Excited electron transfer across semiconductor-molecule heterogeneous interfaces is central to various future electronic and optoelectronic devices. At the same time, first-principles modeling of such dynamical processes remains as a great challenge in theoretical chemistry and condensed matter physics for developing … Read more

In artificial photosynthesis, the sun drives water splitting into H2 and O2 or converts CO2 into a useful form of carbon. In most schemes, water oxidation is typically the limiting half-reaction. Here, we introduce a molecular approach to the design … Read more

A comprehensive mechanistic study of electrocatalytic CO2 reduction by ruthenium 2,2′:6′,2″-terpyridine (tpy) pyridyl-carbene catalysts reveals the importance of stereochemical control to locate the strongly donating N-heterocyclic carbene ligand trans to the site of CO2 activation.  Computational studies were undertaken to … Read more

This paper describes the preparation and characterization of a photocathode assembly for CO2 reduction to CO in 0.1M LiClO4 acetonitrile. The assembly was formed on 1.0 µm thick mesoporous films of NiO using a layer-by-layer procedure based on Zr(IV)-phosphonate bridging … Read more

Halide photoredox chemistry is of both practical and fundamental interest. Practical applications have largely focused on solar energy conversion with hydrogen gas, through HX splitting, and electrical power generation, in regenerative photoelectrochemical and photovoltaic cells. On a more fundamental level, … Read more

A mesoporous atomic layer deposition (ALD) double-shell electrode, Al2O3 (insulating core)//ALD ZnO|ALD TiO2, on a fluorine-doped tin oxide (FTO) conducting substrate was explored for a photoanode assembly, FTO//Al2O3 (insulating core)//ALD ZnO|ALD TiO2|–chromophore–catalyst, for light-driven water oxidation. Photocurrent densities at photoanodes based on … Read more

Surface passivation with fluorine atoms results in a significant slow down of hot electron relaxation because there exist particular electronic states that retain the hot electron for an extended time, and the relaxation time scale is largely influenced by shuttling … Read more

A tandem cell for artificial photosynthesis with CO2 and water as the oxidants and an organic alcohol as the reductant is described. The use of molecular catalysts with high activity and selectivity, in an appropriate cell configuration, leads to electrochemical reduction … Read more

The silane-derivatized catalyst, Ru(bda)(L)2 (bda = 2,2′-bipyridine-6,6′-dicarboxylate, L = 4-(6-(triethoxysilyl)hexyl)pyridine), is stabilized on metal oxide electrode surfaces over an extended pH range. It maintains its reactivity on the electrode surface toward electrochemical oxidation over a wide range of conditions. On … Read more

Transparent conductive oxides (TCOs) are widely-used commercially available materials for opto‐electronic applications, yet have received very little attention for dye‐sensitization applications. This paper reports that mesoporous thin films of conductive indium‐doped tin oxide (ITO) nanocrystallites support long‐lived charge separation with … Read more

The development of molecular organometallic electrocatalysts for the reduction of carbon dioxide (CO2) is reviewed. Organometallic complexes are a promising subset of the many catalysts capable of electrochemical reduction of carbon dioxide to organic small molecules such as carbon monoxide (CO), formate (HCO2−), and oxalate (C2O42−). The carbon-based supporting ligands of organometallic complexes … Read more

Dye-sensitized bromide oxidation was investigated using a series of  ruthenium polypyridyl photocatalysts anchored to SnO2/TiO2 core/shell mesoporous thin films through 2,2’-bipyridine-4,4’-diphosphonic acid anchoring groups. The ground- and excited-state reduction potentials were tuned over 500 mV by the introduction of electron-withdrawing … Read more

Stabilized photoanodes for light-driven water oxidation were prepared on nanoparticle core/shell electrodes with surface-stabilized donor–acceptor chromophores, a water oxidation catalyst, and an electron-transfer mediator. For the electrode, fluorine-doped tin oxide FTO|SnO2/TiO2|-Org1-|1.1 nm Al2O3|-RuP2+-WOC (water oxidation catalyst) with Org1 (1-cyano-2-(4-(diphenylamino)phenyl)vinyl)phosphonic acid), … Read more

The organic chromophore, 2,2′-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-3-carboxylic acid), was prepared and investigated along with metal complex [Ru(bda)(pyP)2] (bda = 2,2’-bipyridine-6,6’-dicarboxylate; pyP = 3-(pyridine-4-yloxy)propyl)phosphonic acid), for light-driven water splitting in dye-sensitized photoelectrochemical cells. The resulting co-loaded organic chromophore plus catalyst surface assembly was evaluated … Read more

A ruthenium polypyridyl chromophore with electronically isolated triarylamine substituents models the role of tyrosine in the electron transport chain in photosystem II. When bound to the surface of a TiO2 electrode, electron injection from a Ru(II) Metal-to-Ligand Charge Transfer (MLCT) excited … Read more