Au／ZnO，Pd／ZnO和Au-Pd／ZnO催化剂甲醇部分氧化制氢性能的研究

采用PVP保护乙醇还原法制备Au/ZnO,Pd/ZnO和Au-Pd/ZnO催化剂,研究了Au,Pd和Au-Pd负载ZnO催化荆对甲醇部分氧化制氢性能的影响,并运用XRD,TPR和TPD等手段对催化剂进行了表征.结果表明,与Au/ZnO和Pd/ZnO催化剂相比,Au-Pd/ZnO双金属催化剂显示出较高的催化活性和氢气选择性、较低的CO选择性以及较好的稳定性.表征结果表明,Pd的加入抑制了Au粒子的烧结,使Au粒子变小,生成了富Au型Aux,Pdy合金,且Au-Pd与载体之间发生了一定的协同作用,从而提高了催化刺的活性和稳定性.     

介孔CeO_2载体织构性质对Au-Pd催化剂性能的影响

以硝酸铈铵为前驱体,分别采用表面活性剂嵌段共聚物F127、十六烷基三甲基溴化铵(CTAB)和十六胺(HDA)合成介孔CeO2(m-CeO2)载体,研究了m-CeO2织构性质对Au-Pd双金属催化剂甲醇部分氧化制氢性能的影响,并运用HRTEM、XRD、TPR、H2-TPD、CO2-TPD和低温N2吸附等手段对Au-Pd双金属催化剂进行了表征。结果表明,HDA为表面活性剂合成的m-CeO2(H4)具有较大的比表面、孔容和孔径。H4负载的Au-Pd催化剂显示出较高的催化活性和氢气选择性。表征结果表明,Au-Pd/H4催化剂中贵金属的分散度较高、形成的Au、Pd活性中心较多,金属与载体的相互作用较强,表面的碱中心较多,产物H2较易脱附。     

Au/CeO2催化剂乙醇部分氧化制氢的研究

采用共沉淀法制备了纳米Au/CeO2催化剂,并用XRD、TPR、ICP等方法对催化剂进行了表征.以乙醇部分氧化制氢为探针反应,系统考察了O2/C2H5OH摩尔比及反应温度对Au/CeO2催化性能的影响.结果表明,Au/CeO2催化剂活性组分Au与载体CeO2 存在较强的相互作用,对乙醇部分氧化制氢反应具有较好的低温催化活性和良好的稳定性,其最佳的反应条件是O2/C2H5OH摩尔比为1.6,反应温度573K.     

Y2O3对CuO-ZnO-ZrO2催化剂结构及性能的影响

考察了Y2O3对CuO-ZnO-ZrO2催化剂性能的影响,以甲醇水蒸汽重整为探针反应,并利用XRD、TPR、BET、H2-TPD、CO-TPD和IR等手段对催化剂的结构及性能进行了表征.结果表明,Y2O3的加入提高了催化剂中CuO的分散度、H2吸附量、Cu+的含量及Cu+/Cu0x比,加强了CuO和ZnO之间的相互作用,抑制了Cu+的深度还原,使CuO-ZnO-ZrO2催化剂的甲醇水蒸汽重整制氢反应的活性增大.     

铈和其它助剂对Pd/m-ZnO催化剂甲醇水蒸气重整制氢性能的影响

以三嵌段高聚物F-127为模板剂采用水热法分别合成了介孔ZnO-MOx(m-ZnO-MOx,M=Ce、Mg和Zr)复合氧化物,研究了铈和其它助剂对Pd/m-ZnO催化剂甲醇水蒸气重整制氢反应性能的影响,并运用XRD、H2-TPR和BET等手段对载体及催化剂进行了表征.与Pd/m-ZnO-MgO 和Pd/m-ZnO-ZrO2催化剂相比,Pd/m-ZnO-CeO2催化剂具有较高的甲醇水蒸气重整制氢活性,m-ZnO-CeO2复合载体较大的比表面积、较小Pd粒子以及Pd与m-ZnO-CeO2较强的相互作用有利于Pd基催化剂制氢活性的提高.     

CeO_2对Pt/TiO_2-Al_2O_3催化剂氧化及抗老化性能的影响

Pt/TiO_2-Al_2O_3对CO,HC以及NOx均有较好的催化氧化活性,但钛铝载体在高温下易发生相变,导致Pt团聚烧结而失活,CeO_2作为助剂可与贵金属发生电子间作用,提高其抗老化性能。通过分步负载的方法,采用浸渍法先对钛铝载体负载不同质量分数的CeO_2,烘干后再对其二次浸渍,负载0.7%(质量分数)的Pt,考查CeO_2负载量对催化剂催化氧化活性的影响,由此筛选出性能较好的催化剂,在1000℃条件下进行老化处理,对比老化前后其物理化学性质以及催化性能,最后对催化剂老化样进行了物相分析。结果表明负载1%(质量分数)的CeO_2不但可以提高催化剂对CO和C_3H_6的氧化活性,而且显著改善了催化剂的抗老化性能,老化样的NO_2最大生成量可达112×10~(-6),较未添加CeO_2的催化剂老化样增加了23×10~(-6),且其温度窗口更宽,说明CeO_2作为Pt/TiO_2-Al_2O_3催化剂助剂有很大的潜在应用价值。     

In-Ag/CeO_2-γ-Al_2O_3催化剂上CO-SCR脱除NO的研究

选用CO还原剂及负载不同比例In、Ag活性组分的CeO_2-γ-Al_2O_3催化剂进行脱硝实验,发现8%In-8%Ag具有较高的催化活性,在300~450℃温度区间内NO的转化率达到80%以上。研究了不同浓度CO、CO_2和H_2O对8%In-8%Ag/CeO_2-γ-Al_2O_3催化剂的影响,结果显示CO与NO体积比为1.5时,NO脱除率最高,且该催化剂具有较强的抗H_2O、抗CO_2存在性能,在有H_2O和CO_2的环境下催化剂仍有较强的脱硝活性。BET实验研究结果表明,8%In-8%Ag/CeO_2-γ-Al_2O_3催化剂具有较高的比表面积和较大的孔容,XRD和XPS分析揭示了In、Ag主要以In_2O_3与Ag_2O形式存在,且二者之间具有强相互作用而促使AgInO_2形成,从而使得8%In-8%Ag/CeO_2-γ-Al_2O_3催化剂具有高催化活性。     

聚合物稳定的Au-Pd/TiO2-Al2O3催化剂的还原方法及其催化性能的研究

以PVP为稳定剂，乙醇和K1BH4为还原剂制备了Au-Pd／TiO2-Al2O3催化剂，考察了还原剂对Au-Pd负载型双金属催化剂加氢脱硫性能的影响，并运用XRD，TPD，TPR等技术对催化剂进行表征。结果表明，以乙醇还原的Au-Pd／TiO2-AlO3催化剂的加氢脱硫活性较好。乙醇还原的Au-Pd／TiO2．Al2O3催化剂中Au-Pd之间及活性组分与载体之间的相互作用较强，形成Au-Pd，合金的晶粒较小，活性组分的分散度和活性表面积较大，反应活化能较低，这些均有利于催化剂活性的提高。     

模板法制备Ce_xZr_(1-x)O_2及催化餐饮废油合成生物柴油

以松木为模板,使用模板法制备了不同铈锆含量的Ce_xZr_(1-x)O_2复合氧化物的催化剂,用于餐饮废油与甲醇进行酯交换反应合成生物柴油.采用BET、SEM对Ce_xZr_(1-x)O_2进行表征分析.研究不同制备方法、CeO_2的负载量和煅烧温度对催化剂活性的影响,以及不同的酯交换反应条件对生物柴油产率的影响.制备的Ce_xZr_(1-x)O_2具有松木的生物形态,并有助于催化剂形成多孔道结构.以Ce_xZr_(1-x)O_2为催化剂,考察甲醇和餐饮废油的酯交换反应.结果表明:当x=0.5,煅烧温度为600℃时,甲醇与餐饮废油物质的量比为60∶1,催化剂用量(基于餐饮废油的质量)的质量分数为5%,反应温度为190℃,反应时间为6 h的反应条件下,酯交换反应的甲酯收率达到91.1%.     

LiCl熔盐中直接电解还原制备Ce-Ni/Zn/Bi合金

在923K、LiCl熔盐中,通过两电极体系直接电解还原CeO_2-5NiO、CeO_2-2.5Bi_2O_3、CeO_2-5ZnO三种混合氧化物制备相应的金属间化合物。从热力学上计算了3种混合氧化物的理论分解电压,并采用循环伏安法研究其电化学行为,验证了电解还原的可行性。结果表明,3种混合氧化物分别在3.2V被直接电解还原4h,NiO、Bi_2O_3、ZnO均能在CeO_2发生还原反应前生成对应的金属单质,然后促进CeO_2还原。得到的电解产物分别为CeNi_5/Ni、CeBi/Bi、CeZn_5/Ce_3Zn_(22)/CeZn_3。3种电解产物的微观形貌分别为絮状、堆积状和块状。     

Modification of Cu/ZSM-5 catalyst with CeO_2 for selective catalytic reduction of NO_x with ammonia

Cu/ZSM-5 and CeO_2-modified Cu/ZSM-5 catalysts were prepared by a wetness impregnation method. The addition of CeO_2 was found to enhance the NO_x selective catalytic reduction(SCR) activity of the catalyst at low temperatures, but the high-temperature activity was weakened. The catalysts were characterized by X-ray diffraction(XRD), nitrogen physisorption, inductively coupled plasma optical emission spectrometry(ICP-OES), X-ray photoelectron spectroscopy(XPS), electron paramagnetic resonance(EPR), H_2 temperature-programmed reduction(TPR) and NH_3 temperature-programmed desorption(TPD). The results showed that more CuO clusters instead of isolated Cu~(2+) species were obtained on the modified catalyst. These active CuO clusters, as well as the Cu-Ce synergistic effect, improved the redox property of the catalyst and low-temperatures SCR activity via promoting the oxidation of NO to NO_2 and fast SCR reaction. The loss in high-temperatures activity was attributed to the enhanced competitive oxidation of NH_3 by O_2 and decreased surface acidity of the catalyst.     

Influence of cobalt on performance of Cu-CeO_2 catalysts for preferential oxidation of CO

Copper and cobalt oxides supported on CeO_2 were investigated for preferential oxidation of carbon monoxide(CO-PROX) in the presence of excess hydrogen and CO_2.(Cuo)_(1-x)(Co_3 O_4)_(x/3)-(CeO_2)_(2.5)(x=0,0.25,0.50,0.75,0.85 and 1) catalysts were prepared by coprecipitation method.These mixed oxide catalysts were characterized by several physicochemical techniques,such as BET surface area(S_(BET)),X-ray diffraction(XRD),high resolution transmission electron microscopy(HRTEM),temperature programmed reduction(TPR) and X-ray photoelectron spectroscopy(XPS).XRD studies show the peaks related to CuO and Co_3 O_4 phases in copper and cobalt containing CeO_2 catalysts.The average particle size of the CeO_2 crystallites is in the range of 8-10 nm as evaluated from HRTEM studies.XPS studies demonstrate that Cu,Co and Ce in(cuO)_(1-x)(Co_3O_4)_(x/3)-(CeO_2)_(2.5) catalysts are presented in+2 and +1,+3 and +2 and +4 and +3 oxidation states,respectively.The catalyst with x=0.75 shows better activity and selectivity towards CO-PROX.Though the catalyst with only copper(CuO-CeO_2,x=0) shows good activity but reverse water gas shift(RWGS) reaction is noticed at high temperature.On the other hand,RWGS reaction is suppressed on the cobalt containing CuO-ceO_2 catalyst.Cobalt on CeO_2 with x=1 shows hardly any activity for PRoX reaction at low temperatures.No methanation activity is observed on CuO-CeO_2 or Co_3O_4-CeO_2 catalysts.In contrast,combination of copper and cobalt on CeO_2 shows methanation of CO where enhanced activity is observed with increasing in cobalt content.     

Influence of CeO_2 loading on structure and catalytic activity for NH_3-SCR over TiO_2-supported CeO_2

A series of supported CeO_2/TiO_2 catalysts were prepared to explore the influence of CeO_2 loading on these catalysts for the selective catalytic reduction of NO_3 by NH_3(NH_3-SCR).The catalysts were investigated in detail by means of XRD,Raman,H_2-TPR,NH_3-TPD,XPS,in situ DRIFTS,and NH3-SCR reaction.The activity of the catalyst is closely related to the content of CeO_2.When the loading of CeO_2 is near the dispersion capacity(1.16 mmol Ce~(4+)/100 m~2 TiO_2),the catalytic activity is better.This may be because that the dispersed CeO_2 is the active species and the catalyst has appropriate redox property,along with the larger amounts of surface Ce content and surface adsorbed oxygen species.Finally,a possible reaction mechanism via the Langmuir-Hinshelwood(L-H) mechanism is tentatively proposed to further understand the NH_3-SCR reaction.     

CeO_2/CuO catalysts using different template agent for preferential CO oxidation in H_2-rich stream

The CeO_2/CuO catalysts using different template agent(F68 L64, F127 and P123) were synthesized by the simple template and impregnation method. They were characterized by FESEM, XRD, N2 physisorption and H2-TPR techniques. It is found that the CeO_2/CuO catalysts are double pore distribution, and CeO_2 can enter into the gap of CuO supports and form the contact interface of copper and cerium. Among the asprepared catalysts, the CeO_2/CuO-F127 catalyst displays better activity at lower temperature and the CeO_2/CuO-P123 catalyst presents higher activity at higher temperature. The CeO_2/CuO-P123 catalyst has the smallest crystallite sizes of CuO and CeO_2 as well as the largest size of cubes, which may improve the interaction of copper and cerium and enhance the performance of CO oxidation.     

Effect of Rare Earth Oxides on Catalysts Mo-Te System

Surface compositions,structures,and acidities of the Mo-Te-Fe-Ni catalysts added with La_2O_3,CeO_2,Pr_6O_(12),Nd_2O_3 and Sm_2O_3 were measured and related with the activities of the catalysts for selective oxidationof olefins.It was found that adding rare earth elements to the Mo-Te catalysts increases obviously theirselectivities to methacrolein(MAL),and the yield percentage of MAL changes periodically with the increase ofatomic numbers of rare earth elements added,and the highest yield was obtained with the catalyst containingCeO_2.The addition of CeO_2 to 9-component Mo-Te catalyst increases not only the activity of the catalyst,but also its thermostability remarkably.The mechanism of rare earth elements in the catalysts was discussed.     

Effect of praseodymium additive on CeO_2(ZrO_2)/TiO_2 for selective catalytic reduction of NO by NH_3

A series of praseodymium added CeO_2(ZrO_2)/TiO_2 catalysts separately prepared by methods of sol-gel and impregnation were tested for selective catalytic reduction of NO, and characterized by X-ray diffraction(XRD), N_2-brumauer-emmett-teller(N_2-BET), NH_3-temperature programmed desorption(NH_3-TPD), H_2-temperature programmed reduction(H_2-TPR), PL spectra, Raman spectra, electron paramagnetic resonance(EPR) and X-ray photoelectron spectroscopy(XPS), respectively. Influence of preparation method on catalytic performance was studied. Results showed that the influence of Pr addition on catalytic performance of the CeO_2(ZrO_2)/TiO_2 catalysts was different between the sol-gel method and the impregnation method. The Pr addition tended to interact with TiO_2 and formed the structure of Ti-O-Pr in the sol-gel method while it was more likely to interact with CeO_2 forming the structure of Ce-O-Pr in the impregnation method. The total acid amount and redox properties of the catalysts prepared by sol-gel method decreased with the addition of Pr element, which resulted in decrease of catalytic activity. In contrast, the Pr-added catalyst prepared by impregnation method was found to possess easier reducibility, more total acid amount and higher proportion of Ce~(3+) species, which was favourable for higher catalytic activity.     

Effect of CeO_2-ZrO_2 on Pt/C electrocatalysts for alcohols oxidation

The electrocatalytic activity and stability of Pt/C catalyst modified by using CeO_2-ZrO_2 mixed oxides for the alcohols electrochemical oxidation as probes were investigated. The catalyst samples were characterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM). The electrochemical properties were measured by a three electrode system on electrochemical workstation(IVIUM). The results showed that the presence of CeO_2-ZrO_2 might be associated with the presence of Pt, which indicated that possibly there was synergistic effect between CeO_2-ZrO_2 and Pt nanoparticles. The electrocatalytic activity and stability of Pt-MO_x/C(M=Ce, Zr) for methanol and ethanol oxidation was better than that of Pt-CeO_2/C, which was attributed to that CeO_2-ZrO_2 composited oxides enhanced oxygen mobility and promoted oxygen storage capacity(OSC). Furthermore, the best performance was found when the molar ratio of CeO_2 to ZrO_2 was 2:1 for the oxidation of methanol and ethanol. The forward peak current density of Pt-MO_x/C(M=Ce, Zr, Ce:Zr=2:1) towards the methanol electrooxidation was about 3.8 times that of Pt-CeO_2/C. Pt-MO_x/C(M=Ce, Zr) appeared to be a promising and less expensive methanol oxidation anode catalyst.     

Synergistic catalytic removals of NO,CO and HC over CeO2 modified Mn-Mo-W-Ox/TiO2-SiO2 catalyst

A series of Mn-Mo-W-O_x/TiO_2-SiO_2 catalysts was modified with CeO_2 using an extrusion molding method. The catalytic activities of the obtained catalysts were tested for the synergistic catalytic removals of CO, NO and C_3H_8. The ratio of catalyst composition on catalytic activities for NH_3-SCR was optimized, which reveals that the molar ratio of Ti/Si was 9:1 and the catalyst containing 1.5 wt% CeO_2 and 12 wt% Mn-Mo-W-O_x exhibits the best catalytic performances. These samples were characterized by XRD, N_2-BET, Py-IR, NH_3-TPD, SEM/element mapping, H_2-TPR and XPS, respectively. Results show that the optimal catalyst exhibits more than 99% NO conversion, 86% CO conversion and 100% C_3H_8 conversion under GHSV of 5000 h~(-1). In addition, the GHSV has little influence on removal of NO when it is less than 15,000 h~(-1). Furthermore, the addition of CeO_2 will enhance the surface acidity, increase Mn~(4+)concentration and inhibit the grain growth, which are favorable for the excellent catalytic performance.Anyway,the 1.5 wt% CeO_2-12 wt% Mn-Mo-W-O_x/TiO_2-SiO_2 possesses outstanding redox properties,abundant acid sites and high Mn~(4+) concentration, which provide a guarantee for synergistic catalytic removal of CO, NO and HC.     

Catalytic oxidation of formaldehyde over CeO_2-Co_3O_4 catalysts

A series of CeO_2-Co_3O_4 mixed oxide catalysts with different Co/(Co+Ce) atomic ratios were synthesized by citric acid sol-gel method and used for catalytic oxidation of formaldehyde(HCHO). Many techniques such as Brumauer-Emmett-Teller(BET), X-ray diffraction(XRD), scanning electron microscopy(FE-SEM), temperature programmed reduction(H_2-TPR), temperature-programmed desorption(O_2-TPD) and X-ray photoelectron spectroscopy(XPS) were used to characterize catalysts. The results of catalytic performance tests showed that the catalyst CeO_2-Co_3O_4 with Co/(Co+Ce) ratio of 0.95 exhibited the best performance, and the temperature of complete oxidation of HCHO was 80 oC. The analytical results indicated that the addition of CeO_2 enhanced the specific surface area of Co_3O_4 and the fine dispersion of both of them. Moreover, the strong interaction between CeO_2 and Co_3O_4 resulted in the unique redox properties, which enhanced the available surface active oxygen and led to high valence state of cobalt oxide species. All those effects played crucial roles in the excellent performance of CeO_2-Co_3O_4 for the HCHO oxidation.     

Effect of cerium oxide prepared under different hydrothermal time on electrocatalytic performance of Pt-based anode catalysts

In this paper,CeO_2 with a pore size of 2-4 nm was synthesized by hydrothermal method.The CeO_2 modified graphene-supported Pt catalyst was prepared by the microwave-assisted ethylene glycol reduction chloroplatinic acid method,and the effect of the addition of CeO_2 prepared by different hydrothermal reaction time on the catalytic performance of Pt-based catalysts was investigated.The microstructures of CeO_2 and catalysts were characterized by X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),specific surface area and pore size analyzer(BET),scanning electron microscopy(SEM) and electron spectroscopy(EDAX),transmission electron microscopy(TEM),and the catalysts electrochemical performance was tested by electrochemical workstation.The results show that the catalytic performance of the four catalysts with CeO_2 is better than that of the catalyst without CeO_2.Adding CeO_2 with a specific surface area of 120.15 m~2/g prepared by hydrothermal reaction time of 39 h to Pt/C synthesis catalyst,its electrocatalytic performance,stability and resistance to poisoning are the best.The electrochemical active surface area is 102.83 m~2/g,the peak current density of ethanol oxidation is 757.17 A/g and steady-state current density of 1100 s is 108.17 A/g which shows the lowest activation energy for ethanol oxidation reaction.When the cyclic voltammogram is scanned for 500 cycles,the oxidation peak current density retention rate is 87.74%.