Donor-acceptor type light-harvesting molecular wires are covalently attached to a boron-doped diamond surface via a combination of diazonium electrografting and Suzuki cross-coupling. For the Suzuki reaction, various catalytic systems are compared with respect to their imposed surface coverage. Combining 2dicyclohexylphosphino-2 0 ,6 0-dimethoxybiphenyl (SPhos) and Pd(0), the diamond coverage improves considerably (by 98%) as compared to the standard tetrakis(triphenylphosphine)palladium(0) (Pd(PPh 3) 4) catalyst. As the energy levels between the molecular chromophores and the diamond film align well, the sophisticated functionalized diamond surfaces present a first step towards the development of fully carbon-based devices for light to electricity conversion.
Novel highly active, optically-transparent electrode catalyst containing Pt, PtO x , graphene oxide and stacked graphene platelet nanofibers is developed for a cathode of Cu(II/I)-mediated dye-sensitized solar cells. The catalyst layer is deposited on a FTO substrate, which thus becomes smoother than the parent FTO, but the button-like Pt/PtO x nanoparticles are still distinguishable. The found electrocatalytic activity for the Cu(tmby) 2 2+/+ redox couple (tmby is 4,4',6,6'-tetramethyl-2,2'-bipyridine) is outperforming that of alternative catalysts, such as PEDOT or platinum. Exchange current densities exceeding 20 mA/cm 2 are provided exclusively by our novel catalyst. The synergic boosting of electrocatalytic activity is seen, if we normalize it to the catalytic performance of individual components, i.e. Pt and graphene nanofibers. The outstanding properties of our cathode are reflected by the performance of the corresponding solar cells using the Y123-sensitized titania photoanode.Champion solar-conversion efficiency (11.3 % at 0.1 sun) together with a fill factor of 0.783 compare favorably to all other so far reported best values for this kind of solar cells and the given experimental conditions.
A novel simple and versatile synthetic strategy is developed for the surface modification of boron-doped diamond. In a two-step procedure, polyethyleneimine is adsorbed on the hydrogenated diamond surface and subsequently modified with a model light-harvesting donor-π-bridge-acceptor molecule (coded P1). The sensitized diamond exhibits stable cathodic photocurrents under visible-light illumination in aqueous electrolyte solution with dimethylviologen serving as an electron mediator. In spite of the simplicity of the surface sensitization protocol, the photoelectrochemical performance is similar to or better than that of other sensitized diamond electrodes which were reported in previous studies (2008-2014).
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