轮型二十核铜取代多金属氧酸盐催化剂:光催化制氢的机理和稳定性研究

能源危机和环境污染已成为影响全人类的严峻问题,太阳能驱动水分解制备清洁可再生的氢能是解决以上问题的有效途径之一,因此,近年来环境友好的光驱动制氢方式受到广泛关注.现阶段太阳能驱动水分解体系的研究热点和难点在于研发高催化活性且廉价的非贵金属催化剂.作为具有较大应用潜力的多电子转移催化剂,廉价过渡金属取代的多金属氧酸盐因其...

Wheel-shaped icosanuclear Cu-containing polyoxometalate catalyst: Mechanistic and stability studies on light-driven hydrogen generation

In this paper, we report the synthesis and characterization of a wheel-shaped icosanuclear Cu-containing (K12Li13-Cu20P8W48). The resulting cation-exchanged tetrabutylammonium salt of the polyoxoanion Cu20P8W48 (TBA-Cu20P8W48) exhibits high efficiency for visible-light-driven H2 production in the presence of an Ir(ppy)2(dtbbpy)]PF6] photosensitizer and a triethanolamine electron donor. Un-der optimal conditions, the turnover number for H2 production reaches ～2892 after 5 h of photoca-talysis and thereafter continuously increases to ～13400 in a long-term 120 h reaction, representing the best performance among all reported transition-metal-substituted POM catalysts. Mechanistic studies confirm the existence of reductive and oxidative quenching processes, of which the reduc-tive quenching pathway is dominant. Various stability tests demonstrate that the TBA-Cu20P8W48 catalyst slowly dissociates Cu ions under turnover conditions; however, both the starting TBA-Cu20P8W48 and its molecular decomposition products are dominant active species for efficient and long-term H2 production.