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Near thermal, selective liberation of hydrogen from formic acid catalysed by copper hydride ate complexes


Ma, HZ and Canty, AJ and O'Hair, RAJ, Near thermal, selective liberation of hydrogen from formic acid catalysed by copper hydride ate complexes, Dalton Transactions, 52 pp. 1574-1581. ISSN 1477-9226 (2023) [Refereed Article]

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DOI: doi:10.1039/d2dt03764e


A near thermal two-step catalytic cycle for the selective release of hydrogen from formic acid by mononuclear cuprate anions was revealed using multistage mass spectrometry experiments, deuterium labelling and DFT calculations. In gas-phase ion-molecule reactions, mononuclear copper hydride anions [(L)Cu(H)] (where L = H, O2CH, BH4 and CN) were found to react with formic acid (HCO2H) to yield [(L)Cu(O2CH)] and H2. The copper formate anions [(L)Cu(O2CH)] can decarboxylate via collision-induced dissociation (CID) to reform the copper hydride [(L)Cu(H)], thereby closing the two-step catalytic cycle. Analogous labelling experiments with d1-formic acid (DCO2H) reveal that the decarboxylation process also occurs spontaneously. A kinetic study was carried out to provide further insights into the species involved in this reaction. Energetics from density functional theory (DFT) calculations show that the key decarboxylation step can occur without CID, thus in support of experimental observations.

Item Details

Item Type:Refereed Article
Keywords:hydrogen storage, copper hydride, DFT, mass spectrometry, computation, formic acid
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Transition metal chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Canty, AJ (Professor Allan Canty)
ID Code:155257
Year Published:2023
Deposited By:Chemistry
Deposited On:2023-02-08
Last Modified:2023-02-08

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