Near-unity photocatalytic dehydrocoupling of thiophenols into disulfides and hydrogen using coupled CdS Nanorods and Ni-containing polyoxometalate

doi:10.1016/S1872-2067(24)60025-2

Abstract

Abstract:

Simultaneously harnessing the photogenerated electrons and holes to convert thiols into the value-added disulfides with the concomitant formation of H₂ represents a highly promising strategy for maximizing the conversion of solar energy into chemical energy. Herein, we report an effective catalytic system comprising CdS nanorods (NRs) and Ni-containing polyoxometalate (Na₆K₄[Ni₄(H₂O)₂(PW₉O₃₄)₂] (Ni₄P₂)) (Ni₄P₂/CdS), which exhibited efficient photocatalytic activities towards the near-unity dehydrocoupling of 4-methoxythiophenol (4-MTP) into disulfide and H₂ evolution. The photooxidative dehydrocoupling of 4-MTP can be finished after 4 h photocatalysis, leading to 98.39% conversion of 4-MTP with the yield of disulfide and H₂ reaching 24.45 and 25.96 μmol, respectively. The Ni₄P₂/CdS catalytic system also showed good photocatalytic recycling stability. Comprehensive experimental and characterization results indicated that the synergistic cooperation between CdS NRs and Ni₄P₂ facilitated the separation and migration of the photogenerated electron-hole pairs, thereby improving the photocatalytic dehydrocoupling of 4-MTP to disulfide coupling with hydrogen production.

Key words: Dehydrocoupling, Polyoxometalate, CdS, Hydrogen evolution, Photocatalysis

Mengzhen Ren, Tianfu Liu, Yuanyuan Dong, Zheng Li, Jiaxin Yang, Zhenheng Diao, Hongjin Lv, Guo-Yu Yang. Near-unity photocatalytic dehydrocoupling of thiophenols into disulfides and hydrogen using coupled CdS Nanorods and Ni-containing polyoxometalate[J]. Chinese Journal of Catalysis, 2024, 61: 312-321.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60025-2

https://www.cjcatal.com/EN/Y2024/V61/I6/312

Figures/Tables 8

Fig. 1. (a) PXRD pattern of CdS NRs. The high-resolution Cd 3d (b) and S 2p (c) XPS spectra of CdS NRs. TEM (d) and HR-TEM (e) images of CdS NRs. (f) The lattice fringes of CdS NRs in the enlarged image of the red area in (e). The HAADF-STEM (g) and element mapping (h,i) images of CdS NRs.

Scheme 1. The equation of the dehydrocoupling of 4-MTP into 4-MPD and H2 evolution.

Fig. 2. The photocatalytic dehydrocoupling of 4-MTP as a function of usage amount of CdS NRs (a,b) and the H2O content (c,d). Standard conditions: 50 μmol 4-MTP, 10 mg CdS NRs, 6 mL CH3CN/H2O (1% vol. H2O), 10 μmol L-1 Ni4P2, under the illumination of blue LED light (450 nm) at 20 °C, 3 h, and using CH4 as an internal standard for GC quantification of H2 gas.

Fig. 3. (a) Comparison experiments using Ni4P2 and NiCl2 (40 μmol L?1, equivalent moles of Ni) as H2 evolution catalysts for 4 h photocatalysis. (b, c) The effects of the concentration of Ni4P2 on the photocatalytic activities. Standard conditions: 50 μmol 4-MTP, 10 mg CdS NRs, 6 mL CH3CN/H2O (1% vol. H2O), 10 μmol L?1 Ni4P2, under the illumination of blue LED light (450 nm) at 20 °C, 3 h, and using CH4 as an internal standard for GC quantification of H2gas. (d) The time profiles of the photooxidative dehydrocoupling of 4-MTP. (e) The photocatalytic recycling tests using fresh and isolated 10 mg CdS NRs + 10 μmol L?1 Ni4P2 catalyst. (f) FT-IR spectra of Ni4P2 before and after photocatalytic reaction.

Table 1 The photooxidative dehydrocoupling of other thiophenols using Ni4P2/CdS catalytic system a.

Entry	-R	Con.^b (%)	Sel.^c (%)	H₂ (μmol)	Disulfides (μmol)	e^-/h^{+ d}
1	-NH₂	62.75	99.64	16.59	16.81	0.99
2	-C₂H₅	62.89	97.60	15.76	15.73	1.00
3	-CH₃	77.23	98.99	19.25	19.31	1.00
4	-Cl	27.34	98.50	7.17	6.84	1.05
5	-F	32.26	98.94	7.77	7.98	0.97

Fig. 4. UV-vis spectrum (a) and the Mott-Schottky plots (b) of CdS NRs. The inset in (a) is the Tauc plots for CdS NRs. (c) The schematic potential diagram of the photooxidation of 4-MTP integrated with H2 evolution using Ni4P2/CdS catalytic system. The PL spectra (d), fittings of normalized photoluminescence decay kinetics (e), and the photocurrent tests (f) of CdS NRs, CdS NRs + Ni4P2, and CdS NRs + substrate.

Fig. 5. (a) The photocatalytic activities of control experiments. (b) The EPR signals of the reaction solution in the dark and light illustration after 5 min in the presence of CdS NRs and Ni4P2/CdS.

Scheme 2. The proposed photocatalytic mechanism of the present Ni4P2/CdS catalytic system towards the oxidative dehydrocoupling of 4-MTP and H2 evolution reaction.

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