Conversion of V6 to V10 cluster: Decavanadate-based Mn-polyoxovanadate as robust heterogeneous catalyst for sulfoxidation of sulfides

Li, Jikun; Wei, Chuanping; Wang, Yuying; Zhang, Mei; Lv, Xinrong; Hu, Changwen

doi:10.1016/j.inoche.2017.11.009

Cited by 12 publications

(5 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…47 In our subsequent works, we also explored the heterogeneous catalytic activity of POVH materials containing {V 6 O 13 (OMe) 6 }, {V 10 O 28 } and {V 4 O 12 } anion clusters toward the oxidative detoxification of CEES. 24,36,37,48…”

Section: Povh Materials With O-bridging Metal–organic Complexesmentioning

confidence: 99%

Recent advances in oxidative catalytic applications of polyoxovanadate-based inorganic–organic hybrids

Li,

Wei,

Han

et al. 2023

Dalton Trans.

View full text Add to dashboard Cite

show abstract

Section: Povh Materials With O-bridging Metal–organic Complexesmentioning

confidence: 99%

Recent advances in oxidative catalytic applications of polyoxovanadate-based inorganic–organic hybrids

Li,

Wei,

Han

et al. 2023

Dalton Trans.

View full text Add to dashboard Cite

show abstract

“…Similarly, several vanadium-substituted polyoxometalates are known to exhibit excellent ODS activities by forming catalytically active peroxovanadium species with H 2 O 2 . , Nevertheless, reports on isopolyoxovanadates-based catalysts for sulfide oxidation are scarce in the literature. , There are only countable reports on [V 10 O 28 ] 6– cluster-based ODS catalysts so far. In these reports, the [V 10 O 28 ] 6– cluster is clubbed with different moieties such as graphene-like boron nitride, three-dimensional (3D)-porous carbon nitride, long alkyl chain ammonium counterions, or even an Mn complex, to make it heterogeneous. ,− Recently, we successfully employed a simple strategy of using aryl sulfonium counterions (ASCIs) to control the solubility of a series of Keggin-type clusters and make them exceptional heterogeneous photocatalysts for Cr(VI) reduction . In continuation of that, herein, we wanted to explore ASCIs bearing salicylaldehyde-type functional moieties to tune the solubility, redox properties, and catalytic properties of a series of [V 10 O 28 ] 6– cluster-based POV hybrids.…”

Section: Introductionmentioning

confidence: 99%

Multifunctional Aryl Sulfonium Decavanadates: Tuning the Photochromic and Heterogeneous Oxidative Desulfurization Catalytic Properties Using Salicylaldehyde-type Functional Moieties on Counterions

Routh

Pradeep

2023

Inorg. Chem.

View full text Add to dashboard Cite

Multifunctional materials based on polyoxovanadates (POVs) have rarely been reported. Herein, we used aryl sulfonium counterions (ASCIs) bearing a salicylaldehyde-type functionality to tune the properties of decavanadate ([V10O28]6–)-based hybrids for their application in photochromism and heterogeneous oxidative desulfurization (ODS) catalysis. The counterions FHPDS ((3-formyl-4-hydroxyphenyl)dimethylsulfonium), DFHPDS ((3,5-diformyl-4-hydroxyphenyl)dimethylsulfonium), and EFPDS ((4-ethoxy-3-formylphenyl)dimethylsulfonium) were clubbed with the decavanadate cluster to generate the hybrids (FHPDS)4[H2V10O28](H2O)4 (HY1), (DFHPDS)4[H2V10O28](H2O)3 (HY2), and (EFPDS)4[H2V10O28](H2O)6 (HY3). The photochromic properties of these hybrids were tested under 365 nm irradiation, which showed a color change from yellow to green. Different hybrids exhibited different photocoloration half-life (t 1/2) values in the range of 0.77–28.38 min, suggesting the dependence of the photocoloration properties upon functional groups on the counterions. The hybrid HY2, having a 2,6-diformyl phenol moiety on the ASCI, exhibited an impressive t 1/2 of 0.77 min. UP to 70% reversibility of photocoloration was achieved for the best photochromic hybrid HY2 in 48 h at 70 °C under an oxygen atmosphere. Theoretical and experimental data suggested that some of these aryl sulfonium POVs follow a different e––h+ stabilization mechanism than traditional sulfonium POM hybrids. Further, the salicylaldehyde-type ASCIs control the solubility of the decavanadate hybrids, which enables their application as heterogeneous catalysts for the selective oxidation of various sulfides. The nature of the substituents on the ASCIs also affected their catalytic activities; the counterion that facilitates the reversible V4+/V5+ switching enhances the catalytic ODS efficiency of the hybrids. Using HY2 as the catalyst, up to 99% conversion and 96% selectivity toward sulfones were achieved in dibenzothiophene (DBT) oxidation. The present study suggests a new promising approach for controlling POVs’ photoresponsive and catalytic properties by using ASCIs bearing salicylaldehyde-type functional moieties.

show abstract

“…Recognizing the need to strike a balance between the activity and selectivity of the catalyst, and to enhance its durability for recovery and reuse, extended structures featuring POV units as building blocks bridged by complex fragments of various transition metal ions (M n + ) have been constructed. , On the one hand, enabled by the gathering of multiple POV units into one unified platform, the catalytic activity of the extended structure is enhanced over a single POV cluster so that a milder and more environmentally friendly oxidant such as H 2 O 2 or O 2 can be used in the place of the more costly oxidant such as TBHP. On the other hand, any resulting but unwanted overoxidation is to be suppressed due to the isolation or separation between the component POV units.…”

Section: Introductionmentioning

confidence: 99%

Modulating the Catalytic Properties of Polyoxovanadates with Transition-Metal-Complex Units for Selective Oxidation of Sulfides

Pan,

Tian,

Zheng

2024

Inorg. Chem.

View full text Add to dashboard Cite

Selective oxidation of sulfides to sulfoxides is of great significance in the synthesis of pharmaceuticals, desulfurization of fuels, and detoxification of sulfur mustard chemical warfare agents. Designing selective catalysts to achieve the efficient transformation of sulfides to sulfoxides is thus highly desired. Herein, we report three transition metal-complex-functionalized polyoxovanadates,(3) (BPB = 1,4-bis(pyrid-4yl)benzene)), and explore their applications for selective oxidation of sulfides using H 2 O 2 as an oxidant. All three compounds were catalytically effective for the oxidation of methyl phenyl sulfide to methyl phenyl sulfoxide, with 1 being best-performing with complete conversion and a selectivity of 96.7%. In the selective oxidation of a series of aromatic and aliphatic sulfides to corresponding sulfoxides, 1 also showed satisfactory performance; in particular, the chemical warfare agent stimulant 2-chloroethyl ethyl sulfide can be completely and selectively oxidized to the nontoxic 2-chloroethyl ethyl sulfoxide within 20 min at room temperature. Catalyst 1 can be recycled and reused at least six times with uncompromised performance. The perfect performance of 1 is attributed to the synergistic effect of coordinatively unsaturated V and Zn sites in bimetallic oxide, as revealed by comparative structural and catalytic studies.

show abstract

Conversion of V6 to V10 cluster: Decavanadate-based Mn-polyoxovanadate as robust heterogeneous catalyst for sulfoxidation of sulfides

Cited by 12 publications

References 20 publications

Recent advances in oxidative catalytic applications of polyoxovanadate-based inorganic–organic hybrids

Recent advances in oxidative catalytic applications of polyoxovanadate-based inorganic–organic hybrids

Multifunctional Aryl Sulfonium Decavanadates: Tuning the Photochromic and Heterogeneous Oxidative Desulfurization Catalytic Properties Using Salicylaldehyde-type Functional Moieties on Counterions

Modulating the Catalytic Properties of Polyoxovanadates with Transition-Metal-Complex Units for Selective Oxidation of Sulfides

Contact Info

Product

Resources

About