锶掺杂的铈锆固溶体与贵金属相互作用的研究
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摘要
近年来各国科学家开发了能够同时转化CO、HC和NOx的贵金属三效催化剂,以Pt、Rh、Pd等贵金属为活性组分的催化剂不仅有合适的烃类吸附位,还有大量的氧吸附位。随着表面反应的进行,能快速的发生氧活化和烃类的吸附。但贵金属资源有限,价格昂贵,这类催化剂的成本较高。铈锆固溶体以其高的热稳定性、良好的储放氧能力使催化剂最大限度的发挥三效作用,尤其是汽车刚启动时的低温过程。系统而深入地研究铈锆固溶体与贵金属之间相互作用,对于汽车尾气净化催化剂的发展会起到宏观指导作用。
本文以溶胶凝胶法制备锶掺杂的铈锆固溶体,以锶掺杂的铈锆固溶体为载体采用浸渍法制备贵金属负载的催化剂,并对新鲜样品进行水热老化处理。采用动态储放氧测试和模拟配气催化剂评价手段,研究PM和CZS之间的相互作用。考察PM对CZS的OSC性能和高温热稳定性的影响及CZS对PM催化性能的作用效果。利用XRD,HRTEM,BET和XPS对样品的结构、晶相、比表面积和表面元素组成进行研究。
通过动态储放氧测试,发现锶掺杂可以提高铈锆固溶体的OSC性能,但是PM负载后,纯的铈锆固溶体显示出最佳的储放氧性能。这可能是由PM与载体之间的强相互作用所导致。通过CO脉冲实验,可以得出锶掺杂有助于提高体相氧的迁移,Pd和Rh对CZS所表现的不同的促进作用,可以归结为Pd和Rh与载体发生的不同的SMSI。CZS能够提高PM的催化活性,特别是老化载体上负载PM的催化剂,同时表明载体的比表面积对活性的影响不大。
Automotive exhaust is the main source of air pollution now. Generally engine modification and after-treatment control technique are used for this problem, and setting three-way-catalyst, one of after-treatment control, is the most effective solution. At present, the hot issues about three-way-catalyst include improving cold-start performance, reducing noble metal dosage and prolonging the used life.
Pd, Pt and Rh played the important role in TWC application; Pd and Pt have influence on HC and CO oxidation, whereas Rh has effects on NOx reduction. As we known, HC, CO and NOx can reach the best conversion around the A/F=14.6. For the redox couple of Ce~(3+)/Ce~(4+), Ceria-zirconia mixed oxides was used to accommodate the fluctuation of A/F around the 14.6 which storage oxygen when lean fuel condition and release oxygen when rich fuel condition, resulting in best conversion efficiency of HC, CO and NOx. The research of the interaction between the PM and CZ in application, resulting in changing in catalytic activity and OSC performance is of
important influence. In this paper, Sr doping samples Ce_(0.67)Zr_(0.33)Sr_xO_(2+x) (CZS_x) were prepared by sol-gel method and aged under H2O/air condition as the aged samples. PM (Pd, Rh) loaded on fresh and aged CZS samples were prepared by impregnation. Both fresh and aged samples were characterized on home-made dynamic OSC measure instrument and TWC measure equipment for their dynamic OSC and TWC performance. Structure analysis were also done by Brunnauer-Emmett-Teller (BET), X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS)and high resolution transmission electron microscopy(HRTEM).
OSC results show that the oxygen storage capacity is enhanced by Sr~(2+) doping. However, after supporting Pd or Rh, undoped CZ shows higher dynamic OSC of CZ than Sr-doped samples, which may be ascribed to the SMSI effect. Sr doping can efficiently promote the catalytic activities, especially for PM supported on aged samples.Pd/aged CZS5 and Rh/aged CZS5 exhibit good performance indicating potential in practical applications.
本文以溶胶凝胶法制备锶掺杂的铈锆固溶体,以锶掺杂的铈锆固溶体为载体采用浸渍法制备贵金属负载的催化剂,并对新鲜样品进行水热老化处理。采用动态储放氧测试和模拟配气催化剂评价手段,研究PM和CZS之间的相互作用。考察PM对CZS的OSC性能和高温热稳定性的影响及CZS对PM催化性能的作用效果。利用XRD,HRTEM,BET和XPS对样品的结构、晶相、比表面积和表面元素组成进行研究。
通过动态储放氧测试,发现锶掺杂可以提高铈锆固溶体的OSC性能,但是PM负载后,纯的铈锆固溶体显示出最佳的储放氧性能。这可能是由PM与载体之间的强相互作用所导致。通过CO脉冲实验,可以得出锶掺杂有助于提高体相氧的迁移,Pd和Rh对CZS所表现的不同的促进作用,可以归结为Pd和Rh与载体发生的不同的SMSI。CZS能够提高PM的催化活性,特别是老化载体上负载PM的催化剂,同时表明载体的比表面积对活性的影响不大。
Automotive exhaust is the main source of air pollution now. Generally engine modification and after-treatment control technique are used for this problem, and setting three-way-catalyst, one of after-treatment control, is the most effective solution. At present, the hot issues about three-way-catalyst include improving cold-start performance, reducing noble metal dosage and prolonging the used life.
Pd, Pt and Rh played the important role in TWC application; Pd and Pt have influence on HC and CO oxidation, whereas Rh has effects on NOx reduction. As we known, HC, CO and NOx can reach the best conversion around the A/F=14.6. For the redox couple of Ce~(3+)/Ce~(4+), Ceria-zirconia mixed oxides was used to accommodate the fluctuation of A/F around the 14.6 which storage oxygen when lean fuel condition and release oxygen when rich fuel condition, resulting in best conversion efficiency of HC, CO and NOx. The research of the interaction between the PM and CZ in application, resulting in changing in catalytic activity and OSC performance is of
important influence. In this paper, Sr doping samples Ce_(0.67)Zr_(0.33)Sr_xO_(2+x) (CZS_x) were prepared by sol-gel method and aged under H2O/air condition as the aged samples. PM (Pd, Rh) loaded on fresh and aged CZS samples were prepared by impregnation. Both fresh and aged samples were characterized on home-made dynamic OSC measure instrument and TWC measure equipment for their dynamic OSC and TWC performance. Structure analysis were also done by Brunnauer-Emmett-Teller (BET), X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS)and high resolution transmission electron microscopy(HRTEM).
OSC results show that the oxygen storage capacity is enhanced by Sr~(2+) doping. However, after supporting Pd or Rh, undoped CZ shows higher dynamic OSC of CZ than Sr-doped samples, which may be ascribed to the SMSI effect. Sr doping can efficiently promote the catalytic activities, especially for PM supported on aged samples.Pd/aged CZS5 and Rh/aged CZS5 exhibit good performance indicating potential in practical applications.
引文
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[2]P.Forzatti,Environmental catalysis for stationary applications,Catalysis Today,2000,62(1),51～65
[3]P.Stefanov,D.Stoychev,A.Aleksandrova et al,Compositional and structural characterization of alumina coatings deposited electrochemically on stainless steel,Applied Surface Science,2004,235 (1～2),80～85
[4]蒋晓原,陆峥,周仁贤等,高比表面积 Ce-Zr-O 复合氧化物的制备与表征,浙江大学学报(理学版),2002,29(4),424～429
[5]A.Trobarelli,Design better cerium-based oxidation catalysts,CHEMTECH,1997,47(6),32～37
[6]J.Ka?par,P.Fornasiero,M.Graziani,Use of CeO_2-based oxides in the three-way catalysis,Catalysis Today,1999,50(2),285～298
[7]罗孟飞,林瑞,陈敏等,Ce-Zr-O 固溶体的制备和表征,中国稀土学报,2000,18(1),35～37
[8]赵建军,刘源,汽车尾气净化催化剂用Ce_xZr_(1-x)O_2固溶体的研究进展,稀土,2002,23(3),52～55
[9]P.Formasiero,G.Balducci,R.Di Monte,et al,Modification of the Redox Behaviour of CeO_2 Induced by Structural Doping with ZrO_2,Journal of Catalysis,1996,164(1),173～183
[10]O.Masakuni,Role of cerium-zirconium mixed oxides as catalysts for car pollution: A short review,Journal of Alloys and Compounds,1998,275～277,886～890
[11]Masahiro Sugiura, TOYOTA Central R&D Labs. Inc.,Oxygen storage materials for automotive catalysts: ceria-zirconia solid solutions,Catalysis Surveys from Asia,2003,7(1),77~86
[12]S.Rossignol,Y.Madier,D.Duprez,Preparation of zirconia-ceria materials by soft chemistry,Catalysis Today,1999,50,261～270
[13]H.Vidal,S.Bernal,J.Kaspar,et al,Influence of high temperature treatments under net oxidizing and reducing conditions on the oxygen storage and buffering properties of a Ce0.68Zr0.32O_2 mixed oxide,Catalysis Today,1999,54,93～100
[14]P.Formasiero,R.Di Monte,G.Ranga Rao,et al,Rh-loaded CeO_2-ZrO_2 solid solutions as highly effects oxygen exchanges: Dependence of the reductions behavior and the oxygen storage capacity on the structural properties,Journal of Catalysis,1995,151(1),168～177
[15]A.Trovarelli,F.Zamar,J.Llorca,et al,Nanophase Fluorite-Structured CeO_2-ZrO_2 Catalysts Prepared by High-Energy Mechanical Milling,Journal of Catalysis,1997,169,490
[16]Tadashi Suzuki,Alumina-ceria-zirconia composite oxide for three-way catalyst,R&D Review of Toyata CRDL,37(4),28～33
[17]肖莉,三效低贵金属催化剂中铈-锆固溶体助剂的制备、结构和催化活性的关系,博士学位论文,中国科学技术大学,2000
[18]F.Fally, V.Perrichon, H. Vidal et al, Modification of the oxygen storage capacity of CeO_2-ZrO_2 mixed oxides after redox cycling aging. Journal of Applied Catalysts B: Environmental. 2000, 59(3~4),373~386
[19]Tauster S J, Fung S C, Garten R L,Strong metal-support interactions-group-8 noble-metals supported on TiO_2. Journal of the American Chemical Society, 1978, 100(1), 170~175
[20]Tauster S J, Strong metal-support interactions. Accornts of Chemical Research, 1987, 20(11), 389~394
[21]M.G. Sanchez, J.L.Gazquea, Oxygen Vacancy Model in Strong Metal-Support Interaction. Journal of Catalysis, 1987, 104, 120~135
[22]S.Bernal et al, Some recent results on metal/support interaction effects in NM/CeO_2 (NM: noble metal) catalysts, Catalysis Today, 1999, 50, 175~206
[23]L.F.Liotta,A.Longo,A.Macaluso,et al, Influence of the SMSI effect on the catalytic activity of a Pt(1%)/Ce0.6Zr0.4O_2 catalyst: SAXS, XRD, XPS and TPR investigations,Applied Catalysis,2004,48,133～149
[24]G.W.Graham, H.W. Jen, W.Chun et al, Encapsulation of Pd particles by ceria-zirconia mixed oxides, Catalysis Letters ,1997, 44,185~187
[25]K. R. Priolkar, Parthasarathi Bera et al. Formation of Ce_(1-x)PdxO__(2-δ)Solid Solution in Combustion-Synthesized Pd/CeO_2 Catalyst: XRD, XPS, and EXAFS Investigation, Chem. Mater, 2002, 14, 2120~2128
[26]Parthasarathi Bera et al, Ionic Dispersion of Pt and Pd on CeO_2 by Combustion Method: Effect of Metal–Ceria Interaction on Catalytic Activities for NO Reduction and CO and Hydrocarbon Oxidation, J. Catal, 2000, 196, 293~301
[27]Arup Gayen, K. R. Priolkar, P. R. Sarode et al, Ce_(1-x)RhxO_(2-δ) Solid Solution Formation in Combustion-Synthesized Rh/CeO_2 Catalyst Studied by XRD, TEM, XPS, and EXAFS, Chem. Mater, 2004, 16, 2317~2328
[28]Parthasarathi Bera et a, Promoting Effect of CeO_2 in Combustion Synthesized Pt/CeO_2 Catalyst for CO Oxidation, J. Phys. Chem. B, 2003, 107, 6122~6130
[29]A. Iglesias-Juez, A. Martínez-Arias, and M. Fernández-García, Metal–promoter interface in Pd/(Ce,Zr)Ox/Al2O3 catalysts: effect of thermal aging, J. Catal, 2004, 221, 148~161
[30]K. Kenevey, F. Valdivieso et al. Thermal stability of Pd or Pt loaded Ce0.68Zr0.32O_2 and Ce0.50Zr0.50O_2 catalyst materials under oxidising conditions, Applied Catalysis B, Environmental, 2001, 29, 93~101
[31]G. Ranga Rao, Reduction of NO over Partially Reduced Metal-Loaded CeO_2-ZrO_2 Solid Solutions, J. Catal, 1996, 162, 1~9
[32]N. Hickey, P. Fornasiero et al. Effects of the Nature of the Reducing Agent on the Transient Redox Behavior of NM/Ce0.68Zr0.32O_2 (NM=Pt, Pd, and Rh), J. Catal, 2001, 200, 181~193
[33]Sumeya Bedrane, Claude Descorme, Daniel Duprez, Investigation of the oxygen storage process on ceria- and ceria–zirconia-supported catalysts, Catalysis Today, 2002, 75, 401~405
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