Covalent attachment of catalyst molecules to conductive diamond: CO2 reduction using "smart" electrodes.

We report here covalent attachment of a catalytically active cobalt complex onto boron-doped, p-type conductive diamond. Peripheral acetylene groups were appended on a cobalt porphyrin complex, and azide-alkyne cycloaddition was used for covalent linking to a diamond surface decorated with alkyl azides. The functionalized surface was characterized by X-ray photoelectron spectroscopy and Fourier transform IR spectroscopy, and the catalytic activity was characterized using cyclic voltammetry and FTIR.

Transient 2D IR spectroscopy of charge injection in dye-sensitized nanocrystalline thin films.

We use nonlinear 2D IR spectroscopy to study TiO(2) nanocrystalline thin films sensitized with a Re dye. We find that the free electron signal, which often obscures the vibrational features in the transient absorption spectrum, is not observed in the 2D IR spectra. Its absence allows the vibrational features of the dye to be much better resolved than with the typical IR absorption probe.

Highly stable molecular layers on nanocrystalline anatase TiO2 through photochemical grafting.

Well-defined molecular layers can be formed on the surface of nanocrystalline anatase TiO2 by photochemically grafting organic molecules bearing a terminal vinyl group. The molecular layers produced are shown to have minimal oxidation and are able to be patterned and uniformly grafted through optically thick nanocrystalline films. Stability tests show that the layers have excellent stability in deionized water at 80 degrees C, aqueous solutions at pH=1.