Ni(II) complexes for hydrogen oxidation and hydrogen production: An ab-initio molecular dynamics investigation

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Abstract

We present a detailed theoretical study of [Ni(P R 2N R' 2) 2] 2+ electrocatalysts for H 2 oxidation and H 2 formation developed at the EFRC Center for Molecular Electrocatalysis at PNNL. P R 2N R' 2 denotes cyclic diphosphine ligands that incorporate an amine base in each ligand chelate ring. Density functional theory-based calculations and hybrid QM/MM molecular dynamics simulations have been employed to efficiently map the complex chemistry of these catalysts. Results are rationalized in terms of the P and N substituents and their capability to tune the pK a of the pendant amines and the hydricity of the metal center. A detailed analysis of the conformational dynamics of the reaction intermediates and their role on the catalytic activity is also presented, along with a discussion on the role of solvent (acetonitrile) and of small amounts of water, which have been shown to have a dramatic effect on rates of H 2 production.

Original languageEnglish
Title of host publicationACS National Meeting Book of Abstracts
Publication statusPublished - 2011
Event242nd ACS National Meeting and Exposition - Denver, CO, United States
Duration: Aug 28 2011Sep 1 2011

Other

Other242nd ACS National Meeting and Exposition
CountryUnited States
CityDenver, CO
Period8/28/119/1/11

Fingerprint

Hydrogen production
Amines
Molecular dynamics
Hydrogen
Ligands
Electrocatalysis
Reaction intermediates
Oxidation
Electrocatalysts
Acetonitrile
Density functional theory
Catalyst activity
Metals
Catalysts
Water
Computer simulation
acetonitrile

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Ni(II) complexes for hydrogen oxidation and hydrogen production : An ab-initio molecular dynamics investigation. / Raugei, Simone; Chen, Shentan; Ho, Mingshun; Rousseau, Roger; Dupuis, Michel; DuBois, Daniel L; Bullock, R Morris.

ACS National Meeting Book of Abstracts. 2011.

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Raugei, S, Chen, S, Ho, M, Rousseau, R, Dupuis, M, DuBois, DL & Bullock, RM 2011, Ni(II) complexes for hydrogen oxidation and hydrogen production: An ab-initio molecular dynamics investigation. in ACS National Meeting Book of Abstracts. 242nd ACS National Meeting and Exposition, Denver, CO, United States, 8/28/11.
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AU - DuBois, Daniel L

AU - Bullock, R Morris

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