A synthetic nickel electrocatalyst with a turnover frequency above 100,000 s-1 for H2 production

Monte Helm, Michael P. Stewart, R Morris Bullock, M. Rakowski DuBois, Daniel L DuBois

Research output: Contribution to journalArticle

667 Citations (Scopus)

Abstract

Reduction of acids to molecular hydrogen as a means of storing energy is catalyzed by platinum, but its low abundance and high cost are problematic. Precisely controlled delivery of protons is critical in hydrogenase enzymes in nature that catalyze hydrogen (H2) production using earth-abundant metals (iron and nickel). Here, we report that a synthetic nickel complex, [Ni(PPh2NPh)2](BF4)2, (PPh2NPh = 1,3,6-triphenyl-1-aza-3,6- diphosphacycloheptane), catalyzes the production of H2 using protonated dimethylformamide as the proton source, with turnover frequencies of 33,000 per second (s-1) in dry acetonitrile and 106,000 s-1 in the presence of 1.2 M of water, at a potential of -1.13 volt (versus the ferrocenium/ferrocene couple). The mechanistic implications of these remarkably fast catalysts point to a key role of pendant amines that function as proton relays.

Original languageEnglish
Pages (from-to)863-866
Number of pages4
JournalScience
Volume333
Issue number6044
DOIs
Publication statusPublished - Aug 12 2011

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Nickel
Protons
Hydrogen
Hydrogenase
Dimethylformamide
Platinum
Amines
Iron
Metals
Costs and Cost Analysis
Acids
Water
Enzymes

ASJC Scopus subject areas

  • General

Cite this

A synthetic nickel electrocatalyst with a turnover frequency above 100,000 s-1 for H2 production. / Helm, Monte; Stewart, Michael P.; Bullock, R Morris; DuBois, M. Rakowski; DuBois, Daniel L.

In: Science, Vol. 333, No. 6044, 12.08.2011, p. 863-866.

Research output: Contribution to journalArticle

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