To exploit the use of solar energy in photocatalysis, metal ion doping is one of the most effective ways. At present, atomically precise heterometallic polyoxotitanium clusters (HPTCs) are of great interest as well-defined models for the way in which metal ions are doped into bulk titanium dioxide. Recently, researchers have contributed great efforts in HPTCs where majority metal ions throughout the periodic table have successfully incorporated. The incorporation of particular characteristics of metal dopants provides the opportunity to modify the microscopic electronic structure, then optical response, and ultimate macroscopical performances. In this review, we aim to summarize the recent progress on such a rapidly evolving topic of HPTCs and provide potential theoretical models for the rational design of photocatalysts and solar energy capture. Firstly, a brief summary of the synthetic strategies and bonding models between the metals and PTCs is provided. Then clear definition and classification of the HPTCs reported up to date is given. Moreover, representative examples are illustrated from experimental, theoretical and photophysical/photochemical perspectives, particularly in light absorption, fluorescence, photocatalysis, and gas sorption etc. Finally, the main challenges and opportunities are proposed with the goal of expanding the sunlight harvesting application range of HPTCs.

为了在光催化中利用太阳能，金属离子掺杂是最有效的方法之一。目前，原子精确的杂金属多氧钛金属簇（HPTC）作为将金属离子掺杂到块状二氧化钛中的定义明确的模型而引起了极大的兴趣。最近，研究人员在HPTC中做出了巨大的努力，其中整个元素周期表中的大多数金属离子均已成功掺入。掺入金属掺杂剂的特定特性提供了修改微观电子结构，光学响应以及最终宏观性能的机会。在这篇综述中，我们旨在总结在如此迅速发展的HPTC主题上的最新进展，并为光催化剂和太阳能捕获的合理设计提供潜在的理论模型。首先，简要概述了金属与PTC之间的合成策略和键合模型。然后给出了最新报告的HPTC的明确定义和分类。此外，从实验，理论和光物理/光化学角度阐述了代表性实例，尤其是在光吸收，荧光，光催化和气体吸收方面等。最后，提出了主要挑战和机遇，目的是扩大HPTC的日光收集应用范围。