稀土掺杂对LaSrCoO4催化剂性能的影响

采用聚丙烯胺溶胶-凝胶法制备了类钙钛矿La0.7Nd0.3SrCoO4和La0.7Ce0.3SrCoO4复合氧化物催化剂,考察了它们对CO和C3H8的催化氧化活性,并运用XRD,IR,TPR和TPD等手段对催化剂进行了表征.结果表明,稀土掺杂后的LaSrCoO4复合氧化物均为K2NiF4型结构,不同稀土掺杂对LaSrCoO4复合氧化物的CO和C3H8氧化活性的影响不同,Nd掺杂能增加Co3+、化学吸附氧和晶格氧的数量,提高复合氧化物的活性.     

Pt/LaSrCoO4催化剂的物化性质及对己烷完全氧化活性的影响

采用聚乙二醇凝胶法、球磨法及浸渍法合成了类钙钛矿型复合氧化物和负载型催化剂,以己烷完全氧化为探针反应,运用FT-IR、TPD、TPR和XPS等手段进行表征.结果表明,样品都具有K2NiF4结构,己烷完全氧化活性不仅与催化剂的物相及氧空穴有关,还与催化剂表面的Co含量有关;LaSrCoO4(650℃)催化剂显示出较高的催化活性;负载适量的Pt,不仅没改变催化剂的K2NiF4结构,而且还能促进己烷完全氧化催化活性的提高,且负载量为0.5%时最适宜.     

Pt/PrSrCoO4催化剂的物化性质及对NO+CO催化性能

分别采用聚乙二醇凝胶法、球磨法及浸渍法合成了类钙钛矿型复合氧化物和负载型催化剂,利用XRD、BET、TPD、TPR和XPS等手段对催化剂的物化性能进行表征,考察了它们对CO还原NO反应的催化性能.结果表明,样品都具有K2NiF4结构,CO还原NO反应的催化活性不仅与催化剂的比表面积、物相及氧空穴有关,还与催化剂表面的Co含量有关;PrSrCoO4(650℃)催化剂显示出较高的催化活性;负载适量的贵金属Pt,不仅不会改变催化剂的K2NiF4结构,而且还能促进CO还原NO的催化活性提高,且负载量为0.5%时最适宜.     

LaCo_(0.9)Cu_(0.1)O_3的葡萄糖溶胶—凝胶法合成及二甲苯催化氧化性能研究

本文以葡萄糖溶胶—凝胶法合成了稀土钙钛矿型复合氧化物 L a Co0 .9Cu0 .1 O3,并对其进行了 XRD、BET、TPR表征和二甲苯催化氧化性能测试 ,同时与柠檬酸溶胶—凝胶法作了比较。结果表明 ,葡萄糖作为络合剂成胶和干胶容易 ,粒径较小 ,具有进一步降低 L a Co0 .9Cu0 .1 O3形成温度的作用 ,以葡萄糖作为络合剂在 70 0℃所制备的催化剂 L a Co0 .9Cu0 .1 O3低温活性较好     

CeO2及其复合催化剂对煤粉燃烧效率的影响

 利用热重分析法研究了稀土氧化物CeO2和其复合催化剂对煤粉燃烧特性的影响。研究了稀土氧化物及其复合催化剂的添加量、配比对煤粉燃烧特性的影响。结果表明：CeO2可以促进烟煤挥发分析出和燃烧,改善其燃烧性能,CeO2添加质量分数为4%时其催化效果最为显著;不同催化剂对无烟煤燃烧的催化效果各异,MnO2有利于挥发分析出,而CeO2促进了残碳的燃烧,其催化作用不同于烟煤;Ce-Fe-Mn系复合催化剂催化效果优于单组分催化剂,其中CeFeMn(3∶1∶1)的催化效果最佳。利用Coats-Redfern动力学模型分析了煤粉燃烧活化能、指前因子等动力学参数,添加CeFeMn(3∶1∶1)的煤粉反应速率常数较大,催化效果显著。     

变价稀土氧化物对催化剂性能的影响

本文从原子结构分析了变价稀土元素原子的结构特点 ,从机理上分析了变价稀土氧化物对催化剂原子氧化价的稳定性、贮氧能力和热稳定性等性能增强的根源 ,从理论上深入认识了稀土氧化物的助催化作用。     

尖晶石型Co0.7Ce0.3Co2O4催化剂的制备及其甲烷催化燃烧性能的研究

采用共沉淀法、溶胶凝胶法和溶液燃烧法制备了一系列Co0.7Ce0.3Co2O4催化剂,研究了制备办法对催化剂甲烷催化燃烧反应性能的影响,并运用XRD、BET和TPR等技术对催化剂进行了表征.结果表明,共沉淀法制备的Co0.7Ce0.3Co2O4催化剂有较好的催化活性和热稳定性,与溶胶凝胶法和溶液燃烧法制备的Co0.7Ce0.3Co2O4催化剂相比,共沉淀法制备的Co0.7Ce0.3Co2O4催化剂有较高的晶格畸变率和比表面积、较大的孔径和孔容、较小的品粒度、较强的氧活动性和较低的甲烷催化燃烧反应的表观活化能.     

沉淀剂对尖晶石型Co0.7Ce0.3Co2O4催化剂甲烷催化燃烧性能的影响

分别以(NH4)2CO3、K2CO3和H2C2O4为沉淀剂,采用共沉淀法制备了Co0.7Ce0.3Co2O4催化剂,考察了沉淀剂对甲烷催化燃烧反应性能的影响,并运用XRD、BET和TPR等方法对催化剂进行了表征.结果表明,沉淀剂种类对催化剂的催化活性、结构、比表面积和还原能力等均有一定的影响,其中以K2CO3为沉淀剂所制备的Co0.7Ce0.3Co2O4催化剂具有最好的催化活性(T10=262℃,T100=428℃)和热稳定性,因为该催化剂的晶格畸变率、孔容、比表面积和氧活动性较大,晶粒度较小,表观活化能较低.     

稀土氧化物催化苯胺与硝基苯缩合制备4-氨基二苯胺

苯胺与硝基苯缩合制备4-氨基二苯胺,通常采用季铵碱作为催化剂.由于季铵碱热稳定性差,需要在高真空较低温度下进行缩合反应,催化剂与产物必须加氢之后才能分离.为克服上述缺点,本文尝试采用稀土氧化物作为固体碱催化该缩合反应,沸石负载季铵碱作为对照催化体系,就不同稀土氧化物、碱金属氢氧化物、相转移催化剂、含水量等方面进行了比较研究,实验结果表明,稀土氧化物对苯胺和硝基苯的缩合具有催化作用,碱金属氢氧化物具有增强稀土氧化物碱性的作用,体系水分越少,硝基苯的转化率越高;相转移催化剂起到促进作用,以PEG-350作用最佳.该催化剂重复使用5次后,活性稳定.     

LaCo0.9Cu0.1O3的葡萄糖溶胶-凝胶法合成及二甲苯催化氧化性能研究

本文以葡萄糖溶胶-凝胶法合成了稀土钙钛矿型复合氧化物LaCo0.9Cu0.1O3,并对其进行了XRD、BET、TPR表征和二甲苯催化氧化性能测试,同时与柠檬酸溶胶-凝胶法作了比较.结果表明,葡萄糖作为络合剂成胶和干胶容易,粒径较小,具有进一步降低LaCo0.9Cu0.1O3形成温度的作用,以葡萄糖作为络合剂在700℃所制备的催化剂LaCo0.9Cu0.1O3低温活性较好.     

Rare earth oxides and their supported noble metals in application of environmental catalysis

Volatile organic compounds(VOCs),methane,carbon monoxide,soot,automotive exhaust,and nitrogen oxides are harmful to the atmosphere and human health.It is urgent to strictly control their emissions.Heterogeneous catalysis is an effective pathway for the removal of these pollutants,and the critical issue is the development of novel and high-performance catalysts.In this review,we briefly summarize the preparation methods,physicochemical properties,catalytic activities,and related reaction mechanisms for the above pollutants removal of the rare earth oxides,mixed rare earth oxide,rare earth oxidesupported noble metal,and mixed rare earth oxide-supported noble metal catalysts that have been investigated by our group and other researchers.It was found that catalytic performance was associated with the factors,such as specific surface area,pore structure,particle size and dispersion,adsorbed oxygen species concentration,reducibility,reactant activation ability or interaction between metal nanoparticles and support.Furthermore,we also envision the development trend of such a topic in future work.     

Research advances of rare earth catalysts for catalytic purification of vehicle exhausts-Commemorating the 100th anniversary of the birth of Academician Guangxian Xu

Nowadays,air pollution has become a prominent environmental problem and has attracted much attention.With the increase of vehicle retention quantity,the exhaust emissions have become the main sources of air pollution.To reduce pollution and hazards,vehicle exhaust emission regulations are becoming stricter and stricter,which puts forward higher requirements for purification of vehicle exhausts.At present,rare earths have been widely applied in vehicle exhaust purification because of their good catalytic performance,which is attributed to their unique 4 f electron layer structure occupied without full electrons,excellent oxygen storage/release capacity and redox ability.In this paper,the current status of rare earth catalysts and application of rare earth in different fuel vehicle exhaust catalysts,including three-way catalysts(TWCs) for gasoline vehicles,diesel exhaust catalysts for different pollutants(particulate matter(PM),NO_x,CO and HC) and catalysts for new energy vehicles with different fuels,are summarized in detail.Meanwhile,the corresponding mechanisms and the role of rare earth in vehicle exhaust catalysts are also simultaneously described.Furthermore,the challenges and development directions of rare earth catalysts for the purification of vehicle exhausts are also proposed.     

Effects of Light Rare Earth on Acidity and Catalytic Performance of HZSM-5 Zeolite for Catalytic Cracking of Butane to Light Olefins

The effects of rare earth（RE）on the structure,acidity,and catalytic performance of HZSM-5 zeolite were investigated.A series of RE/HZSM-5 catalysts,containing 7.54% RE（RE=La,Ce,Pr,Nd,Sm,Eu or Gd）,were prepared by the impregnation of the ZSM-5 type zeolites（Si/Al=64：1）with the corresponding RE nitrate aqueous solutions.The catalysts were characterized by means of FT-IR,UV-Vis,NH3-TPD,and IR spectroscopy of adsorbed pyridine.The catalytic performances of the RE/HZSM-5 for the catalytic cracking of mixed butane to light olefins were also measured with a fixed bed microreactor.The results revealed that the addition of light rare earth metal on the HZSM-5 catalyst greatly enhanced the selectivity to olefins,especially to propylene,thus increasing the total yield of olefins in the catalytic cracking of butane.Among the RE-modified HZSM-5 samples,Ce/HZSM-5 gave the highest yield of total olefins,and Nd/HZSM-5 gave the highest yield of propene at a reaction temperature of 600℃.The presence of rare earth metal on the HZSM-5 sample,not only modified the acidic properties of HZSM-5 including the amount of acid sites and acid type,that is,the ratio of L/B（Lewis acid/Brnsted acid）,but also altered the basic properties of it,which in turn promoted the catalytic performance of HZSM-5 for the catalytic cracking of butane.     

Effect of cerium ions initial distribution on the crystalline structure and catalytic performance of CeY zeolite

Ce Y samples with different cerium(Ce) ions initial distribution were prepared by diverse preparation processes. The correlative influence of Ce ions distribution on the intracrystalline structure and catalytic mechanism of Y-type zeolite was studied by X-ray diffraction(XRD), Rietveld refinement, X-ray fluorescence spectrometry(XRF), energy-dispersive X-ray spectroscopy(EDS), infrared(IR) spectra, NH_3 temperature-programmed desorption(NH_3-TPD), N_2 physical adsorption-desorption and micro-activity test(MAT). The results indicated that Ce ions were concentrated on the surface(supercage) of Ce Y zeolite would reduce the number of acid sites and the ratio of Br?nsted acid and Lewis acid(B/L). Once Ce ions concentrated in the sodalite cage, it would participate in the coordination with framework oxygen atoms under the condition of steric hindrance. Meanwhile, Ce ions would preferentially promote the B/L value of weak acid by retaining more intracrystalline framework Al atoms in sodalite cage, which was beneficial to the conversion of heavy oil in FCC process. The optimal initial-distribution of Ce ions could not only save the consumption of rare earth resources but also give the best catalytic performance of Ce Y zeolite catalysts, and these advantages and attributes enabled it to have the potential to be applied in industrial applications.     

Phase Behavior of Rare Earth Manganites

Among complex oxides containing rare earth and manganese BaLn2Mn2O7(Ln=rare earth) with the layered perovskite type and Ln2(Mn,M)O7 with pyrochlore-related structure were studied since these compounds show many kinds of phases and unique phase transitions. In BaLn2Mn2O7 there appear many phases, depending on the synthetic conditions for each rare earth. The tetragonal phase of so-called Ruddlesden-Popper type is the fundamental structure and many kinds of deformed modification of this structure are obtained. For BaEuzMn207 at least five phases have been identified from the re-sults of X-ray diffraction analysis with the space group P42/mnm, Fmmm, Immm and A2/m in addition to the fundamental tetragonal 14/mmm phase. In the pyrochlore-related type compounds, LnzMn2-xMxO7(M=Ta,Nb,W etc),there also appear several phases with different crystal structures. With regard to every rare earth, Ln2MnTaO7 phase is stable only for excess Ta and can be obtained under high oxygen partial pressure process. This group has trigonal structure with zirkelite type (P3121 space group). On the other hand Ln2Mn2/3Nb4/307 phase has monoclinic (C2/c space group)and zireonolite type structure. All of these structural models have the fundamental structure based on HTB (hexagonal tungsten bronze) layers formed by the arrangement of oxygen octahedra.     

汽车尾气净化催化剂载体表面改性的研究

采用国内(A,B)及国外(C)的孔密度为62cell/cm2堇青石蜂窝陶瓷载体作为研究对象,对三种载体的表面进行改性。在自制的铝胶中添加了适量的含La等混合稀土,测定其物理、化学性能的变化,结果证明表面积和热稳定性随改性剂的配比不同而不同;载体C在晶相结构、孔壁厚度及TSP循环次数均优于A,B。用上述表面改性的载体制成的车用催化器,经测定,热劣化系数≤1.08,初活性CO、THC、NOx均大于90%。     

以聚(苯乙烯-丙烯酰胺)载体氯化钕配合物催化合成的聚4-乙烯吡啶及表征

采用聚(苯乙烯-丙烯酰胺)载体氯化钕配合物催化剂催化合成聚4-乙烯吡啶,研究了Al3+/Nd3+摩尔比、单体浓度、不同类型催化剂、反应时间和温度对聚合活性、单体转化率、相对分子量的影响规律。结果表明,Al3+/Nd3+摩尔比为200、单体浓度为0.25 g.mL-1,聚合时间为5h,聚合温度为50℃,催化活性达到最大。氯化钕配合物的催化活性高于稀土氯化物,聚合物载体氯化钕配合物催化性能高于同类小分子体系配合物。并通过傅里叶变换红外光谱(IR)、核磁共振氢谱(H-HMR)、核磁共振碳谱(13C-HMR)、差示扫描量热分析(DSC)测试手段对4乙烯吡啶聚合物结构进行表征。     

Catalytic decomposition of ethyl acetate over La-modified Cu-Mn oxide supported on honeycomb ceramic

The La-modified Cu-Mn spinel oxide was successfully coated onto honeycomb ceramic by a washcoating method for complete catalytic decomposition of ethyl acetate.The La-modified Cu-Mn oxides were characterized by X-ray diffraction,X-ray fluorescence,H_2-temperature programmed reduction,Brunauer-Emmett-Teller method,field-emission scanning electron microscopy and high-resolution transmission electron microscopy.The effects of different precipitants and rare earth doping on the structure and catalytic performance of the catalysts were investigated.The results show that the CuMn_2 O_4 spinel with(NH_4)_2 CO_3 as a precipitant can form a larger specific surface area and a suitable pore size,which is beneficial to the absorption of ethyl acetate.Although the rare earth doping does not significantly change the crystal phase structure of the catalyst,it improves its reducibility and lowers the temperature of the catalytic decomposition.With respect to the catalytic decomposition of ethyl acetate,the rare earth-modified Cu-Mn oxide supported on honeycomb ceramic shows excellent catalytic performance with 100% conversion under the conditions of 239℃,space velocity of 12500 h~(-1) and1000 ppm.And the ethyl acetate removal rate is still 100% after 1440 min of continuous reaction.     

Study on Coke Formation and Stability of Nickel-Based Catalysts in CO2 Reforming of CH4

CO2 reforming of CH4 over nickel-based catalysts was investigated by using a fixed-bed reactor. Catalytic activity and amount of carbon deposition effects by nickel loading content, rare earth promoter and promoter contents were evaluated. It is found that nickel loading as well as reaction temperature can influence the activity and carbon deposition amounts, and with the addition of rare earth promoter, it can greatly improve the catalytic activity and exert a strong effect on the anticoking performance of the catalysts. The 5.0% (mass fraction)Ni-0.75% La BaTiO3 catalyst shows great resistance to coke formation and higher thermal stability as well as the catalytic activity.     

Study on Polymerization of 4-Vinylpyridine by Neodymium Complex Catalyst

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