Bio-inspired molecular catalysts for hydrogen oxidation and hydrogen production

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

5 Citations (Scopus)

Abstract

Recent advances in Ni-based bio-inspired catalysts obtained in the Center for Molecular Electrocatalysis, an Energy Frontier Research Center (EFRC) led by the Pacific Northwest National Laboratory, demonstrated the possibility of cleaving H2 or generating H2 heterolytically with turnover frequencies comparable or superior to those of hydrogenase enzymes. In these catalysts the transformation between H2 and protons proceeds via an interplay between proton, hydride and electron transfer steps, and involves the interaction of a dihydrogen molecule with both a Ni(II) center and pendent amine bases incorporated in six-membered rings, which function as proton relays. These catalytic platforms are well designed in that when protons are correctly positioned (endo) toward the metal center, catalysis proceeds at very high rates. We show here that the proton removal from the molecular catalysts (for H2 oxidation) and proton delivery to the molecular catalysts (for H2 production) are often the rate-determining steps. Furthermore, the presence of multiple protonation sites gives rise to reaction intermediates with protons incorrectly positioned (exo relative to the metal center). These isomers are kinetically easily accessible and are detrimental to catalysis because the isomerization processes necessary to convert them to the catalytically competent endo isomers are slow. In this chapter we give an overview of the major findings of our computational investigation of proton relays for H2 chemistryand provide guidelines for the design of catalysts with enhanced activity.

Original languageEnglish
Title of host publicationACS Symposium Series
PublisherAmerican Chemical Society
Pages89-111
Number of pages23
Volume1133
ISBN (Print)9780841228207
DOIs
Publication statusPublished - 2013

Publication series

NameACS Symposium Series
Volume1133
ISSN (Print)00976156
ISSN (Electronic)19475918

Fingerprint

Hydrogen production
Protons
Hydrogen
Oxidation
Catalysts
Isomers
Catalysis
Metals
Hydrogenase
Electrocatalysis
Reaction intermediates
Protonation
Isomerization
Hydrides
Amines
Enzymes
Molecules
Electrons

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Ho, M. H., Chen, S., Rousseau, R., Dupuis, M., Bullock, R. M., & Raugei, S. (2013). Bio-inspired molecular catalysts for hydrogen oxidation and hydrogen production. In ACS Symposium Series (Vol. 1133, pp. 89-111). (ACS Symposium Series; Vol. 1133). American Chemical Society. https://doi.org/10.1021/bk-2013-1133.ch006

Bio-inspired molecular catalysts for hydrogen oxidation and hydrogen production. / Ho, Ming Hsun; Chen, Shentan; Rousseau, Roger; Dupuis, Michel; Bullock, R Morris; Raugei, Simone.

ACS Symposium Series. Vol. 1133 American Chemical Society, 2013. p. 89-111 (ACS Symposium Series; Vol. 1133).

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

Ho, MH, Chen, S, Rousseau, R, Dupuis, M, Bullock, RM & Raugei, S 2013, Bio-inspired molecular catalysts for hydrogen oxidation and hydrogen production. in ACS Symposium Series. vol. 1133, ACS Symposium Series, vol. 1133, American Chemical Society, pp. 89-111. https://doi.org/10.1021/bk-2013-1133.ch006
Ho MH, Chen S, Rousseau R, Dupuis M, Bullock RM, Raugei S. Bio-inspired molecular catalysts for hydrogen oxidation and hydrogen production. In ACS Symposium Series. Vol. 1133. American Chemical Society. 2013. p. 89-111. (ACS Symposium Series). https://doi.org/10.1021/bk-2013-1133.ch006
Ho, Ming Hsun ; Chen, Shentan ; Rousseau, Roger ; Dupuis, Michel ; Bullock, R Morris ; Raugei, Simone. / Bio-inspired molecular catalysts for hydrogen oxidation and hydrogen production. ACS Symposium Series. Vol. 1133 American Chemical Society, 2013. pp. 89-111 (ACS Symposium Series).
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