Metal-organic frameworks derived transition metal phosphides for electrocatalytic water splitting

It is critical to synthesize high-efficiency electrocatalysts to boost the performance of water splitting to meet the requirements of industrial applications. Metal-organic frameworks (MOFs) can function as ideal molecular platforms for the design of highly reactive transition metal phosphides (TMPs), a kind of candidates for high-efficiently electrocatalytic water splitting. The intrinsic activity of the electrocatalysts can be greatly improved via modulating the electronic structure of the catalytic center through the MOF precursors/templates. Moreover, the carbon layer converted in-situ by the organic ligands can not only protect the TMPs from being degraded in the harsh electrochemical environments, but also avoid agglomeration of the catalysts, thereby promoting their activities and stabilities. Furthermore, heteroatom-containing ligands can incorporate N, S or P, etc. atoms into the carbon matrixes after conversion, regulating the coordination microenvironments of the active centers as well as their electronic structures. In this review, we first summarized the latest developments in MOF-derived TMPs by the unique advantages in metal, organic ligand, and morphology regulations for electrocatalytic water splitting. Secondly, we concluded the critical scientific issues currently facing for designing state-of-the-art TMP-based electrocatalysts. Finally, we presented an outlook on this research area, encompassing electrocatalyst construction, catalytic mechanism research, etc. (c) 2021 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.

合成高效电催化剂对于提高水分解性能以满足工业应用需求至关重要。金属 - 有机框架（MOFs）可作为设计高活性过渡金属磷化物（TMPs）的理想分子平台，TMPs是一类高效电催化水分解的候选材料。通过MOF前驱体/模板调节催化中心的电子结构，可极大提高电催化剂的本征活性。此外，由有机配体原位转化的碳层不仅能保护TMPs在恶劣的电化学环境中不被降解，还能避免催化剂团聚，从而提高其活性和稳定性。再者，含杂原子的配体在转化后可将N、S或P等原子掺入碳基体中，调节活性中心的配位微环境及其电子结构。在本综述中，我们首先总结了MOF衍生的TMPs在电催化水分解中金属、有机配体和形貌调控方面的独特优势以及最新进展。其次，我们总结了当前设计先进的基于TMP的电催化剂所面临的关键科学问题。最后，我们对该研究领域进行了展望，包括电催化剂构建、催化机制研究等。（c）2021科学出版社和中国科学院大连化学物理研究所。由爱思唯尔出版社和科学出版社出版。版权所有。