New insights in the electrocatalytic proton reduction and hydrogen oxidation by bioinspired catalysts: A DFT investigation

Ali Kachmar, Valentina Vetere, Pascale Maldivi, Alejandro A. Franco

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

In this paper, we present a DFT study of the proton reduction mechanism catalyzed by the complex [Ni(P2 HN2 H)2]2+, bioinspired from the hydrogenases. A detailed analysis of the reactive isomers is discussed together with the localizations of the transitions states and energy minima. The reactive catalytic species is a biprotonated Ni(0) complex that can show different conformations and that can be protonated on different sites. The energies of the different conformations and biprotonated species have been calculated and discussed. Energy barriers for two different reaction mechanisms have been identified in solvent and in gas phase. Frequency calculations have been performed to check the nature of the energy minima and for the calculations of entropic energetic terms and zero point energies. We show that only one conformation is mostly reactive. All the others species are nonreactive in their original form, and they have to pass through conformational barriers in order to transform in the reactive species.

Original languageEnglish
Pages (from-to)11861-11867
Number of pages7
JournalJournal of Physical Chemistry A
Volume114
Issue number43
DOIs
Publication statusPublished - 4 Nov 2010
Externally publishedYes

Fingerprint

Hydrogenase
Discrete Fourier transforms
Conformations
Protons
Hydrogen
Gases
catalysts
Oxidation
oxidation
Catalysts
protons
hydrogen
Energy barriers
Isomers
energy
zero point energy
isomers
vapor phases

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

New insights in the electrocatalytic proton reduction and hydrogen oxidation by bioinspired catalysts : A DFT investigation. / Kachmar, Ali; Vetere, Valentina; Maldivi, Pascale; Franco, Alejandro A.

In: Journal of Physical Chemistry A, Vol. 114, No. 43, 04.11.2010, p. 11861-11867.

Research output: Contribution to journalArticle

Kachmar, Ali ; Vetere, Valentina ; Maldivi, Pascale ; Franco, Alejandro A. / New insights in the electrocatalytic proton reduction and hydrogen oxidation by bioinspired catalysts : A DFT investigation. In: Journal of Physical Chemistry A. 2010 ; Vol. 114, No. 43. pp. 11861-11867.
@article{0e155208a1d543a6ae9d6799a4c5edbf,
title = "New insights in the electrocatalytic proton reduction and hydrogen oxidation by bioinspired catalysts: A DFT investigation",
abstract = "In this paper, we present a DFT study of the proton reduction mechanism catalyzed by the complex [Ni(P2 HN2 H)2]2+, bioinspired from the hydrogenases. A detailed analysis of the reactive isomers is discussed together with the localizations of the transitions states and energy minima. The reactive catalytic species is a biprotonated Ni(0) complex that can show different conformations and that can be protonated on different sites. The energies of the different conformations and biprotonated species have been calculated and discussed. Energy barriers for two different reaction mechanisms have been identified in solvent and in gas phase. Frequency calculations have been performed to check the nature of the energy minima and for the calculations of entropic energetic terms and zero point energies. We show that only one conformation is mostly reactive. All the others species are nonreactive in their original form, and they have to pass through conformational barriers in order to transform in the reactive species.",
author = "Ali Kachmar and Valentina Vetere and Pascale Maldivi and Franco, {Alejandro A.}",
year = "2010",
month = "11",
day = "4",
doi = "10.1021/jp107104k",
language = "English",
volume = "114",
pages = "11861--11867",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "43",

}

TY - JOUR

T1 - New insights in the electrocatalytic proton reduction and hydrogen oxidation by bioinspired catalysts

T2 - A DFT investigation

AU - Kachmar, Ali

AU - Vetere, Valentina

AU - Maldivi, Pascale

AU - Franco, Alejandro A.

PY - 2010/11/4

Y1 - 2010/11/4

N2 - In this paper, we present a DFT study of the proton reduction mechanism catalyzed by the complex [Ni(P2 HN2 H)2]2+, bioinspired from the hydrogenases. A detailed analysis of the reactive isomers is discussed together with the localizations of the transitions states and energy minima. The reactive catalytic species is a biprotonated Ni(0) complex that can show different conformations and that can be protonated on different sites. The energies of the different conformations and biprotonated species have been calculated and discussed. Energy barriers for two different reaction mechanisms have been identified in solvent and in gas phase. Frequency calculations have been performed to check the nature of the energy minima and for the calculations of entropic energetic terms and zero point energies. We show that only one conformation is mostly reactive. All the others species are nonreactive in their original form, and they have to pass through conformational barriers in order to transform in the reactive species.

AB - In this paper, we present a DFT study of the proton reduction mechanism catalyzed by the complex [Ni(P2 HN2 H)2]2+, bioinspired from the hydrogenases. A detailed analysis of the reactive isomers is discussed together with the localizations of the transitions states and energy minima. The reactive catalytic species is a biprotonated Ni(0) complex that can show different conformations and that can be protonated on different sites. The energies of the different conformations and biprotonated species have been calculated and discussed. Energy barriers for two different reaction mechanisms have been identified in solvent and in gas phase. Frequency calculations have been performed to check the nature of the energy minima and for the calculations of entropic energetic terms and zero point energies. We show that only one conformation is mostly reactive. All the others species are nonreactive in their original form, and they have to pass through conformational barriers in order to transform in the reactive species.

UR - http://www.scopus.com/inward/record.url?scp=78049492296&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=78049492296&partnerID=8YFLogxK

U2 - 10.1021/jp107104k

DO - 10.1021/jp107104k

M3 - Article

C2 - 20942496

AN - SCOPUS:78049492296

VL - 114

SP - 11861

EP - 11867

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 43

ER -