Using Molecular Design to Control the Performance of Hydrogen-Producing Polymer-Brush-Modified Photocathodes
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- 作者：Diana Cedeno ; Alexandra Krawicz ; Peter Doak ; Min Yu ; Jeffrey B. Neaton ; Gary F. Moore
- 刊名：The Journal of Physical Chemistry Letters
- 出版年：2014
- 出版时间：September 18, 2014
- 年：2014
- 卷：5
- 期：18
- 页码：3222-3226
- 全文大小：292K
- ISSN：1948-7185
文摘
Attachment of difluoroborylcobaloxime catalysts to a polymer-brush-modified GaP 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.