Selective coupling of methyl chloride to vinyl chloride over dispersed NaVO3

doi:10.1016/S1872-2067(25)64732-2

Abstract

Abstract:

The production of C₂H₃Cl from CH₃Cl (MCTV) represents a promising non-petroleum route for synthesizing C₂ alkenes from C₁ molecules. Exploration of new MCTV catalysts is crucial for advancing sustainable chemical production. In this study, we present NaVO₃as a surface-confined coupling center for^•CH₂Cl radicals, demonstrating its superior performance in the selective coupling of methyl chloride to synthesize vinyl chloride. By incorporating NaVO₃onto the surface of CeO₂, the catalyst enables effective capture of ^•CH₂Cl radicals during the CH₃Cl oxidative pyrolysis and their subsequent conversion into C₂H₃Cl. We experimentally validate the capability of highly dispersed NaVO₃ to controllably couple ^•CH₂Cl radicals through in-situ synchrotron-based vacuum ultraviolet photoionization mass spectrometry. The results demonstrate that the dispersion of NaVO₃ on the catalyst surface has a considerable impact on the reaction efficiency of ^•CH₂Cl radicals and the overall MCTV performance. This discovery holds substantial implications for the controlled C₁ radical transformation and provides a guidance for the design of catalysts for sustainable production of C₂H₃Cl.

Key words: Vinyl chloride, Methyl chloride, ?CH2Cl radicals, Surface coupling, NaVO3

Liu Fangwei, Wei Kunkun, Chen Youwen, Hu Jingbo, Wang Yue, Liu Chengyuan, Pan Yang, Chen Xutao, Zou Shihui, Fan Jie. Selective coupling of methyl chloride to vinyl chloride over dispersed NaVO₃[J]. Chinese Journal of Catalysis, 2025, 75: 1-8.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64732-2

https://www.cjcatal.com/EN/Y2025/V75/I8/1

Figures/Tables 5

Fig. 1. Catalytic Performance. (a,b) The distribution of products and C2H3Cl yield across different catalysts at CH3Cl conversion of ~60%. (c) The different catalysts' catalytic performances in MCTV. The bed temperature range for the reaction is 600-750 °C. Detailed data are summarized in Table S2. (d) Stability tests over NaVO3/CeO2 catalyst at 700 °C. Reaction parameters: P = 1 atm, 150 mg catalyst, CH3Cl = 1 mL min?1, O2 = 2 mL min?1, N2 = 57 mL min?1.

Fig. 2. Structural characterization. (a) The XRD patterns of NaVO3-based catalysts. (b) The Raman spectra of NaVO3-based catalysts. (c) V K-edge XANES spectra of pure α-NaVO3 and NaVO3-based catalysts. (d) The AC-TEM image of NaVO3/CeO2. (e) The HAADF-STEM image with elemental mapping of NaVO3/CeO2.

Fig. 3. Kinetic studies. (a) Conversion of CH3Cl and selectivity of C2H3Cl in oxy pyrolysis and MCTV (NaVO3/CeO2) as a function of reaction temperature. (b) The dependence of the rate of CH3Cl conversion over various catalysts at different PCH3Cl/Ptotal ratios. Reaction parameters: TNaVO3/CeO2 = 650 °C, TCeO2 = 540 °C, TBlank = 840 °C, 150 mg catalyst, O2 flow rate = 2 mL min?1, total flow rate = 60 mL min?1.

Fig. 4. Mechanism studies. (a) The diagrammatic illustration of the in-situ SVUV-PIMS studies. (b) The RE of NaVO3/CeO2 about ?CH2Cl produced by oxidative pyrolysis of CH3Cl. (c) ?CH2Cl, C2H3Cl, CO2, CO observed at 750 °C using in-situ SVUV-PIMS over NaVO3-based catalysts. (d) Correlation of C2H3Cl intensity with reaction efficiency of ?CH2Cl radicals catalyzed by NaVO3-based catalysts at 750 °C. Reaction parameters: P = 2 torr, 150 mg catalyst, CH3Cl = 4 mL min?1, O2 = 8 mL min?1, Ar = 48 mL min?1.

Fig. 5. The reaction efficiency of ?CH2Cl radicals and C2H3Cl yield at 750 °C as a function of surface V/M across NaVO3-based catalysts. The surface area ratio V/M (where M represents Si, Zr, Ce) is obtained from the XPS data (see Table S1).

References

[1]	R. Lin, A. P. Amrute, J. Pérez-Ramírez, Chem. Rev., 2017, 117, 4182-4247.
[2]	G. Malta, S. A. Kondrat, S. J. Freakley, C. J. Davies, L. Lu, S. Dawson, A. Thetford, E. K. Gibson, D. J. Morgan, W. Jones, P. P. Wells, P. Johnston, C. R. A. Catlow, C. J. Kiely, G. J. Hutchings, Science, 2017, 355, 1399-1403.
[3]	S. K. Kaiser, E. Fako, G. Manzocchi, F. Krumeich, R. Hauert, A. H. Clark, O. V. Safonova, N. López, J. Pérez-Ramírez, Nat. Catal., 2020, 3, 376-385.
[4]	G. J. Hutchings, D. T. Grady, Appl. Catal., 1985, 17, 155-160.
[5]	H. Schobert, Chem. Rev., 2014, 114, 1743-1760.
[6]	P. Johnston, N. Carthey, G. J. Hutchings, J. Am. Chem. Soc., 2015, 137, 14548-14557.
[7]	M. Scharfe, P. A. Lira-Parada, A. P. Amrute, S. Mitchell, J. Pérez-Ramírez, J. Catal., 2016, 344, 524-534.
[8]	H. Ma, G. Ma, Y. Qi, Y. Wang, Q. Chen, K. R. Rout, T. Fuglerud, D. Chen, Angew. Chem. Int. Ed., 2020, 59, 22080-22085.
[9]	H. Ma, Y. Wang, Y. Qi, K. R. Rout, D. Chen, ACS Catal., 2020, 10, 9299-9319.
[10]	M. Wang, D. Ma, Chem, 2022, 8, 886-887.
[11]	W. Zhao, M. Sun, H. Zhang, Y. Dong, X. Li, W. Li, J. Zhang, RSC Adv., 2015, 5, 104071-104078.
[12]	Y. Yao, H. Zhuo, F. Wang, G. Bi, J. Xu, X. Yang, Y. Huang, Catal. Sci. Technol., 2024, 14, 5599-5607.
[13]	W. Ren, L. Duan, Z. Zhu, W. Du, Z. An, L. Xu, C. Zhang, Y. Zhuo, C. Chen, Environ. Sci. Technol., 2014, 48, 2321-2327.
[14]	G. Zichittella, J. Pérez-Ramírez, Angew. Chem. Int. Ed., 2021, 60, 24089-24095.
[15]	G. Zichittella, A. Ceruti, G. Guillén-Gosálbez, J. Pérez-Ramírez, Chem, 2022, 8, 883-885.
[16]	P.-M. Marquaire, M. Al Kazzaz, Y. Muller, J. Saint Just, Stud. Surf. Sci. Catal., 1997, 107, 269-274.
[17]	C. Lombard, P.-M. Marquaire, Stud. Surf. Sci. Catal., 2004, 147, 529-534.
[18]	Y. Wang, S. Zou, A. Nabera, X. Chen, Y. Pan, K. Wei, Y. Bao, J. Hu, Y. Zhao, C. Liu, J. Liu, Y. Wang, Y. Ren, G. Guillén-Gosálbez, J. Pérez-Ramírez, J. Fan, J. Am. Chem. Soc., 2025, 147, 7757-7764.
[19]	S. A. Schmidt, N. Kumar, A. Reinsdorf, K. Eränen, J. Wärnå, D. Y. Murzin, T. Salmi, Chem. Eng. Sci., 2013, 95, 232-245.
[20]	M. Pelucchi, C. Cavallotti, A. Frassoldati, E. Ranzi, P. Glarborg, T. Faravelli, Int. J. Chem. Kinet., 2021, 53, 403-418.
[21]	A. Granada, S. B. Karra, S. M. Senkan, Ind. Eng. Chem. Res., 1987, 26, 1901-1905.
[22]	A. Cesarini, S. Mitchell, G. Zichittella, M. Agrachev, S. P. Schmid, G. Jeschke, Z. Pan, A. Bodi, P. Hemberger, J. Pérez-Ramírez, Nat. Catal., 2022, 5, 605-614.
[23]	M. Weissman, S. W. Benson, Int. J. Chem. Kinet., 1984, 16, 307-333.
[24]	S. L. Hung, L. D. Pfefferle, Combust. Sci. Technol., 1993, 87, 91-107.
[25]	S. Zou, Z. Li, Q. Zhou, Y. Pan, W. Yuan, L. He, S. Wang, W. Wen, J. Liu, Y. Wang, Y. Du, J. Yang, L. Xiao, H. Kobayashi, J. Fan, Chin. J. Catal., 2021, 42, 1117-1125.
[26]	S. Zou, J. Wang, J. Liu, Q. Zhou, Y. Pan, W. Yuan, J. Hu, Y. Wang, J. Yang, Y. Wang, J. Liu, L. Ma, Y. Du, B. Yang, J. Fan, ChemRxiv, 2024, 1-56.
[27]	H.-X. Mai, L.-D. Sun, Y.-W. Zhang, R. Si, W. Feng, H.-P. Zhang, H.-C. Liu, C.-H. Yan, J. Phys. Chem. B, 2005, 109, 24380-24385.
[28]	M. Nadjafi, P. M. Abdala, R. Verel, D. Hosseini, O. V. Safonova, A. Fedorov, C. R. Müller, ACS Catal., 2020, 10, 2314-2321.
[29]	M. Nadjafi, A. M. Kierzkowska, P. M. Abdala, R. Verel, O. V. Safonova, A. Fedorov, C. R. Müller, Catal. Sci. Technol., 2020, 10, 7186-7193.
[30]	Y. Li, Z. Wei, J. Sun, F. Gao, C. H. F. Peden, Y. Wang, J. Phys. Chem. C, 2013, 117, 5722-5729.
[31]	L. E. Briand, O. P. Tkachenko, M. Guraya, X. Gao, I. E. Wachs, W. Grünert, J. Phys. Chem. B, 2004, 108, 4823-4830.
[32]	Y. Tong, M. P. Rosynek, J. H. Lunsford, J. Phys. Chem., 1989, 93, 2896-2898.

Selective coupling of methyl chloride to vinyl chloride over dispersed NaVO₃

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