高分散NaVO3催化氯甲烷选择性偶联制氯乙烯

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

催化学报 ›› 2025, Vol. 75: 1-8.DOI: 10.1016/S1872-2067(25)64732-2

• 论文 • 下一篇

高分散NaVO₃催化氯甲烷选择性偶联制氯乙烯

刘芳维^a, 卫锟锟^a, 陈幼雯^a, 胡景波^a, 王玥^a, 刘成园^c, 潘洋^c, 陈旭涛^a^,^*(), 邹世辉^b^,^*(), 范杰^a^,^*()

^a浙江大学化学系, 全省高值化学品低碳合成重点实验室, 浙江杭州 310058
^b浙江工业大学材料科学与工程学院, 浙江杭州 310014
^c中国科学技术大学国家同步辐射实验室, 安徽合肥 230029

收稿日期:2025-02-11 接受日期:2025-04-09 出版日期:2025-08-18 发布日期:2025-07-22
通讯作者: *电子信箱: jfan@zju.edu.cn (范杰), xueshan199@163.com (邹世辉), 12037066@zju.edu.cn(陈旭涛).
基金资助:
国家重点研发项目(2022YFA1505500);国家自然科学基金(92045301);国家自然科学基金(91845203)

Selective coupling of methyl chloride to vinyl chloride over dispersed NaVO₃

Liu Fangwei^a, Wei Kunkun^a, Chen Youwen^a, Hu Jingbo^a, Wang Yue^a, Liu Chengyuan^c, Pan Yang^c, Chen Xutao^a^,^*(), Zou Shihui^b^,^*(), Fan Jie^a^,^*()

^aZhejiang Key Laboratory of Low-Carbon Synthesis of Value-Added Chemicals, Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang, China
^bCollege of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China
^cNational Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, Anhui, China

Received:2025-02-11 Accepted:2025-04-09 Online:2025-08-18 Published:2025-07-22
Contact: *E-mail: jfan@zju.edu.cn (J. Fan), xueshan199@163.com (S. Zou), 12037066@zju.edu.cn(X. Chen).
Supported by:
National Key Research and Development Program of China(2022YFA1505500);National Natural Science Foundation of China(92045301);National Natural Science Foundation of China(91845203)

摘要/Abstract

摘要：

氯乙烯(C₂H₃Cl)作为聚氯乙烯的核心单体, 其生产技术革新对全球化工行业的可持续发展具有重要战略意义. 当前主流的氯乙烯生产工艺均以石油或煤基的C₂烃为原料, 存在碳排放强度高、能源消耗大等问题. 近年来, 基于C₁平台分子(如甲烷、氯甲烷等)的催化转化技术, 因其原料来源广泛且符合“碳达峰”和“碳中和”的战略需求, 已成为学术界与工业界共同关注的焦点. 利用重要的C₁平台分子氯甲烷(CH₃Cl)生产氯乙烯(即氯甲烷选择性偶联制氯乙烯, MCTV)是一条具有前景的非石油基氯乙烯生产新路线. 作为新兴的C₁转化反应, 当前的MCTV过程面临的关键挑战在于如何发掘更多的氯甲基自由基(^•CH₂Cl)表面偶联活性位点, 以及如何提升MCTV反应的关键性能指标.

本文通过简单的浸渍法, 在二氧化锆(ZrO₂)和二氧化铈(CeO₂)载体上负载了多种金属氧酸钠盐(Na_xMO_y, 其中M = Cr, Re, Ti, W, V, Nb, Mo), 并系统测试了其在MCTV反应中的催化性能. 结果表明, 高分散的NaVO₃是一种新型高效的^•CH₂Cl自由基表面偶联活性位点, 能够将氯甲烷高选择性偶联为氯乙烯. 其中, NaVO₃/CeO₂作为新型高效的MCTV催化剂, 在750 °C反应温度下实现了56.7%的C₂H₃Cl选择性和32.1%的C₂H₃Cl收率. X射线衍射、高角环形暗场扫描透射电镜、拉曼光谱、X射线光电子能谱及X射线精细结构吸收谱证实NaVO₃/CeO₂中的活性相为高度分散的NaVO₃. 此外, 本文采用原位同步辐射紫外光电离质谱技术, 对MCTV反应过程中关键的自由基中间体及^•CH₂Cl, C₂H₃Cl等代表产物的演变进行了原位探测, 进一步证实了高度分散的NaVO₃是一种全新且高效的^•CH₂Cl自由基表面偶联活性位点. 具体而言, NaVO₃/CeO₂催化剂对^•CH₂Cl的反应效率高达90%, 并能将其高效、选择性地转化为C₂H₃Cl. 通过将催化剂对^•CH₂Cl自由基的反应效率作为桥梁, 建立了催化剂表面NaVO₃分散程度与其MCTV催化活性之间的内在关联, 阐明NaVO₃的分散程度是影响催化剂是调控^•CH₂Cl自由基反应效率和MCTV性能的关键因素. 本文强调了提高催化剂中金属氧酸盐活性位点的分散程度可以有效提升偶联催化剂对^•CH₂Cl自由基的反应效率, 进而增强MCTV性能.

综上, 本文揭示了一种全新的金属氧酸盐偶联中心—NaVO₃, 其能够选择性地将^•CH₂Cl自由基转化为C₂H₃Cl, 这一发现是自由基可控转化领域的重要进展, 不仅深化了对金属氧酸盐催化剂偶联机制的理解, 也为设计并构建更高效的MCTV催化剂提供了科学指导.

关键词: 氯乙烯, 氯甲烷, ^?CH₂Cl自由基, 表面偶联, NaVO₃

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

刘芳维, 卫锟锟, 陈幼雯, 胡景波, 王玥, 刘成园, 潘洋, 陈旭涛, 邹世辉, 范杰. 高分散NaVO₃催化氯甲烷选择性偶联制氯乙烯[J]. 催化学报, 2025, 75: 1-8.

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.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64732-2

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

图/表 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).

参考文献

[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.

高分散NaVO₃催化氯甲烷选择性偶联制氯乙烯

Selective coupling of methyl chloride to vinyl chloride over dispersed NaVO₃

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 5

参考文献

相关文章 15

编辑推荐

Metrics

[1]	于晴, 王诗怡, 王梦茹, 牟效玲, 林荣和, 丁云杰. M/C₃N₄/AC (M = Au, Pt, Ru)催化乙炔与二氯乙烷耦合反应: 双功能催化剂性能如何?[J]. 催化学报, 2022, 43(3): 820-831.
[2]	邹世辉, 李志年, 周秋月, 潘洋, 袁文涛, 贺磊, 王申亮, 文武, 刘娟娟, 王勇, 杜永华, 杨玖重, 肖丽萍, 小林久芳, 范杰. 表面偶联甲基自由基实现低温高效甲烷氧化偶联[J]. 催化学报, 2021, 42(7): 1117-1125.
[3]	Matthias Scharfe, Guido Zichittella, Vladimir Paunovic, Javier Pérez-Ramírez. 卤素化学中的铈[J]. 催化学报, 2020, 41(6): 915-927.
[4]	冯晓珊, 郑颖滨, 林代峰, 吴恩惠, 罗永晋, 游钰锋, 薛珲, 钱庆荣, 陈庆华. 用于氯乙烯废气高效催化氧化的Ce-Cu-W-O微球的新颖合成[J]. 催化学报, 2020, 41(12): 1864-1872.
[5]	王丽, 谢鸿凯, 王杏丹, 张桂珍, 郭杨龙, 郭耘, 卢冠忠. 制备方法对LaMnO₃上氯乙烯催化燃烧性能的影响[J]. 催化学报, 2017, 38(8): 1406-1412.
[6]	杨勇, 蓝国钧, 王小龙, 李瑛. 原位掺杂法制备氮掺杂中孔炭及乙炔氢氯化反应性能[J]. 催化学报, 2016, 37(8): 1242-1248.
[7]	Catherine J. Davies, Peter J. Miedziak, Gemma L. Brett, Graham J. Hutchings. 金催化制备氯乙烯单体进展[J]. 催化学报, 2016, 37(10): 1600-1607.
[8]	Yu-lun Fang, Kimberly N. Heck, Zhun Zhao, Lori A. Pretzer, Neng Guo, Tianpin Wu, Jeffrey T. Miller, Michael S. Wong. 金掺杂对碳负载钯催化还原性能的促进作用[J]. 催化学报, 2016, 37(10): 1776-1786.
[9]	孔令涛, 沈本贤. SAPO-34分子筛中多甲基苯分子与卤代甲烷偕甲基化反应的密度泛函理论研究[J]. 催化学报, 2015, 36(7): 1017-1022.
[10]	牛怀成, 李利春, 李瑛, 郭荔, 唐浩东, 韩文锋, 刘化章. Cr 掺杂对中孔 MgF₂ 酸性及孔结构的影响[J]. 催化学报, 2013, 34(2): 373-378.
[11]	徐霆, 宋航, 邓卫平, 张庆红, 王野. 改性H-ZSM-34上氯甲烷催化转化制低碳烯烃[J]. 催化学报, 2013, 34(11): 2047-2056.
[12]	万义玲, 张传辉, 郭杨龙, 郭耘, 卢冠忠. CeO₂-MnO_x 催化剂上氯乙烯有机废气的催化燃烧[J]. 催化学报, 2012, 33(3): 557-562.
[13]	吕永康 1, 郗瑞鑫 1, 任瑞鹏 1,2. 在预吸附氧原子的 Ag(100) 面上氯乙烯环氧化反应的密度泛函理论研究[J]. 催化学报, 2011, 32(3): 451-455.
[14]	刘杰;周广栋;吕学举;甄开吉;张文祥;程铁欣. MgO改性的γ-Al2O3负载CuCl2-KCl催化剂上乙烷氧氯化制氯乙烯[J]. 催化学报, 2007, 28(9): 799-804.
[15]	王幸宜;戴启广;郑翊. MCM-41负载的La, Ce和Pt催化剂上三氯乙烯的低温催化燃烧[J]. 催化学报, 2006, 27(6): 468-470.