Using Molecular Design to Control the Performance of Hydrogen-Producing Polymer-Brush-Modified Photocathodes

作者：Cedeno Diana; Krawicz Alexandra; Doak Peter; Yu Min; Neaton Jeffrey B; Moore Gary F^*

来源：Journal of Physical Chemistry Letters, 2014, 5(18): 3222-3226.

DOI：10.1021/jz5016394

Attachment of difluoroborylcobaloxime catalysts to a polymer-brush-modified Gal) semiconductor allows improved hydrogen production levels and photoelectrochemical performance under aqueous acidic conditions (pH = 4.5) as compared to the performance of electrodes without catalyst treatment. The catalytic assembly used in this work incorporates a boron difluoride (BF2) capping group on the glyoximate ligand of the catalyst, a synthetic modification previously used to enhance the stability of nonsurface-attached complexes toward acid hydrolysis and to shift the cobalt reduction potentials of the complex to less negative, and thus technologically more relevant, values. The pH-dependent photoresponses of the cobaloxime- and difluoroborylcobaloxime- modified semiconductors are shown to be consistent with those from analogous studies using non-surface-attached cobaloxime catalysts as well as catalysts supported on conductive electrodes. Thus, this work illustrates the potential to control and optimize the properties of visible-light-absorbing semiconductors using polymeric overcoating techniques coupled with the principles of synthetic molecular design.

• 出版日期2014-9-18