In this paper,we report the synthesis and characterization of a wheel-shaped icosanuclear Cu-containing polyoxometalate(POM),K_(12)Li_(13)[Cu_(2)0Cl(OH)_(24)(H_(2)O)_(12)(P_(8)W_(48)O_(184))]·22H_(2)O(K_(12)Li_(1...In this paper,we report the synthesis and characterization of a wheel-shaped icosanuclear Cu-containing polyoxometalate(POM),K_(12)Li_(13)[Cu_(2)0Cl(OH)_(24)(H_(2)O)_(12)(P_(8)W_(48)O_(184))]·22H_(2)O(K_(12)Li_(13)-Cu_(2)0P_(8)W_(48)).The resulting cation-exchanged tetrabutylammonium salt of the polyoxoanion Cu_(2)0P_(8)W_(48)(TBA-Cu_(2)0P_(8)W_(48))exhibits high efficiency for visible-light-driven H_(2) production in the presence of an[Ir(ppy)2(dtbbpy)][PF_(6)]photosensitizer and a triethanolamine electron donor.Under optimal conditions,the turnover number for H_(2) production reaches~2892 after 5 h of photocatalysis 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 reductive quenching pathway is dominant.Various stability tests demonstrate that the TBA-Cu_(2)0P_(8)W_(48) catalyst slowly dissociates Cu ions under turnover conditions;however,both the starting TBA-Cu_(2)0P_(8)W_(48) and its molecular decomposition products are dominant active species for efficient and long-term H_(2) production.展开更多
文摘In this paper,we report the synthesis and characterization of a wheel-shaped icosanuclear Cu-containing polyoxometalate(POM),K_(12)Li_(13)[Cu_(2)0Cl(OH)_(24)(H_(2)O)_(12)(P_(8)W_(48)O_(184))]·22H_(2)O(K_(12)Li_(13)-Cu_(2)0P_(8)W_(48)).The resulting cation-exchanged tetrabutylammonium salt of the polyoxoanion Cu_(2)0P_(8)W_(48)(TBA-Cu_(2)0P_(8)W_(48))exhibits high efficiency for visible-light-driven H_(2) production in the presence of an[Ir(ppy)2(dtbbpy)][PF_(6)]photosensitizer and a triethanolamine electron donor.Under optimal conditions,the turnover number for H_(2) production reaches~2892 after 5 h of photocatalysis 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 reductive quenching pathway is dominant.Various stability tests demonstrate that the TBA-Cu_(2)0P_(8)W_(48) catalyst slowly dissociates Cu ions under turnover conditions;however,both the starting TBA-Cu_(2)0P_(8)W_(48) and its molecular decomposition products are dominant active species for efficient and long-term H_(2) production.
