Zhou Xiao, Zhao Mei-Huan, Yao Shan-Ming, Dong Hongliang, Wang Yonggang, Chen Bin, Xing Xianran, Li Man-Rong
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China.
Center for High Pressure Science and Technology Advanced Research, Shanghai 201203, China.
Natl Sci Rev. 2023 Jul 10;10(9):nwad190. doi: 10.1093/nsr/nwad190. eCollection 2023 Sep.
Chemical stabilization of a high-pressure metastable state is a major challenge for the development of advanced materials. Although chemical pressure () can effectively simulate the effect of physical pressure (), experimental calibration of the pressure passed to local structural motifs, denoted as local chemical pressure () which significantly governs the function of solid materials, remains absent due to the challenge of probing techniques. Here we establish an innovative methodology to experimentally calibrate the and build a bridge between and via an optical probe strategy. Site-selective Bi-traced VO ( = Y, Gd) is adopted as a prototype to introduce Bi optical probes and on-site sense of the experienced by the O motif. The cell compression of BiVO under is chemically simulated by smaller-ion substitution (Sc → ) in ScBiVO. The consistent red shift () of the emission spectra of Bi, which is dominated by locally pressure-induced O dodecahedral variation in BiVO () and ScBiVO (), respectively, is evidence of their similar pressure-dependent local structure evolution. This innovative -based experimental calibration of in the crystal-field dimension portrays the anisotropic transmission of to the local structure and builds a bridge between and to guide a new perspective for affordable and practical interception of metastable states.
高压亚稳态的化学稳定化是先进材料开发面临的一项重大挑战。尽管化学压力（）能够有效模拟物理压力（）的作用，但由于探测技术的挑战，传递到局部结构基序的压力（即显著影响固体材料功能的局部化学压力（））的实验校准仍然缺失。在此，我们建立了一种创新方法，通过光学探针策略对进行实验校准，并在和之间搭建桥梁。采用位点选择性Bi追踪的VO（=Y、Gd）作为原型，引入Bi光学探针并现场感知O基序所经历的。通过在ScBiVO中进行较小离子取代（Sc→）来化学模拟BiVO在压力下的晶胞压缩。Bi发射光谱一致的红移（），分别由BiVO（）和ScBiVO（）中局部压力诱导的O十二面体变化主导，证明了它们相似的压力依赖性局部结构演化。这种基于的晶体场维度实验校准描绘了向局部结构的各向异性传递，并在和之间搭建桥梁，为经济实用地拦截亚稳态提供新视角。
