Materials and Structures Laboratory, ‡Materials Research Center for Element Strategy, and ∥Frontier Research Center, Tokyo Institute of Technology , Yokohama 226-8503, Japan.
J Am Chem Soc. 2014 May 21;136(20):7221-4. doi: 10.1021/ja502277r. Epub 2014 May 12.
Compositionally tunable vanadium oxyhydrides Sr2VO(4-x)H(x) (0 ≤ x ≤ 1.01) without considerable anion vacancy were synthesized by high-pressure solid-state reaction. The crystal structures and their properties were characterized by powder neutron diffraction, synchrotron X-ray diffraction, thermal desorption spectroscopy, and first-principles density functional theory (DFT) calculations. The hydrogen anions selectively replaced equatorial oxygen sites in the VO6 layers via statistical substitution of hydrogen in the low x region (x < 0.2). A new orthorhombic phase (Immm) with an almost entirely hydrogen-ordered structure formed from the K2NiF4-type tetragonal phase with x > 0.7. Based on the DFT calculations, the degree of oxygen/hydrogen anion ordering is strongly correlated with the bonding interaction between vanadium and the ligands.
通过高压固态反应合成了组成可调的钒氧氢化物 Sr2VO(4-x)H(x)（0 ≤ x ≤ 1.01），其中没有明显的阴离子空位。通过粉末中子衍射、同步加速器 X 射线衍射、热解吸光谱和第一性原理密度泛函理论（DFT）计算对晶体结构及其性质进行了表征。在低 x 区域（x < 0.2）中，氢阴离子通过氢在统计上的取代，选择性地取代 VO6 层中的赤道氧位。新的正交相（Immm）在 x > 0.7 时由 K2NiF4 型四方相形成，几乎完全具有有序的氢结构。基于 DFT 计算，氧/氢阴离子有序的程度与钒与配体之间的键合相互作用密切相关。
