Confining polyoxometalates in porphyrin-based porous cationic polymer toward boosting visible-light-driven synthesis of sulfoxides and detoxification of mustard gas simulants

Zhu, Qingshan; An, Haiyan; Wei, Yuting; Sun, Hao; Fu, Jie; Xu, Tie-Qi

doi:10.1016/j.jcat.2024.115627

Journal of Catalysis

2024

DOI: 10.1016/j.jcat.2024.115627

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Confining polyoxometalates in porphyrin-based porous cationic polymer toward boosting visible-light-driven synthesis of sulfoxides and detoxification of mustard gas simulants

Qingshan Zhu,

Haiyan An,

Yuting Wei

et al.

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2024

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Cited by 3 publications

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CdWO₄ Sub‐1 nm Nanowires for Visible‐Light CO₂ Photoreduction

Liu,

Zhu,

Zhao

et al. 2024

Angewandte Chemie

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Quantum size effect usually causes energy level splitting and band broadening as material size decreases. However, this may change again by the surface adsorbents, doping and defects, which rarely attracts much attention. Herein, CdWO4 sub‐1 nm nanowires (SNWs) with oleylamine adsorption, PO43‐‐doping and oxygen defects are synthesized by combining Cd(CH3COO)2, H3PW12O40 (PW12) and oleylamine (abbreviated as PO43‐‐CdWO4‐X SNWs). Compared with bulk CdWO4, they exhibit unexpected absorption spectra (extended from 292 nm to 453 nm) and bandgap (reduced from 4.25 eV to 2.74 eV), thus bringing remarkable visible‐light CO2 photoreduction activity. Under 410 nm LED light irradiation, PO43‐‐CdWO4‐40 SNWs exhibit the highest photocatalytic performance with a CO2‐to‐CO generation rate of 1685 µmol g‐1 h‐1. Density functional theory (DFT) calculations demonstrate the adsorbed oleylamine raises the valence band and enhances the adsorption of reaction substrate and intermediates, thus decreasing their reduction energy barriers. Furthermore, PO43‐‐doping and oxygen defects will generate defect energy band below the conduction band of PO43‐‐CdWO4‐40 SNWs, resulting in remarkable visible light absorption and superior photocatalytic CO2 reduction performance. This work highlights the significant impacts of surface adsorbents, doping and defects on the physicochemical and catalytic properties of sub‐nano materials.

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CdWO₄ Sub‐1 nm Nanowires for Visible‐Light CO₂ Photoreduction

Liu,

Zhu,

Zhao

et al. 2024

Angewandte Chemie

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CdWO₄ Sub‐1 nm Nanowires for Visible‐Light CO₂ Photoreduction

Liu,

Zhu,

Zhao

et al. 2024

Angew Chem Int Ed

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Amorphous Mo_aZr_0.8O_x-500 catalyzed selective oxidation of sulfides to sulfoxides mediated by ¹O₂ from direct heterolytic cleavage of H₂O₂

Li,

Qin,

Zhang

et al. 2024

Inorg. Chem. Front.

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Confining polyoxometalates in porphyrin-based porous cationic polymer toward boosting visible-light-driven synthesis of sulfoxides and detoxification of mustard gas simulants

Cited by 3 publications

References 61 publications

CdWO₄ Sub‐1 nm Nanowires for Visible‐Light CO₂ Photoreduction

CdWO₄ Sub‐1 nm Nanowires for Visible‐Light CO₂ Photoreduction

CdWO₄ Sub‐1 nm Nanowires for Visible‐Light CO₂ Photoreduction

Amorphous Mo_aZr_0.8O_x-500 catalyzed selective oxidation of sulfides to sulfoxides mediated by ¹O₂ from direct heterolytic cleavage of H₂O₂

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Confining polyoxometalates in porphyrin-based porous cationic polymer toward boosting visible-light-driven synthesis of sulfoxides and detoxification of mustard gas simulants

Cited by 3 publications

References 61 publications

CdWO4 Sub‐1 nm Nanowires for Visible‐Light CO2 Photoreduction

CdWO4 Sub‐1 nm Nanowires for Visible‐Light CO2 Photoreduction

CdWO4 Sub‐1 nm Nanowires for Visible‐Light CO2 Photoreduction

Amorphous MoaZr0.8Ox-500 catalyzed selective oxidation of sulfides to sulfoxides mediated by 1O2 from direct heterolytic cleavage of H2O2

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CdWO₄ Sub‐1 nm Nanowires for Visible‐Light CO₂ Photoreduction

CdWO₄ Sub‐1 nm Nanowires for Visible‐Light CO₂ Photoreduction

CdWO₄ Sub‐1 nm Nanowires for Visible‐Light CO₂ Photoreduction

Amorphous Mo_aZr_0.8O_x-500 catalyzed selective oxidation of sulfides to sulfoxides mediated by ¹O₂ from direct heterolytic cleavage of H₂O₂