Importance of V4+ and optimal acid environment in the hydroxylation of inert benzene via activation of Csp2-H bond

doi:10.1016/j.cjche.2024.06.021

Chinese Journal of Chemical Engineering ›› 2024, Vol. 74 ›› Issue (10): 216-226.DOI: 10.1016/j.cjche.2024.06.021

Importance of V⁴⁺ and optimal acid environment in the hydroxylation of inert benzene via activation of C_sp2-H bond

Peng Dong^1,2, Yang Xin¹, Yanwei Li¹, Xiaohui Zhang¹, Xiaorui Wang³, Yu Zhao^1,2, Dongqiang Zhang^1,2, Haowen Ma⁴, Guixian Li^1,2

1 School of Petrochemical Engineering, Lanzhou University of Technology, Lanzhou 730050, China;
2 Key Laboratory of Low Carbon Energy and Chemical Engineering of Gansu Province, Lanzhou 730050, China;
3 Lanzhou Petrochemical University of Vocational Technology, Lanzhou 730060, China;
4 Lanzhou Petrochemical Research Center, Petrochemical Research Institute, PetroChina Company Limited, Lanzhou 730060, China

Received:2024-01-13 Revised:2024-06-20 Accepted:2024-06-20 Online:2024-08-08 Published:2024-10-28
Contact: Peng Dong,Tel.:+86 931 7823125;Fax:+86 931 7823001.E-mail:pdong@lut.edu.cn;Guixian Li,E-mail:lgxwyf@163.com
Supported by:
We acknowledge financial support from the Support Program for Hongliu Young Teachers of Lanzhou University of Technology (02/062214), Young Talent Innovation Project of Lanzhou (2023-QN-103), and Major science and technology projects of Gansu Province (22ZD6GA013).

Importance of V⁴⁺ and optimal acid environment in the hydroxylation of inert benzene via activation of C_sp2-H bond

Peng Dong^1,2, Yang Xin¹, Yanwei Li¹, Xiaohui Zhang¹, Xiaorui Wang³, Yu Zhao^1,2, Dongqiang Zhang^1,2, Haowen Ma⁴, Guixian Li^1,2

1 School of Petrochemical Engineering, Lanzhou University of Technology, Lanzhou 730050, China;
2 Key Laboratory of Low Carbon Energy and Chemical Engineering of Gansu Province, Lanzhou 730050, China;
3 Lanzhou Petrochemical University of Vocational Technology, Lanzhou 730060, China;
4 Lanzhou Petrochemical Research Center, Petrochemical Research Institute, PetroChina Company Limited, Lanzhou 730060, China

通讯作者: Peng Dong,Tel.:+86 931 7823125;Fax:+86 931 7823001.E-mail:pdong@lut.edu.cn;Guixian Li,E-mail:lgxwyf@163.com
基金资助:
We acknowledge financial support from the Support Program for Hongliu Young Teachers of Lanzhou University of Technology (02/062214), Young Talent Innovation Project of Lanzhou (2023-QN-103), and Major science and technology projects of Gansu Province (22ZD6GA013).

Abstract

Abstract: Hydroxylation of inert benzene through the activation of the C_sp2-H bond is a representative reaction about the transformation of C-H bonds to C-O bonds, which has far-reaching guiding significance but remains a challenging scientific problem. To overcome this problem, a series of VO-Ga₂O₃/SiO₂-Al₂O₃ were prepared to achieve an efficient and economical hydroxylation path of benzene to phenol. The results showed that the phenol yield was 72.89% (selectivity > 98.1%) under the optimum conditions. The reason is that the C-H bond in the benzene ring is activated by heterolysis over a VO-Ga₂O₃/SiO₂-Al₂O₃ catalyst. Meanwhile, the introduction of aluminum (Al) and gallium (Ga) made a qualitative change in the catalyst, enhancing the electron motion and spin motion of vanadium species, resulting in the increase of V⁴⁺/V⁵⁺ ratio. In addition, the catalyst can provide an optimal acidic environment and a three-dimensional cross-linked surface structure that facilitates product diffusion.

Key words: C_sp2-H activation, V⁴⁺/V⁵⁺ ratio, Acid microenvironment, Catalysis, Support, Catalyst activation

摘要： Hydroxylation of inert benzene through the activation of the C_sp2-H bond is a representative reaction about the transformation of C-H bonds to C-O bonds, which has far-reaching guiding significance but remains a challenging scientific problem. To overcome this problem, a series of VO-Ga₂O₃/SiO₂-Al₂O₃ were prepared to achieve an efficient and economical hydroxylation path of benzene to phenol. The results showed that the phenol yield was 72.89% (selectivity > 98.1%) under the optimum conditions. The reason is that the C-H bond in the benzene ring is activated by heterolysis over a VO-Ga₂O₃/SiO₂-Al₂O₃ catalyst. Meanwhile, the introduction of aluminum (Al) and gallium (Ga) made a qualitative change in the catalyst, enhancing the electron motion and spin motion of vanadium species, resulting in the increase of V⁴⁺/V⁵⁺ ratio. In addition, the catalyst can provide an optimal acidic environment and a three-dimensional cross-linked surface structure that facilitates product diffusion.

关键词: C_sp2-H activation, V⁴⁺/V⁵⁺ ratio, Acid microenvironment, Catalysis, Support, Catalyst activation

Peng Dong, Yang Xin, Yanwei Li, Xiaohui Zhang, Xiaorui Wang, Yu Zhao, Dongqiang Zhang, Haowen Ma, Guixian Li. Importance of V⁴⁺ and optimal acid environment in the hydroxylation of inert benzene via activation of C_sp2-H bond[J]. Chinese Journal of Chemical Engineering, 2024, 74(10): 216-226.

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Importance of V⁴⁺ and optimal acid environment in the hydroxylation of inert benzene via activation of C_sp2-H bond

Importance of V⁴⁺ and optimal acid environment in the hydroxylation of inert benzene via activation of C_sp2-H bond

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