Bridging green light photocatalysis over hierarchical Nb<sub>2</sub>O<sub>5</sub> for the selective aerobic oxidation of sulfides

Ma, Xiaoming; Hao, Huimin; Sheng, Wenlong; Huang, Fengwei; Lang, Xianjun

doi:10.1039/d0ta10757c

Cited by 31 publications

(10 citation statements)

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“…51 TEMPO has a cooperative impact with dye−metal oxide semiconductors on the photocatalytic selective oxidation of sulfides to sulfoxides according to our previous studies. 52,53 However, no previous reports of using a Zr-based MOF photocatalyst with TEMPO to conduct this reaction have been disclosed. Meanwhile, the photocatalysts mentioned above are unable to respond to red light.…”

Section: ■ Introductionmentioning

confidence: 99%

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

Sheng

Wang

et al. 2022

ACS Catal.

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Metal–organic frameworks (MOFs) are promising visible light photocatalysts due to their adaptable building blocks. In principle, further optimization of the activity could be envisaged by integrating a redox mediator into a MOF to assemble cooperative photocatalysis. Considering the abundant mesopores and the accessible hydroxyl binding sites, PCN-222, consisting of Zr6(μ-OH)8 clusters and carboxyl porphyrin ligands, was synthesized to integrate with 4-carboxy-2,2,6,6-tetramethylpiperidine-1-oxyl (HOOC-TEMPO). As a proof of concept, the selective aerobic oxidation of sulfides was selected as the model reaction. Significantly, PCN-222 exhibited a cooperative impact with HOOC-TEMPO on selective aerobic oxidation of sulfides powered by 660 nm red light. In contrast, PCN-226, devoid of accessible hydroxyl sites, only had an inconspicuous cooperation with HOOC-TEMPO. The density functional theory calculations reveal that HOOC-TEMPO could be spontaneously adsorbed on the Zr6(μ-OH)8 clusters via the bidentate model. Due to the lack of binding sites of Zr6(μ-OH)8, TEMPO was proven to be much less effective than HOOC-TEMPO in promoting the oxidation of sulfides over PCN-222. The covalent integration of HOOC-TEMPO into PCN-222 is essential for the effectiveness and durance of cooperative photocatalysis for the selective aerobic oxidation of a wide range of organic sulfides. This work suggests that MOFs, a versatile platform, could be integrated with a redox mediator to enable smooth photocatalytic selective transformations.

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Section: ■ Introductionmentioning

confidence: 99%

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

Sheng

Wang

et al. 2022

ACS Catal.

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“…Outstandingly, the photocatalytic efficiency of CCNU-16 is obviously superior to those of the reported MOFs-based photocatalysts UNLPF-10, NNU-45, and Zr 12 -NBC (Table S8†). 28,30,62 In particular, it is higher than that of inorganic semiconductor photocatalysts, such as surface-modified TiO 2 , 63 a – c and common transition-metal oxides semiconductor ARS-Nb 2 O 5 (ref. 63d) (Table S8,† entries 15–19).…”

Section: Resultsmentioning

confidence: 99%

Effective charge and energy transfers within a metal–organic framework for efficient photocatalytic oxidation of amines and sulfides

et al. 2022

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“…We comprehensively evaluated the influence of solvents, oxidants, and light sources on catalysis (Table S2), and the optimal reaction conditions proved to be 5 mL of CH 3 CN, 60 °C, blue LED (5 W), 200 mL of TBHP (tert-butyl hydroperoxide), 10 mg of TEMPO, and 0.07 mmol % catalyst. According to the relevant study on the TiO 2 /dye/TEMPO system, 36 we proposed a probable mechanism for this TOC/TEMPO system (Figure 7). The photosensitive Sa will directly inject an electron into the conduction band of the TOC core under irradiation, engendering the radical cation Sa •+ in this step.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Self-Assembly of Chiral Ferrocene-Functionalized Polyoxotitanium Clusters for Photocatalytic Selective Sulfide Oxidation

Han

Wang

et al. 2022

Inorg. Chem.

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Here, we systematically studied the self-assembly behavior of chiral polyoxytitanium clusters for the first time. Through the cooperative assembly of ferrocenecarboxylic acid and ketoxime ligands, we successfully incorporated the planar chirality of ferrocene (Fc) into the layered {Ti5} building blocks. The resulting {Ti5Fc} clusters can be used as structural units to assemble into large ordered structures in various ways; either a pair of {Ti5Fc} enantiomers are bridged by organic adhesive to form sandwich structures or two homochiral {Ti5Fc} units participate in the assembly to form the large clusters. Depending on the assembly modes, the chirality of {Ti5Fc} can be transferred to large nanoclusters or disappear to form mesostructures. The difference of the assembly modes between the {Ti5Fc} units can also tune the photoelectric activity of the resulting clusters, which has been verified by using {Ti 10 Fc-6/7} as catalysts for photocatalytic selective sulfide oxidation. This work not only is an important breakthrough in the study of the self-assembly of chiral nanoclusters but also provides an important reference for understanding of chiral transfer on the nanoscale.

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Bridging green light photocatalysis over hierarchical Nb₂O₅ for the selective aerobic oxidation of sulfides

Abstract: A highly selective aerobic oxidation of sulfides into sulfoxides has been achieved by bridging green light photocatalysis over hierarchical Nb2O5.

Cited by 31 publications

References 50 publications

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

Effective charge and energy transfers within a metal–organic framework for efficient photocatalytic oxidation of amines and sulfides

Self-Assembly of Chiral Ferrocene-Functionalized Polyoxotitanium Clusters for Photocatalytic Selective Sulfide Oxidation

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Bridging green light photocatalysis over hierarchical Nb2O5 for the selective aerobic oxidation of sulfides

Abstract: A highly selective aerobic oxidation of sulfides into sulfoxides has been achieved by bridging green light photocatalysis over hierarchical Nb2O5.

Cited by 31 publications

References 50 publications

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

Effective charge and energy transfers within a metal–organic framework for efficient photocatalytic oxidation of amines and sulfides

Self-Assembly of Chiral Ferrocene-Functionalized Polyoxotitanium Clusters for Photocatalytic Selective Sulfide Oxidation

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Bridging green light photocatalysis over hierarchical Nb₂O₅ for the selective aerobic oxidation of sulfides