The doping of CdS quantum dots (QDs) with Cu(I) disrupts electron–hole correlation due to hole trapping by the dopant ion, post-photoexcitation. The present paper examines the effect of such disruption on the rate of photoinduced electron transfer (PET) from the QDs to methyl viologen (MV2+), with implications in their photocatalytic activity. A significantly greater efficiency of PL quenching by MV2+ is observed for the doped QDs than for the undoped ones. Interestingly, the Stern–Volmer plots constructed using PL intensities exhibit an upward curvature for both the cases, while the PL lifetimes remain unaffected. This observation is rationalized by considering the adsorption of the quencher on the surface of the QDs and ultrafast PET post-photoexcitation. Ultrafast transient absorption experiments confirm a faster electron transfer for the doped QDs. It is also realized that the transient absorption experiment yields a more accurate estimate of the binding constant of the quencher with the QDs, than the PL experiment.
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