title: Towards multielectron photocatalysis: a porphyrin array for lateral hole transfer and capture on a metal oxide surface.
abstract: Current molecular water-oxidation photoelectrocatalytic cells have substantial kinetic limitations under normal solar photon flux where electron-hole recombination processes may outcompete charge buildup on the catalytic centers. One method of overcoming these limitations is to design a system where multiple light-harvesting dyes work cooperatively with a single catalyst. We report a porphyrin monomer/dyad array for analysis of lateral hole transfer on a SnO2 surface consisting of a free-base porphyrin that functions to absorb light and initiate charge injection into the conduction band of SnO2, which leaves a positive charge on the organic moiety, and a free-base porphyrin/Zn-porphyrin dyad molecule that functions as a thermodynamic trap for the photoinduced holes. By using transient absorption spectroscopy, we have determined that the holes on the surface-bound free-base porphyrins are highly mobile via electron self-exchange between close-packed neighbors. The lateral charge-transfer processes were modelled by treating the system statistically with a random-walk method that utilizes experimentally derived kinetic parameters. The results of the modelling indicate that each self-exchange (hop) occurs within 25 ns and that the holes are efficiently transferred to the Zn-porphyrin. This hole-harvesting scheme provides a framework for enhancing the efficiency of multielectron photoelectrocatalytic reactions such as the four-electron oxidation of water.
authors.affiliation: Energy Sciences Institute and Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA. gary.brudvig@yale.edu.
authors.forename: Bradley J
authors.initials: BJ
authors.lastname: Brennan
authors.forename: Alec C
authors.initials: AC
authors.lastname: Durrell
authors.forename: Matthieu
authors.initials: M
authors.lastname: Koepf
authors.forename: Robert H
authors.initials: RH
authors.lastname: Crabtree
authors.forename: Gary W
authors.initials: GW
authors.lastname: Brudvig