Lacunary silicotungstic heteropoly salts as high-performance catalysts in oxidation of cyclopentene

doi:10.1016/j.cjche.2022.07.004

中国化学工程学报 ›› 2023, Vol. 56 ›› Issue (4): 152-159.DOI: 10.1016/j.cjche.2022.07.004

• Full Length Article • 上一篇下一篇

Lacunary silicotungstic heteropoly salts as high-performance catalysts in oxidation of cyclopentene

Peiyin Chen^1,2, Yanxiong Fang^1,2, Kaihong Xie^1,2, Yao Chen¹, Yang Liu³, Hongliang Zuo³, Weijian Lu¹, Baoyu Liu¹

1. School of Chemical Engineering and Light Industry, Guangdong Provincial Key Laboratory of Plant Resources Biorefinery, Guangzhou Key Laboratory of Clean Transportation Energy Chemistry, Guangdong University of Technology, Guangzhou 510006, China;
2. Jieyang Branch of Chemistry and Chemical Engineering Guangdong Laboratory (Rongjiang Laboratory), Jieyang 515200, China;
3. Guangdong Xinhuayue Petrochemical Group Stock Company, No.18, Youcheng 4 Road, Maoming 525000, China

收稿日期:2022-04-18 修回日期:2022-06-15 出版日期:2023-04-28 发布日期:2023-06-13
通讯作者: Yanxiong Fang,E-mail:fangyx@gdut.edu.cn;Baoyu Liu,E-mail:baoyu.liu@gdut.edu.cn
基金资助:
We are grateful for the Science and Technology Project of Maoming (China) (200203094555139) for financial support, and Sun Yat-sen University Instrumental Analysis & Research Center for technical support.

Lacunary silicotungstic heteropoly salts as high-performance catalysts in oxidation of cyclopentene

Peiyin Chen^1,2, Yanxiong Fang^1,2, Kaihong Xie^1,2, Yao Chen¹, Yang Liu³, Hongliang Zuo³, Weijian Lu¹, Baoyu Liu¹

1. School of Chemical Engineering and Light Industry, Guangdong Provincial Key Laboratory of Plant Resources Biorefinery, Guangzhou Key Laboratory of Clean Transportation Energy Chemistry, Guangdong University of Technology, Guangzhou 510006, China;
2. Jieyang Branch of Chemistry and Chemical Engineering Guangdong Laboratory (Rongjiang Laboratory), Jieyang 515200, China;
3. Guangdong Xinhuayue Petrochemical Group Stock Company, No.18, Youcheng 4 Road, Maoming 525000, China

Received:2022-04-18 Revised:2022-06-15 Online:2023-04-28 Published:2023-06-13
Contact: Yanxiong Fang,E-mail:fangyx@gdut.edu.cn;Baoyu Liu,E-mail:baoyu.liu@gdut.edu.cn
Supported by:
We are grateful for the Science and Technology Project of Maoming (China) (200203094555139) for financial support, and Sun Yat-sen University Instrumental Analysis & Research Center for technical support.

摘要/Abstract

摘要： The development of polyoxometalates for olefin oxidation is critical to achieving the green chemical process of the C5 fraction further processing. Di-lacunary silicotungstic anions were easily obtained by continuously adjusting the pH instead of the traditional step-by-step method, which exhibited excellent performance in the catalytic oxidation of cyclopentene (CPE) to aldehydes or alcohols. The 93.69% CPE conversion and 97.15% total product selectivity (41.38% for glutaraldehyde (GA) and 55.77% for 1,2-cyclopentanediol (1,2-diol) were achieved by using H₂O₂ as the oxidant and acetonitrile as the solvent. Through complementary characterization, it was found that the optimized di-lacunary silicotungstic polyoxometalate retained a complete Keggin structure, and exhibited better catalytic activity and stability than the mono-lacunary or saturated silicodecatungstate because it exposed more catalytic active centers. Furthermore, in situ FT-IR spectra was utilized to monitor the reaction process, revealing the formation of the active species W(O₂) on the di-lacunary silicotungstic polyoxometalate and the intermediate epoxycyclopentane during the catalytic oxidation of cyclopentene.

关键词: Lacunary silicotungstic heteropoly salts, Cyclopentene (CPE), Catalytic oxidation, Glutaraldehyde (GA), 1,2-Cyclopentanediol (1,2-diol)

Abstract: The development of polyoxometalates for olefin oxidation is critical to achieving the green chemical process of the C5 fraction further processing. Di-lacunary silicotungstic anions were easily obtained by continuously adjusting the pH instead of the traditional step-by-step method, which exhibited excellent performance in the catalytic oxidation of cyclopentene (CPE) to aldehydes or alcohols. The 93.69% CPE conversion and 97.15% total product selectivity (41.38% for glutaraldehyde (GA) and 55.77% for 1,2-cyclopentanediol (1,2-diol) were achieved by using H₂O₂ as the oxidant and acetonitrile as the solvent. Through complementary characterization, it was found that the optimized di-lacunary silicotungstic polyoxometalate retained a complete Keggin structure, and exhibited better catalytic activity and stability than the mono-lacunary or saturated silicodecatungstate because it exposed more catalytic active centers. Furthermore, in situ FT-IR spectra was utilized to monitor the reaction process, revealing the formation of the active species W(O₂) on the di-lacunary silicotungstic polyoxometalate and the intermediate epoxycyclopentane during the catalytic oxidation of cyclopentene.

Key words: Lacunary silicotungstic heteropoly salts, Cyclopentene (CPE), Catalytic oxidation, Glutaraldehyde (GA), 1,2-Cyclopentanediol (1,2-diol)

Peiyin Chen, Yanxiong Fang, Kaihong Xie, Yao Chen, Yang Liu, Hongliang Zuo, Weijian Lu, Baoyu Liu. Lacunary silicotungstic heteropoly salts as high-performance catalysts in oxidation of cyclopentene[J]. 中国化学工程学报, 2023, 56(4): 152-159.

参考文献

[1] S. Naseer, J. Ouyang, X. Chen, S.J. Pu, Y.T. Guo, X. Zhang, D.L. Li, C.L. Yang, Immobilization of β-glucosidase by self-catalysis and compared to crosslinking with glutaraldehyde, Int. J. Biol. Macromol. 154 (2020) 1490–1495.
[2] H. Chen, W.L. Dai, J.F. Deng,K.N. Fan, Novel heterogeneous W-doped MCM-41 catalyst for highly selective oxidation of cyclopentene to glutaraldehyde by aqueous H₂O₂, Catal. Lett.81 (2002)1-2.
[3] Y.M. Qi, Q. Han, L. Wu, J. Li, Selective oxidation of cyclopentene to glutaraldehyde by H₂O₂ over Nb-SBA-15, New J. Chem. 45 (41) (2021) 19264–19272.
[4] L.V. Mel’nik, A.E. Meshechkina, G.V. Rybina, S.S. Srednev, Y.A. Moskvichev, O.S. Kozlova, Synthesis of 1, 2-epoxycyclopentane and/or 1, 2-cyclopentanediol by oxidation of cyclopentene with aqueous solution of hydrogen peroxide, Pet. Chem. 52 (5) (2012) 313–317.
[5] Y.N. Ding, Selective Oxidation of Cyclopentene to Glutaraldehyde Catalyzed by Reaction Control Phase Transfer Catalyst, Ph. D. Thesis, Qingdao University of Science & Technology, Qingdao, 2019.
[6] P. Wu, Preparation of Tungsten-containing Catalysts and Its Applications on Glutaraldehyde by Oxidation of Cyclopentene, Ph. D. Thesis, Hebei University of Technology, Baoding, 2013.
[7] Q.J. Zhu, X.F. Chu, Z.Y. Zhang, W.L. Dai, K.N. Fan, A novel green process for the synthesis of glutaraldehyde by WS₂@HMS material with aqueous H₂O₂, RSC Adv. 3 (6) (2013) 1744–1747.
[8] X.L. Yang, L.M. Qiao, W.L. Dai, Phosphotungstic acid encapsulated in metal-organic framework UiO-66: An effective catalyst for the selective oxidation of cyclopentene to glutaraldehyde, Microporous Mesoporous Mater. 211 (2015) 73–81.
[9] R.H. Jin, H.X. Li, J.F. Deng, Selective oxidation of cyclopentene to glutaraldehyde by H₂O₂ over the WO₃/SiO₂ catalyst, J. Catal. 203 (1) (2001) 75–81.
[10] Z.Q. Zhu, W. Bian, Characterization of tungsten-based catalyst used for selective oxidation of cyclopentene to glutaraldehyde, Chin. J. Chem. Eng. 16 (6) (2008) 895–900.
[11] Y.L. Luo, C.J. Liu, H.R. Yue, S.Y. Tang, Y.M. Zhu, B. Liang, Selective oxidation of cyclopentene with H₂O₂ by using H₃PW₁₂O₄₀ and TBAB as a phase transfer catalyst, Chin. J. Chem. Eng. 27 (8) (2019) 1851–1856.
[12] Y. Wu, Epoxidation of Olefins with Hydrogen Peroxide by A Monolacunary-Keggin Type Heterpolyphosphotungstate, Ph. D. Thesis, Xiangtan University, Xiangtan, 2013.
[13] J.S. Zhang, Selective Oxidation of Cyclopentene to Glutaraldehyde Catalyzed by Heteropoly Organic-inorganic Salt, Ph. D. Thesis, Qingdao University of Science & Technology, Qingdao, 2018.
[14] H. Furukawa, T. Nakamura, H. Inagaki, E. Nishikawa, C. Imai,M. Misono, Oxidation of Cyclopentene with Hydrogen Peroxide Catalyzed by 12-Heteropoly Acids.pdf, Chem. Lett., 24 (1988)877-880.
[15] L. Salles, C. Aubry, R. Thouvenot, F. Robert, C. Doremieux-Morin, G. Chottard, H. Ledon, Y. Jeannin, J.M. Bregeault, 31P and 183W NMR spectroscopic evidence for novel peroxo species in the “H₃[PW₁₂O₄₀].cntdot.yH₂O/H₂O₂” system. synthesis and X-ray structure of tetrabutylammonium (.mu.-hydrogen phosphato)bis(.mu.-peroxo)bis(oxoperoxotungstate) (2-): A catalyst of olefin epoxidation in a biphase medium, Inorg. Chem. 33 (5) (1994) 871–878.
[16] Y. Ding, B.C. Ma, Q. Gao, G.X. Li, L. Yan, J.S. Suo, A spectroscopic study on the 12-heteropolyacids of molybdenum and tungsten (H₃PMo_12-nW_nO₄₀) combined with cetylpyridinium bromide in the epoxidation of cyclopentene, J. Mol. Catal. A Chem. 230 (1–2) (2005) 121–128.
[17] G. Lewandowski, Efficiency of selected phase transfer catalysts for the synthesis of 1, 2-epoxy-5, 9-cyclododecadiene in the presence of H₂O₂/H₃PW₁₂O₄₀ as catalytic system, pjct 15 (3) (2013) 96–99.
[18] B.C. Ma, W. Zhao, F.M. Zhang, Y.S. Zhang, S.Y. Wu, Y. Ding, A new halide-free efficient reaction-controlled phase-transfer catalyst based on silicotungstate of [(C₁₈H₃₇)₂(CH₃)₂N]₃[SiO₄H(WO₅)₃]for olefin epoxidation, oxidation of sulfides and alcohols with hydrogen peroxide, RSC Adv. 4 (61) (2014) 32054–32062.
[19] D.Z. Huang, H.Y. Lan, Q.P. Chen, Z.B. He, F.H. Lei,T. Zeng, Epoxidation of methyl abietic acid catalyzed by n-butyl quaternary ammonium salt of two-vacancy silicotungstate, Journal of Nanjing Forestry University 33 (2009)95-100.
[20] W.J. An, L. Xu, Highly selective oxidation of cyclohexene via tricant Keggin-type phosphotungstate as catalysts, Chem. Res. Chin. Univ., 32 (2001)783-786.
[21] L. Hua, Y.X. Qiao, H. Li, B. Feng, Z.Y. Pan, Y.Y. Yu, W.W. Zhu, Z.S. Hou, Epoxidation of olefins with hydrogen peroxide catalyzed by a reusable lacunary-type phosphotungstate catalyst, Sci. China Chem. 54 (5) (2011) 769–773.
[22] A. Téazéa, G. Hervéa, R.G. Finke, D.K. Lyon, Α-, β-, and γ-dodecatungstosilicic acids: Isomers and related lacunary compounds, in: Inorganic Syntheses, John Wiley & Sons, Inc., Hoboken, 2007(85–96).
[23] Y. Ding, Q. GAO,G.X. Li, A spectroscopic study on the epoxidation of cyclopentene catalyzed by Keggin HPA compounds, Acta Chim. Sin., 63 (2005)1167-1174.
[24] W.Y. Li, Y.Y. Liu, H.Y. Zheng,Z. Li, Molecular structure and application of heteropolyacid（salt）catalysts for organic synthesis, Chem. Ind. Eng. Prog. 29 (2010)243-249.
[25] W.L. Yang, R.H. Ma, Synthesis and Structure Characterization of Heteropoly Complexes, Beijing, 2016.
[26] R.H. Ma , C.T. Liu, Heteropoly Complex Isomers, Harbin Engineering University Press, Harbin, 2004.
[27] T.J. Li, Preparation and Catalytic Application of Lacunary Heteropolyoxometallates in Reactions of Alcohol, Ph. D. Thesis, Northwest Normal University, Lanzhou, 2015.
[28] Y.X. Xue, Synthesis, Characterization and Catalytic Performance of Modified Heteropoly Compounds, Ph. D. Thesis, Jilin University, Changchun, 2013.
[29] K. Kamata, K. Yonehara, Y. Sumida, K. Yamaguchi, S. Hikichi, N. Mizuno, Efficient epoxidation of olefins with >/=99% selectivity and use of hydrogen peroxide, Science 300 (5621) (2003) 964–966.
[30] J. H. Xu, W. L. Dai, X. L. Yang, Y. Xu,F. N. Fan, Novel MCM-41 supported niobium acid for the catalytic oxidation of cyclopentene to glutaraldehyde, Acta Chim. Sin. 16 (2004)1467-1471.
[31] B. Hincapie, S.M. Llano, H.F. Garces, D. Espinal, S.L. Suib, L.J. Garces, Epoxidation of cyclopentene by a low cost and environmentally friendly bicarbonate/peroxide/manganese system, Adsorpt. Sci. Technol. 36 (1–2) (2018) 9–22.
[32] C. Beyer, L.R. Oellrich, M.A. McHugh, Effect of copolymer composition and solvent polarity on the phase behavior of mixtures of poly(ethylene-co-vinyl acetate) with cyclopentane and cyclopentene, Chem. Eng. Technol. 23 (7) (2000) 592–595.
[33] P. Venkatesu, Thermophysical contribution of N, N-dimethylformamide in the molecular interactions with other solvents, Fluid Phase Equilibria 298 (2) (2010) 173–191.
[34] Y. Jin, D.Y. Zhuang, N.Y. Yu, H.H. Zhao, Y. Ding, L.S. Qin, J.F. Liu, D.H. Yin, H.Y. Qiu, Z.H. Fu, D.L. Yin, Epoxidation of styrene over gold nanoparticles supported on organic-inorganic hybrid mesoporous silicas with aqueous hydrogen peroxide, Microporous Mesoporous Mater. 126 (1–2) (2009) 159–165.
[35] C. Aubry, G. Chottard, N. Platzer, J.M. Bregeault, R. Thouvenot, F. Chauveau, C. Huet, H. Ledon, Reinvestigation of epoxidation using tungsten-based precursors and hydrogen peroxide in a biphase medium, Inorg. Chem. 30 (23) (1991) 4409–4415.
[36] S. Pathan, A. Patel, Keggin-type mono lacunary silicotungstate supported onto zirconia: Synthesis, characterization, and esterification reaction, J. Coord. Chem. 63 (23) (2010) 4041–4049.
[37] M.L. WANG, T.H. HUANG, W.T. Wu, Kinetic study of the phase transfer catalytic epoxidation of dicyclopentadiene in a two-phase medium, Chem. Eng. Commun. 191 (1) (2004) 27–46.
[38] K. Kamata, M. Kotani, K. Yamaguchi, S. Hikichi, N. Mizuno, Olefin epoxidation with hydrogen peroxide catalyzed by lacunary polyoxometalate[gamma-SiW₁₀O₃₄H₂O₂]₄, Chemistry 13 (2) (2007) 639–648.

Lacunary silicotungstic heteropoly salts as high-performance catalysts in oxidation of cyclopentene

Lacunary silicotungstic heteropoly salts as high-performance catalysts in oxidation of cyclopentene

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 11

编辑推荐

Metrics

本文评价

[1]	Chenyang Zhao, Yinhan Cheng, Guangfei Qu, Yongheng Yuan, Fenghui Wu, Ye Liu, Shan Liu, Junyan Li, Ping Ning. High-performance liquid-phase catalytic purification of phosphine in tail gas using Pd(II)/Cu(II) composite[J]. 中国化学工程学报, 2023, 57(5): 98-108.
[2]	Juan Lei, Peng Wang, Shuang Wang, Jinping Li, Yongping Xu, Shuying Li. Enhancement effect of Mn doping on Co₃O₄ derived from Co-MOF for toluene catalytic oxidation[J]. 中国化学工程学报, 2022, 52(12): 1-9.
[3]	Zhen Wei, Xuanqi Kang, Shangyuan Xu, Xiaokang Zhou, Bo Jia, Qing Feng. Electrochemical oxidation of Rhodamine B with cerium and sodium dodecyl benzene sulfonate co-modified Ti/PbO₂ electrodes: Preparation, characterization, optimization, application[J]. 中国化学工程学报, 2021, 32(4): 191-202.
[4]	Zhihao Yi, Jie Sun, Jigang Li, Tian Zhou, Shouping Wei, Hongjia Xie, Yulin Yang. High efficient removal of HCN over porous CuO/CeO₂ micro-nano spheres at lower temperature range[J]. 中国化学工程学报, 2021, 38(10): 155-164.
[5]	Mohammad Hossein Sheikh-Mohseni, Sajjad Sedaghat, Pirouz Derakhshi, Aliakbar Safekordi. Green bio-synthesis of Ni/montmorillonite nanocomposite using extract of Allium jesdianum as the nano-catalyst for electrocatalytic oxidation of methanol[J]. 中国化学工程学报, 2020, 28(10): 2555-2565.
[6]	Pengyu Zhu, Kaijin Zhu, Rob Puzey, Xiaoli Ren. Degradation analysis of A²/O combined with AgNO₃ + K₂FeO₄ on coking wastewater[J]. Chinese Journal of Chemical Engineering, 2018, 26(7): 1555-1560.
[7]	Vasu Chaudhary, Sweta. Synthesis and catalytic activity of SBA-15 supported catalysts for styrene oxidation[J]. Chinese Journal of Chemical Engineering, 2018, 26(6): 1300-1306.
[8]	佘远斌, 王维洁, 李国君. Oxidation of p/o-Cresols to p/o-Hydroxybenzaldehydes Catalyzed by Metalloporphyrins with Molecular Oxygen[J]. Chinese Journal of Chemical Engineering, 2012, 20(2): 262-266.
[9]	田文玉, 薛为岚, 曾作祥, 邵记. Kinetics of 2-Methyl-6-acetyl-naphthalene Liquid Phase Catalytic Oxidation[J]. , 2009, 17(1): 72-77.
[10]	张玉坤, 李初福, 何小荣, 陈丙珍. Simulation and Optimization in the Process of Toluene Liquid-phase Catalytic Oxidation[J]. Chinese Journal of Chemical Engineering, 2008, 16(1): 36-38.
[11]	刘平乐, 邹丽珊, 罗和安, 王良芥, 郑金华. 基于一种改进的自适应遗传算法估算环已烷自催化氧化反应动力学参数[J]. , 2004, 12(1): 49-54.