Partial Phosphorization: A Strategy to Improve Some Performance(s) of Thiolated Metal Nanoclusters Without Notable Reduction of Stability

Thiolates endow metal nanoclusters with stability while sometimes inhibit the catalytic activity due to the strong M−S interaction (M: metal atom). To improve the catalytic activity and keep the stability to some extent, one strategy is the partial phosphorization of thiolated metal nanoclusters. Th...

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Bibliographic Details
Published in:Chemistry : a European journal 2022-05, Vol.28 (25), p.e202200212-n/a
Main Authors: He, Zongbing, Yang, Ying, Zou, Jiafeng, You, Qing, Feng, Lei, Li, Man‐Bo, Wu, Zhikun
Format: Article
Language:English
Subjects:
catalysis
Catalytic activity
Chemistry
Intermediates
Light diffraction
Mass spectrometry
Mass spectroscopy
Metals
Nanoclusters
Oxidation
partial phosphorization
Phosphating (coating)
Photoluminescence
Photons
Photooxidation
Reduction (metal working)
Single crystals
Stability
Thioanisole
thiolated gold nanocluster
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Summary:Thiolates endow metal nanoclusters with stability while sometimes inhibit the catalytic activity due to the strong M−S interaction (M: metal atom). To improve the catalytic activity and keep the stability to some extent, one strategy is the partial phosphorization of thiolated metal nanoclusters. This is demonstrated by successful partial phosphorization of Au23(SC6H11)16 and by revealing that the products Au22(SC6H11)14(PPh3)2 and Au22(SC6H11)12(PPh3)4, with varied degree of phosphorization, both show excellent activity in the photocatalytic oxidation of thioanisole without notable reduction of stability. Furthermore, Au22(SC6H11)12(PPh3)4 exhibits better photoluminescence performance than the mother nanocluster Au23(SC6H11)16, indicating that partial phosphorization can also improve some other performance(s) except for the catalytic performance. The intermediates Au22‐xCux(SC6H11)12(PPh3)4 (x=1, 2) in the transformation from Au23(SC6H11)16 (Au22(SC6H11)14(PPh3)2) to Au22(SC6H11)12(PPh3)4 were captured and identified by mass spectrometry and single crystal X‐ray diffraction, which throws light on the understanding of the non‐alloyed anti‐galvanic reaction. A partial phosphorization strategy is introduced to improve the catalytic and PL performances of thiolated metal nanoclusters without notable reduction of stability, by illustrating the partial phosphorization of Au23(SC6H11)16 and its performances improvement. The transformation intermediates were captured and identified, throwing light on the understanding of the non‐alloyed anti‐galvanic reaction.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202200212