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

张彤; 李巧艳; 王小燕; 梁美生; 莱卓君

PDF(1853 KB)

中国环境科学 ›› 2023, Vol. 43 ›› Issue (10) : 5157-5169.

水污染与控制

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

张彤, 李巧艳, 王小燕, 梁美生, 莱卓君

作者信息 +

Pr-doped Ni~(Ce-Zr)O₂/Al₂O₃ for TWC reaction: Defect property-activity relationship

ZHANG Tong, LI Qiao-yan, WANG Xiao-yan, LIANG Mei-sheng, LAI Zhuo-jun

Author information +

文章历史 +

摘要

为探究稀土金属掺杂CeZrO_x催化剂引发的缺陷结构对汽车尾气污染控制的影响，合成了不同Pr掺杂量的Ni~（Ce₆Zr_4-xPr_x）O₂/Al₂O₃系列催化剂，并对其进行了TWC催化活性评价、耐SO₂性能测试和系统性表征，研究Pr掺杂引起的缺陷性质对催化性能的影响.结果表明，Pr掺杂Ni~（Ce-Zr）O₂/Al₂O₃产生两种缺陷：氧空位（O_v）和晶格扭曲，Pr的掺杂水平控制着缺陷位的类型和浓度.O_v在TWC反应中起关键作用.在Pr掺杂的Ni~（Ce₆Zr_4-xPr_x）O₂/Al₂O₃催化剂中，TWC的催化性能显著地依赖于O_v浓度， Pr掺杂产生的O_v可改善NiO的分散，加速本体氧的迁移和扩散，促进大量活性氧物种的形成，促进CO和HC的吸附和氧化，也可激活和削弱N-O键促进NO的解离.具有最多O_v数量的Ni~（Ce6Zr3Pr1）O2/Al2O3在200 ~ 600 ℃时表现出最突出的三效催化性能和较好的抗硫性能，而晶格扭曲对催化性能影响并不大.

Abstract

To investigate the influence of defect structures in CeZrO_x catalysts, which induced by rare earth metal doping, on the control of automotive exhaust pollution, series of Ni~(Ce₆Zr_4-xPr_x)O₂/Al₂O₃ catalysts with varied Pr doping content were synthesized, and their TWC activities and SO₂ resistance performance were tested. The prepared catalysts were also systematically characterized. The collected results suggested that two kinds of defects in Ni~(Ce-Zr)O₂/Al₂O₃ were generated after Pr doping, including oxygen vacancies (O_v) and lattice distortion, whose types and concentrations depended on the Pr doping content. The results also indicated that O_v play a vital role on the catalytic performance, whereas lattice distortion play a small effect on it. In addition, it is found that the concentrations of O_v in as-prepared catalysts determined their TWC catalytic performance, the Ni~(Ce₆Zr₃Pr₁)O₂/Al₂O₃ catalyst with most O_v concentrations performed superior three-way catalytic performance at 200~600℃ and also exhibited excellent anti-sulfur poisoning performance after introducing 100ppm SO₂ at 600℃. This is because O_v not only promoted the dispersion of NiO, accelerating the migration and diffusion of bulk oxygen to form active oxygen species, thus promoting the adsorption and oxidation of CO and HC species on the catalyst, but also the O_v can weaken the N-O bonds boosting the dissociative adsorption and reduction of NO species.

导出引用

张彤, 李巧艳, 王小燕, 梁美生, 莱卓君. 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 Tong, LI Qiao-yan, WANG Xiao-yan, LIANG Mei-sheng, LAI Zhuo-jun. Pr-doped Ni~(Ce-Zr)O₂/Al₂O₃ for TWC reaction: Defect property-activity relationship[J]. China Environmental Science. 2023, 43(10): 5157-5169

中图分类号： X703.5

参考文献

[1] Farrauto R J, Deeba M, Alerasool S.Gasoline automobile catalysis and its historical journey to cleaner air[J]. Nature Catalysis, 2019,2(7):603-13.
[2] Chen K, Wan J, Lin J, et al. Comparative study of three-way catalytic performance over Pd/CeO₂-ZrO₂-Al₂O₃ and Pd/La-Al₂O₃ catalysts:New insights into microstructure and thermal stability[J]. Molecular Catalysis, 2022,526112361.
[3] Lambert C K. Current state of the art and future needs for automotive exhaust catalysis[J]. Nature Catalysis, 2019,2(7):554-557.
[4] 张昭良,何洪,赵震.汽车尾气三效催化剂研究和应用40年[J]. 环境化学, 2021,40(7):1937-1944. Zhang Z L, He H, Zhao Z. 40years of research and application of three-way catalysts for gasoline automobiles[J]. Environmental Chemistry, 2021,40(7):1937-1944.
[5] Granger P, Parvulescu V I.Catalytic NO_x Abatement Systems for Mobile Sources:From Three-Way to Lean Burn after-Treatment Technologies[J]. Chemical Reviews, 2011,111(5):3155-316.
[6] Liu H, Liu L, Wei L,et al.Preparation of three-dimensionally ordered macroporous MFe₂O₄ (M=Co, Ni, Cu) spinel catalyst and its simultaneous catalytic application in CO oxidation and NO+CO reaction[J]. Fuel, 2020,272117738.
[7] Escandón L S, Ordóñez S, Vega A, et al. Sulphur poisoning of palladium catalysts used for methane combustion:Effect of the support[J]. Journal of Hazardous Materials, 2008,153(1):742-50.
[8] Hilli Y, Kinnunen N M, Suvanto M, et al. Preparation and characterization of Pd-Ni bimetallic catalysts for CO and C₃H₆ oxidation under stoichiometric conditions[J]. Applied Catalysis A:General, 2015,49785-49795.
[9] Wen J J, Xie Y, Ma Y P, et al. Engineering of surface properties of Ni-CeZrAl catalysts for dry reforming of methane[J]. Fuel, 2022,308.
[10] Tang K, Liu W, Li J, et al. The Effect of Exposed Facets of Ceria to the Nickel Species in Nickel-Ceria Catalysts and Their Performance in a NO + CO Reaction[J]. ACS Appl Mater Interfaces, 2015,7(48):26839-26849.
[11] Wang Y, Zhu A, Zhang Y, et al. Catalytic reduction of NO by CO over NiO/CeO₂ catalyst in stoichiometric NO/CO and NO/CO/O₂ reaction[J]. Applied Catalysis B:Environmental, 2008,81(1):141-149.
[12] Tang C, Sun B, Sun J, et al. Solid state preparation of NiO-CeO₂ catalyst for NO reduction[J]. Catalysis Today, 2017,281575-582.
[13] 侯丽敏,吕秉娱,付善聪,等.Ni改性对稀土尾矿NH₃-SCR脱硝性能的影响[J]. 中国环境科学, 2023,43(4):1574-1581. Hou L M, Lü B Y, Fu S C, et al. Effect of Ni modification on NH₃-SCR denitrification performance of rare earth tailings. China Environmental Science, 2023,43(4):1574-1581.
[14] 郭磊,张涛,常化振,等.Ce掺杂改性Ni-Al-O_x催化剂CO-NO反应性能[J]. 中国环境科学, 2018,38(9):3313-3321. Guo L, Zhang T, Chang H Z, et al. Study on Ce-doped Ni-Al-O_x catalysts for NO reduction by CO. China Environmental Science, 2018, 38(9):3313-3321.
[15] Zhang Y, Qu T, Bi F,et al.Trimetallic (Co/Ni/Cu) Hydroxyphosphate Nanosheet Array as Efficient and Durable Electrocatalyst for Oxygen Evolution Reaction[J]. ACS Sustainable Chemistry & Engineering, 2018,6(12):16859-16866.
[16] Li G, Zhao B, Wang Q, et al. The effect of Ni on the structure and catalytic behavior of model Pd/Ce_0.67Zr_0.33O₂ three-way catalyst before and after aging[J]. Applied Catalysis B:Environmental, 2010, 97(1):41-48.
[17] Gao F, Tang X, Yi H, et al. Promotional mechanisms of activity and SO₂ tolerance of Co-or Ni-doped MnO_x-CeO₂ catalysts for SCR of NO_x with NH₃ at low temperature[J]. Chemical Engineering Journal, 2017,31720-31731.
[18] Zhang L, Qu H, Du T, et al. H₂O and SO₂ tolerance, activity and reaction mechanism of sulfated Ni-Ce-La composite oxide nanocrystals in NH₃-SCR[J]. Chemical Engineering Journal, 2016, 296122-296131.
[19] Wang L, Yu X, Wei Y, et al. Research advances of rare earth catalysts for catalytic purification of vehicle exhausts-Commemorating the 100th anniversary of the birth of Academician Guangxian Xu[J]. Journal of Rare Earths, 2021,39(10):1151-1180.
[20] Wang G, Jing Y, Ting K W, et al. Effect of oxygen storage materials on the performance of Pt-based three-way catalysts[J]. Catalysis Science & Technology, 2022,12(11):3534-3548.
[21] Xie C, Yan D, Li H, et al. Defect Chemistry in Heterogeneous Catalysis:Recognition, Understanding, and Utilization[J]. ACS Catalysis, 2020,10(19):11082-11098.
[22] Zhang Z, Wang Y, Lu J, et al. Pr-Doped CeO₂ catalyst in the Prins Condensation-Hydrolysis Reaction:Are all of the defect sites catalytically active?[J]. ACS Catalysis, 2018,8(4):2635-2644.
[23] Ke J, Xiao J W, Zhu W, et al. Dopant-induced modification of active site structure and surface bonding mode for high-performance Nanocatalysts:CO Oxidation on Capping-free (110)-oriented CeO₂:Ln (Ln=La-Lu) Nanowires[J]. Journal of the American Chemical Society, 2013,135(40):15191-15200.
[24] Chen S, Su Z, Wang H,et al.Lattice distortion in Mn₃O₄/SmO_x nanocomposite catalyst for enhanced carbon monoxide oxidation[J]. Chemical Engineering Journal, 2023,451138635.
[25] Shen Y, Ma Y, Zhu S. Promotional effect of zirconium additives on Ti_0.8Ce_0.2O₂ for selective catalytic reduction of NO[J]. Catalysis Science & Technology, 2012,2(3):589-599.
[26] Westermann A, Geantet C, Vernoux P, et al. Defects band enhanced by resonance Raman effect in praseodymium doped CeO₂[J].Journal of Raman Spectroscopy, 2016,47(10):1276-1279.
[27] Xiong Y, Yao X, Tang C, et al. Effect of CO-pretreatment on the CuO-V₂O₅/γ-Al₂O₃ catalyst for NO reduction by CO[J]. Catalysis Science & Technology, 2014,4(12):4416-4425.
[28] Wang T, Li Y, Zhou R X. The relation of structure and metal-support interaction with three-way catalytic performance of Rh/(Ce,Zr,La)O₂ catalysts[J]. Environmental Science and Pollution Research, 2020,27(24):30352-30366.
[29] Deng C, Qian, et al. Influences of doping and thermal stability on the catalytic performance of CuO/Ce₂₀M₁O_x (M=Zr, Cr, Mn, Fe, Co, Sn) catalysts for NO reduction by CO[J]. RSC Advances, 2016, 6113630-611363.
[30] Xue Y, Yang L, Lin S, et al. New insight into the doping effect of Pr₂O₃ on the structure-activity relationship of Pd/CeO₂-ZrO₂ catalysts by Raman and XRD rietveld analysis[J]. Journal of Physical Chemistry C, 2015,119(11):150309065540001.
[31] Wang Q, Zhao B, Li G, et al. Application of rare earth modified Zr-based ceria-zirconia solid solution in three-way catalyst for automotive emission control[J]. Environmental Science & Technology, 2010,44(10):3870-3875.
[32] Wang Q, Li G, Bo Z, et al. The effect of rare earth modification on ceria-zirconia solid solution and its application in Pd-only three-way catalyst[J]. Journal of Molecular Catalysis A Chemical, 2011,339(1/2):52-60.
[33] Zhang Z, Wang Y, Lu J, et al. Conversion of isobutene and formaldehyde to diol using praseodymium-doped CeO₂ catalyst[J]. ACS Catalysis, 2016,6(12):8248-8254.
[34] Zhou B, Zhou J, Li H, et al. A study of the microstructures and mechanical properties of Ti₆Al₄V fabricated by SLM under vacuum[J]. Materials Science and Engineering:A, 2018,7241-7210.
[35] Guo M, Liu X, Amorelli A. Activation of small molecules over praseodymium-doped ceria[J]. Chinese Journal of Catalysis, 2019, 40(11):1800-1809.
[36] Martínez-munuera J C, Zoccoli M, Giménez-mañogil J, et al. Lattice oxygen activity in ceria-praseodymia mixed oxides for soot oxidation in catalysed Gasoline Particle Filters[J]. Applied Catalysis B:Environmental, 2019,245706-245720.
[37] Frizon V, Bassat J M, Pollet M F, et al.Tuning the Pr valence state to design high oxygen mobility, redox and transport properties in the CeO₂-ZrO₂-PrO_x phase diagram[J].The Journal of Physical Chemistry C, 2019,123(11)DOI:10.1021/acs.jpcc.8b11469.
[38] Tsiotsias A I, Charisiou N D, Harkou E, et al. Enhancing CO₂ methanation over Ni catalysts supported on sol-gel derived Pr₂O₃-CeO₂:An experimental and theoretical investigation[J]. Applied Catalysis B:Environmental, 2022,318121836.
[39] Tsiotsias A I, Charisiou N D, Alkhoori A, et al. Optimizing the oxide support composition in Pr-doped CeO₂ towards highly active and selective Ni-based CO₂ methanation catalysts[J]. Journal of Energy Chemistry, 2022,71547-71561.
[40] Jing Y, Cai Z, Liu C, et al. Promotional effect of La in the three-way catalysis of La-loaded Al₂O₃-supported Pd catalysts (Pd/La/Al₂O₃)[J]. ACS Catalysis, 2020,10(2):1010-1023.
[41] Hoffman A J, Asokan C, Gadinas N, et al. Experimental and theoretical characterization of Rh single atoms supported on γ-Al₂O₃ with varying hydroxyl contents during NO reduction by CO[J]. ACS Catalysis, 2022,12(19):11697-11715.
[42] Zheng Y, Liu Q, Shan C, et al. Defective ultrafine MnO_x nanoparticles confined within a carbon matrix for low-temperature oxidation of volatile organic compounds[J]. Environmental Science & Technology, 2021,55(8):5403-5411.
[43] Zhong J, Zeng Y, Chen D, et al. Toluene oxidation over Co³⁺-rich spinel Co₃O₄:Evaluation of chemical and by-product species identified by in situ DRIFTS combined with PTR-TOF-MS[J]. Journal of Hazardous Materials, 2020,386121957.
[44] Marinho A L A, Toniolo F S, Noronha F B, et al. Highly active and stable Ni dispersed on mesoporous CeO₂-Al₂O₃ catalysts for production of syngas by dry reforming of methane[J]. Applied Catalysis B:Environmental, 2021,281119459.
[45] Si W, Wang Y, Zhao S, et al. A facile method for in situ preparation of the MnO₂/LaMnO₃ catalyst for the removal of toluene[J]. Environmental Science & Technology, 2016,50(8):4572-4578.
[46] Wang Q, Li G, Zhao B, et al. Investigation on properties of a novel ceria-zirconia-praseodymia solid solution and its application in Pd-only three-way catalyst for gasoline engine emission control[J]. Fuel, 2011,90(10):3047-3055.
[47] Fahed S, Pointecouteau R, Aouine M, et al. Pr-rich cerium-zirconium-praseodymium mixed oxides for automotive exhaust emission control[J]. Applied Catalysis A:General, 2022,644118800.
[48] Jiang Y, Gao J, Zhang Q, et al. Enhanced oxygen vacancies to improve ethyl acetate oxidation over MnO_x-CeO₂ catalyst derived from MOF template[J]. Chemical Engineering Journal, 2019,37178-37187.
[49] Siakavelas G I, Charisiou N D, Alkhoori S, et al. Highly selective and stable nickel catalysts supported on ceria promoted with Sm₂O₃, Pr₂O₃ and MgO for the CO₂ methanation reaction[J]. Applied Catalysis B:Environmental, 2021,282119562.
[50] Cárdenas-Arenas A, Quindimil A, Davó-quiñonero A, et al. Design of active sites in Ni/CeO₂ catalysts for the methanation of CO₂:tailoring the Ni-CeO₂ contact[J]. Applied Materials Today, 2020,19100591.
[51] Papageridis K N, Charisiou N D, Douvartzides S L, et al. Effect of operating parameters on the selective catalytic deoxygenation of palm oil to produce renewable diesel over Ni supported on Al₂O₃, ZrO₂ and SiO₂ catalysts[J]. Fuel Processing Technology, 2020,209106547.
[52] Grosvenor A P, Biesinger M C, Smart R S C, et al. New interpretations of XPS spectra of nickel metal and oxides[J]. Surface Science, 2006,600(9):1771-1779.
[53] Tang C, Li J, Yao X, et al. Mesoporous NiO-CeO₂ catalysts for CO oxidation:Nickel content effect and mechanism aspect[J]. Applied Catalysis A:General, 2015,49477-49486.
[54] Wang W W, Yu W Z, Du P P, et al. Crystal Plane Effect of Ceria on Supported Copper Oxide Cluster Catalyst for CO Oxidation:Importance of Metal-Support Interaction[J]. ACS Catalysis, 2017, 7(2):1313-1329.
[55] Kang L, Han L, Wang P, et al. SO₂-Tolerant NO_x Reduction by Marvelously Suppressing SO₂ Adsorption over Fe_δCe_1−δVO₄Catalysts[J]. Environmental Science & Technology, 2020,54(21):14066-14075.
[56] Trovarelli A. Catalytic Properties of Ceria and CeO₂-Containing Materials[J]. Catalysis Reviews, 1996,38(4):439-520.
[57] Zheng X H, Li Y L, Zhang L Y, et al. Insight into the effect of morphology on catalytic performance of porous CeO₂ nanocrystals for H₂S selective oxidation[J]. Applied Catalysis B:Environmental, 2019, 25298-252110.
[58] Ahn K, Yoo D S, Prasad D H, et al. Role of multivalent Pr in the formation and migration of oxygen vacancy in Pr-Doped ceria:Experimental and first-principles investigations[J]. Chemistry of Materials, 2012,24(21):4261-4267.
[59] Michel K, Bjørheim T S, Norby T, et al. Importance of the Spin-Orbit Interaction for a Consistent Theoretical Description of Small Polarons in Pr-Doped CeO₂[J]. The Journal of Physical Chemistry C, 2020, 124(29):15831-15838.
[60] 吴筱笛,吴晓东,张颖一,等.Pr-Ce-Zr复合氧化物的结构与储氧性能研究[J]. 中国稀土学报, 2008,(3):272-275. Wu Y D, Wu X D, Zhang Y Y, et al. Study on structure and oxygen storage properties of Pr-Ce-Zr composite oxides[J]. Journal of the Chinese Society of Rare Earths, 2008,(3):272-275.
[61] Waldvogel A, Fasolini A, Basile F, et al. Effect of the support synthetic method on the activity of Ni/CeZrPr mixed oxide in the Co-methanation of CO₂/CO mixtures for application in power-to-gas with Co-electrolysis[J]. Energy & Fuels, 2021,35(16):13304-13314.
[62] Mo S, Zhang Q, Li J, et al. Highly efficient mesoporous MnO₂ catalysts for the total toluene oxidation:Oxygen-Vacancy defect engineering and involved intermediates using in situ DRIFTS[J]. Applied Catalysis B:Environmental, 2020,264118464.
[63] Xu Z, Li Y, Lin Y, et al. A review of the catalysts used in the reduction of NO by CO for gas purification[J]. Environmental Science and Pollution Research, 2020,27(7):6723-6748. 致谢:感谢本课题组杨超老师对本文英文部分的修改及润色.