La-Ba-Cu-O体系汽车尾气净化催化剂及其抗老化性能研究
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摘要
钙钛矿型结构的复合氧化物作为具有众多功能的材料，已引起了国内外许多科研人员的关注。在对文献调研和分析钙钛矿型复合氧化物催化剂的研究现状及进展的基础上选择稀土钙钛矿型复合氧化物作为研究对象，研究材料制备及其性能，为汽车尾气催化转化器材料提供理论与实验数据。
采用柠檬酸溶胶-凝胶法制备了类钙钛矿型复合氧化物La_4BaCu_5O_(13+δ)基催化剂，并在A，B位掺杂了Sr、Ce、Ni、Fe等多种金属元素，采用XRD，SEM，BET，TPD等手段对其组成、结构和性能进行了表征，考察了焙烧温度，A、B位掺杂对催化剂性能的影响，测试了催化剂对CO，CH_4的催化燃烧活性及抗硫老化能力，并探讨了催化剂的物理化学性质与活性的关联。
XRD结果表明，用柠檬酸为络合剂，用溶胶凝胶法制备的类钙钛矿型复合氧化物La_4BaCu_5O_(13+δ)在750℃焙烧时材料中有部分杂相存在，900℃下焙烧是单一的类钙钛矿结构，测试表明随焙烧温度的上升，粒径增加，材料的比表面积减小。BET测试表明B位少量金属的掺杂有利于试样比表面积的提高，过量的B位取代又会使比表面积下降，A位的掺杂则会降低试样的比表面积。TPD测试表明催化剂的表面氧浓度对催剂的催化活性有一定的影响。催化活性测试表明750℃焙烧的试样相比900℃有更好的催化活性，A位单一取代会降低催化剂的活性，B位Ni，Fe取代会使活性升高，其中，La_4BaCu_2Ni_3O_(13+δ)，La_4BaCu_2Fe_3O_(13+δ)分别有最好的催化活性，两者相比La_4BaCu_2Fe_3O_(13+δ)活性更好。
硫化实验表明Ni，Fe的掺杂可以增强催化剂的抗硫化性能，测试表明SO_2可以引起催化剂结构的解体，XRD测试表明其中先生成CuSO_4，然后生成BaSO_4而使稳定的La_4BaCu_5O_(13+δ)结构破坏，硫化后催化剂团聚增加。
Perovskte-type oxides have attracted particularly attentions because of their special applications as functional materials. According to the reported literatures and analysing the researsh and the development of the perovskite-type compound oxides, choose perovskte-type oxides as disquisitive object, research their preparation and properties, provide academic and experimental data for automobile's exhaust catalytic instrument.
A series of layered perovskite-type compound oxides were synthesized by citrate acid sol-gel method,adulterated A, B-site with different metal ions(A-site with Sr, Ce, B-site with Ni, Fe), the physicochemcal properties and function mechanism of the materials were characterized by means of XRD, SEM, BET, TPD, considered the affected factor of the catalytic activity such as differern calcined temperature, A, B-site adulteration,tested the catalytic activity with CO, CH_4 and anti-sulfuration, associated the characters with their physicochemcal properties.
The XRD spectrum demonstrated that at the calcined tempereture 900℃, the perovskte-type phase is simple, when the calcined tempereture was 750℃, some foreign matter phases apper.The SEM test indicateed the particle size increase with the calcined temperature increases. The BET test results indicate the specific surface area of the materials increase when the quantity of doping Ni, Fe in the B-site is low, when the quantity is high, the specific suefece area could descend.the doping Ce, Sr in A-site reduce the specific suefece area. TPD results show that the concentration of oxygen at the sueface is associated with catalytic activity.
The catalytic activity decrease with the calcined temperature increases, but it increase when the quantity of doping Ni, Fe is appropriate,then decrease when the doping is excessive.among these materials, La_4BaCu_2Ni_30_(13+δ), La_4BaCu_2Fe_3O_(13+δ) have the best catalytic activity,between the two, La_4BaCu_2Fe_3O_(13+δ) is better.
The sulfuration results show the doping Ni, Fe increase the anti-sulfuration, SO_2 make the structure disaggregate, XRD spectrum show CuSO_4 appers firstly, then the appear of BaSO_4 makes the structure disaggregate.
采用柠檬酸溶胶-凝胶法制备了类钙钛矿型复合氧化物La_4BaCu_5O_(13+δ)基催化剂，并在A，B位掺杂了Sr、Ce、Ni、Fe等多种金属元素，采用XRD，SEM，BET，TPD等手段对其组成、结构和性能进行了表征，考察了焙烧温度，A、B位掺杂对催化剂性能的影响，测试了催化剂对CO，CH_4的催化燃烧活性及抗硫老化能力，并探讨了催化剂的物理化学性质与活性的关联。
XRD结果表明，用柠檬酸为络合剂，用溶胶凝胶法制备的类钙钛矿型复合氧化物La_4BaCu_5O_(13+δ)在750℃焙烧时材料中有部分杂相存在，900℃下焙烧是单一的类钙钛矿结构，测试表明随焙烧温度的上升，粒径增加，材料的比表面积减小。BET测试表明B位少量金属的掺杂有利于试样比表面积的提高，过量的B位取代又会使比表面积下降，A位的掺杂则会降低试样的比表面积。TPD测试表明催化剂的表面氧浓度对催剂的催化活性有一定的影响。催化活性测试表明750℃焙烧的试样相比900℃有更好的催化活性，A位单一取代会降低催化剂的活性，B位Ni，Fe取代会使活性升高，其中，La_4BaCu_2Ni_3O_(13+δ)，La_4BaCu_2Fe_3O_(13+δ)分别有最好的催化活性，两者相比La_4BaCu_2Fe_3O_(13+δ)活性更好。
硫化实验表明Ni，Fe的掺杂可以增强催化剂的抗硫化性能，测试表明SO_2可以引起催化剂结构的解体，XRD测试表明其中先生成CuSO_4，然后生成BaSO_4而使稳定的La_4BaCu_5O_(13+δ)结构破坏，硫化后催化剂团聚增加。
Perovskte-type oxides have attracted particularly attentions because of their special applications as functional materials. According to the reported literatures and analysing the researsh and the development of the perovskite-type compound oxides, choose perovskte-type oxides as disquisitive object, research their preparation and properties, provide academic and experimental data for automobile's exhaust catalytic instrument.
A series of layered perovskite-type compound oxides were synthesized by citrate acid sol-gel method,adulterated A, B-site with different metal ions(A-site with Sr, Ce, B-site with Ni, Fe), the physicochemcal properties and function mechanism of the materials were characterized by means of XRD, SEM, BET, TPD, considered the affected factor of the catalytic activity such as differern calcined temperature, A, B-site adulteration,tested the catalytic activity with CO, CH_4 and anti-sulfuration, associated the characters with their physicochemcal properties.
The XRD spectrum demonstrated that at the calcined tempereture 900℃, the perovskte-type phase is simple, when the calcined tempereture was 750℃, some foreign matter phases apper.The SEM test indicateed the particle size increase with the calcined temperature increases. The BET test results indicate the specific surface area of the materials increase when the quantity of doping Ni, Fe in the B-site is low, when the quantity is high, the specific suefece area could descend.the doping Ce, Sr in A-site reduce the specific suefece area. TPD results show that the concentration of oxygen at the sueface is associated with catalytic activity.
The catalytic activity decrease with the calcined temperature increases, but it increase when the quantity of doping Ni, Fe is appropriate,then decrease when the doping is excessive.among these materials, La_4BaCu_2Ni_30_(13+δ), La_4BaCu_2Fe_3O_(13+δ) have the best catalytic activity,between the two, La_4BaCu_2Fe_3O_(13+δ) is better.
The sulfuration results show the doping Ni, Fe increase the anti-sulfuration, SO_2 make the structure disaggregate, XRD spectrum show CuSO_4 appers firstly, then the appear of BaSO_4 makes the structure disaggregate.
引文
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[3] 吴越．科技通报,37,97(1992)
[4] Rauah E M, Gndenough J.B.J. Appl. Phys., 39, 1209(1984)
[5] Chengxian W, Bosheng D, Shuring F. Chinese Science, B, 27, 718, (1984)
[6] Tofield B. C, Greaves C and Fender B.E.F. The SrFeO_(2.5) SrFeO_(3.0) system. Evidence of a new phase Sr_4Fe_4O_(11) (SrFeO2.75). Materials Research Bulletin, Vol10, Issue 7, 1975, 737-745
[7] Misono M, Nitadori T. Adsorption and catalysis on oxides, Elsevier, Amsterdam, 1985, p409
[8] Mizusaki J etal, Nonstoichiometry of the perovskite-type oxides La_(1-x)Sr_xCoO_(3-δ). J. Solid State Chem., 80, 102(1989)
[9] Yue Wu, Tao Yu, Bosheng Dou. A comparative study on perovskite-type mixed oxide catalysts A'_xA_(1-x)BO_(3-λ)(A'=Ca, Sr, A=La, B = Mn, Fe, Co) for NH_3 oxidation. J. Catal., 120, 88(1989)
[10] 周克斌，李学隽，王道等．汽车尾气净化用稀土钙钛石型复合氧化物催化剂．大学化学，第16卷第2期，2001年4月
[11] Shu J, Kaliaguine S. Well-dispersed perovskite-type oxidation catalysts. Applied Catalysis B: Environmental 16 (1998) L303-L308
[12] 罗宁，姚金华，刘治中等．稀土催化剂在汽车尾气净化方面的应用．重庆环境科学，1998年6月，第20卷第3期
[13] Nakallura.Tadao. Recording process and transparent recorded products. 1994, JP06, 315, 634
[14] Cleude G. Propertied of perovskite-type oxides Ⅱ: Stydies in catalysis. Less-common metal. 1989, 146:261
[15] 冯长根，张江山，王亚军等．安全与环境学报，钙钛矿型复合氧化物用于汽车尾气催化净化的研究进展．2004年8月，第4卷第4期
[16] 韩巧凤，魏宝国，汪信等．陆路德纳米钙钛矿型LaMnO_3的制备与汽车尾气处理． 环境污染与防治，第23卷第4期，2001年8月
[17] 嵇世山，李增喜，谭瑞琴等．La-Ce-Cu复合金属氧化物的结构表征及催化性能．稀土，1999，20(1)：53-57
[18] 朱振忠，田群，陈宏德等．汽车尾气三效催化剂．中国环保产业CEPI，2002，7
[19] 郭建军，罗来涛，李松军等．汽车尾气催化剂的研究进展．江西化工，2001(2)
[20] Shimada H, Hyomen, Kagaku. 9, 489(1988)
[21] Yasutake.Teraoka, Tomohiro Harada and Shuichi Kagawa. Reaction mechanism of direct decomosition of nitric oxide over Co and Mn- based perovskkite-tipe oxides. J.Chem. Soc.Faraday Trans., 1998, 94(13): 1887-1891
[22] 何元．汽车排气催化剂的技术动向．小型内燃机，1990．3：60
[23] Stojanovic M, Haverkamp R G, Mims c A,et al. Synthesis and characterization of LaCr_(1-x)Ni_xO_3 perovskite oxide catalysts. [J].J.Catalysis, 1997, 166 (2) : 315～323.
[24] 郭绪民．钙钛矿型稀土复合氧化物催化剂．稀土，1986．5：46
[25] X．M．米纳切夫．稀土在催化中的应用．北京：北京科学出版社，1987．289
[26] Fierro J,L.G. Catal.Today, 1990,8:153
[27] Seiyama T, Catal.Rev.-Sci. Eng., 1992, 34:281
[28] Chen K S, Ma J, Jaeniche S, et al. Appl.Catal A, 1994, 107:201
[29] Petrolekas P D, Metcalfe I S . J.Catal., 1995, 152:147
[30] Zhang H M, Teraoka Y, Yamazoe N et al. Sci.Lett., 1989, 8:995
[31] Mizuno N, Fujiwara Y, Misono M et al. Soc.Chem.Commun., 1989,316
[32] Ruiqin Tan, Yongfa Zhu . Poisoning mechanism of perovskite LaCoO_3 catalyst by organophosphorous gas . Applied Catalysis B:Environmental 58 (2005) 61 68
[33] 钟铱均，陈平，周碧等．CuO/CeO_2和CuO/Al2O3催化剂的催化性能．应用化学,1997,14(1)：49
[34] Engler E.M. CHEMTECH IT, 542(1987)
[35] Raveau B, Michel C, Hervieu M. What about structure and nonstoichiometry in superconductive layered cuprates? . J. Solid. State Chem., 85, 181 (1990)
[36] 罗伯特·卡瓦著，路多，张伟译．科技导报,6,17(1990)
[37] Khan Y . J.Materials Science Letters, 8, 249(1989)
[38] Peter S.D. Activity enhancement of mixed lanthanum-copper-iron-perovskites in the CO+NO reaction. Applied Catalysis A: General 205 (2001) 147 158
[39] Michel C, Rakho LEr, Hhervieu M. BaLa_4Cu_5O_(13+δ), an oxygen-deficient perovskite built up from corner-sharing CuO_6 octahedra and CuO_5 pyramids. J.Solid State Chem., 68, 143(1983)
[40] W.T.Fu, Mi]hoff F.C., W.Ijdo D.J. et al. Crystal structure of the new metallic copper oxide La_2Sr_6Cu_8O_(18-δ),Solid State Communications,Vol 83,Issue 1,1992, 59-62
[41] Shivakumara C, Hegde M.S, Sooryanarayana K, et al. J Mater Chem 8 (1998)2695
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