Three isostructural pillared-layer frameworks with M-BDC-X layers supported by ditopic HL connectors, [M(HL)(BDC)0.5X]n (HL = 4'-(4-hydroxyphenyl)-4,2':6',4''-terpyridine, BDC = terephthalate, M = Cd, X = Cl for 1, M = Cd, X = formate for 2, and M = Co, X = formate for 3), were solvothermally synthesized, and used as photocatalysts for Pt-assisted visible-light-initiated hydrogen evolution from water splitting. These water-durable frameworks exhibit varied hydrogen production rates of 361.2, 271.3, and 327.5 μmol·g-1·h-1 in 12 hour due to their slightly different donor environments of the octahedral CdII and CoII ions. Further experimental and theoretical investigations reveal that the metal ions and the local coordination surroundings have essentially dominated the conduction band minimum and electric resistance of the charge transport, which play highly important roles for the improved catalytic hydrogen evolution ability. These findings demonstrate the electronic effect of the slightly ligand field modifications on the boosting hydrogen generation activity in the noble metal-assisted MOF photocatalytic systems.

中文翻译：

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以过渡金属离子和局部配位环境为主的铂辅助金属有机骨架上的光催化析氢活性

三个同构柱撑层框架，具有双位 HL 连接器支持的 M-BDC-X 层，[M(HL)(BDC)0.5X]n (HL = 4'-(4-hydroxyphenyl)-4,2':6' ,4''-三联吡啶，BDC = 对苯二甲酸酯，M = Cd，X = Cl 1，M = Cd，X = 甲酸盐 2，M = Co，X = 甲酸盐 3)，溶剂热合成，并用作用于 Pt 辅助可见光引发的水分解析氢的光催化剂。由于八面体 CdII 和 CoII 离子的供体环境略有不同，这些耐水骨架在 12 小时内表现出 361.2、271.3 和 327.5 μmol·g-1·h-1 的不同产氢率。进一步的实验和理论研究表明，金属离子和局部配位环境基本上主导了电荷传输的导带最小值和电阻，这对于提高催化析氢能力起着非常重要的作用。这些发现证明了在贵金属辅助 MOF 光催化系统中，轻微的配体场修饰对提高产氢活性的电子效应。