Hydrogen is one of the most ideal clean fuels because of its high density of energy and environmentally benign combustion product (water). Photocatalytic hydrogen production from water splitting has attracted much attention because it is promising for conversion of sustainable solar energy into chemical energy. In this project, we focus on the construction of a variety of molecular assemblies for hydrogen evolution under illumination of visible light. By modulating energy/electron transfer and long-lived charge separation, we are able to achieve photocatalytic hydrogen productive with higher efficiency and stability in the designed molecular assemblies. For example, hierarchical Sn2Nb2O7 hollow spheres were prepared for the first time via a facile hydrothermal route using bubbles generated in situ from the decomposition of urea as soft templates. Flower-like spherical ZnIn2S4 superstructures about 500 nm in diameter composed of ultrathin 2~3 nm thick mesoporous nanosheets were synthesized in several minutes by facile polyol-mediated hot-injection. These as-obtained hollow spheres and lower-like spherical ZnIn2S4 with a large specific surface area show improved visible-light-driven photocatalytic hydrogen production activity in aqueous solutions. Inspired by natural photosynthesis, a series of artificial [FeFe]-H2ase photocatalytic systems have been constructed using poly(aryl ether) dendrimers, poly(acrylic acid), and chitosan with PS and Fe2S2 active site of [FeFe]-H2ase mimics. Irradiation of these systems with visible light results in the formation of long-lived reduced intermediates, and thus increasing the efficiency and durability of hydrogen photoproduction remarkably.%氢是一种清洁高效的理想燃料。利用太阳能制氢是直接将太阳能高效转化为化学能的有效方式。通过分子组装构筑了一系列高效太阳能光催化制氢的新体系，分子组装体高效的能量传递、电子转移和电荷分离过程显著提高了催化体系的产氢效率和稳定性。例如：采用低温水热方法制备的多级Sn2Nb2O7空心球可见光催化剂和采用多元醇热注入法制备的由超薄纳米片组装而成的分等级花状结构ZnIn2S4亚微米球均表现出优异的光解水产氢性能；利用树枝状聚合物、聚丙烯酸和壳聚糖开展对铁氢化酶外围保护蛋白的模拟和功能性研究，在国际上率先突破了铁氢化酶模拟化合物稳定性差、催化效率低的瓶颈，实现了太阳光驱动铁氢化酶模拟化合物的水相高效产氢。
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