Evidence That Delta S-Double Dagger Controls Interfacial Electron Transfer Dynamics From Anatase Tio2 To Molecular Acceptors

Recombination of electrons injected into TiO2 with molecular acceptors present at the interface represents an important loss mechanism in dye-sensitized water oxidation and electrical power generation. Herein, the kinetics for this interfacial electron transfer reaction to oxidized triphenylamine (TPA) acceptors was quantified over a 70 degrees temperature range for para-methyl-TPA (Me-TPA) dissolved in acetonitrile solution, 4-[N,N-di(p-tolyl)amino]benzylphosphonic acid (a-TPA) anchored to the TiO2, and a TPA covalently bound to a ruthenium sensitizer, [Ru(tpy-C6H4-PO3H2)(tpy-TPA)](2+) "RuTPA", where tpy is 2,2':6',2''-terpyridine. Activation energies extracted from an Arrhenius analysis were found to be 11 +/- 1 kJ mol(-1) for Me-TPA and 22 +/- 1 kJ mol(-1) for a-TPA, values that were insensitive to the identity of different sensitizers. Recombination to RuTPA(+) proceeded with E-a = 27 +/- 1 kJ mol(-1) that decreased to 19 +/- 1 kJ mol(-1) when recombination occurred to an oxidized para-methoxy TPA (MeO-TPA) dissolved in CH3CN. Eyring analysis revealed a smaller entropy of activation |Delta S-double dagger| when the a-TPA was anchored to the surface or covalently linked to the sensitizer, compared to that when Me-TPA was dissolved in CH3CN. In all cases, Eyring analysis provided large and negative Delta(double dagger) values that point toward unfavorable entropic factors as the key contributor to the barrier that underlies the slow recombination kinetics that are generally observed at dye-sensitized TiO2 interfaces.