The development of robust and efficient hydrogen-evolving system remains a substantial but promising challenge to convert solar energy into clean fuel. Herein, we report the construction of water-compatible, robust, and ultraefficient hydrogen-evolving system by coupling water-soluble CdSe light-absorbers with Ni-substituted polyoxometalate (Ni-POM) catalysts and AA electron donor. Such facile catalytic system exhibits superior and robust hydrogen production activity to date even among known semiconductor/POM hybrids-based hydrogen production systems. Multiple stability experiments confirm the molecular stability of Ni-POM catalysts under turnover conditions. Various experimental and spectroscopic analyses reveal that the synergistic cooperation between high photostability of CdSe light-absorber, outstanding reversible multi-electron-transferring property of Ni-POM catalyst, and the fast hole-removing ability of AA electron donor account for the exceptional performance of present catalytic system. Our present work provides new research insights into the continued development of effective hydrogen-evolving systems through coupling other QDs-based light-absorbers and earth-abundant transition-metal-substituted POM catalysts.

开发强大而高效的氢进化系统仍然是将太阳能转化为清洁燃料的重大但有希望的挑战。在此，我们报告了通过将水溶性 CdSe 光吸收剂与 Ni 取代的多金属氧酸盐 (Ni-POM) 催化剂和 AA 电子供体偶联，构建了与水相容、稳健且超高效的析氢系统。迄今为止，即使在已知的基于半导体/POM 混合物的制氢系统中，这种简便的催化系统也表现出卓越和稳健的制氢活性。多项稳定性实验证实了 Ni-POM 催化剂在周转条件下的分子稳定性。各种实验和光谱分析表明，CdSe 光吸收剂的高光稳定性之间的协同作用，Ni-POM 催化剂优异的可逆多电子转移性能和 AA 电子给体的快速空穴去除能力是目前催化体系优异性能的原因。我们目前的工作通过耦合其他基于量子点的光吸收剂和地球上丰富的过渡金属取代的 POM 催化剂，为持续开发有效的氢演化系统提供了新的研究见解。