Issue 23, 2023

Infrared spectroscopic study of solvation and size effects on reactions between water molecules and neutral rare-earth metals

Abstract

Elucidating the solvation and size effects on the reactions between water and neutral metals is crucial for understanding the microscopic mechanism of the catalytic processes but has been proven to be a challenging experimental target due to the difficulty in size selection. Here, MO4H6 and M2O6H7 (M = Sc, Y, La) complexes were synthesized using a laser–vaporization cluster source and characterized by size-specific infrared-vacuum ultraviolet spectroscopy combined with quantum chemical calculations. The MO4H6 and M2O6H7 complexes were found to have H˙M(OH)3(H2O) and M22-OH)21-OH)31-OH2) structures, respectively. A combination of experiments and theory revealed that the formation of H˙M(OH)3(H2O) and M22-OH)21-OH)31-OH2) is both thermodynamically exothermic and kinetically facile in the gas phase. The results indicated that upon the addition of water to H˙M(OH)3, the feature of the hydrogen radical is retained. In the processes from mononuclear H˙M(OH)3 to binuclear M22-OH)21-OH)31-OH2), the active hydrogen atom undergoes the evolution from hydrogen radical → bridging hydrogen → metal hydride → hydrogen bond, which is indicative of a reduced reactivity. The present system serves as a model for clarifying the solvation and size effects on the reactions between water and neutral rare-earth metals and offers a general paradigm for systematic studies on a broad class of the reactions between small molecules and metals at the nanoscale.

Graphical abstract: Infrared spectroscopic study of solvation and size effects on reactions between water molecules and neutral rare-earth metals

Supplementary files

Article information

Article type
Paper
Submitted
11 Okt. 2023
Accepted
25 Okt. 2023
First published
26 Okt. 2023
This article is Open Access
Creative Commons BY-NC license

Nanoscale Adv., 2023,5, 6626-6634

Infrared spectroscopic study of solvation and size effects on reactions between water molecules and neutral rare-earth metals

T. Wang, S. Li, W. Yan, S. Jiang, H. Xie, G. Li and L. Jiang, Nanoscale Adv., 2023, 5, 6626 DOI: 10.1039/D3NA00873H

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