Secondary coordination sphere accelerates hole transfer for enhanced hydrogen photogeneration from [FeFe]-hydrogenase mimic and CdSe QDs in water.

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.