K<sup>+</sup>诱导Mn-Ce固溶体增强酸性和活性氧协同促进NH<sub>3</sub>-SCR

摘要
图/表
参考文献
相关文章 (15)

全文: PDF (2340 KB) HTML (1 KB)
输出: BibTeX | EndNote (RIS)

摘要 In this work, K ions were successfully introduced into the lattice of as-prepared Mn-Ce solid solutions (MnCeO_x) by a hydrothermal method, and that was applied in NH₃-SCR. The Mn-O bonding was deeply weakened, leading to a better reducibility and oxygen desorption capacity of the K-contained catalysts according to H₂-TPR and O₂-TPD. Furthermore, the introduction of K ions could facilitate the adsorptive capacity of Brønsted acid sites for NH₃ due to the enhanced electron transfer between Mn/Ce elements according to the characterizations of XPS, NH₃-TPD and in situ DRIFT. Then, the synergy among the acidity and adsorbed active oxygen could promote the activities of catalyst MnCeK_yO_x on NH₃-SCR. With the proportion of 1:5:5 for the amounts of K, Ce and Mn elements, the best performed catalyst MnCeK₁O_x could achieve 94.6% conversion of NO at a lower temperature of 120℃. The broader temperature ranging from 40~260℃ is beneficial for the conversion of NO at many conditions. Finally, in situ DRIFTs of NH₃ and NO adsorption on MnCeO_x and MnCeK₁O_x suggested that the reaction was more sensitive to the adsorption of NH₃ than NO. For MnCeO_x, NH₃ was primarily bound on Lewis then Brønsted acid sites, resulting in the rapid aggregation of both monodentate and bidentate nitrate. For MnCeK₁O_x, the simultaneous adsorption of NH₃ on Lewis and Brønsted acid sites led to less accumulation of intermediates like bidentate nitrate. The results indicated that the introduction of K ions could efficiently improve the activity of Mn-Ce solid solution in NH₃-SCR reaction.

	服务

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	陈曦
	王小燕
	李巧艳
	王梦雪
	梁美生

关键词 ： NH₃-SCR, 钾离子, Mn-Ce固溶体, 酸性, 活性氧

Abstract：In this work, K ions were successfully introduced into the lattice of as-prepared Mn-Ce solid solutions (MnCeO_x) by a hydrothermal method, and that was applied in NH₃-SCR. The Mn-O bonding was deeply weakened, leading to a better reducibility and oxygen desorption capacity of the K-contained catalysts according to H₂-TPR and O₂-TPD. Furthermore, the introduction of K ions could facilitate the adsorptive capacity of Brønsted acid sites for NH₃ due to the enhanced electron transfer between Mn/Ce elements according to the characterizations of XPS, NH₃-TPD and in situ DRIFT. Then, the synergy among the acidity and adsorbed active oxygen could promote the activities of catalyst MnCeK_yO_x on NH₃-SCR. With the proportion of 1:5:5 for the amounts of K, Ce and Mn elements, the best performed catalyst MnCeK₁O_x could achieve 94.6% conversion of NO at a lower temperature of 120℃. The broader temperature ranging from 40~260℃ is beneficial for the conversion of NO at many conditions. Finally, in situ DRIFTs of NH₃ and NO adsorption on MnCeO_x and MnCeK₁O_x suggested that the reaction was more sensitive to the adsorption of NH₃ than NO. For MnCeO_x, NH₃ was primarily bound on Lewis then Brønsted acid sites, resulting in the rapid aggregation of both monodentate and bidentate nitrate. For MnCeK₁O_x, the simultaneous adsorption of NH₃ on Lewis and Brønsted acid sites led to less accumulation of intermediates like bidentate nitrate. The results indicated that the introduction of K ions could efficiently improve the activity of Mn-Ce solid solution in NH₃-SCR reaction.

Key words： NH₃-SCR kions Mn-Ce solid solutions acidity active oxygen

收稿日期: 2024-03-25

PACS:

X511

基金资助:国家自然科学基金(22376156);山西省基础研究计划项目(20210302124478,202203021211140);太原市生态环境局委托项目(RH2400000291)

通讯作者: 梁美生,教授,liangmeisheng@tyut.edu.cn E-mail: liangmeisheng@tyut.edu.cn

作者简介: 陈曦(1986-),男,山西太原人,讲师,博士,主要从事VOCs与NO_x的去除与控制研究.发表论文8篇.Chenxio2@tyut.edu.cn.

引用本文:

陈曦, 王小燕, 李巧艳, 王梦雪, 梁美生. K⁺诱导Mn-Ce固溶体增强酸性和活性氧协同促进NH₃-SCR[J]. 中国环境科学, 2024, 44(11): 6036-6046. CHEN Xi, WANG Xao-yan, LI Qiao-yan, WANG Meng-xue, LIANG Mei-sheng. The synergy between K⁺-induced enhanced acidity and active oxygen in Mn-Ce solid solution for promotion of NH₃-SCR. CHINA ENVIRONMENTAL SCIENCECE, 2024, 44(11): 6036-6046.

链接本文:

http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2024/V44/I11/6036

[1] 葛子豪,尹航,徐龙,等.重型柴油车实际道路氮氧化物和碳排放研究 [J]. 中国环境科学, 2024,44(2):646-653. Ge Z H, Yi H, Xu L, et al. Emissions of nitrogen oxides and carbon dioxide from heavy-duty diesel vehicles based on remote monitoring [J]. China Environmental Science, 2024,44(2):646-653.
[2] 仇滔,赵亚坤,郭冬冬,等.国Ⅵ增程式天然气重型客车实际道路排放特性 [J]. 中国环境科学, 2023,43(S1):55-61. Qiu T, Zhao Y K, Guo D D, et al. The real road emission characteristics of China VI extended-range natural gas heavy buses [J]. China Environmental Science, 2023,43(S1):55-61.
[3] 熊尚超,钟若兰,周诗雨,等.固定源氨选择性催化还原脱硝催化剂研究进展 [J]. 中国环境科学, 2023,43(5):2161-2170. Xiong S C, Zhong R L, Zhou S Y, et al. Research progress on denitrification catalysts for selective catalytic reduction of ammonia from stationary sources [J]. China Environmental Science, 2023,43(5): 2161-2170.
[4] 杨润农,余林,赵向云,等.无模板法合成的Phi分子筛在NO选择性催化还原中的应用 [J]. 化工学报, 2020,71(12):5578-5588. Yang R N, Yu L, Zhao X Y, et al. Phi zeolite synthesized by template-free method for selective catalytic reduction of NO [J]. CIESC Journal, 2020,71(12):5578-5588.
[5] Rood S, Eslava S, Manigrasso A, et al. Recent advances in gasoline three-way catalyst formulation: A review [J]. Proceedings of the Institution of Mechanical Engineers Part D-Journal of Automobile Engineering, 2020,234(4):936-949.
[6] Yao X J, Li L L, Zou W X, et al. Preparation, characterization, and catalytic performance of high efficient CeO₂-MnO_x-Al₂O₃ catalysts for NO elimination [J]. Chinese Journal of Catalysis, 2016,37(8): 1369-1380.
[7] Chen G Y, Wang Z, Lin F W, et al. Comparative investigation on catalytic ozonation of VOCs in different types over supported MnO_x catalysts [J]. Journal of Hazardous Materials, 2020,391:122218.
[8] Liu F Y, Li J Q, Sohn H Y, et al. Redox on Mn-Ce interface and its effects on low temperature selective catalytic reduction for NO_x removal [J]. Fuel, 2023,350:128806.
[9] Liu Z M, Yi Y, Zhang S X, et al. Selective catalytic reduction of NO_xwith NH₃over Mn-Ce mixed oxide catalyst at low temperatures [J]. Catalysis Today, 2013,216:76-81.
[10] Youn J R, Kim M J, Lee S J, et al. The influence of CNTs addition on Mn-Ce/TiO₂ catalyst for low-temperature NH₃-SCR of NO [J]. Catalysis Communications, 2021,152:106282.
[11] Chen L, Ren S, Liu L, et al. Catalytic performance over Mn-Ce catalysts for NH₃-SCR of NO at low temperature: Different zeolite supports [J]. Journal of Environmental Chemical Engineering, 2022, 10(2):107162.
[12] Sun Y, Fang J R, Ma T K, et al. The contrastive study of Mn-Ce/clay and Mn-Ce/TiO₂catalysts in denitration performance [J]. IOP Conference Series: Materials Science and Engineering, 2018, 2018, 423(1): 012180.
[13] Shen Z H, Xing X D, Wang S X, et al. Effect of K-modified blue coke-based activated carbon on low temperature catalytic performance of supported Mn-Ce/activated carbon [J]. Acs Omega, 2022,7(10): 8798-8807.
[14] Wang C Z, Zhao Y G, Zhang C, et al. Effect of iron doping on SO₂ and H₂O resistance of honeycomb cordierite-based Mn-Ce/Al₂O₃ catalyst for NO removal at low temperature [J]. Research on Chemical Intermediates, 2018,44(5):3135-3150.
[15] Yang Z Z, Tang P F, Xu C H, et al. Graphitic carbon nitride (g-C₃N₄) as a super support for Mn-Ce based NH₃-SCR catalyst: Improvement of catalytic performance and H₂O/SO₂ tolerance for NO_x removal [J]. Journal of the Energy Institute, 2023,108:101201.
[16] Jiménez-Fabian I, De Leon A, Jalbout A F. Interaction of alkaline-earth metals encapsulated in SWNT with simple polar molecules [J]. Journal of Molecular Structure-Theochem, 2008,849(1-3):17-22.
[17] Pillai R S, Jorge M, Gomes J R B. A DFT study on the interaction of small molecules with alkali metal ion-exchanged ETS-10 [J]. Zeitschrift Fur Kristallographie-Crystalline Materials, 2019,234(7/8): 483-493.
[18] Xu Y, Wang P, Pu Y, et al. MnCe/GAC-CNTs catalyst with high activity, SO₂ and H₂O tolerance for low-temperature NH₃-SCR [J]. Separation and Purification Technology, 2023,305:122498.
[19] Tosun R B, Hamaloğlu K Ö, Kavaklı P A, et al. A synergistic catalyst based on a multivalence monodisperse-porous microspheres with oxygen vacancies for benzyl alcohol oxidation [J]. Molecular Catalysis, 2020,497:111227.
[20] Zlatanova Z, Marinova D, Kukeva R, et al. Layered manganese oxide Mn₅O₈as a structural matrix for fast lithium and magnesium intercalation [J]. Journal of Alloys and Compounds, 2021,851:156706.
[21] Arshad F, Parveen N, Ansari S A, et al. Microwave-mediated synthesis of tetragonal Mn₃O₄ nanostructure for supercapacitor application [J]. Environmental Science and Pollution Research, 2022,30:71464-71471.
[22] Chen X, Chen X, Cai S, et al. MnO_x/Cr₂O₃ composites prepared by pyrolysis of Cr-MOF precursors containing in situ assembly of MnO_xas high stable catalyst for toluene oxidation [J]. Applied Surface Science, 2019,475:312-324.
[23] Wei Y, Liu J, Su W, et al. Controllable synthesis of Ce-doped α-MnO₂ for low-temperature selective catalytic reduction of NO [J]. Catalysis Science & Technology, 2017,7(7):1565-1572.
[24] Zhong L, Fang Q, Li X, et al. Influence of preparation methods on the physicochemical properties and catalytic performance of Mn-Ce catalysts for lean methane combustion [J]. Applied Catalysis A: General, 2019,579:151-158.
[25] Chen X, Chen X, Yu E, et al. In situ pyrolysis of Ce-MOF to prepare CeO₂ catalyst with obviously improved catalytic performance for toluene combustion [J]. Chemical Engineering Journal, 2018,344:469-479.
[26] 张彤,李巧艳,王小燕,等.Pr掺杂Ni~(Ce-Zr) O₂/Al₂O₃用于三效催化(TWC)反应:缺陷性质-活性关系 [J]. 中国环境科学, 2023, 43(10):5157-5169. Zhang T, Li Q Y, Wang X Y, et al. Pr-doped Ni~(Ce-Zr) O₂/Al₂O₃ for TWC reaction: defect property-activity relationship [J]. China Environmental Science, 2023,43(10):5157-5169.
[27] Krause S, Reuter F S, Ehrling S, et al. Impact of defects and crystal size on negative gas adsorption in DUT-49analyzed by in situ Xe-129NMR spectroscopy [J]. Chemistry of Materials, 2020,32(11): 4641-4650.
[28] Lu S, Yang H, Zhou Z, et al. Effect of In₂O₃ particle size on CO₂ hydrogenation to lower olefins over bifunctional catalysts [J]. Chinese Journal of Catalysis, 2021,42(11):2038-2048.
[29] Araia A, Wang Y, Robinson B, et al. Microwave-assisted ammonia synthesis over Cs-Ru/CeO₂ catalyst at ambient pressure: Effects of metal loading and support particle size [J]. Catalysis Communications, 2022,170:106491.
[30] Zhao L, Yang Y, Liu J. Atomic-level mechanism and microkinetics of HCHO oxidation over K-doped MnO₂ catalysts [J]. Journal of Environmental Chemical Engineering, 2023,11(5):110958.
[31] 李叶,殷喜平,朱玉霞,等.催化裂化催化剂比表面积的测定 [J]. 石油学报(石油加工), 2017,33(6):1053-1060. Li Y, Yin X P, Zhu Y X, et al. Test method for specific surface area of FCC catalyst [J]. Acta Petrolei Sinia (Petroleum Processing Section), 2017,33(6):1053-1060.
[32] Wang L, Chen M, Yu X, et al. Preparation, characterization and catalytic performance of ordered macroporous-mesoporous SiO₂-supported MnMO_x catalysts for soot combustion [J]. Catalysis Today, 2021,364:21-34.
[33] Qing M, Zhang L, Liu L, et al. Depth investigation of the regulation mechanism of SiO₂ on the denitrification performance and sulfur resistance of MnCe/Ti SCR catalyst [J]. Chemical Engineering Journal, 2023,475:145852.
[34] Liu Y, Deng H, Lu Z, et al. The study of MnO₂ with different crystalline structures for U(VI) elimination from aqueous solution [J]. Journal of Molecular Liquids, 2021,335:116296.
[35] Wang H, Liu F, Yang W, et al. Toluene conversion by using different morphology MnO₂ catalyst [J]. Aerosol and Air Quality Research, 2022,22(2):210365.
[36] Xie L, Du K, Ren S, et al. Promoting effect of N₂ calcination on FeCeO_xfor selective catalytic reduction of NO_x with NH₃ [J]. Journal of Chemical Technology and Biotechnology, 2023,98(10):2568-2576.
[37] Utara S, Jantachum P, Hunpratub S, et al. Enhanced dielectric constant and mechanical investigation of epoxidized natural rubber with TM-doped CeO₂ nanocomposites [J]. Journal of Alloys and Compounds, 2023,939:168601.
[38] Grabchenko M V, Mamontov G V, Zaikovskii V I, et al. The role of metal-support interaction in Ag/CeO₂ catalysts for CO and soot oxidation [J]. Applied Catalysis B: Environmental, 2020,260:118148.
[39] Bu Y, Chen Y, Jiang G, et al. Understanding of Au-CeO₂ interface and its role in catalytic oxidation of formaldehyde [J]. Applied Catalysis B: Environmental, 2020,260:118138.
[40] Zhang B, Zhang S, Liu B. Effect of oxygen vacancies on ceria catalyst for selective catalytic reduction of NO with NH₃ [J]. Applied Surface Science, 2020,529:147068.
[41] Gangwar D, Rath C. Structural, optical and magnetic properties of α-and β-MnO₂ nanorods [J]. Applied Surface Science, 2021,557:149693.
[42] Li R, Zhang L, Zhu S, et al. Layered δ-MnO₂ as an active catalyst for toluene catalytic combustion [J]. Applied Catalysis A: General, 2020, 602:117715.
[43] Liu S, Xue W, Ji Y, et al. Interfacial oxygen vacancies at Co₃O₄-CeO₂ heterointerfaces boost the catalytic reduction of NO by CO in the presence of O₂ [J]. Applied Catalysis B: Environmental, 2023,323: 122151.
[44] Guo K, Ji J, Song W, et al. Conquering ammonium bisulfate poison over low-temperature NH₃-SCR catalysts: A critical review [J]. Applied Catalysis B: Environmental, 2021,297:120388.
[45] Wang C, Gao F, Ko S, et al. Structural control for inhibiting SO₂ adsorption in porous MnCe nanowire aerogel catalysts for low-temperature NH₃-SCR [J]. Chemical Engineering Journal, 2022,434: 134729.
[46] Yang C, Yang J, Jiao Q, et al. Promotion effect and mechanism of MnO_x doped CeO₂ nano-catalyst for NH₃-SCR [J]. Ceramics International, 2020,46(4):4394-4401.
[47] Gao G, Shi J W, Liu C, et al. Mn/CeO₂ catalysts for SCR of NO_x with NH₃: comparative study on the effect of supports on low-temperature catalytic activity [J]. Applied Surface Science, 2017,411:338-346.
[48] Díaz C C, Pilar Yeste M, Vidal H, et al. In situ generation of Mn_1−xCe_x system on cordierite monolithic supports for combustion of n-hexane. Effects on activity and stability [J]. Fuel, 2020,262:116564.
[49] Fan A, Jing Y, Guo J, et al. Investigation of Mn doped perovskite La-Mn oxides for NH₃-SCR activity and SO₂/H₂O resistance [J]. Fuel, 2022,310:122237.
[50] Li M, Zeng Y, Zhang S, et al. Inhibition effect of naphthalene on V₂O₅-WO₃/TiO₂ catalysts for low-temperature NH₃-SCR of NO [J]. Fuel, 2022,322:124157.
[51] Yi Y, Liu H, Chu B, et al. Catalytic removal NO by CO over LaNi_0.5M_0.5O₃ (M=Co, Mn, Cu) perovskite oxide catalysts: Tune surface chemical composition to improve N₂ selectivity [J]. Chemical Engineering Journal, 2019,369:511-521.
[52] Yao X, Kong T, Chen L, et al. Enhanced low-temperature NH₃-SCR performance of MnO_x/CeO₂ catalysts by optimal solvent effect [J]. Applied Surface Science, 2017,420:407-415.
[53] Wang H, Zhu T, Qiao Y, et al. Investigation of the promotion effect of Mo doped CuO catalysts for the low-temperature performance of NH₃-SCR reaction [J]. Chinese Chemical Letters, 2022,33(12):5223-5227.
[54] Ma N, Hao Z, Liu G, et al. Mechanistic insight into the dynamic transformation of acid sites on ceria supported molybdenum oxide catalyst for NO_x reduction [J]. Journal of Environmental Chemical Engineering, 2022,10(5):108114.
[55] Li Y, Gao W, Deng J, et al. CuO_x and WO_x modified CeO₂-TiO₂ with various morphologies for the selective catalytic reduction of NO_x with NH₃ [J]. Applied Surface Science, 2023,641:158438.
[56] Jiang Y, Shi W, Lai C, et al. The deactivation effect of Na₂O and NaCl on CeO₂-TiO₂ catalysts for selective catalytic reduction of NO with NH₃ [J]. Journal of the Energy Institute, 2020,93(4):1332-1340.
[57] Fan J, Ning P, Song Z, et al. Mechanistic aspects of NH₃-SCR reaction over CeO₂/TiO₂-ZrO₂-SO₄²⁻ catalyst: In situ DRIFTS investigation [J]. Chemical Engineering Journal, 2018,334:855-863.
[58] Zang P, Liu J, He Y, et al. LDH-derived preparation of CuMgFe layered double oxides for NH₃-SCR and CO oxidation reactions: Performance study and synergistic mechanism [J]. Chemical Engineering Journal, 2022,446:137414.
[59] Liu S, Yao P, Lin Q, et al. Optimizing acid promoters of Ce-based NH₃-SCR catalysts for reducing NO_x emissions [J]. Catalysis Today, 2021,382:34-41.
[60] Xue H, Guo X, Meng T, et al. NH₃-SCR of NO over M/ZSM-5 (M = Mn, Co, Cu) catalysts: An in-situ DRIFTS study [J]. Surfaces and Interfaces, 2022,29:101722.