About this item:

26 Views | 13 Downloads

Author Notes:

Clifford P. Kubiak, ckubiak@ucsd.edu

Victor S. Batista, victor.batista@yale.edu

Tianquan Lian, tlian@emory.edu

∥ S.T.G. and L.M.K. contributed equally to this work.

The authors declare no competing financial interest.



  • Photocatalyst

Amine Hole Scavengers Facilitate Both Electron and Hole Transfer in a Nanocrystal/Molecular Hybrid Photocatalyst


Journal Title:

Journal of the American Chemical Society


Volume 145, Number 5


, Pages 3238-3247

Type of Work:

Article | Final Publisher PDF


A well-known catalyst, fac-Re(4,4′-R2-bpy)(CO)3Cl (bpy = bipyridine; R = COOH) (ReC0A), has been widely studied for CO2 reduction; however, its photocatalytic performance is limited due to its narrow absorption range. Quantum dots (QDs) are efficient light harvesters that offer several advantages, including size tunability and broad absorption in the solar spectrum. Therefore, photoinduced CO2 reduction over a broad range of the solar spectrum could be enabled by ReC0A catalysts heterogenized on QDs. Here, we investigate interfacial electron transfer from Cd3P2 QDs to ReC0A complexes covalently bound on the QD surface, induced by photoexcitation of the QD. We explore the effect of triethylamine, a sacrificial hole scavenger incorporated to replenish the QD with electrons. Through combined transient absorption spectroscopic and computational studies, we demonstrate that electron transfer from Cd3P2 to ReC0A can be enhanced by a factor of ∼4 upon addition of triethylamine. We hypothesize that the rate enhancement is a result of triethylamine possibly altering the energetics of the Cd3P2-ReC0A system by interacting with the quantum dot surface, deprotonation of the quantum dot, and preferential solvation, resulting in a shift of the conduction band edge to more negative potentials. We also observe the rate enhancement in other QD-electron acceptor systems. Our findings provide mechanistic insights into hole scavenger-quantum dot interactions and how they may influence photoinduced interfacial electron transfer processes.

Copyright information:

© 2023 The Authors. Published by American Chemical Society

This is an Open Access work distributed under the terms of the Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0/).
Export to EndNote