Transition metal–based materials have become significant family of electrocatalysts for hydrogen and oxygen evolution because of their low cost, various compositions and structures, and their excellent electronic transfer ability. Because of their tunable compositions and diverse structures, polyoxometalates (POMs) are promising catalytic components and are promising precursors for the fabrication of early transition metal–based materials, especially for Mo and W, for hydrogen and oxygen evolution electrocatalysis. By incorporating POMs into metal–organic frameworks (MOFs) , the target POM/MOF will promote the dispersion of POMs and increase the compositional and structural complexity of the derived materials. In this review, recent relevant research fruits focusing on POM/MOF composites and their derivatives (such as carbides, oxides, phosphides, sulfides, and selenides) are summarized. Their designable synthesis, structure modulation, and electrocatalytic performance in HER and OER are highlighted to figure out the structure-property relationship. The existing problems of POM/MOF materials and their derivatives in electrocatalysis are also discussed. Then we propose the future prospective, providing a brand new vision of design and development of other POM/MOF-based/derived advanced electrocatalysts for water splitting.

过渡金属基材料的低成本，各种组成和结构以及出色的电子转移能力，已成为氢和氧释放的重要电催化剂家族。由于多金属氧酸盐（POM）具有可调谐的组成和多样的结构，它们是有希望的催化成分，并且是制造早期过渡金属基材料（尤其是用于钼和钨的氢和氧逸出电催化）的有希望的前体。通过将POM纳入金属有机框架（MOF）中，目标POM / MOF将促进POM的分散并增加衍生材料的成分和结构复杂性。在这篇评论中，最近的相关研究成果集中于POM / MOF复合材料及其衍生物（例如碳化物，氧化物，磷化物，总结了硫化物和硒化物。重点介绍了它们在HER和OER中可设计的合成，结构调节和电催化性能，以弄清其结构性质之间的关系。还讨论了POM / MOF材料及其衍生物在电催化中存在的问题。然后，我们提出了未来的前景，为设计和开发其他基于POM / MOF的/衍生的用于水分解的高级电催化剂提供了崭新的愿景。