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Reduction of Alkenes: Catalytic Hydrogenation02:13

Reduction of Alkenes: Catalytic Hydrogenation

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Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
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Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

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Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
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Proton Reduction Using a Hydrogenase-Modified Nanoporous Black Silicon Photoelectrode.

Yixin Zhao1, Nicholas C Anderson1, Michael W Ratzloff1

  • 1National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States.

ACS Applied Materials & Interfaces
|May 25, 2016
PubMed
Summary
This summary is machine-generated.

Earth-abundant metalloenzymes offer efficient hydrogen evolution catalysis. A nanoporous black silicon photocathode enables effective interfacing of [FeFe]-hydrogenase for high-performance artificial photosynthesis.

Keywords:
bio-assistedblack siliconhydrogen productionhydrogenasephotoelectrochemical water splittingsilicon photoelectrode

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Area of Science:

  • Bioinorganic Chemistry
  • Materials Science
  • Renewable Energy

Background:

  • Metalloenzymes with earth-abundant metals show catalytic activity for hydrogen evolution comparable to noble metals.
  • Interfacing metalloenzymes with electrodes for efficient charge transfer in artificial systems is a significant challenge.

Purpose of the Study:

  • To demonstrate a novel interface for binding metalloenzymes to an electrode surface.
  • To evaluate the catalytic performance of a metalloenzyme-electrode system for hydrogen generation.

Main Methods:

  • Fabrication of a nanoporous black silicon (b-Si) photocathode.
  • Immobilization of [FeFe]-hydrogenase enzyme ([FeFe]-H2ase) onto the b-Si surface.
  • Electrochemical characterization of the [FeFe]-H2ase/b-Si photoelectrode for hydrogen evolution.

Main Results:

  • The [FeFe]-H2ase/b-Si photoelectrode exhibited a 280 mV more positive onset potential for hydrogen generation compared to bare b-Si.
  • Achieved a turnover frequency of ≥1300 s⁻¹ and a turnover number >10⁷, sustaining current densities of ≥1 mA/cm².
  • Performance was comparable to a b-Si/Pt electrode at similar light intensities.

Conclusions:

  • Nanoporous black silicon provides an effective interface for immobilizing [FeFe]-hydrogenase, enabling high catalytic performance for hydrogen generation.
  • This study extends the proof-of-concept for interfacing biologically derived metalloenzymes with inorganic substrates for technologically relevant current densities.
  • Long-term stability of the enzyme on the b-Si surface requires further improvement for practical applications.