Aromatic bromination with hydrogen production on organic-inorganic hybrid perovskite-based photocatalysts under visible light irradiation

doi:10.1016/S1872-2067(22)64101-9

Abstract

Abstract:

Aromatic bromides are important chemicals in nature and chemical industries. However, their traditional synthesis routes suffer from low atomic economy and pollutant formation. Herein, we show that organic-inorganic hybrid perovskite methylammonium lead bromide (MAPbBr₃) nanocrystals stabilized in aqueous HBr solution can achieve simultaneous aromatic bromination and hydrogen evolution using HBr as the bromine source under visible light irradiation. By hybridizing MAPbBr₃ with Pt/Ta₂O₅ and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate as electron- and hole-transporting motifs, aromatic bromides were achieved from aromatic compounds with high yield (up to 99%) and selectivity (up to 99%) with the addition of N,N-dimethylformamide or its analogs. The mechanistic studies revealed that the bromination proceeds via an electrophilic attack pathway and that HOBr may be the key intermediate in the bromination reaction.

Key words: Photocatalysis, Bromination, Hydrogen, Organic-inorganic hybrid perovskite material, Methylammonium lead bromide

Yanfei Zhang, Hong Wang, Yan Liu, Can Li. Aromatic bromination with hydrogen production on organic-inorganic hybrid perovskite-based photocatalysts under visible light irradiation[J]. Chinese Journal of Catalysis, 2022, 43(7): 1805-1811.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64101-9

https://www.cjcatal.com/EN/Y2022/V43/I7/1805

Figures/Tables 7

Fig. 1. XRD pattern (a) and UV-vis diffuse reflectance spectrum (b) of the as-synthesized MAPbBr3 powder.

Fig. 2. Photocatalytic bromination performance over several catalysts. Reaction conditions: MAPbBr3 (150 mg), Pt (0.75 wt%)/Ta2O5 (7.5 mg), PEDOT:PSS (200 μL), saturated aqueous HBr solution (5 mL), substrate (0.05 mmol), 300-W Xe lamp (λ > 420 nm, 160 mW cm-2), Ar atmosphere, room temperature, 6 h. Conversion and selectivity were determined using crude proton nuclear magnetic resonance (1H NMR) spectroscopy. The amount of H2 was determined using a gas chromatograph.

Fig. 3. (a) Effect of organic solvents on the photocatalytic reaction. (b) Effect of the amount of DMF on the photocatalytic reaction. (c) Effect of the DMF analogs S on the photocatalytic reaction. Reaction conditions: MAPbBr3 (150 mg), Pt (0.75 wt%)/Ta2O5 (7.5 mg), PEDOT:PSS (200 μL), saturated aqueous HBr solution (5 mL), substrate (0.05 mmol), organic solvent, 300-W Xe lamp (λ > 420 nm, 160 mW cm-2), Ar atmosphere, room temperature, 6 h. Conversion and selectivity were determined using crude 1H NMR spectroscopy. The amount of H2 was determined using a gas chromatograph.

Table 1 Photocatalytic bromination of aromatic compounds a.

Entry	Time (h)	Conversion ^b (%)	Selectivity ^b (%)	[H₂] ^c (%)
1	6	>99	>99	>99
2	12	86	>99	76
3	16	>99	>99	>99
4	12	>99	>99	77
5	18	>99	>99	>99
6	6	>99	>99	80
7	6	>99	>99	89
8	12	>99	>99	97
9	19	>99	>99	>99
10	6	>99	>99	94
11	36	>99	>99	80
12	23	>99	>99	91
13	12	>99	>99	>99
14	12	45	>99	>99
15	12	>99	>99	80
16	12	>99	>99	>99
17	24	>99	>99	90

Table 2 Direct photocatalytic bromination of the natural product, drug and intermediate of materials.

Entry	Time (h)	Conversion^b(%)	Selectivity^b(%)	[H₂]^c(%)
1	48	73	>99	>99
2	72	72	>99	>99
3	24	>99	>99	>99

Fig. 4. Mechanistic studies. (a) UV-Vis spectra of the solutions for photocatalytic reactions (before reaction, under light, and under light with H3PO2) and 3% bromine water. (b) The Hammett equation of the substituted anisole. Reaction conditions for figure (b): MAPbBr3 (150 mg), Pt(0.75 wt%)/Ta2O5 (7.5 mg), PEDOT:PSS (200 μL), saturated aqueous HBr solution (5 mL), substrate (0.05 mmol), DBF (0.05 mmol), 300-W Xe lamp (λ > 420 nm, 160 mW cm-2), Ar atmosphere, room temperature, 6 h.

Fig. 5. Schematic illustration of the reaction mechanism.

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