Solution Combustion Synthesis and Characterization of Magnesium Copper Vanadates
Solution Combustion Synthesis and Characterization of Magnesium Copper Vanadates
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DOI：
10.1021/acs.inorgchem.3c00452
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发表时间：
2023-06
影响因子：
4.6
通讯作者：
A. Rawat;Laura Clark;Chuzhong Zhang;J. Cavin;V. Sangwan;P. Tóth;C. Janáky;R. Ananth;Elise A. Goldfine;M. Bedzyk;E. Weiss;J. Rondinelli;M. Hersam;E. Meletis;K. Rajeshwar
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文献类型：
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作者：
A. Rawat;Laura Clark;Chuzhong Zhang;J. Cavin;V. Sangwan;P. Tóth;C. Janáky;R. Ananth;Elise A. Goldfine;M. Bedzyk;E. Weiss;J. Rondinelli;M. Hersam;E. Meletis;K. Rajeshwar
采用溶液燃烧法合成了钒酸镁（MgV2O6）及其与钒酸铜的合金。在密度泛函理论（DFT）的电子结构模拟支持下，通过多种实验技术证实了相纯度和固溶体形成。粉末x射线衍射结合Rietveld细化、激光拉曼光谱、漫反射光谱和高分辨率透射电镜显示，MgV2O6和CuV2O6端元分别表现为单斜晶系和三斜晶系，但形成了单相合金。dft计算的光学带隙与实验推导值吻合较好。表面光电压谱、大气压光发射谱和开尔文探针接触电位差（功函数）测量证实了光学带隙修正和带对准的系统变化是合金成分化学计量的函数。这些数据表明了所有样品的n型半导体行为，并通过光电化学测量证实了这一点。
Magnesium vanadate (MgV2O6) and its alloys with copper vanadate were synthesized via the solution combustion technique. Phase purity and solid solution formation were confirmed by a variety of experimental techniques, supported by electronic structure simulations based on density functional theory (DFT). Powder X-ray diffraction combined with Rietveld refinement, laser Raman spectroscopy, diffuse reflectance spectroscopy, and high-resolution transmission electron microscopy showed single-phase alloy formation despite the MgV2O6 and CuV2O6 end members exhibiting monoclinic and triclinic crystal systems, respectively. DFT-calculated optical band gaps showed close agreement in the computed optical bandgaps with experimentally derived values. Surface photovoltage spectroscopy, ambient-pressure photoemission spectroscopy, and Kelvin probe contact potential difference (work function) measurements confirmed a systematic variation in the optical bandgap modification and band alignment as a function of stoichiometry in the alloy composition. These data indicated n-type semiconductor behavior for all the samples which was confirmed by photoelectrochemical measurements.