A continuous-flow photocatalytic system for highly selective oxidation of p-xylene to terephthalic acid by decatungstate catalyst

doi:10.1016/S1872-2067(24)60134-8

Abstract

Abstract:

The selective oxidation of para-xylene (PX) to terephthalic acid (TPA) has received increasing attention due to the industrial applications of TPA. However, the oxidation of the C(sp³)-H bond of PX is still a main challenge because of the higher bond dissociation energy. Herein, an efficient photocatalytic system for the oxidation of PX to TPA was developed by using tetrabutylammonium decatungstate (TBADT) photocatalyst using atmospheric oxygen as oxidant and 365 nm LED light irradiation. The resulting TPA product was easily separated from the post-reaction solution through simple filtration treatment with a 93.4% yield in CH₃CN (37.5% 1 mol L⁻¹ HCl) solvent after 19-h photocatalysis. Given the easy separation of TPA and the excellent recycling stability of TBADT, a continuous-flow photoreactor was successfully designed with promising prospect for potential industrial application. Mechanistic studies elucidated that the presence of HCl additive benefits the structural integrity of [W₁₀O₃₂]⁴⁻ anions and the transition from excited states [W₁₀O₃₂]⁴⁻* to wO active species, leading to enhanced photooxidation performance.

Key words: Photocatalysis, Decatungstate, Aerobic oxidation, Continuous-flow catalysis, Self-separation of product

Zheng Li, Yuanyuan Dong, Ying Zeng, Mo Zhang, Hongjin Lv, Guo-Yu Yang. A continuous-flow photocatalytic system for highly selective oxidation of p-xylene to terephthalic acid by decatungstate catalyst[J]. Chinese Journal of Catalysis, 2024, 66: 282-291.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60134-8

https://www.cjcatal.com/EN/Y2024/V66/I11/282

Figures/Tables 10

Scheme 1. (a) The current industrial method for the oxidation of PX. (b) The electrocatalytic method for the oxidation of PX. (c) Our strategy for the photocatalytic oxidation of PX.

Table 1 The photocatalytic oxidation activities of TBADT in various reaction conditions.

Entry	Oxidant	Solvent	Yield (%)
Entry	Oxidant	Solvent	TPA	4-CBA	4-MBA	Others
1	1 atm air	CH₃CN	57.0	1.4	16.2	25.4
2	1 atm oxygen	CH₃CN	57.2	4.5	15.6	22.7
3	1 atm argon	CH₃CN	0	0	0	1.7
4^*	1 atm air	CH₃CN	0	0	0	0
5	1 atm air	CH₃CN (37.5% 1 mol L^-1 HCl)	93.4	2.1	4.3	0.1
6	1 atm air	CH₃CN (37.5% H₂O)	57.1	0.4	16.2	26.3

Fig. 1. (a) The optical images of reaction solution before and after irradiation. (b) The photocatalytic recycling tests of the TBADT catalyst.

Table 2 The photocatalytic activities of other substrates catalyzed by TBADT.

Fig. 2. (a) Schematic diagram of the flow microreactor. (b) The optical images of the continuous-flow microreactor in this work and the observed heteropoly blue caused by the single-electron reduced of TBADT. The length of PTFE pipe that exposed to light is 7.5 m, the reaction liquid flow rate is 0.056 μL min-1, the gas flow rate is 0.206 μL min-1. (c) The yield of TPA as the function of the oxygen content in the flow microreactor.

Fig. 3. (a) UV-vis spectra of TBADT in various solvent. The UV-vis spectra of the evolution of [W10O32]4? during photocatalysis in CH3CN (b), CH3CN (37.5% H2O) (c) and CH3CN (37.5% 1 mol L-1 HCl) (d).

Fig. 4. (a) The general pathway for the C(sp3)-H functionalization under [W10O32]4? photocatalysis. (b) PL spectra of TBADT in various solvents. (c) The time profiles of PX conversion in various solvents. (d) The conversion of PX under TBADT photocatalysis in CH3CN (37.5% 1 mol L-1 HCl) with adding ethanol as the wO quencher. (e) PL spectra of TBADT with the addition of coumarin as ?OH radical fluorescence probe in CH3CN (37.5% H2O). (f) The conversion of PX catalyzed by TBADT in CH3CN (37.5% H2O) with NB as ?OH radical quencher.

Fig. 5. (a) The time profiles of photocatalytic oxidation of PhCH3 by TBADT. (b) The influences of ethanol as the wO quencher on the photocatalytic oxidation of PhCHO. (c) The DRIFTs spectra of PX transformation during the photocatalytic oxidation process.

Fig. 6. Photocatalytic oxidation of PX or PX-d10 at different time intervals.

Scheme 2. The proposed photocatalytic oxidation mechanism of PX catalyzed by TBADT.

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