Green and Efficient Oxidation of Sulfides to Sulfoxides Catalyzed by Vanadium-Based Complex

doi:10.16553/j.cnki.issn1000-985x.2025.0119

Abstract

Abstract: Using environmentally friendly H₂O₂ as the oxidant， the selective oxidative catalytic performance of the vanadium-based crystalline material ［Ni（H₂O）₄］［VO（PO₄）］₂ （complex 1） for sulfides was investigated. The results show that under 60 ℃， methyl phenyl sulfide achieves a conversion of up to 99% within 30 min， with a selectivity of 97% for the corresponding methyl phenyl sulfoxide. Substrate expansion experiments demonstrate that the catalytic activity of complex 1 is not significantly affected by steric hindrance or electronic effects. After five catalytic cycles， complex 1 still maintains its structural integrity and catalytic activity， confirming its practicality as a reusable catalyst. The research results of this paper provide new insights into the development of efficient， selective， and reusable sulfide oxidation catalysts， and have potential application value in fields such as organic synthesis and environmental governance.

Key words: vanadium-based catalyst; crystal structure; sulfide; catalysis; selective oxidation

CLC Number:

O641

ZHANG Shan, FENG Jianxuan, LIU Ling, GUO Yu. Green and Efficient Oxidation of Sulfides to Sulfoxides Catalyzed by Vanadium-Based Complex[J]. Journal of Synthetic Crystals, 2025, 54(11): 1983-1989.

Figures/Tables 6

Fig.1 Structure and characterization of complex 1. （a） 3D open framework；（b）｛VOPO4｝nn- infinite extended anionic layer；（c） PXRD patterns

Fig.2 Catalytic performance of complex 1. （a） GC signals for the catalytic oxidation of MPS to form MPSO and MPSO2；（b） MPS conversion over time

Table 1 Complex 1 in catalyzing the conversion of MPS to MPSO under different conditions

Entry	Contents of catalyst/μmol	Contents of oxidant/mmol	Temperature/℃	Conversion/%	Selectivity/%
1	28	H₂O₂ （0.42）	Room temperature	40	92
2	28	H₂O₂ （0.42）	50	92	97
3	28	H₂O₂ （0.42）	60	99	97
4	28	H₂O₂ （0.42）	70	99	95
5	28	H₂O₂ （0.40）	60	80	97
6	28	H₂O₂ （0.45）	60	99	93
7	24	H₂O₂ （0.42）	60	88	95
8	32	H₂O₂ （0.42）	60	99	97
9	28	TBHP （0.42）	60	75	92
10	0	H₂O₂ （0.42）	60	25	—
11	28	0	60	<1	—
12	0	0	60	0	—
13 Ethanol	28	H₂O₂ （0.42）	60	89	97
Reaction condition： MPS （0.4 mmol）， solvent （5 mL）， 30 min

Table 2 Complex 1 catalyzes the conversion of various sulfides to sulfoxides

Entry	Conversion/%	Selectivity/%
1	99	97
2	92	98
3	93	98
4	94	94
5	98	86
6	95	96
Reaction condition： catalyst （28 μmol）， sulfides （0.4 mmol）， methanol （5 mL）， H₂O₂（0.42 mmol）， 30 min， 60 ℃

Fig.3 Cyclic stability test of complex 1. （a） Leaching test；（b） recycling catalytic performance；（c） PXRD patterns before and after catalysis

Fig.4 A possible mechanistic study of sulfide oxidation catalyzed by complex 1. （a） Conversion of MPS under different catalysts；（b） possible reaction mechanisms of sulfide catalytic oxidation；（c） UV-Vis spectra of complex 1 before and after the addition of H2O2

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