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Anionic dopants, such as O-atom vacancies, alter the thermochemical and kinetic parameters of proton coupled electron transfer (PCET) at metal oxide surfaces; understanding their impact(s) is essential for informed material design for efficient energy conversion processes. To circumvent challenges associated with studying extended solids, we employ polyoxovanadate–alkoxide clusters as atomically precise models of reducible metal oxide surfaces. In this work, we examine net hydrogen atom (H-atom) uptake to an oxygen deficient vanadium oxide assembly, [V 6 O 6 (MeCN)(OCH 3 ) 12 ] 0 . Addition of two H-atom equivalents to [V 6 O 6 (MeCN)(OCH 3 ) 12 ] 0 results in formation of [V 6 O 5 (MeCN)(OH 2 )(OCH 3 ) 12 ] 0 . Assessment of the bond dissociation free energy of the O–H bonds of the resultant aquo moiety reveals that the presence of an O-atom defect weakens the O–H bond strength. Despite a decreased thermodynamic driving force for the reduction of [V 6 O 6 (MeCN)(OCH 3 ) 12 ] 0 , kinetic investigations show the rate of H-atom uptake at the cluster surface is ∼100× faster than its oxidized congener, [V 6 O 7 (OCH 3 ) 12 ] 0 . Electron density derived from the O-atom vacancy is shown to play an important role in influencing H-atom uptake at the cluster surface, lowering activation barriers for H-atom transfer.
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Coordination-induced bond weakening of water at the surface of an oxygen-deficient polyoxovanadate cluster
Hydrogen-atom (H-atom) transfer at the surface of heterogeneous metal oxides has received significant attention owing to its relevance in energy conversion and storage processes. Here, we present the synthesis and characterization of an organofunctionalized polyoxovanadate cluster, (calix)V6O5(OH2)(OMe) 8 (calix = 4- tert -butylcalix[4]arene). Through a series of equilibrium studies, we establish the BDFE(O–H) avg of the aquo ligand as 62.4 ± 0.2 kcal mol −1 , indicating substantial bond weaking of water upon coordination to the cluster surface. Subsequent kinetic isotope effect studies and Eyring analysis indicate the mechanism by which the hydrogenation of organic substrates occurs proceeds through a concerted proton–electron transfer from the aquo ligand. Atomistic resolution of surface reactivity presents a novel route of hydrogenation reactivity from metal oxide surfaces through H-atom transfer from surface-bound water molecules.
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- PAR ID:
- 10397912
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 13
- Issue:
- 43
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 12726 to 12737
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D2SC04843D
