新一代三效催化剂的关键材料—CexZr1—xO2固溶体研究进展

汽车尾气排放法规的日趋严格迫切要求开发高性能的三效催化剂。传统三效催化剂中的CeO2高温下易发生烧结而降低或失去储氧能力。而加入锆所形成的CexZr1-xO2固溶体具有良好的抗高温老化性能、低温还原性能和较高的储氧能力，可以作为新一代三效催化剂的关键材料。     

三效汽车净化催化剂性能研究

以汽车尾气模拟装置中产生的气体作为模拟废气,对JFG型催化剂处理汽车排气中CO、HC和NO_x的三效性能进行了研究。结果表明,该催化剂具有低起燃温度,良好的三效性能和热稳定性。利用TPD-MS测定了催化剂表面氧数目及脱附性能。通过汽车发动机怠速试验和初步行车30000km,证明该催化剂具有较好的应用开发前景。     

钯、铜、锰、铈三效催化剂性能研究

应用脉冲－火焰反应装置、ＸＲＤ、ＴＰＲ和氢氧滴定技术来研究Ｐｄ－Ｃｕ－Ｍｎ－Ｃｅ－Ｏ三效催化剂的性能。实验结果表明，不同的制备Ｐｄ－Ｃｕ－Ｍｎ－Ｃｅ－Ｏ催化剂的方法，则催化活性各不相同。在分层制备的催化剂中，催化性能主要以外层组分性能为主；以混合浸渍法制备的样品中，ＣｕＭｎ＿２Ｏ＿４相消失，Ｃｕ－Ｍｎ－Ｃｅ－Ｏ表面氧环境发生变化；表面活性剂的添加改变了Ｐｄ的分布，使催化剂表面易于还原；这些改变均对催化剂的三效性能发生影响。催化剂表面的有效贮氧量与三效活性没有明显的关系。     

光Fenton反应的Ce-Fe/Al2O3催化剂制备及性能表征

采用等量浸渍法制备具有相同铁负载量的Fe/Al2O3和Ce-Fe/Al2O3催化剂,以解决光Fenton反应过程中催化剂溶出的问题并提高反应过程的pH值.通过X射线衍射(XRD)、扫描电镜(SEM)、氢程序升温还原(H2-TPR)及紫外-可见漫反射(UV-Vis DRS)等手段分别表征催化剂的物相结构、表面形貌、还原性能及光吸收特性,利用媒介黄的光Fenton脱色反应来考察催化剂的活性和稳定性.结果表明,铈掺杂使活性组分Fe2O3分散均匀,有效防止Fe2O3颗粒的长大,增加催化剂对光的吸收,增强催化剂的储氧能力,提高了催化剂的催化活性,降低铁的溶出.该催化剂在pH3.0～6.0条件下,60min内可将100mg/L媒介黄完全脱色,在pH6.0连续使用10次,其催化能力保持稳定.     

用改性三效催化剂净化汽车尾气的试验研究

在制备Cu-Mn-Ce-O三效催化剂的基础上，通过实验研究了制备各种催化剂的空燃比特性和温度特性，结果表明：掺杂非贵金属K、Fe和TiO2只能提高尾气中某些组分的转化率，缩小催化剂的操作窗口；贵金属Pd的加入提高了催化剂的三效活性，加宽了催化剂的操作窗口，而催化剂的起燃温度没有明显降低。     

Ce掺杂改性Ni-Al-Ox催化剂CO-NO反应性能

通过尿素法制备了一系列Ce掺杂改性的Ni-Al-O_x复合氧化物催化剂,并研究了催化剂的CO-NO反应性能.活性测试结果表明,Ni-Al-Ce-O_x的催化活性明显优于Ni-Al-O_x,且活性随着Ce含量的增加而提高.当Ce的掺杂量为20%时,250℃条件下,NO转化率高达95%以上,同时催化剂具有良好的抗H₂O性能.XRD和Raman分析表明,Ce掺杂Ni-Al-O_x催化剂促进了氧空位产生.而XPS结果显示,氧空位随着Ce含量的增加而增加.H₂-TPR结果表明,Ce的掺杂使催化剂的氧化还原性能增强.结合NO-TPD和FTIR的表征结果,进一步发现Ce的加入使表面氧难以将NO氧化成硝酸盐,有利于NO在Ce的氧空位上分解为N₂或N₂O,促进CO-NO反应的进行.     

Pt/CeO2催化氧化甲苯反应机制研究

采用浸渍法制备了Pt/CeO_2和Pt/Al2O_3催化剂,并通过XRD、BET、ICP-OES、H2-TPR、XPS等手段表征其物理化学性质.结果发现,Pt/CeO_2和Pt/Al2O_3催化剂上Pt负载量约为0.6%,Al2O_3载体上Pt颗粒尺寸更小,Pt/CeO_2的可还原性更强.甲苯催化氧化活性评价结果表明,Pt/CeO_2催化剂表现出更好的催化活性,T50=170℃,T90=190℃.通过UV-Raman、甲苯TPD、GC/MS、In-situ FTIR等手段进一步研究发现,Pt/CeO_2活化甲苯及反应供氧的机制与Pt/Al2O_3存在区别,其活性更好是因为:(1)负载在CeO_2表面存在高电子密度的Pt原子,具有更强的活化甲苯能力,可以直接使苯基和甲基间的C—C链发生断裂;(2)Pt的负载促进了CeO_2氧空位形成,进一步提高了CeO_2的储氧性能,加速氧循环.除了Pt解离气相氧之外,CeO_2还可以提供活性氧物种参与催化氧化甲苯的反应,进一步提高甲苯催化氧化效率.     

Pd/CeO2-Al2O3对烟气中多环芳烃的催化氧化性能研究

采用浸渍法制备了不同负载量及不同钯铈比(Pd:Ce)的Pd/CeO2-Al2O3催化剂,并结合XRD、BET、SEM、O2-TPD和H2-TPR等方法对催化剂的性质进行了表征,研究了所制备的催化剂对燃煤烟气中多环芳烃(PAHs)的催化转化效率.XRD和SEM结果表明,Ce和Pd在Al2O3表面呈高度分散状态,有利于PAHs的催化氧化.BET测试表明,Ce的引入改变了催化剂表面孔径结构,提高其比表面积.O2-TPD和H2-TPR测试表明,适当钯铈比条件下制备的催化剂有较强的储氧能力和活性.催化氧化实验结果表明,所制备的Pd/CeO2-Al2O3催化剂对PAHs具有较高的转化效率,其平均转化率均在80%以上,且PAHs的毒性当量显著降低,钯铈比对PAHs的催化氧化性能影响较大,当催化剂的钯铈比为1:1时,PAHs的转化率最高,可达90%以上.     

Pd／Ce02-A1203对烟气中多环芳烃的催化氧化性能研究

采用浸渍法制备了不同负载量及不同钯铈比（Pd：Ce）的Pd/CeO2-Al2O3催化剂,并结合XRD、BET、SEM、O2-TPD和H2-TPR等方法对催化剂的性质进行了表征,研究了所制备的催化剂对燃煤烟气中多环芳烃（PAHs）的催化转化效率.XRD和SEM结果表明,Ce和Pd在Al2O3表面呈高度分散状态,有利于PAHs的催化氧化.BET测试表明,Ce的引入改变了催化剂表面孔径结构,提高其比表面积.O2-TPD和H2-TPR测试表明,适当钯铈比条件下制备的催化剂有较强的储氧能力和活性.催化氧化实验结果表明,所制备的Pd/CeO2-Al2O3催化剂对PAHs具有较高的转化效率,其平均转化率均在80%以上,且PAHs的毒性当量显著降低,钯铈比对PAHs的催化氧化性能影响较大,当催化剂的钯铈比为1：1时,PAHs的转化率最高,可达90%以上.     

汽车尾气净化催化剂研究进展

介绍了汽车尾气净化催化剂的发展过程、三效催化剂的净化原理以及催化剂的组成等.     

焙烧温度对CeO_2(ZrO_2)/TiO_2选择性催化脱硝性能的影响

采用溶胶-凝胶法并以不同温度焙烧制备一系列CeO_2(ZrO_2)/TiO_2(CZT)催化剂,考察了CZT催化剂固相结构、酸量、比表面积等性能与催化活性的关系。采用XRD、BET、NH3-TPD、H2-TPR以及XPS等表征技术对催化剂进行表征。结果表明:焙烧温度为450℃时CZT催化剂具有最高的催化活性,其在240~400℃的温度窗口内活性均高于90%,且具有较好的抗水和抗硫中毒能力。随着焙烧温度的提高,催化剂表面的Ce和Zr原子进入体相晶格且Ce0.5Zr0.5O2向Ce0.75Zr0.25O2转变,导致催化剂的储释氧能力和氧化还原性能降低。另外,锐钛矿和金红石型TiO_2晶粒尺寸的增加,催化剂的有效比表面积和总酸量降低,因此CZT催化活性随着焙烧温度的提高而有所降低。换言之,大的比表面积、良好的氧化还原性能、表面Ce4+的富集以及酸性位的增多均有利于NH3-SCR活性的提高。     

Ce含量对Pd/Al_2O_3催化剂加氢脱硫性能的影响

采用浸渍法制备了Pd/Al2O3和Pd-CeO2/Al2O3催化剂,研究了不同Ce含量对Pd/Al2O催化剂加氢脱硫性能的影响,并运用XRD、TPR、TPD和噻吩吸附等手段表征了催化剂的吸附性能和酸性。结果表明,CeO2的加入导致Pd/Al2O3催化剂H2吸附性能的减弱和酸量的减少,但提高了噻吩的吸附性能。在噻吩加氢脱硫反应中,Ce含量为2%时Pd-CeO2/Al2O3催化剂的活性最高,随Ce含量的继续增加催化剂的活性下降,是由于催化剂对H2吸附和噻吩吸附综合影响的结果。     

CuxCe1-xO2/γ-Al2O3催化剂催化燃烧甲苯性能的研究

以γ-Al₂O₃ 为载体,以复合氧化物Cu_xCe_1-xO₂为活性组分,其中,x=0.1,0.2,0.4,0.6,0.8,通过浸渍法制备了一系列Cu_xCe_1-xO₂/γ-Al₂O₃催化剂.在固定床反应器中评价了催化剂对甲苯的催化活性,通过XRD、SEM对催化剂进行表征,并运用ICP-MS分析并计算Cu、Ce的摩尔比以及活性组分的负载量.结果表明,在Cu_xCe_1-xO₂/γ-Al₂O₃催化剂中Cu、Ce摩尔比的实际值与理论值相近,活性组分的负载量在19%以上,而且对甲苯都有较好的低温催化活性,其中当x=0.2时,即Cu_0.2Ce_0.8O₂/γ-Al₂O₃催化剂对甲苯的催化活性最高,其中T₁₀=160 ℃,T₉₀=265 ℃;当甲苯的进口浓度在700~3000 mg·m^-3时,进口浓度对Cu_0.2Ce_0.8O₂/γ-Al₂O₃催化剂的催化活性影响较小,且经过连续80 h的稳定性操作后转化率仍然保持在90%以上.     

Ce/Zr系列催化剂上碳颗粒物燃烧行为

分别在TG和TPO上考察了CeO₂,ZrO₂及不同Ce/Zr比的CexZr1-xO₂固溶体催化剂上soot的燃烧性能,同时考察了反应气氛对活性的影响.结果表明:Ce基催化剂能明显降低soot的起燃温度,Ce/Zr比的不同导致Ce_xZr_1-xO₂催化剂性能的差异.反应的速度控制步骤随O₂浓度的不同而改变;H₂O对Ce_0.5Zr_0.5O₂上soot的氧化活性基本没有影响;由于NO氧化产生的NO₂具有更强的的氧化能力,因此NO对soot的燃烧具有促进作用,起燃温度降低了30℃.催化剂上的β氧种参与了soot燃烧过程.     

Cu-Mn-Ce ternary mixed-oxide catalysts for catalytic combustion of toluene

Cu–Mn, Cu–Mn–Ce, and Cu–Ce mixed-oxide catalysts were prepared by a citric acid sol–gel method and then characterized by XRD, BET, H_2-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu–Mn–Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu–Mn–Ce catalyst, a portion of Cu and Mn species entered into the Ce O_2 fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu–Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu–Mn and Cu–Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.     

Cu–Mn–Ce ternary mixed-oxide catalysts for catalytic combustion of toluene

Cu–Mn, Cu–Mn–Ce, and Cu–Ce mixed-oxide catalysts were prepared by a citric acid sol–gel method and then characterized by XRD, BET, H₂-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu–Mn–Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu–Mn–Ce catalyst, a portion of Cu and Mn species entered into the CeO₂ fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu–Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu–Mn and Cu–Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.     

Complete catalytic oxidation of o-xylene over Ce02 nanocubes

The activities of CeO2 nanocubes calcined at different temperatures were tested for catalytic oxidation of o-xylene. Using CeO2 nanocubes as catalysts, complete catalytic oxidation of o-xylene was achieved below 210℃. The CeO2 nanomaterials were characterized by means of BET, X-ray diffraction (XRD), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). From the TEM images, all Ce02 nanocubes displayed cubic morphology irrespective of calcination temperature. The HRTEM images revealed that these nanocubes were enclosed by reactive {001}planes, which may contribute to the intrinsically catalytic property of o-xylene oxidation. The higher activity of Ce02 nanocubes calcined at 550℃ than those calcined at above 550℃ was attributed to their smaller crystallite size and larger surface area. The influences of reaction conditions were also studied, which found that a higher reaction temperature was necessary for complete catalytic oxidation of o-xylene at higher weight hourly space velocity (WHSV) and o-xylene concentration.     

Photocatalytic performance of TiO2 catalysts modified by H3PW12O40, ZrO2 and CeO2

The binary composite photo-catalysts CeO2/TiO2, ZrO2/TiO2 and the ternary composite photo-catalysts H3PW12O40-CeO2/TiO2,H2PW12O40-ZrO2/TiO2 were prepared by sol-gel method. The catalysts were characterized by thermogravimetric-differential thermal analysis (TG-DTA), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The photocatalyfic elimination of methanol was used as model reaction to evaluate the photocatalytic activity of the composite catalysts under ultraviolet light irradiation. The effects of doped content, activation temperature, time, initial concentration of methanol and gas flow rate on the catalytic activity were investigated. The results showed that after doping a certain amount of CeO2 and ZrO2, crystaniTation process of TiO2 was restrained, particles of catalysts are smaller and more uniform. Doping ZrO2 not only significantly improved the catalytic activity, but also increased thermal stability. Doping H3PW12O40 also enhanced the catalytic activity. The catalytic activities of binary and ternary composite photocatalysts were significantly higher than tin-doped TiO2. The dynamics law of photocatalytic reaction over the binary CeO2/TiO2 and ZrO2/TiO2 catalysts has been studied. The activation energy 15.627 and 15.631 kJ/mol and pre-exponential factors 0.5176 and 0.9899 s-1 over each corresponding catalyst were obtained. This reaction accords to the first order dynamics law.     

Ce掺杂低钒V2O5-WO3/TiO2催化剂脱除烟气元素汞的研究

制备了Ce掺杂的低矾V₂O₅-WO₃/TiO₂催化剂,在模拟燃煤烟气条件下开展Hg⁰的脱除实验.结果表明该催化剂具有很好的Hg⁰脱除能力,在200～500℃的温度范围内能脱除烟气中95%的Hg⁰.催化剂表征结果表明,比表面积、 孔容和孔径与汞脱除能力没有显著相关性.XPS的结果表明,催化剂表面的Ce是以Ce⁴⁺的形式存在,有利于Hg⁰的脱除反应.抗硫抗水实验表明,H₂O会轻微抑制Hg⁰的脱除反应,主要原因是H₂O和Hg⁰在样品表面的竞争吸附;SO₂会促进Hg⁰的脱除反应,原因是SO₂能增加样品表面的酸吸附位且增加表面Hg⁰的吸附量.     

Decomposition of hexachlorobenzene over Al2O3 supported metal oxide catalysts

Decomposition of hexachlorobenzene(HCB)was investigated over several metal oxides(i.e.,MgO,CaO,BaO,La2O3,CeO2,MnO2, Fe2O3,and Co3O4)supported on Al2O3,which was achieved in closed system at a temperature of 300°C.Catalysts were prepared by incipient wetness impregnation with different metal oxides loading and impregnating solvents.The decomposition effciency of different catalysts for this reaction depends on the nature of the metal oxide used,and Al2O3 supported La2O3 was found to be the most active one.Pe...