利用氧化石墨烯桥接剂无焙烧高效合成柔性SCR催化剂: 催化性能、机理和动力学研究

doi:10.1016/S1872-2067(25)64722-X

摘要/Abstract

摘要： 选择性催化还原(SCR)是目前NO_x处理的主流技术, 其核心为脱硝催化剂. NH₃-SCR反应涉及NH₃, NO和O₂的传输/吸附/活化, 反应物的有效快速扩散传输尤为重要, 因此SCR催化剂常采用阻力相对较小的整体催化剂. 整体催化剂从物理特性上可分为刚性和柔性两种. 柔性催化剂因其优异的可塑性、轻质性和可加工性而在气体污染物处理领域展现出巨大的应用潜力, 然而其在实际工业应用中仍面临力学性能差、金属活性组分易脱落、催化效率不高等关键问题. 如何在保持柔性结构的同时实现高效、稳定的催化性能, 是当前该领域研究的重要方向. 为此, 本文引入氧化石墨烯(GO)作为桥接剂, 构建出一种兼具机械柔性和高催化活性的复合催化材料.
本文以三聚氰胺海绵为基体, 并引入GO进行表面改性, 通过负载二元金属活性组分Mn和Co, 制备出柔性SCR催化剂MnCo-MS@xGO (其中x为GO的添加量), 制备过程无需高温煅烧. 通过优选GO负载量, MnCo-MS@0.05GO催化剂NO_x转化率可达95%以上, 该催化剂在多个温度段均表现出高效的催化活性和良好的抗失活能力, 显示出优异的热稳定性和重复使用性能. 结构表征结果表明, 引入GO后催化剂表面粗糙度显著增加, 金属活性位点分布更加均匀稳定, 有效避免了传统柔性载体中金属颗粒易脱落、团聚等问题. 理化性能表征结果表明, GO的加入促进了催化剂表面高价态Mn和Co的形成, 提高了有效催化物种的比例, 从而增强了NH₃-SCR反应中的氧化还原能力. 电子传输性能的提升也通过电化学测试得到验证, GO的存在有效降低了电荷传递阻抗, 促进电子在催化反应过程中的流动, 提升了整体反应速率. 为深入探讨NO还原机制, 进一步通过原位漫反射红外光谱、瞬态反应实验以及稳态动力学进行机理研究. 在SCR反应过程中, N₂的生成速率与气相NO浓度之间呈线性关系. SCR反应中N₂O的生成主要受L-H和E-R两种机理控制, 随反应温度升高, E-R机理的贡献占比逐渐增加, E-R和L-H机理协同促进了催化速率的提升.
综上所述, 本研究为柔性SCR催化剂设计提供了新的功能调控策略, 通过引入二维GO纳米片修饰三聚氰胺海绵, 增强其与活性组分的结合力, 促进材料内部的电子传输. 制备方法无需高温预处理和煅烧, 提高催化剂循环利用性, 为环保高效的柔性催化剂制备提供了新的研究思路.

关键词: 柔性材料, 氨-选择性催化还原, 氧化石墨烯, 氧化还原媒介, 动力学研究

Abstract: The mechanical performance of flexible catalysts remains a significant challenge for industrial applications. In this study, graphene oxide (GO) functions as both a binder and a redox mediator, serving as a crucial "bridge" between metal species and the organic foam, thereby substantially enhancing NO_x conversion efficiency. Catalytic activity tests demonstrate that the GO-modified MnCo-MS@0.05GO catalyst achieves a NO_x conversion rate exceeding 95%. The incorporation of GO strengthens the adhesion between the organic foam and metal components, increases the surface roughness of the sponge, and ensures the uniform and stable distribution of metal active sites. Additionally, GO enhances the content of effective catalytic species, improves electron transfer efficiency in the selective catalytic reduction reaction, and reduces diffusion resistance. To elucidate the NO reduction mechanism, in situ diffuse reflectance infrared Fourier transform spectroscopy and transient reaction studies were performed. The results indicate that as the reaction temperature increases, both the Eley-Rideal and Langmuir-Hinshelwood mechanisms contribute to promoting the SCR reaction rate.

Key words: Flexible materials, Selective catalytic reduction by NH₃, Graphene oxide, Redox mediator, Kinetics studies

熊廷楷, 高凤雨, 温佳俊, 易红宏, 赵顺征, 唐晓龙. 利用氧化石墨烯桥接剂无焙烧高效合成柔性SCR催化剂: 催化性能、机理和动力学研究[J]. 催化学报, DOI: 10.1016/S1872-2067(25)64722-X.

Tingkai Xiong, Fengyu Gao, Jiajun Wen, Honghong Yi, Shunzheng Zhao, Xiaolong Tang. Efficient synthesis of flexible SCR catalysts utilizing graphene oxide as a bridging agent without calcination: Catalytic performance, mechanism and kinetics studies[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(25)64722-X.

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参考文献

[1] K. Guo, J. Ji, W. Song, J. Sun, C. Tang, L. Dong,Appl. Catal. B, 2021, 297, 120388.
[2] X. Fang, Y. Liu, L. Chen, Y. Cheng,Chem. Eng. J., 2020, 399, 125798.
[3] X. Wu, H. Meng, Y. Du, J. Liu, B. Hou, X. Xie,ACS Appl. Mater. Interfaces, 2019, 11, 32917-32927.
[4] C. Wang, F. Gao, S. Ko, H. Liu, H. Yi, X. Tang,Chem. Eng. J., 2022, 434, 134729.
[5] K. Zhang, N. Luo, Z. Huang, G. Zhao, F. Chu, R. Yang, X. Tang, G. Wang, F. Gao, X. Huang,Chem. Eng. J., 2023, 476, 146889.
[6] J. Gao, C. Lu, W. Su, Z. Li, X. Li, Y. Zhao, G. Deng, K. Li,Process. Saf. Environ. Prot., 2022, 161, 658-668.
[7] J. Xie, J. Ye, F. Pan, X. Sun, K. Ni, H. Yuan, X. Wang, N. Shu, C. Chen, Y. Zhu,Adv. Mater., 2019, 31, 1805654.
[8] H. Guan, R. Lian, R. Li, J. Zhu, Z. Zhao, L. Liu, X. Chen, C. Jiao, S. Kuang,Adv. Funct. Mater., 2024, 34, 2313224.
[9] D. Lin, P. Duan, W. Yang, X. Huang, Y. Zhao, C. Wang, Q. Pan,Chem. Eng. J., 2022, 430, 132817.
[10] R. Chen, X. Fang, J. Li, Y. Zhang, Z. Liu,Chem. Eng. J., 2023, 452, 139207.
[11] W. Song, Q. Cheng, L. Han, J. Ji, Y. Cai, W. Tan, J. Sun, C. Tang, L. Dong,Appl. Catal. B, 2024, 344, 123607.
[12] L. Han, S. Cai, M. Gao, J.-Y. Hasegawa, P. Wang, J. Zhang, L. Shi, D. Zhang,Chem. Rev., 2019, 119, 10916-10976.
[13] Y. Shen, T. Li, J. Yang, A. Wang, L. Wang, W. Zhan, Y. Guo, Y. Guo,Chem. Eng. J., 2023, 473, 145275.
[14] J. Lin, X. Hu, Y. Li, W. Shan, X. Tan, H. He,Appl. Catal. B, 2023, 331, 122705.
[15] X. Li, Y. Niu, J. Li, M. Yang, R. Chen, D. Shao, X. Zheng, C. Zhang, Y. Qi,Chem. Eng. J., 2023, 454, 140180.
[16] W. Zhang, X. Shi, Z. Yan, Y. Shan, Y. Zhu, Y. Yu, H. He,ACS Catal., 2021, 11, 9825-9836.
[17] T. Xiong, F. Gao, J. Wang, J. Wen, Y. Zhou, H. Yi, S. Zhao, X. Tang,Sep. Purif. Technol., 2024, 333, 125949.
[18] H. Chen, Z. Yu, R. Jiang, J. Huang, Y. Hou, Y. Zhang, H. Zhu, B. Wang, M. Wang, W. Tang,Nanoscale, 2021, 13, 6644-6653.
[19] L. Shi, C. Wu, Y. Wang, Y. Dou, D. Yuan, H. Li, H. Huang, Y. Zhang, I. D. Gates, X. Sun, T. Ma,Adv. Funct. Mater., 2022, 32, 2202571.
[20] Z. Zhao, H. Ren, D. Yang, Y. Han, J. Shi, K. An, Y. Chen, Y. Shi, W. Wang, J. Tan, X. Xin, Y. Zhang, Z. Jiang,ACS Catal., 2021, 11, 9986-9995.
[21] S. Mou, J. Huang, J. Hou, C. Gao, J. Bai, G. Xu, P. Li,ACS Appl. Nano Mater., 2022, 5, 5326-5334.
[22] S. Presolski, M. Pumera,Angew. Chem. Int. Ed., 2018, 57, 16713-16715.
[23] J.-M. Jeon, T. L. Kim, Y.-S. Shim, Y. R. Choi, S. Choi, S. Lee, K. C. Kwon, S.-H. Hong, Y.-W. Kim, S. Y. Kim, M. Kim, H. W. Jang,Adv. Mater., 2017, 29, 1605929.
[24] C.-H. Deng, J.-L. Gong, P. Zhang, G.-M. Zeng, B. Song, H.-Y. Liu,J. Colloid Interface Sci., 2017, 488, 26-38.
[25] Z. Chen, S. Ren, X. Xing, X. Li, L. Chen, M. Wang,Fuel, 2023, 335, 126986.
[26] X. Tang, C. Li, H. Yi, L. Wang, Q. Yu, F. Gao, X. Cui, C. Chu, J. Li, R. Zhang,Chem. Eng. J., 2018, 333, 467-476.
[27] N. Zhang, L. Li, Y. Guo, J. He, R. Wu, L. Song, G. Zhang, J. Zhao, D. Wang, H. He,Appl. Catal. B, 2020, 270, 118860.
[28] G. Xu, X. Guo, X. Cheng, J. Yu, B. Fang,Nanoscale, 2021, 13, 7052-7080.
[29] L. Jiang, Q. Liu, G. Ran, M. Kong, S. Ren, J. Yang, J. Li,Chem. Eng. J., 2019, 370, 810-821.
[30] A. Y. Molokova, R. K. Abasabadi, E. Borfecchia, O. Mathon, S. Bordiga, F. Wen, G. Berlier, T. V. W.Janssens, K. A. Lomachenko,Chem. Sci., 2023, 14, 11521-11531.
[31] J. D. Bjerregaard, M. Votsmeier, H. Grönbeck,J. Catal., 2023, 417, 497-506.
[32] T. Zhao, X. Huang, R. Cui, G. Zhang, Z. Tang,Nanoscale, 2023, 15, 12540-12557.
[33] G. Huang, J. Yang, C. Lv, D. Li, D. Fang,J. Environ. Chem. Eng., 2023, 11, 110966.
[34] D. Y. Kornilov, S. P. Gubin,Russ. J. Inorg. Chem., 2020, 65, 1965-1976.
[35] Y. Zhu, Z. Zhang,J. Build. Eng., 2021, 44, 103302.
[36] L. Sun, K. Li, Z. Zhang, X. Hu, H. Tian, Y. Zhang, X. Yang,Catal. Sci. Technol., 2019, 9, 1602-1608.
[37] W. Liu, Y. Gao, Y. Yang, Q. Zou, G. Yang, Z. Zhang, H. Li, Y. Miao, H. Li, Y. Huo,ChemCatChem, 2018, 10, 2394-2400.
[38] J.-B. Wu, M.-L. Lin, X. Cong, H.-N. Liu, P.-H. Tan,Chem. Soc. Rev., 2018, 47, 1822-1873.
[39] S. Wan, Y. Chen, Y. Wang, G. Li, G. Wang, L. Liu, J. Zhang, Y. Liu, Z. Xu, A. P. Tomsia, L. Jiang, Q. Cheng,Matter, 2019, 1, 389-401.
[40] J. Liu, Y. Liu, H.-B. Zhang, Y. Dai, Z. Liu, Z.-Z. Yu,Carbon, 2018, 132, 95-103.
[41] N. Aljammal, C. Jabbour, S. Chaemchuen, T. Juzsakova, F. Verpoort,Catalysts, 2019, 9, 512.
[42] N. Al Amery, H. R. Abid, S. Al-Saadi, S. Wang, S. Liu,Mater. Today Chem., 2020, 17, 100343.
[43] W. Liu, M. Li, H. Jiang, X. Zhang, J. Qiao,J. Nanopart. Res., 2019, 21, 36.
[44] C. Chen, X. Zhu, B. Chen,Environ. Sci. Technol., 2019, 53, 1509-1517.
[45] X. Zhu, G. Zhou, G. He, L. Ma, B. Xu, F. Sun,Surf. Interfaces, 2023, 36, 102575.
[46] T. Bakhiia, A. Y. Romanchuk, K. I. Maslakov, A. A. Averin, S. N. Kalmykov,Energies, 2022, 15, 7371.
[47] C. Wang, X. Tang, H. Yi, F. Gao, S. Ni, R. Zhang, Y. Shi,Colloids Surf. A, 2021, 612, 126007.
[48] J. O. Olowoyo, M. Kumar, B. Singh, V. O. Oninla, J. O. Babalola, H. Valdés, A. V. Vorontsov, U. Kumar,Carbon, 2019, 147, 385-397.
[49] I. Shown, H.-C. Hsu, Y.-C. Chang, C.-H. Lin, P. K. Roy, A. Ganguly, C.-H. Wang, J.-K. Chang, C.-I. Wu, L.-C. Chen, K.-H. Chen,Nano Lett., 2014, 14, 6097-6103.
[50] X. Tang, C. Wang, F. Gao, R. Zhang, Y. Shi, H. Yi,J. Colloid Interface Sci., 2021, 603, 291-306.
[51] T. Zhang, T. Shi, Y. Wang, Y. Hao, Y. Gao, H. Li, L. Jia, F. Liu, S. Zeng,J. Catal., 2024, 429, 115260.
[52] X. Xu, X. Liu, L. Ma, N. Liang, S. Yang, H. Liu, J. Sun, F. Huang, C. Sun, L. Dong,ACS Catal., 2024, 14, 3028-3040.
[53] F. Liu, J. Li, H. Y. Sohn, C. Chen, J. Yang, X. Liu, Y. Lan, W. Zhang, Q. Wang, L. Liu,Fuel, 2023, 350, 128806.
[54] Y. Wu, Y. Li, J. He, X. Fang, P. Hong, M. Nie, W. Yang, C. Xie, Z. Wu, K. Zhang, L. Kong, J. Liu,J. Colloid Interface Sci., 2020, 562, 1-11.
[55] A. Ambrosi, C. K. Chua, N. M. Latiff, A. H. Loo, C. H. A.Wong, A. Y. S. Eng, A. Bonanni, M. Pumera,Chem. Soc. Rev., 2016, 45, 2458-2493.
[56] H. Liu, F. Gao, S. Ko, N. Luo, X. Tang, H. Yi, Y. Zhou,Appl. Catal. B, 2023, 330, 122651.
[57] S. Yang, C. Wang, J. Li, N. Yan, L. Ma, H. Chang,Appl. Catal. B, 2011, 110, 71-80.
[58] L.-Y. Lin, Y.-C. Wang, Z.-L. Liu,Chem. Eng. J., 2024, 484, 149637.
[59] S. Yang, Y. Fu, Y. Liao, S. Xiong, Z. Qu, N. Yan, J. Li,Catal. Sci. Technol., 2014, 4, 224-232.
[60] S. Yang, S. Xiong, Y. Liao, X. Xiao, F. Qi, Y. Peng, Y. Fu, W. Shan, J. Li,Environ. Sci. Technol., 2014, 48, 10354-10362.