Sinclair Jordan, Siebert Jan P, Juelsholt Mikkel, Shen Chen, Zhang Hongbin, Birkel Christina S
School of Molecular Sciences, Arizona State University, Tempe, Arizona 85282, United States.
Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH, U.K.
Inorg Chem. 2022 Oct 31;61(43):16976-16980. doi: 10.1021/acs.inorgchem.2c02880. Epub 2022 Oct 20.
More than 150 MAX phases are known to date. Their chemical diversity is the result of mixing-and-matching early-to-mid transition metals (M), main group elements (A), and carbon and/or nitrogen (X). The vast majority of the respective carbides and (carbo)nitrides contain group 13 and 14 as the A element, such as Al, Ga, and Si. VPC is among the least studied members of this family of materials; as a matter of fact, it is only mentioned in two pieces of original literature. The solid-state synthesis is extremely vaguely described and working with elemental phosphorus poses additional synthetic challenges. Here, we confirm these experimental difficulties and present an alternative sol gel-based approach to prepare almost single-phase VPC. The versatility of the sol gel chemistry is further demonstrated by variation of the gel-building agent moving beyond citric acid as the carbon source. DFT calculations support the experimentally obtained structural parameters and show VPC is a metal.
迄今为止已知的MAX相超过150种。它们的化学多样性是早期到中期过渡金属（M）、主族元素（A）以及碳和/或氮（X）混合匹配的结果。绝大多数相应的碳化物和（碳）氮化物含有第13族和第14族元素作为A元素，如Al、Ga和Si。VPC是这类材料中研究最少的成员之一；事实上，它仅在两篇原始文献中被提及。固态合成的描述极其模糊，并且使用元素磷会带来额外的合成挑战。在此，我们证实了这些实验困难，并提出了一种基于溶胶-凝胶的替代方法来制备几乎单相的VPC。通过改变作为碳源的凝胶形成剂，超越柠檬酸，进一步证明了溶胶-凝胶化学的多功能性。密度泛函理论计算支持了实验获得的结构参数，并表明VPC是一种金属。
