Electrocatalysts for CO2 reduction based on first-row transition metal ions have attracted attention as abundant and affordable candidates for energy conversion applications. Yet very few molecular iron electrocatalysts exhibit high selectivity for CO. Iron complexes supported by a redox-active 2,2′:6′,2″-terpyridine … Read more

The mechanism for interfacial electron transfer (ET) from a metal oxide core|shell nanostructure to a [RuIII(2,2′-bipyridine)2(4,4′-(PO3H2)2-2,2′-bipyridine)]3+ sensitizer was probed through spectroscopic quantification of the ET kinetics over a 70 °C temperature range in an aqueous 0.1 M HClO4 solution. Mesoporous thin films … Read more

Photoelectrodes consisting of wide-band gap metal oxides functionalized with chromophores and catalysts are a potential low-cost solution to generate solar fuels from aqueous solution. NiO is a common photocathode material used in these systems, yet it generally exhibits poor performance … Read more

The power conversion efficiency of tandem dye-sensitized photoelectrosynthesis cells is limited by the number of p-type metal oxide semiconductors and chromophores available for the photocathode. Here, a new class of donor–acceptor–donor organic chromophores is introduced with deep highest occupied molecular … Read more

The kinetics for interfacial electron transfer (ET) from a transparent conductive oxide (tin-doped indium oxide, ITO, Sn:In2O3) to molecular acceptors 4-[N,N-di(p-tolyl)amino]benzylphosphonic acid, TPA, and [RuII(bpy)2(4,4′-(PO3H2)2-bpy)]2+, RuP, positioned at variable distances within and beyond the electric double layer (EDL), were quantified … Read more

Recent advances in our mechanistic understanding of dye-sensitized electron transfer reactions occurring at metal oxide interfaces are described. These advances were enabled by the advent of mesoporous thin films, comprised of anatase TiO2 nanocrystallites, that are amenable to spectroscopic and … Read more

Energy transfer was explored in a series of poly(phenylene ethynylene) (PPE) polymers with increasing lengths that were end-capped with thiophene-benzothiadiazole (TBT) groups to form fully conjugated donor–acceptor polymers. For the polymers in solution, ultrafast transient absorption and time-resolved fluorescence spectroscopy … Read more

Two osmium(II) photocatalysts bearing a dicationic 4,4′-bis-(trimethylaminomethyl)-2,2′-bipyridine (tmam) ligand and 2,2′-bipyridine {[Os(bpy)2(tmam)]4+} or 4,4′-(CF3)2-2,2′-bipyridine {[Os((CF3)2bpy)2(tmam)]4+} ancillary ligands were synthesized and characterized for application in HX splitting. Iodide titration studies in acetone solutions provided evidence for an in situ formed terionic complex with two iodide … Read more

Classical capacitance studies have revealed that the first layer of water present at an aqueous metal-electrolyte interface has a die-lectric constant less than 1/10th that of bulk water. Modern theory indicates that under such solvent conditions the barrier for elec-tron … Read more

The presence of narrow, degenerately-doped axial silicon nanowire (SiNW) p–n junctions via off-axis electron holography (EH) has been confirmed. SiNWs were grown via the vapor-solid-liquid (VLS) mechanism using gold (Au) as the catalyst, silane (SiH4 ), diborane (B2H6 ) and phosphine (PH3 ) as the … Read more

Maximizing the efficiency of solar energy conversion using dye assemblies rests on understanding where the energy goes following absorption. Transient spectroscopies in solution are useful for this purpose, and the time-resolved data are usually analyzed with a sum of exponentials. … Read more

Comparative kinetic studies of a series of new ruthenium complexes provide a platform for understanding how strong trans effect ligands and redox-active ligands work together to enable rapid electrochemical CO2 reduction at moderate overpotential. After synthesizing isomeric pairs of ruthenium … Read more

The performance of dye sensitized solar cells (DSSCs) depends on the properties and interactions of three fundamental components: the semiconductor, chromophore, and electrolyte. For the electrolyte, the dependence of DSSC performance on the identity and valence state of the spectator … Read more

The synthesis, characterization, electrochemical and photophysical properties of the phosphonate-derivatized Carbazole (CBZ) and boron dipyrromethene (BODIPY) chromophores in the dyes, BODIPY(CBZ)2PO3H2 [8] and BODIPY(Tol)2PO3H2 [7], are described. The oxide-bound dyes have been explored as light absorbers in dye-sensitized photoelectrosynthesis cell … Read more