The experimental findings are complemented with all-electron density functional theory based WIEN2k calculations of the density of electron states and of the electron energy-loss near-edge structure. The theoretical results provide further information on the electronic changes induced by the experimentally verified oxygen vacancies.

引用

页码：3593 / 3600

页数：8

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