过渡金属-铈复合氧化物对碳烟的催化燃烧性能和表征

采用共沉淀法制备了不同过渡金属(Fe、V、Mn、Co、Cu)和铈的复合体氧化物催化剂,并用程序升温还原法(H2-TPR)、BET、XRD、拉曼光谱(RS)和光电子能谱(XPS)对催化剂进行了表征.同时,利用热重法测试了催化剂对碳烟的催化活性.实验结果表明,过渡金属的添加极大地提高了氧化铈的催化活性,其中,铈铁复合氧化物的催化活性最高.催化剂催化燃烧碳烟的活性与催化剂表面的耗氢量以及催化剂表面氧种OⅡ的含量紧密相关.     

由贵金属取代的钙钛矿催化剂对碳烟的催化性能

用柠檬酸法制备了不同贵金属取代的钙钛矿LaCo0.96X0.04O3(X为Pt、Pd、Rh、Au、Ag)催化剂,用热重法测试了催化剂对碳烟的催化活性,采用程序升温还原法(H2-TPR)、X-射线衍射仪(XRD)、能量谱仪(EDS)和红外光谱(FTIR)对催化剂进行了测试.结果表明,催化剂LaCo0.96Ag0.04O3催化活性最高,起燃温度为449℃,远低于LaCoO3的504℃;各贵金属取代的钙钛矿LaCoO3的TPR还原峰变化各异;XRD特征峰的衍射角向高角度偏移,说明各贵金属进入了钙钛矿结构相;能谱图显示各贵金属进入钙钛矿相的量不同.     

La1-xCexFe0.7Co0.3O3-δ网状多层纳米纤维对碳烟催化燃烧性能研究

采用静电纺丝法制备了一系列钙钛矿催化剂La_(1-x)Ce_xFe_(0.7)Co_(0.3)O_(3-δ)(x=0、0.1、0.2、0.3和0.4),并采用XRD、SEM、FT-IR、H2-TPR和O_2-TPD等技术分析了Ce掺杂量对催化剂结构、微观形貌及理化特性的影响.同时,采用程序升温氧化(TPO)技术评价了催化剂对碳烟的催化燃烧活性,探讨了催化剂对碳烟的催化燃烧机理.结果表明:在La_(1-x)Ce_xFe_(0.7)Co_(0.3)O_(3-δ)中掺杂适宜的Ce有助于提高催化剂活性,改善催化剂比表面积和孔容积.在催化剂与碳烟松散接触条件下,当Ce掺杂量(质量百分比)为0.3时,所制备的La_(0.7)Ce_(0.3)Fe_(0.7)Co_(0.3)O_(3-δ)对碳烟的起燃温度(T_(ig))、最大燃烧温度(T_m)和燃尽温度(T_f)分别为329.5、409.8和421.1℃,呈现良好的催化氧化活性.碳烟最大转化效率为98.7%,平均活化能为123 kJ·mol~(-1),CO_2选择率为98.2%,实现了对柴油机碳烟排放污染物有效"过滤+催化燃烧"的双重目标.     

氧化甲苯的MnOx-CeO2催化剂表面活性物种研究

采用氧化还原共沉淀法制备了一系列不同Mn/Ce摩尔比的MnOx-CeO2复合氧化物,并考察其对甲苯的催化活性.结果表明,MnOx-CeO2复合氧化物的催化活性优于单一CeO2,MnOx(0.5)-CeO2的催化活性最高,T90=190℃.同时,借助BET、XRD、H2-TPR、Raman和XPS等技术对催化剂的结构及表面活性物种等进行了表征.结果显示,Mn进入CeO2的立方萤石结构后形成固溶体结构,使得MnOx-CeO2复合氧化物的比表面积增大,氧空位和晶格氧含量增多,表面氧流动性增强.最后,对MnOx(0.5)-CeO2进行XPS和不同激发波长的Raman测试.结果显示,Mn主要分布在催化剂表面,且主要以Mn4+形式存在,Ce主要分布在催化剂体相.研究表明,高度分散在催化剂表面的Mn4+在甲苯氧化中起主要作用,Ce4+并未直接参与反应,而是起到了电子传递的作用.     

Ce_(0.65-x)Co_xK_(0.15)Zr_(0.2)O_2催化碳烟燃烧活性研究

采用柠檬酸络合燃烧法制备了不同铈钴摩尔比的Ce_(0.65-x)Co_xK_(0.15)Zr_(0.2)O_2(x=0,0.15,0.23,0.30,0.38,0.45,0.65)催化剂,采用XRD、SEM、FT-IR与H_2-TPR等技术对催化剂进行表征,并通过程序升温氧化反应(TPO)考察了催化剂不同Ce/Co比对碳烟颗粒物催化燃烧活性的影响。研究结果表明:在松散接触条件下,该系列催化剂催化碳烟颗粒物燃烧活性较高,T_m均小于400℃,当x=0.23时活性最高,T_i与T_m分别为321℃与355℃,催化剂所表现出的高活性受益于样品表面具有大量高活性的细小Co_3O_4颗粒物。     

改性赤泥负载Pt催化剂催化氧化甲苯的性能

以改性赤泥为载体,采用浸渍方法制备低成本改性赤泥(MRM)负载Pt催化剂,并探究Pt含量对Pt/MRM催化剂催化氧化甲苯活性影响.结果表明0.4Pt/MRM表现出最佳的催化活性,在230℃时甲苯转化率为100%.当空速高达120000h^-1时0.4Pt/MRM催化剂依然能保持着较高的催化活性.当甲苯进口浓度为5000mg/m³时仍可以有效氧化甲苯.采用XRD、FT-IR、BET、H₂-TPR和O₂-TPD等手段进行表征测试分析发现,MRM的比表面积较RM大幅度提高,使MRM能够更好分散活性组分Pt,成为合适的活性组分Pt的催化剂载体.同时所制备的x Pt/MRM催化剂具有较高的比表面积和良好的孔结构.改性赤泥中Fe₂O₃与活性组分Pt物种相互作用,使催化剂的总氧解吸量增大,提高了催化剂表面氧的迁移率,从而提高了催化效率.     

聚乙二醇辅助Ce0.6Mn0.4Ox催化净化碳烟颗粒物燃烧性能的研究

以进一步提升具有良好碳烟催化燃烧性能的Ce_0.6Mr_0.4O_x催化剂活性为目的,通过共沉淀法制备该催化剂时加入不同分子量的聚乙二醇(PEG).活性测试结果表明,随着PEG分子量的增加,活性先升高后降低.当PEG分子量为6000时,活性最佳,相比未添加PEG的铈锰混合氧化物催化剂,DSC曲线上燃烧最大值对应温度下降了23℃.XRD和Raman测试结果表明,该系列催化剂均形成了立方萤石结构.当添加分子量为6000的PEG时,结合XRD、Raman、XPS、ICP、H₂-TPR和O₂-TPD结果表明,此时Mn^x+进入CeO₂晶格中的量最大,从而产生了更多的表面活性氧,促进了表面化学吸附氧的脱附,表现出了良好的低温还原性能;BET结果表明,该催化剂的比表面积和孔容均优于未添加PEG的催化剂;SEM结果表明,该催化剂在微米和纳米层面均表现出更多的空隙.因此,添加分子量为6000的PEG最有利于促进碳烟催化燃烧.     

La_(0.9)Ce_(0.1)NiO_3钙钛矿型催化剂四效催化性能的研究

采用溶液燃烧法制备了钙钛矿型催化剂La_(0.9)Ce_(0.1)NiO_3,用于净化柴油车尾气中的碳烟颗粒、氮氧化物、CO和烃类物质,利用XRD方法对催化剂进行了表征,并从催化剂活性评价、碳烟颗粒催化转化效率和催化剂对硫的耐久性三方面考察了催化剂对柴油车尾气的四效催化活性评价结果。实验结果表明制备的催化剂存在明显的钙钛矿结构,且NO最大转化率为25.03%,碳烟起燃温度为235℃C_3H_6的完全转化温度为418℃,并且对硫有较好的耐久性。     

钙钛矿LaMnO3负载贵金属在催化氧化碳烟中的作用

采用共沉淀法制备钙钛矿LaMnO3,并用浸渍法在LaMnO3上负载不同的贵金属得到系列催化剂.利用程序升温氧化反应对催化剂催化氧化碳烟的性能进行了测试.程序升温还原(H2-TPR)、BET、XRD、SEM和FY-IR等表征手段对催化荆进行了表征.结果表明,当Pd的负载量在0.5%时,催化剂Pd/LaMnO3的催化性能最好,和单独的LaMnO3相比,最高燃烧速率温度降低了40℃.当负载量较小和较多时,碳烟起燃温度反而会比LaMnO3高.在5种贵金属负载的催化剂中,其中Pd催化性能最好,依次为Au、Ru、Pt和Rh.TPR测试表明贵金属的负载有助于钙钛矿中 Mn4 的还原,对高温时Mn3 的还原作用不大.XRD衍射角向低角度出现了少许偏移,显示负载在表面的贵金属部分进入钙钛矿LaMnO3的晶格结构中,使其晶粒增大;BET和SEM结果表明催化剂在反应后出现了轻微团聚现象.IR图谱显示反应前后,主要特征红外吸收带没有明显变化,表明催化剂具有较好的结构稳定性.适量的贵金属在钙钛矿LaMnO3上负载,能够有效地提高催化燃烧碳烟的活性.     

Mn-Ce/C-Al_2O_3催化剂制备及其处理含苯酚废水研究

将碳材料与Al_2O_3作为催化剂载体的优势互补,将碳包裹在Al_2O_3外侧,开发了新型MnCe/C-Al_2O_3催化剂,探究了制备参数对模拟含苯酚焦化废水中有机物降解的影响,考察了催化剂的稳定性。结果表明:经6%葡萄糖溶液碳负载后,催化剂比表面积增加26.36%;锰的负载提供Lewis酸点并促进了臭氧活化为·OH过程,铈提升了锰的催化效果,在锰铈比为4∶1、450℃条件下烘焙4小时,催化剂对COD、TOC和UV_(254)的降解率可达85.52%、86.06%和90.96%;催化剂在10次降解实验中对COD的去除效果都较为稳定,均值为77.5%,Mn-Ce/C-Al_2O_3催化剂兼具良好的催化活性和稳定性。     

Preparation methods and thermal stability of Ba-Mn-Ce oxide catalyst for NOx-assisted soot oxidation

Manganese oxide-loaded and -doped ceria as well as the corresponding barium-modified oxide catalysts were prepared for soot oxidation in the presence of NOx, and were characterized by using X-ray diffraction, Brunauer-Emmett-Teller and NO temperatureprogrammed oxidation measurements. The activity of catalyst depended strongly on the NO2 production capacity, and the importance of surface nitrates was weakened without heat transfer limitations. The formation of perovskite-type oxides after the high-temperature calcination caused the loss of NOx storage capacity for the Ba-modified catalysts, but did not seem to affect the NO oxidation activity obviously. The addition of barium did not prevent the phase separation of MnOx-CeO2 solid solutions, whereas it inhibited the sintering of oxide crystallites effectively. This, as well as the relatively high surface area, resulted in a small increase in soot oxidation temperature for the thermally aged Ba/Mn-Ce catalyst.     

用于碳烟燃烧的Cu0.05Ce0.95O催化剂活性氧物种的研究 ——等离子体的强化效应

研究等离子体对柠檬酸络合法制备的Cu0.05Ce0.95-CA催化剂表面结构和物种的强化效应. TPO、H2-TPR、O2-TPD、XRD、BET和XPS等测试结果表明,催化剂处于等离子放电区时,其氧化碳烟燃烧的活性显著增强.在介质阻挡放电电压为9kV时,起燃温度为243.1℃,比无等离子的情况降低了65.1℃;燃烧峰值温度为302.8℃,降低92.7℃.在等离子体存在下,Cu0.05Ce0.95-CA催化剂有着更大的比表面积和更小的晶粒粒径;等离子体可以提高催化剂表面游离态的CuO的分散度,并使得更多的Cu2+进入CeO2晶格,形成更多的Cuy2+Ce1-y4+O2-y2-□y固熔体,催化剂储氧容量增大,在催化剂表面生成更多的活性氧物种,其流动、迁移和转化促进催化剂产生更多的氧空穴,如此循环,持续促进碳烟催化燃烧.     

Modification of Ce02-ZrO2 catalyst by potassium for NOx-assisted soot oxidation

Potassium-modified ceria-zirconia catalyst was synthesized by wetness impregnation method. The ageing treatment was performed in static air at 800℃ for 20 hr to evaluate the thermal stability of the catalyst. The catalysts were characterized by X-ray diffraction,BET surface area, oxygen storage capacity, NOx-temperature programmed desorption and soot-temperature programmed oxidation measurements. By introduction of potassium, the maximum soot oxidation rate temperature (Tm) of the ceria-zirconia based catalyst decreased from 525 to 428℃ in the presence of NO under a loose contact mode. The shift of Tm of the K-modified catalyst after ageing is only 15℃. The enhanced activity of the aged catalyst mainly lies in the promotional effect of potassium on the NOx/oxygen storage cacity as well as the soot-catalyst contact.     

Modification of CeO2-ZrO2 catalyst by potassium for NOx-assisted soot oxidation

Potassium-modified ceria-zirconia catalyst was synthesized by wetness impregnation method.The ageing treatment was performed in static air at 800°C for 20 hr to evaluate the thermal stability of the catalyst.The catalysts were characterized by X-ray diffraction,BET surface area,oxygen storage capacity,NOx-temperature programmed desorption and soot-temperature programmed oxidation measurements.By introduction of potassium,the maximum soot oxidation rate temperature(Tm) of the ceria-zirconia based catalyst de...     

Catalytic evaluation of promoted CeO2-ZrO2 by transition, alkali, and alkaline-earth metal oxides for diesel soot oxidation

Series of mixed metal oxides were synthesized by gel-combustion method and their catalytic activities for soot oxidation were investigated. The catalysts were M-Ce-Zr （M = Mn, Cu, Fe, K, Ba, Sr）, and χK-20Mn-Ce-Zr （χ= 0, 5, 10, 20）, they were characterized by XRD, SEM, TPR and BET surface area techniques. The results of soot temperature programmed oxidation （TPO） in an O2 oxidizing atmosphere indicate that K-Ce-Zr has the highest catalytic activity for soot oxidation under loose contact condition, due to enhancement of the soot and catalyst contacts. On the other hand, under a tight contact condition, Mn-Ce-Zr and Cu-Ce-Zr nano-composites have high activities for soot oxidation and lower the soot TPO peak temperatures by about 280 and 270℃, respectively, as compared to non-catalytic soot oxidation. Furthermore, the addition of up to 10 wt.% potassium oxides into Mn-Ce-Zr increases its catalytic activity and further reduces the soot TPO peak temperature by about 40℃ under loose contact condition.     

铂、钯蜂窝催化剂高温老化对甲醇深度氧化的影响

本研究对铂、钯蜂窝催化剂及分别添加助化剂CeO_2或WO_3,并于500℃、700℃、900℃或1100℃下经受热老化4h后,考察催化剂比表面、晶相结构及其对甲醇深度氧化活性、产物分布及反应动力学网络变化的情况。实验证明,添加CeO_2后,降低了铂催化剂的耐高温性能,但对钯催化剂无明显影响。添加WO_3,降低了钯催化剂对甲醇的氧化活性。经X-线衍射分析证明,在1100℃高温下,WO_3与堇青石载体中的氧化镁和氧化钙发生强相互作用,生成了相应的钨酸盐。甲醇氧化反应动力学研究表明,甲醇在新鲜和高温热老化的铂催化剂上,反应动力学网络表示式是有区别的。     

SO2对Pd掺杂La0.9Sr0.1MnO3催化剂去除NOx和碳烟的影响

采用柠檬酸络合法制备了掺杂贵金属Pd的La_0.9Sr_0.1Mn_0.03Pd_0.97O₃钙钛矿型催化剂,并通过X射线衍射光谱及暂态响应、扫描电子显微镜、傅立叶变换红外光谱及程序升温等技术研究了Pd对钙钛矿形貌结构和NOx转化率的影响以及SO₂对La_0.9Sr_0.1Mn_0.97Pd_0.03O₃催化剂脱除NOx的作用机制.结果显示,Pd的成功掺入增大了原催化剂的比表面积,使得催化剂中的活性组分与NOx能够反应的更加充分,有效提高了催化剂对NO的转化率.催化剂La_0.9Sr_0.1Mn_0.97Pd_0.03O₃在含SO₂气氛下反应后出现了微弱的硫酸盐相,说明硫使催化剂发生了一定程度的钝化.在较低浓度SO₂存在时催化剂对NO的转化效率维持在80%以上,碳烟的起燃温度为353℃,但随着SO₂浓度的增加NO的转化效率最高只有67%,碳烟的起燃温度升高到368℃.     

OMS-2负载Pt催化剂的制备及其催化氧化性能研究

采用前掺杂法、沉积-沉淀法和浸渍法制备了氧化锰八面体分子筛(OMS-2)负载Pt催化剂(Pt/OMS-2),对所制催化剂进行了结构和织构表征。并研究了不同制备方法和沉积-沉淀法中不同制备(Pt负载量和溶液的pH值)对Pt/OMS-2催化氧化CO性能的影响。结果表明,沉积-沉淀法制备的Pt/OMS-2-DP催化剂活性最好(T100=100℃)。这与Pt/OMS-2-DP催化剂中Pt颗粒大小及OMS-2载体与Pt之间存在强相互作用有关。Pt负载量明显影响Pt/OMS-2-DP催化剂的催化活性,3Pt/OMS-2-DP催化剂(Pt=3.0 wt%)催化活性最高,这是由于适当Pt负载量,Pt颗粒较小,并与载体OMS-2的相互作用较强,能较好地活化OMS-2晶格氧。pH值对Pt/OMS-2-DP催化剂催化性能影响较大,这与OMS-2的等电点和Pt在不同溶液中存在不同Pt配位体形式有关。     

固体碱催化剂制备生物柴油的研究

以CH3COONa为活性组分,Al2O3载体,采用浸渍法制备Na2O/Al2O3负载型固体碱催化剂.用扫面电镜,表面积与孔径分析,红外三种表征方法对此催化剂表面结构及性能进行了分析,结果显示催化剂表面结构和性能良好;用Na2O/Al2O3作为催化剂进行生物柴油合成实验,催化剂表现出很好的催化活性.通过正交试验考察了醇油...     

Low-temperature VOCs oxidation performance of Pt/zeolites catalysts with hierarchical pore structure

Different zeolites supported Pt catalysts with micro-mesoporous structure were prepared by organic base tetrapropylammonium hydroxide (TPAOH) treatment and their catalytic oxidation activity for various volatile organic compounds (VOCs) were evaluated. The results reveal that the synergistic effect between Pt nanoparticles and surface acid sites plays an important role in VOCs low-temperature removal. The small size and high dispersion of Pt nanoparticles on the surface of the zeolites would promote the catalytic oxidation of aromatics and alkanes over the Pt/zeolite catalysts, while strong acidity and abundant acid sites of catalysts are in favour of the oxidation of the VOCs containing N and O heteroatoms. In addition, it was found that Pt/ZSM-5 catalyst exhibits the highest oxidation activity for various VOCs low-temperature removal amongst all the catalysts due to the balance of both Pt dispersion and abundant acid sites in the catalyst. This comprehensive consideration should be very helpful when designing and preparing novel catalysts for the low-temperature removal of VOCs.