Dec, 2013
Success in Making Zn+ from Atomic Zn-0 Encapsulated in an MFI-Type Zeolite with UV Light Irradiation
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
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- Volume
- 135
- Number
- 49
- First page
- 18481
- Last page
- 18489
- Language
- English
- Publishing type
- Research paper (scientific journal)
- DOI
- 10.1021/ja4077342
- Publisher
- AMER CHEMICAL SOC
For the first time, the paramagnetic Zn+ species was prepared successfully by the excitation with ultraviolet light in the region ascribed to the absorption band resulting from the 4s-4p transition of an atomic Zn-0 species encapsulated in an MFI-type zeolite. The formed species gives a specific electron spin resonance band at g = 1.998 and also peculiar absorption bands around 38,000 and 32,500 cm(-1) which originate from 4s-4p transitions due to the Zn+ species with paramagnetic nature that is formed in MFI. The transformation process (Zn-0 -> Zn+) was explained by considering the mechanism via the excited triplet state (P-3) caused by the intersystem crossing from the excited singlet state produced through the excitation of the 4s-4p transition of an atomic Zn-0 species grafted in MFI by UV light. The transformation process was well reproduced with the aid of a density functional theory calculation. The thus-formed Zn+ species which has the doublet spin state exhibits characteristic reaction nature at room temperature for an O-2 molecule having a triplet spin state in the ground state, forming an eta(1) type of Zn2+-O-2(-) species. These features clearly indicate the peculiar reactivity of Zn+ in MFI, whereas Zn-0-(H+)(2)MFI hardly reacts with O-2 at room temperature. The bonding nature of [Zn2+-O-2(-)] species was also evidenced by ESR measurements and was also discussed on the basis of the results obtained through DFT calculations.
- Link information
- ID information
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- DOI : 10.1021/ja4077342
- ISSN : 0002-7863
- Web of Science ID : WOS:000328438700042