在连续流光催化体系使用十钨酸盐将对二甲苯高选择性催化氧化为对苯二甲酸

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

催化学报 ›› 2024, Vol. 66: 282-291.DOI: 10.1016/S1872-2067(24)60134-8

在连续流光催化体系使用十钨酸盐将对二甲苯高选择性催化氧化为对苯二甲酸

李正^a, 董媛媛^a, 曾影^a, 张默^a, 吕红金^a^,^b^,^*(), 杨国昱^a^,^*()

^a北京理工大学化学与化工学院, 光电转换材料北京市重点实验室, 原子分子簇科学教育部重点实验室, 北京 102488
^b北京理工大学唐山研究院, 河北唐山 063000

收稿日期:2024-07-28 接受日期:2024-09-06 出版日期:2024-11-18 发布日期:2024-11-10
通讯作者: *电子信箱: hlv@bit.edu.cn (吕红金);ygy@bit.edu.cn (杨国昱).
基金资助:
河北省自然科学基金(B2024105003);国家自然科学基金(21871025);国家自然科学基金(21831001);国家自然科学基金(22471019);国家海外高层次人才引进计划青年项目;北理工高层次人才科研启动计划项目

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

Zheng Li^a, Yuanyuan Dong^a, Ying Zeng^a, Mo Zhang^a, Hongjin Lv^a^,^b^,^*(), Guo-Yu Yang^a^,^*()

^aMOE Key Laboratory of Cluster Science, Beijing Key Laboratory of Photoelectric/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China
^bTangshan Research Institute, Beijing Institute of Technology, Tangshan 063000, Hebei, China

Received:2024-07-28 Accepted:2024-09-06 Online:2024-11-18 Published:2024-11-10
Contact: *E-mail: hlv@bit.edu.cn (H. Lv);ygy@bit.edu.cn (G.-Y. Yang).
Supported by:
Hebei Natural Science Foundation(B2024105003);National Natural Science Foundation of China(21871025);National Natural Science Foundation of China(21831001);National Natural Science Foundation of China(22471019);Recruitment Program of Global Experts(Young Talents);BIT Excellent Young Scholars Research Fund, and the instrumental support from the Analysis and Testing Center of Beijing Institute of Technology

摘要/Abstract

摘要：

使用分子氧将有机底物氧化为增值化学品的催化氧化反应受到了广泛关注, 对二甲苯(PX)选择性氧化为对苯二甲酸(TPA)因其工业应用而被认为是最重要的氧化反应之一. 由于PX中的C(sp³)−H键反应活性低(键离解能(BED) = 95 kcal mol⁻¹), 在工业中需在高温(200 °C)、高压(15−30 atm)和特定设备条件下使用Co-Mn-Br催化剂在乙酸中进行反应, 尽管该方法具有对PX高转化率和对TPA高选择性, 但仍面临高碳排放、严重环境污染和大量有害副产物生成等问题. 除了传统的热催化氧化, 电催化氧化由于具有温和的催化体系而被广泛关注, 然而该方法仍然存在使用昂贵的电解质和底物的转化率或产物的选择性不令人满意的问题. 因此, 开发一种温和高效的催化体系, 使用大气O₂将PX和其他甲苯衍生物的C(sp³)−H氧化为相应的羧酸具有重要的研究意义和潜在应用价值.

本文成功构建了一种在室温下光驱动PX催化氧化为TPA的方法, 并对多种甲苯衍生物的C(sp³)−H氧化表现出较好的活性, 该方法使用廉价的十钨酸的四丁基铵盐(TBADT)作为光催化剂、365 nm紫外光为激发光源和常压空气作为氧化剂, 在CH₃CN (37.5% 1 mol L^-1 HCl)混合溶剂反应19 h可获得93.4%产率的TPA. 此外, 合理的溶剂体系选择不仅有助于提升TBADT光催化氧化PX的效率, 还可以实现TPA产物与催化体系的自分离, 经过简单的离心过滤回收操作, 可将滤液中的均相TBADT催化剂进行重复使用, 并表现出较好的循环稳定性. 为验证催化体系的产业化应用潜力, 进一步设计出一种流动反应器, 在使用纯氧作为氧化剂的条件下, TPA的收率可进一步提升至95.6%. 通过多项控制实验和系列表征测试研究了TBADT在CH₃CN (37.5% 1 mol L^-1 HCl)混合溶剂中光驱动PX催化氧化为TPA效率提升的内在原因. 反应溶液的紫外可见吸收光谱结果表明, CH₃CN (37.5%1 mol L^-1 HCl)混合溶剂中水和质子酸添加剂HCl有利于催化剂在光催化氧化过程中的稳定性. 此外, TBADT在不同溶剂条件下的光致发光谱结果表明, CH₃CN (37.5% 1 mol L^-1 HCl)混合溶剂中水和质子酸添加剂HCl能够有效抑制激发态[W₁₀O₃₂]^4-*光生电子-空穴对的复合, 从而提高光氧化性能. 催化氧化动力学同位素效应(k_H/k_D = 1.87)结果表明, TBADT光驱动PX的C(sp³)−H活化过程通过氢原子转移的方式进行, 此外, 原位漫反射红外光谱进一步阐明了光驱动PX催化氧化为TPA的路径, 表明PX中C(sp³)−H通过醛基中间体转化为羧基产物.

综上, 本工作不仅发展了一种在温和条件下高效的光驱动PX催化氧化为TPA的催化策略, 还为不同溶剂条件下十钨酸的光催化氧化活性物种的变化以及如何提高十钨酸的光催化氧化活性提供新见解.

关键词: 光催化, 十钨酸, 有氧氧化, 连续流催化, 产物自分离

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

李正, 董媛媛, 曾影, 张默, 吕红金, 杨国昱. 在连续流光催化体系使用十钨酸盐将对二甲苯高选择性催化氧化为对苯二甲酸[J]. 催化学报, 2024, 66: 282-291.

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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图/表 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.

参考文献

[1]	R. A. F. Tomás, J. C. M. Bordado, J. F. P. Gomes, Chem. Rev., 2013, 113, 7421-7469.
[2]	R. A. Sheldon, Green Chem., 2014, 16, 950-963.
[3]	N. A. M. Fadzil, M. H. A. Rahim, G. P. Maniam, Chin. J. Catal., 2014, 35, 1641-1652.
[4]	K. C. Hwang, A. Sagadevan, P. Kundu, Green Chem., 2019, 21, 6082-6088.
[5]	H. M. Lapa, L. M. D. R. S. Martins, Molecules, 2023, 28, 1922.
[6]	J.-Y. Yeh, S. S. Chen, S.-C. Li, C. H. Chen, T. Shishido, D. C. W. Tsang, Y. Yamauchi, Y.-P. Li, K. C. W. Wu, Angew. Chem. Int. Ed., 2021, 60, 624-629.
[7]	L. Tao, T.-H. Yan, W. Li, Y. Zhao, Q. Zhang, Y.-M. Liu, M. M. Wright, Z.-H. Li, H.-Y. He, Y. Cao, Chem, 2018, 4, 2212-2227.
[8]	A. L. Plekhov, O. V. Kushch, I. O. Opeida, M. A. Kompanets, Russ. J. Appl. Chem., 2014, 87, 982-985.
[9]	M. A. Betiha, N. G. Kandile, A. M. Badawi, S. M. Solyman, A. S. Afify, New J. Chem., 2018, 42, 6343-6353.
[10]	K. Deori, D. Gupta, B. Saha, S. K. Awasthi, S. Deka, J. Mater. Chem. A, 2013, 1. 7091-7099.
[11]	M. Li, F. Niu, X. Zuo, P. D. Metelski, D. H. Busch, B. Subramaniam, Chem. Eng. Sci., 2013, 104, 93-102.
[12]	Y. Lv, M. Peng, W. Yang, M. Liu, A. Kong, Y. Fu, W. Li, J. Zhang, Appl. Catal. B, 2024, 340, 123229.
[13]	M. Balaganesh, S. Lawrence, C. Christopher, A. J. Bosco, K. Kulangiappar, K. J. S. Raj, Electrochim. Acta, 2013, 111, 384-389.
[14]	X. Xu, J. Zhang, Z. Wang, K. Dai, Acta Phys.-Chim. Sin, 2024, 40, 2309031.
[15]	T. Yang, J. Wang, Z. Wang, J. Zhang, K. Dai, Chin. J. Catal., 2024, 58, 157-167.
[16]	J. Wang, Z. Wang, J. Zhang, K. Dai, Chin. J. Struct. Chem., 2023, 42, 100202.
[17]	J. Wang, Z. Wang, K. Dai, J. Zhang, J. Mater. Sci. Technol., 2023, 165, 187-218.
[18]	Z. Wang, J. Zhang, K. Dai, Acta Phys.-Chim. Sin, 2023, 39, 2209037.
[19]	S. Li, K. Dong, M. Cai, X. Li, X. Chen, eScience, 2024, 4, 100208.
[20]	M. Cai, Y. Liu, K. Dong, X. Chen, S. Li, Chin. J. Catal., 2023, 52, 239-251.
[21]	C. Zhuang, Y. Chang, W. Li, S. Li, P. Xu, H. Zhang, Y. Zhang, C. Zhang, J. Gao, G. Chen, T. Zhang, Z. Kang, X. Han, ACS Nano, 2024, 18, 5206-5217.
[22]	M. Zhang, H. Li, J. Zhang, H. Lv, G.-Y. Yang, Chin. J. Catal., 2021, 42, 855-871.
[23]	M. Ren, T. Liu, Y. Dong, Z. Li, J. Yang, Z. Diao, H. Lv, G.-Y. Yang, Chin. J. Catal., 2024, 61, 312-321.
[24]	D.-M. Yan, C. Xiao, J.-R. Chen, Chem, 2018, 4, 2496-2498.
[25]	I. B. Perry, T. F. Brewer, P. J. Sarver, D. M. Schultz, D. A. DiRocco, D. W. C. MacMillan, Nature, 2018, 560, 70-75.
[26]	P. J. Sarver, V. Bacauanu, D. M. Schultz, D. A. DiRocco, Y.-H. Lam, E. C. Sherer, D. W. C. MacMillan, Nat. Chem., 2020, 12, 459-467.
[27]	H. Cao, Y. Kuang, X. Shi, K. L. Wong, B. B. Tan, J. M. C. Kwan, X. Liu, J. Wu, Nat. Commun., 2020, 11, 1956.
[28]	G. Laudadio, Y. Deng, K. van der Wal, D. Ravelli, M. Nuño, M. Fagnoni, D. Guthrie, Y. Sun, T. Noël, Science, 2020, 369, 92-96.
[29]	Q. Wang, S. Ni, X. Wang, Y. Wang, Y. Pan, Sci. China Chem., 2022, 65, 678-685.
[30]	Y. G. Yuan Xiaoya, Yu Bing, Chin. J. Org. Chem., 2020, 40, 3620-3632.
[31]	D. Zhao, J. Zhu, Z. Huang, Q. Wang, Z. Liu, C. Zhang, Y. Liu, Z. Fu, Inorg. Chem., 2024, 63, 10881-10896.
[32]	J. Zhu, Z. Yi, M. Luo, Y. Deng, J. She, Y. Liu, C. Zhang, B. Yang, S. Tang, Z. Fu, Green Chem., 2022, 24, 2988-3000.
[33]	D. Ravelli, M. Fagnoni, T. Fukuyama, T. Nishikawa, I. Ryu, ACS Catal., 2018, 8, 701-713.
[34]	W. Wu, Z. Fu, S. Tang, S. Zou, X. Wen, Y. Meng, S. Sun, J. Deng, Y. Liu, D. Yin, Appl. Catal. B, 2015, 164, 113-119.
[35]	S. Yurdakal, B. S. Tek, O. Alagöz, V. Augugliaro, V. Loddo, G. Palmisano, L. Palmisano, ACS Sustain. Chem. Eng., 2013, 1, 456-461.
[36]	G. Laudadio, S. Govaerts, Y. Wang, D. Ravelli, H. F. Koolman, M. Fagnoni, S. W. Djuric, T. Noël, Angew. Chem. Int. Ed., 2018, 57, 4078-4082.
[37]	J. Fuchs, H. Hartl, W. Schiller, Angew. Chem. Int. Ed., 1973, 12, 420-420.
[38]	B. Yang, Z. Fu, A. Su, J. She, M. Chen, S. Tang, W. Hu, C. Zhang, Y. Liu, Appl. Catal. B, 2019, 242, 249-257.
[39]	V. D. Waele, O. Poizat, M. Fagnoni, A. Bagno, D. Ravelli, ACS Catal., 2016, 6, 7174-7182.
[40]	T. Yamase, T. Kurozumi, J. Chem. Soc. Dalton Trans., 1983, 2205-2209.
[41]	A. Molinari, E. Sarti, N. Marchetti, L. Pasti, Appl. Catal. B, 2017, 203, 9-17.
[42]	A. Molinari, R. Argazzi, A. Maldotti, J. Mol. Catal. A, 2013, 372, 23-28.
[43]	J. Wang, Y. Wu, L. Bu, S. Zhu, W. Zhang, S. Zhou, N. Gao, Water Res., 2021, 190, 116708.
[44]	Y. Nosaka, A. Y. Nosaka, Chem. Rev., 2017, 117, 11302-11336.
[45]	C. B. Musgrave, III, K. Olsen, N. S. Liebov, J. T. Groves, W. A. Goddard, III, T. B. Gunnoe, ACS Catal., 2023, 13, 6382-6395.
[46]	I. Texier, J. A. Delaire, C. Giannotti, Phys. Chem. Chem. Phys., 2000, 2, 1205-1212.
[47]	R. Yuan, S. Fan, H. Zhou, Z. Ding, S. Lin, Z. Li, Z. Zhang, C. Xu, L. Wu, X. Wang, X. Fu, Angew. Chem. Int. Ed., 2013, 52, 1035-1039.
[48]	J. She, Z. Fu, J. Li, B. Zeng, S. Tang, W. Wu, H. Zhao, D. Yin, S. R. Kirk, Appl. Catal. B, 2016, 182, 392-404.
[49]	S. Tang, J. She, Z. Fu, S. Zhang, Z. Tang, C. Zhang, Y. Liu, D. Yin, J. Li, Appl. Catal. B, 2017, 214, 89-99.
[50]	X. Huang, Y. Wang, X. Li, D. Guan, Y. Li, X. Zheng, M. Zhao, C. Shan, B. Pan, Environ. Sci. Technol., 2019, 53, 2036-2044.

在连续流光催化体系使用十钨酸盐将对二甲苯高选择性催化氧化为对苯二甲酸

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

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