Catalysts for Hydrogen Evolution from the [NiFe] Hydrogenase to the Ni2P(001) Surface: The Importance of Ensemble Effect
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- 1 October 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 127 (42), 14871-14878
- https://doi.org/10.1021/ja0540019
Abstract
Density functional theory (DFT) was employed to investigate the behavior of a series of catalysts used in the hydrogen evolution reaction (HER, 2H+ + 2e- → H2). The kinetics of the HER was studied on the [NiFe] hydrogenase, the [Ni(PS3*)(CO)]1- and [Ni(PNP)2]2+ complexes, and surfaces such as Ni(111), Pt(111), or Ni2P(001). Our results show that the [NiFe] hydrogenase exhibits the highest activity toward the HER, followed by [Ni(PNP)2]2+ > Ni2P > [Ni(PS3*)(CO)]1- > Pt > Ni in a decreasing sequence. The slow kinetics of the HER on the surfaces is due to the fact that the metal hollow sites bond hydrogen too strongly to allow the facile removal of H2. In fact, the strong H−Ni interaction on Ni2P(001) can lead to poisoning of the highly active sites of the surface, which enhances the rate of the HER and makes it comparable to that of the [NiFe] hydrogenase. In contrast, the promotional effect of H-poisoning on the HER on Pt and Ni surfaces is relatively small. Our calculations suggest that among all of the systems investigated, Ni2P should be the best practical catalyst for the HER, combining the high thermostability of the surfaces and high catalytic activity of the [NiFe] hydrogenase. The good behavior of Ni2P(001) toward the HER is found to be associated with an ensemble effect, where the number of active Ni sites is decreased due to presence of P, which leads to moderate bonding of the intermediates and products with the surface. In addition, the P sites are not simple spectators and directly participate in the HER.Keywords
This publication has 40 references indexed in Scilit:
- The Mechanism of Activation of a [NiFe]-Hydrogenase by Electrons, Hydrogen, and Carbon MonoxideJournal of the American Chemical Society, 2005
- Infrared Spectroscopic Investigation of Thiophene Adsorption on Silica-Supported Nickel Phosphide CatalystsThe Journal of Physical Chemistry B, 2004
- Inhibition and Aerobic Inactivation Kinetics of Desulfovibrio fructosovorans NiFe Hydrogenase Studied by Protein Film VoltammetryJournal of the American Chemical Society, 2004
- Density Functional Theory Investigation of the Active Site of Fe-Hydrogenases. Systematic Study of the Effects of Redox State and Ligands Hardness on Structural and Electronic Properties of Complexes Related to the [2Fe]H SubclusterInorganic Chemistry, 2004
- Refinement of the nickel site structure in Desulfovibrio gigas hydrogenase using range-extended EXAFS spectroscopyJournal of Inorganic Biochemistry, 2003
- Ni−Fe Hydrogenases: A Density Functional Theory Study of Active Site ModelsInorganic Chemistry, 1999
- A Hybrid Density Functional Theory/Molecular Mechanics Study of Nickel−Iron Hydrogenase: Investigation of the Active Site Redox StatesJournal of the American Chemical Society, 1999
- Nickel(II) Thiolate Complex with Carbon Monoxide and Its Fe(II) Analog: Synthetic Models for CO Adducts of Nickel−Iron-Containing EnzymesJournal of the American Chemical Society, 1996
- Crystal structure of the nickel–iron hydrogenase from Desulfovibrio gigasNature, 1995
- Special points for Brillouin-zone integrationsPhysical Review B, 1976