Abstract: Photocatalytic systems comprising a hydrogenase-type catalyst and CdX (X = S, Se, Te) chalcogenide quantum dot (QD) photosensitizers show extraordinary hydrogen production rates under visible light excitation. What remains unknown is the mechanism of energy conversion in these systems. Here, we have explored this question by comparing the performance of two QD sensitizers, CdSe and CdTe, in photocatalytic systems featuring aqueous suspensions of a [Fe2 (u-1,2-benzenedithiolate) CO6] catalyst and an ascorbic acid sacrificial agent. Overall, the hydrogen production yield for CdSe-sensitized reactions QDs was found to be 13 times greater than that of CdTe counterparts. According to emission quenching experiments, an enhanced performance of CdSe sensitizers reflected a greater rate of electron transfer from the ascorbic acid (kAsc). The observed difference in the QD-ascorbic acid charge transfer rates between the two QD materials was consistent with respective driving forces for these systems.

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