Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry &University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100190, P. R. China.
Sci Rep. 2016 Jul 15;6:29851. doi: 10.1038/srep29851.
Achieving highly efficient hydrogen (H2) evolution via artificial photosynthesis is a great ambition pursued by scientists in recent decades because H2 has high specific enthalpy of combustion and benign combustion product. [FeFe]-Hydrogenase ([FeFe]-H2ase) mimics have been demonstrated to be promising catalysts for H2 photoproduction. However, the efficient photocatalytic H2 generation system, consisting of PAA-g-Fe2S2, CdSe QDs and H2A, suffered from low stability, probably due to the hole accumulation induced photooxidation of CdSe QDs and the subsequent crash of [FeFe]-H2ase mimics. In this work, we take advantage of supramolecular interaction for the first time to construct the secondary coordination sphere of electron donors (HA(-)) to CdSe QDs. The generated secondary coordination sphere helps realize much faster hole removal with a ~30-fold increase, thus leading to higher stability and activity for H2 evolution. The unique photocatalytic H2 evolution system features a great increase of turnover number to 83600, which is the highest one obtained so far for photocatalytic H2 production by using [FeFe]-H2ase mimics as catalysts.
通过人工光合作用实现高效的氢气（H2）转化是近几十年来科学家们的一大追求，因为 H2 具有高热值和良性燃烧产物。[FeFe]-氢化酶（[FeFe]-H2ase）模拟物已被证明是 H2 光生产的有前途的催化剂。然而，由 PAA-g-Fe2S2、CdSe QDs 和 H2A 组成的高效光催化 H2 产生系统由于 CdSe QDs 积累的空穴诱导光氧化以及随后的[FeFe]-H2ase 模拟物的崩溃而遭受低稳定性。在这项工作中，我们首次利用超分子相互作用构建电子供体（HA(-)）到 CdSe QDs 的次级配位球。所产生的次级配位球有助于实现更快的空穴去除，从而使 H2 释放的稳定性和活性更高。独特的光催化 H2 释放系统的周转数大大增加到 83600，这是迄今为止使用[FeFe]-H2ase 模拟物作为催化剂进行光催化 H2 生产所获得的最高值。
