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Title: Proton Reduction Using a Hydrogenase-Modified Nanoporous Black Silicon Photoelectrode

Metalloenzymes featuring earth-abundant metal-based cores exhibit rates for catalytic processes such as hydrogen evolution comparable to those of noble metals. Realizing these superb catalytic properties in artificial systems is challenging owing to the difficulty of effectively interfacing metalloenzymes with an electrode surface in a manner that supports efficient charge-transfer. Here, we demonstrate that a nanoporous 'black' silicon (b-Si) photocathode provides a unique interface for binding an adsorbed [FeFe]-hydrogenase enzyme ([FeFe]-H2ase). The resulting [FeFe]-H2ase/b-Si photoelectrode displays a 280 mV more positive onset potential for hydrogen generation than bare b-Si without hydrogenase, similar to that observed for a b-Si/Pt photoelectrode at the same light intensity. Additionally, we show that this H2ase/b-Si electrode exhibits a turnover frequency of >/=1300 s-1 and a turnover number above 107 and sustains current densities of at least 1 mA/cm2 based on the actual surface area of the electrode (not the smaller projected geometric area), orders of magnitude greater than that observed for previous enzyme-catalyzed electrodes. While the long-term stability of hydrogenase on the b-Si surface remains too low for practical applications, this work extends the proof-of-concept that biologically derived metalloenzymes can be interfaced with inorganic substrates to support technologically relevant current densities.
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Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 1944-8244
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Applied Materials and Interfaces; Journal Volume: 8; Journal Issue: 23
American Chemical Society
Research Org:
NREL (National Renewable Energy Laboratory (NREL), Golden, CO (United States))
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
36 MATERIALS SCIENCE photoelectrochemical water splitting; hydrogen production; hydrogenase; silicon photoelectrode; nanoporous silicon; bio-assisted; black silicon