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Combinatorial alloying improves bismuth vanadate photoanodes via reduced monoclinic distortion†
Energy & Environmental Science ( IF 32.5 ) Pub Date : 2018-06-09 00:00:00 , DOI: 10.1039/c8ee00179k
P. F. Newhouse 1, 2, 3, 4 , D. Guevarra 1, 2, 3, 4 , M. Umehara 1, 2, 3, 4, 5 , S. E. Reyes-Lillo 1, 4, 6, 7, 8 , L. Zhou 1, 2, 3, 4 , D. A. Boyd 1, 2, 3, 4 , S. K. Suram 1, 2, 3, 4 , J. K. Cooper 1, 4, 6, 7, 9 , J. A. Haber 1, 2, 3, 4 , J. B. Neaton 1, 4, 6, 7, 10 , J. M. Gregoire 1, 2, 3, 4
Affiliation  

Improving the efficiency of solar-powered oxygen evolution is both critical for development of solar fuels technologies and challenging due to the broad set of properties required of a solar fuels photoanode. Bismuth vanadate, in particular the monoclinic clinobisvanite phase, has received substantial attention and has exhibited the highest radiative efficiency among metal oxides with a band gap in the visible range. Efforts to further improve its photoelectrochemical performance have included alloying one or more metals onto the Bi and/or V sites, with progress on this frontier stymied by the difficulty in computational modelling of substitutional alloys and the high dimensionality of co-alloying composition spaces. Since substitutional alloying concurrently changes multiple materials properties, understanding the underlying cause for performance improvements is also challenging, motivating our application of combinatorial materials science techniques to map photoelectrochemical performance of 948 unique bismuth vanadate alloy compositions comprising 0 to 8% alloys of P, Ca, Mo, Eu, Gd, and W along with a variety of compositions from each pairwise combination of these elements. Upon identification of substantial improvements in the (Mo,Gd) co-alloying space, structural mapping was performed to reveal a remarkable correlation between performance enhancement and a lowered monoclinic distortion. First-principles density functional theory calculations indicate that the improvements are due to a lowered hole effective mass and hole polaron formation energy, and collectively, our results identify the monoclinic distortion as a critical parameter in the optimization and understanding of bismuth vanadate-based photoanodes.

中文翻译:

组合合金化可通过减少单斜晶畸变来改善钒酸铋光阳极

对于太阳能燃料技术的发展,提高太阳能氧气的释放效率既至关重要,又由于太阳能燃料光电阳极需要广泛的特性,因此具有挑战性。钒酸铋,尤其是单斜斜双菱沸石相,受到了广泛关注,并且在带隙在可见光范围内的金属氧化物中表现出最高的辐射效率。进一步改善其光电化学性能的努力包括将一种或多种金属合金化到Bi和/或V位上,由于替代合金的计算建模困难和共合金组成空间的高维性,在这一前沿上取得了进展。由于替代合金化会同时改变多种材料的特性,理解性能改善的根本原因也具有挑战性,这促使我们应用组合材料科学技术来绘制948种独特的钒酸铋合金组合物的光电化学性能,其中包括0%至8%的P,Ca,Mo,Eu,Gd和W合金这些元素的每个成对组合都具有各种成分。在确定了(Mo,Gd)共合金空间的实质性改进后,进行了结构映射,以揭示性能增强与降低的单斜应变之间的显着相关性。第一性原理密度泛函理论计算表明,这种改进是由于降低了空穴有效质量和空穴极化子形成能,因此,
更新日期:2018-06-09
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