Terebilenko Kateryna V, Bychkov Konstantin L, Baumer Vyacheslav N, Slobodyanik Nikolay S, Pavliuk Mariia V, Thapper Anders, Tokmenko Inna I, Nasieka Iurii M, Strelchuk Viktor V
Department of Chemistry, Taras Shevchenko National University of Kiev, Volodymyrska st, 64/13, 01601, Kiev, Ukraine.
STC "Institute for Single Crystals" NAS of Ukraine, 60 Lenina ave., Kharkiv, 61001, Ukraine.
Dalton Trans. 2016 Mar 7;45(9):3895-904. doi: 10.1039/c5dt04829j.
The influence of molybdenum content in the solid solutions of Bi1-x/3V1-xMoxO4 (x = 0.05-0.20) on the morphology, band gap, structure and light-driven water oxidation properties has been studied by scanning electron microscopy, X-ray powder diffraction and vibrational spectroscopy (Raman and infrared). To find out the peculiarities of structural changes for bismuth scheelite-related oxides containing both vanadium and molybdenum crystals of Bi0.98V0.93Mo0.07O4 have been grown from a K-Bi-V-Mo-O high-temperature melt and characterized by single crystal X-ray diffraction. For the scheelite-related framework both V and Mo were found to occupy the same positions lowering the point group symmetry of tetrahedra from 4/m to 2/m giving monoclinic distortion for solid solutions with x = 0.05-0.10. The most promising photocatalytic performance was obtained for Bi0.96Mo0.10V0.90O4, in which the oxygen evolution could reach 21 μM in 50 s under visible light of LEDs, λ = 470 ± 10 nm, and 820 μE cm(-2) s(-1). The changes in catalytic properties are shown to be governed by a crystal structure strain with a maximum obtained for the boundary sample between the monoclinic and tetragonal phase.
通过扫描电子显微镜、X射线粉末衍射和振动光谱（拉曼光谱和红外光谱）研究了Bi1-x/3V1-xMoxO4（x = 0.05 - 0.20）固溶体中钼含量对其形态、带隙、结构和光驱动水氧化性能的影响。为了找出同时含有钒和钼的白钨矿型铋氧化物结构变化的特点，从K-Bi-V-Mo-O高温熔体中生长出了Bi0.98V0.93Mo0.07O4晶体，并通过单晶X射线衍射对其进行了表征。对于白钨矿型结构，发现V和Mo占据相同的位置，使四面体的点群对称性从4/m降低到2/m，导致x = 0.05 - 0.10的固溶体出现单斜畸变。Bi0.96Mo0.10V0.90O4获得了最有前景的光催化性能，在波长λ = 470 ± 10 nm、光强820 μE cm(-2) s(-1)的LED可见光下，50 s内析氧可达21 μM。结果表明，催化性能的变化受晶体结构应变的控制，在单斜相和四方相之间的边界样品中获得了最大值。
