Prussian blue, a more than three hundred years old inorganic coordination polymer, has drawn immense interest in the field of energy conversion. Prussian blue (PB) and Prussian blue analogs (PBAs) have been extensively used for water oxidation, hydrogen evolution, oxygen reduction, nitrogen reduction reaction, etc. In addition, PB and PBAs were explored as the cocatalysts for photocatalytic and photoelectrochemical energy conversion processes. Although initial studies focused on the development of morphology, porosity, surface area, accessible catalytic sites, core-shell structure, etc., the tuning of the electronic structure was found to largely influence the electrochemical features of PB and PBAs. The inter-valence charge transport in PB and PBAs through the –CN bridge can also be modulated by altering the electronic structure of the metal sites. This, in turn, offers a significant modification of its properties as a cocatalyst when combined with a semiconductor. The present review article addresses the effect of electronic structural modulation in PB and PBAs to improve its electrocatalytic and cocatalytic activities. The recent achievements and challenges in designing PBAs and their application in energy conversion have been highlighted along with potential future advancements. Special emphasis has been given to understanding structural aspects and the subsequent establishment of a structure-activity relationship for energy conversion processes.

中文翻译：

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普鲁士蓝及其类似物中的电子结构调控：能源相关催化研究的进展与挑战


普鲁士蓝是一种拥有 300 多年历史的无机配位聚合物，在能源转换领域引起了极大的兴趣。普鲁士蓝 （PB） 和普鲁士蓝类似物 （PBA） 已广泛用于水氧化、析氢、氧还原、氮还原反应等。此外，还探索了 PB 和 PBAs 作为光催化和光电化学能量转换过程的助催化剂。尽管最初的研究集中在形态、孔隙率、表面积、可接近的催化位点、核壳结构等的发展上，但发现电子结构的调整在很大程度上影响了 PB 和 PBA 的电化学特性。PB 和 PBA 中通过 –CN 桥的价间电荷传输也可以通过改变金属位点的电子结构来调制。反过来，当与半导体结合时，这为其作为助催化剂的性能提供了重大改变。本综述文章讨论了 PB 和 PBAs 中电子结构调制对提高其电催化和共催化活性的影响。本文重点介绍了设计 PBA 的最新成就和挑战及其在能源转换中的应用以及未来可能的进展。特别强调理解结构方面和随后建立能量转换过程的结构-活动关系。