Ryan M. O’Donnell

Electric Fields Control TiO2(e–) + I3– → Charge Recombination in Dye-Sensitized Solar Cells

The electric fields generated by excited-state electron injection into anatase TiO2 nanocrystallites are screened by cations present in the external electrolyte. With some assumptions, a newly discovered electroabsorption signature enables quantification of the electric field strength experienced by surface-anchored dye molecules. Here, it was found that the fields increased in the order Na(+) < Li(+) < Mg(2+) < Ca(2+), with magnitudes of 1.1 MV/cm for Na(+) and 2.2 MV/cm for Ca(2+), values that were insensitive to whether the anion was iodide or perchlorate. The magnitude of the field was directly related to average TiO2(e(-)) + I3(-) → charge recombination rate constants abstracted from time-resolved kinetic data. Extrapolation to zero field provided an estimate of recombination dynamics when diffusion alone controlled I3(-) mass transport, k = 300 s(-1). The decreased rate constants measured after excited-state injection were attributed to migration of I3(-) away from the TiO2. Cation transference coefficients were tabulated that ranged from t = 0.97 for Ca(2+) to 0.40 for Na(+) and represented the ability of the unscreened electric field to block the TiO2(e(-)) + I3(-) → charge recombination reaction. This data provides the first compelling evidence that the anionic nature of I3(-) inhibits unwanted charge recombination in dye-sensitized solar cells.

Photoacidic and Photobasic Behavior of Transition Metal Compounds with Carboxylic Acid Group(s)

Excited state proton transfer studies of six Ru polypyridyl compounds with carboxylic acid/carboxylate group(s) revealed that some were photoacids and some were photobases. The compounds [Ru(II)(btfmb)2(LL)](2+), [Ru(II)(dtb)2(LL)](2+), and [Ru(II)(bpy)2(LL)](2+), where bpy is 2,2-bipyridine, btfmb is 4,4-(CF3)2-bpy, and dtb is 4,4-((CH3)3C)2-bpy, and LL is either dcb = 4,4-(CO2H)2-bpy or mcb = 4-(CO2H),4-(CO2Et)-2,2-bpy, were synthesized and characterized. The compounds exhibited intense metal-to-ligand charge-transfer (MLCT) absorption bands in the visible region and room temperature photoluminescence (PL) with long τ > 100 ns excited state lifetimes. The mcb compounds had very similar ground state pKas of 2.31 ± 0.07, and their characterization enabled accurate determination of the two pKa values for the commonly utilized dcb ligand, pKa1 = 2.1 ± 0.1 and pKa2 = 3.0 ± 0.2. Compounds with the btfmb ligand were photoacidic, and the other compounds were photobasic. Transient absorption spectra indicated that btfmb compounds displayed a [Ru(III)(btfmb(-))L2](2+)* localized excited state and a [Ru(III)(dcb(-))L2](2+)* formulation for all the other excited states. Time dependent PL spectral shifts provided the first kinetic data for excited state proton transfer in a transition metal compound. PL titrations, thermochemical cycles, and kinetic analysis (for the mcb compounds) provided self-consistent pKa* values. The ability to make a single ionizable group photobasic or photoacidic through ligand design was unprecedented and was understood based on the orientation of the lowest-lying MLCT excited state dipole relative to the ligand that contained the carboxylic acid group(s).

Photodriven Oxygen Removal via Chromophore-Mediated Singlet Oxygen Sensitization and Chemical Capture

We report a general, photochemical method for the rapid deoxygenation of organic solvents and aqueous solutions via visible light excitation of transition metal chromophores (TMCs) in the presence of singlet oxygen scavenging substrates. Either 2,5-dimethylfuran or an amino acid (histidine or tryptophan methyl ester) was used as the substrate in conjunction with an iridium or ruthenium TMC in toluene, acetonitrile, or water. This behavior is described for solutions with chromophore concentrations that are pertinent for both luminescence and transient absorption spectroscopies. These results consistently produce TMC lifetimes comparable to those measured using traditional inert gas sparging and freeze-pump-thaw techniques. This method has the added benefits of providing long-term stability (days to months); economical preparation due to use of inexpensive, commercially available oxygen scrubbing substrates; and negligible size and weight footprints compared to traditional methods. Furthermore, attainment of dissolved [O2] < 50 μM makes this method relevant to any solution application requiring low dissolved oxygen concentration in solution, provided that the oxygenated substrate does not interfere with the intended chemical process.