金属掺杂γ-MnO2在乙醇气相选择氧化和CO氧化中的构效关系

doi:10.1016/S1872-2067(20)63551-3

摘要/Abstract

摘要： 二氧化锰（MnO₂）因具有制备简单、Mn⁴⁺/Mn³⁺/Mn²⁺混合的金属价态、可调变的晶型结构（如α，β，γ，δ等）、丰富的表面氧缺陷和活泼的晶格氧等特点，在多相催化领域被广泛用作需氧氧化催化剂.MnO₂催化气相氧化主要集中在催化燃烧或完全氧化，催化性能最佳的MnO₂晶型因反应底物不同会有所差异.由于其氧化催化活性较高、选择性难于控制，MnO₂这类结构丰富、价廉易得的催化剂在气相选择氧化制高附加值化学品中面临着机遇和挑战.乙醇气相选择氧化制乙醛符合绿色和可持续性化学工业的发展需求，被认为是替代传统高污染、高成本的乙烯瓦克氧化工艺的最佳选择.MnO₂在催化乙醇燃烧中应用广泛，不同晶型MnO₂中α-MnO₂的活性最高.我们已经报道了非变价金属离子掺杂α-MnO₂（M-OMS-2），特别是具有最强表面碱性和可还原性的Na-OMS-2在乙醇气相选择氧化中获得了高达66%的乙醛产率和与贵金属催化剂相接近的催化效率.然而，不同晶型MnO₂对乙醇气相选择氧化催化性能的影响，以及选择氧化和完全氧化所需的MnO₂晶型和结构性质是否一致尚不清楚.这些问题的阐明无疑能够指导更高性能MnO₂选择氧化催化剂的设计合成.
本文首先制备了四种晶型（α，β，γ，δ）MnO₂，并将其应用于气相乙醇选择氧化和CO氧化，惊喜地发现γ-MnO₂在这两类反应中均表现出最高的催化活性，这与之前报道的乙醇催化燃烧和CO氧化结果明显不同，证明了MnO₂的晶型结构和反应条件对其催化氧化性能有重要影响.为了深入研究γ-MnO₂在乙醇气相选择氧化和CO氧化中的构效关系，通过一锅水热法制备了金属掺杂的M-γ-MnO₂（M=Cu²⁺，Zn²⁺，Mg²⁺，Co²⁺，Ni²⁺，Ca²⁺，Al³⁺，Fe³⁺，La³⁺）.采用多种表征手段证明了金属掺杂能够有效地调变γ-MnO₂的结构组成、表面酸碱性和可还原性.制得的M-γ-MnO₂催化剂在CO和乙醇氧化中显示出不同的活性顺序，发现CO氧化中催化剂的酸碱性更加重要.具有最高表面碱性/酸性位点摩尔比的Zn-γ-MnO₂在CO氧化中活性最佳，其表面锰物种和氧物种的氧化态在反应前后基本不变，表明M-γ-MnO₂上的CO氧化遵循基于晶格氧的Mars-van Krevelen机理.与之不同的是，催化剂的可还原性是影响乙醇气相选择氧化性能的更主要因素.具有最高表面可还原性的Cu-γ-MnO₂于200℃获得了最高75%的乙醛产率和较好的催化稳定性，这归因于其在较低温度下存在更多的Mn²⁺/Mn³⁺缺陷位和氧空位，这有利于O₂和乙醇的低温活化.进一步的动力学研究表明，O₂和乙醇浓度对反应速率影响不大，而空速的增大能够大幅度提高乙醛的时空收率.同位素效应证明醇羟基断裂仍然是反应的速控步骤，因此表面晶格氧和吸附氧物种均参与了乙醇活化.

关键词: 二氧化锰, 金属掺杂, 乙醇氧化, 乙醛, CO催化氧化

Abstract: Despite of considerable efforts on the MnO₂-based catalytic combustion, the different structural and component requirements of MnO₂ for gas-phase selective oxidation and complete oxidation largely remain unknown. By comparing four types of MnO₂ with different crystal structures (α, β, γ and δ), γ-MnO₂ was found to be the most efficient catalyst for both aerobic selective oxidation of ethanol and CO oxidation. The structural effect of γ-MnO₂ was further investigated by doping metal ions into the framework and by comparing the catalytic performance in the gas-phase aerobic oxidation of CO and ethanol. Among ten M-γ-MnO₂ catalysts, Zn-γ-MnO₂ showed the lowest temperature (160℃) for achieving 90% CO conversion. The CO oxidation activity of the M-γ-MnO₂ catalysts was found to be more relevant to the surface acidity-basicity than the reducibility. In contrast, surface reducibility has been demonstrated to be more crucial in the gas-phase ethanol oxidation. Cu-γ-MnO₂ with higher reducibility and more oxygen vacancies of Mn²⁺/Mn³⁺ species exhibited higher catalytic activity in the selective ethanol oxidation. Cu-γ-MnO₂ achieved the highest acetaldehyde yield (75%) and space-time-yield (5.4 g g_cat^-1 h^-1) at 200℃, which are even comparable to the results obtained by the state-of-the-art silver and gold-containing catalysts. Characterization results and kinetic studies further suggest that the CO oxidation follows the lattice oxygen-based Mars-van Krevelen mechanism, whereas both surface lattice oxygen and adsorbed oxygen species involve in the ethanol activation.

Key words: MnO₂, Metal doping, Ethanol oxidation, Acetaldehyde, Catalytic CO oxidation

王盼盼, 段嘉豪, 王杰, 梅付名, 刘鹏. 金属掺杂γ-MnO₂在乙醇气相选择氧化和CO氧化中的构效关系[J]. 催化学报, 2020, 41(8): 1298-1310.

Panpan Wang, Jiahao Duan, Jie Wang, Fuming Mei, Peng Liu. Elucidating structure-performance correlations in gas-phase selective ethanol oxidation and CO oxidation over metal-doped γ-MnO₂[J]. Chinese Journal of Catalysis, 2020, 41(8): 1298-1310.

×
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(20)63551-3

https://www.cjcatal.com/CN/Y2020/V41/I8/1298

参考文献

[1] S. L. Suib, Acc. Chem. Res., 2008, 41, 479-487.
[2] E. Hayashi, Y. Yamaguchi, K. Kamata, N. Tsunoda, Y. Kumagai, F. Oba, M. Hara, J. Am. Chem. Soc., 2019, 141, 890-900.
[3] L. Pahalagedara, D. A. Kriz, N. Wasalathanthri, C. Weerakkody, Y. Meng, S. Dissanayake, M. Pahalagedara, Z. Luo, S. L. Suib, P. Nandi, R. J. Meyer, Appl. Catal. B, 2017, 204, 411-420.
[4] S. Liang, F. Teng, G. Bulgan, R. Zong, Y. Zhu, J. Phys. Chem. C, 2008, 112, 5307-5315.
[5] J. Zhang, Y. Li, L. Wang, C, Zhang, H. He, Catal. Sci. Technol., 2015, 5, 2305-2313.
[6] B. Zhao, R. Ran, X. Wu, D. Weng, Appl. Catal. A, 2016, 514, 24-34.
[7] X. Weng, Y. Long, W. Wang, M. Shao, Z. Wu, Chin. J. Catal., 2019, 40, 638-646.
[8] S. Guan, W. Li, J. Ma, Y. Lei, Y. Zhu, Q. Huang, X. Dou, J. Ind. Eng. Chem., 2018, 66, 126-140.
[9] C. Angelici, B. M. Weckhuysen, P. C. A. Bruijnincx, ChemSusChem, 2013, 6, 1595-1614.
[10] N. Zheng, G. D. Stucky, J. Am. Chem. Soc., 2006, 128, 14278-14280.
[11] O. A. Simakova, V. I. Sobolev, K. Y. Koltunov, B. Campo, A.-R. Leino, K. Kordás, D. Y. Murzin, ChemCatChem, 2010, 2, 1535-1538.
[12] P. Liu, E. J. M. Hensen, J. Am. Chem. Soc., 2013, 135, 14032-14035.
[13] J. Mielby, J. O. Abildstrøm, F. Wang, T. Kasama, C. Weidenthaler, S. Kegn?s, Angew. Chem. Int. Ed., 2014, 53, 12513-12516.
[14] T. Takei, N. Iguchi, M. Haruta, Catal. Surv. Asia, 2011, 15, 80-88.
[15] H. Zhou, J. Y. Wang, X. Chen, C.-L. O'Young, S. L. Suib, Microporous Mesoporous Mater., 1998, 21, 315-324.
[16] J. Chen, X. Tang, J. Liu, E. Zhan, J. Li, X. Huang, W. Shen, Chem. Mater., 2007, 19, 4292-4299.
[17] L. Lamaita, M. A. Peluso, J. E. Sambeth, H. J. Thomas, Appl. Catal. B, 2005, 61, 114-119.
[18] V. P. Santos, M. F. R. Pereira, J. J. M. Órfão, J. L. Figueiredo, Appl. Catal. B, 2010, 99, 353-363.
[19] J. Li, R. Wang, J. Hao, J. Phys. Chem. C, 2010, 114, 10544-10550.
[20] H. Li, G. Qi, Tana, X. Zhang, X. Huang, W. Li, W. Shen, Appl. Catal. B, 2011, 103, 54-61.
[21] B. Bai, J. Li, J. Hao, Appl. Catal. B, 2015, 164, 241-250.
[22] B. Bai, Q. Qiao, Y. Li, Y. Peng, J. Li, Chin. J. Catal., 2018, 39, 630-638.
[23] V. V. Dutov, G. V. Mamontov, V. I. Sobolev, O. V. Vodyankina, Catal. Today, 2016, 278, 164-173.
[24] P. Liu, J. Duan, Q. Ye, F. Mei, Z. Shu, H. Chen, J. Catal., 2018, 367, 115-125.
[25] W. Y. Hernández, M. A. Centeno, S. Ivanova, P. Eloy, E. M. Gaigneaux, J. A. Odriozola, Appl. Catal. B, 2012, 123-124, 27-35.
[26] J. Yang, H. Zhou, L. Wang, Y. Zhang, C. Chen, H. Hu, G. Li, Y. Zhang, Y. Ma, J. Zhang, ChemCatChem, 2017, 9, 1163-1167.
[27] T. Uematsu, Y. Miyamoto, Y. Ogasawara, K. Suzuki, K. Yamaguchi, N. Mizuno, Catal. Sci. Technol., 2016, 6, 222-233.
[28] X. Li, J. Ma, L. Yang, G. He, C. Zhang, R. Zhang, H. He, Environ. Sci. Technol., 2018, 52, 12685-12696.
[29] R. D. Shannon, Acta Crystallogr. A, 1976, 32, 751-767.
[30] C. K. King'ondu, N. Opembe, C. Chen, K. Ngala, H. Huang, A. Iyer, H. F. Garcés, S. L. Suib, Adv. Funct. Mater., 2011, 21, 312-323.
[31] V. P. Santos, O. S. G. P. Soares, J. J. W. Bakker, M. F. R. Pereira, J. J. M. Órfão, J. Gascon, F. Kapteijn, J. L. Figueiredo, J. Catal., 2012, 293, 165-174.
[32] S. Ming, P. Wang, P. Liu, J. Duan, F. Mei, L. Pang, Z. Chen, T. Li, Chem. Eng. J., 2020, 379, 122287.
[33] J. Nie, H. Liu, J. Catal., 2014, 316, 57-66.
[34] R. Kumar, S. Sithambaram, S. L. Suib, J. Catal., 2009, 262, 304-313.
[35] P. Liu, M. Derchi, E. J. M. Hensen, Appl. Catal. B, 2014, 144, 135-143.
[36] J. Zhang, J.-H. Zhang, C.-B. Zhang, H. He, Acta Phys.-Chim. Sin., 2015, 31, 353-359.
[37] J. Hou, Y. Li, L. Liu, L. Ren, X. Zhao, J. Mater. Chem. A, 2013, 1, 6736-6741.
[38] L. Wang, J. Zhang, Y. Zhu, S. Xu, C. Wang, C. Bian, X. Meng, F.-S. Xiao, ACS Catal., 2017, 7, 7461-7465.
[39] D. Gu, J.-C. Tseng, C. Weidenthaler, H.-J. Bongard, B. Spliethoff, W. Schmidt, F. Soulimani, B. M. Weckhuysen, F. Schüth, J. Am. Chem. Soc., 2016, 138, 9572-9580.
[40] M. Sun, W. Li, B. Zhang, G. Cheng, B. Lan, F. Ye, Y. Zheng, X. Cheng, L. Yu, Chem. Eng. J., 2018, 331, 626-635.
[41] M. Luo, Y. Cheng, X. Peng, W. Pan, Chem. Eng. J., 2019, 369, 758-765.
[42] W. Gac, Appl. Catal. B, 2007, 75, 107-117.
[43] B. Kilos, A. T. Bell, E. Iglesia, J. Phys. Chem. C, 2009, 113, 2830-2836.
[44] G. Zhao, S. Fan, X. Pan, P. Chen, Y. Liu, Y. Lu, ChemSusChem, 2017, 10, 1380-1384.
[45] P. Liu, T. Li, H. Chen, E. J. M. Hensen, J. Catal., 2017, 347, 45-56.
[46] Y.-C. Son, V. D. Makwana, A. R. Howell, S. L. Suib, Angew. Chem. Int. Ed., 2001, 40, 4280-4283.
[47] W. Song, P. Liu, E. J. M. Hensen, Catal. Sci. Technol., 2014, 4, 2997-3003.
[48] W. Zhang, S. T. Oyama, J. Phys. Chem., 1996, 100, 10759-10767.

金属掺杂γ-MnO₂在乙醇气相选择氧化和CO氧化中的构效关系

Elucidating structure-performance correlations in gas-phase selective ethanol oxidation and CO oxidation over metal-doped γ-MnO₂

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	李显泉, 庞纪峰, 赵于嘉, 吴鹏飞, 于文广, 颜佩芳, 苏扬, 郑明远. Cu-MFI催化剂上Cu^δ⁺催化乙醇脱氢制乙醛[J]. 催化学报, 2023, 49(6): 91-101.
[2]	刘成, 刘胡润卿, 余济美, 吴棱, 李朝辉. 高效光催化金属有机框架(MOFs)的构筑策略[J]. 催化学报, 2023, 55(12): 1-19.
[3]	张宁, 杜家毅, 周纳, 王德鹏, 鲍迪, 钟海霞, 张新波. 高价金属钽掺杂无定型氧化铱用于酸性氧析出反应[J]. 催化学报, 2023, 53(10): 134-142.
[4]	王慧宁, 关安翔, 张俊波, 米玉莹, 李思, 袁涛涛, 静超, 张丽娟, 张林娟, 郑耿锋. 铜掺杂的羟基氧化镍用于高效电催化乙醇氧化[J]. 催化学报, 2022, 43(6): 1478-1484.
[5]	于晓慧, 苏海伟, 邹建平, 刘芹芹, 王乐乐, 唐华. 利用掺杂诱导的金属-N活性位点和带隙调控提升石墨相氮化碳的光催化产氢性能[J]. 催化学报, 2022, 43(2): 421-432.
[6]	李伟泽, 卢帮安, 干林, 田娜, 张朋阳, 颜伟, 陈玮鑫, 陈友虎, 周志有, 孙世刚. 高活性和高稳定性的核壳结构PtP_x@Pt/C催化氧还原[J]. 催化学报, 2021, 42(12): 2173-2180.
[7]	Ya-Qiong Su, Long Zhang, Valery Muravev, Emiel J. M. Hensen. 过渡金属掺杂铈中晶格氧的活化[J]. 催化学报, 2020, 41(6): 977-984.
[8]	昂美玉, 王伟伟, 严涵, 卫帅, 贾春江. CO氧化反应中的二氧化铈晶面效应[J]. 催化学报, 2020, 41(6): 1017-1027.
[9]	于东霓, 戴卫理, 武光军, 关乃佳, 李兰冬. 分子筛稳定的Cu物种催化乙醇脱氢制乙醛[J]. 催化学报, 2019, 40(9): 1375-1384.
[10]	张生, 刘海, 张娜, 夏荣, 况思宇, 尹鸽平, 马新宾. 铂纳米晶的电子结构调控用于高效乙醇电化学氧化[J]. 催化学报, 2019, 40(12): 1904-1911.
[11]	Fawad Ahmad, 罗赖昊, 李旭, 黄宏文, 曾杰. 通过表面钨掺杂大幅提升钯纳米立方体的燃料电池催化性能[J]. 催化学报, 2018, 39(7): 1202-1209.
[12]	方亚蓉, 郭彦炳. 铜基非贵金属异相催化剂在环境修复中的应用[J]. 催化学报, 2018, 39(4): 566-582.
[13]	拜冰阳, 乔琦, 李艳萍, 彭悦, 李俊华. 不同KIT-6老化温度制备的介孔MnO₂孔径对其催化氧化乙醇的影响[J]. 催化学报, 2018, 39(4): 630-638.
[14]	孔清泉, 冯威, 朱晓东, 张靖, 孙成华. 兼具高孔隙率和梯度孔隙结构的多孔钯块材的制备、表征及其电化学性能研究[J]. 催化学报, 2017, 38(6): 1038-1044.
[15]	徐志花, 饶丽霞, 宋海燕, 严朝雄, 张利君, 杨水彬. CeO₂修饰的Pt/Ni催化剂在碱性溶液中对乙醇电催化氧化性能的增强[J]. 催化学报, 2017, 38(2): 305-312.