Ce_xTi_(1-x)O_2 Mixed Oxides Supported CuO Catalyst for NO Reduction by CO

Ce x Ti 1- x O 2 mixed oxides of different mole ratios ( x =0, 0.1, 0.2～0.9, 1.0) were prepared by co precipitation of TiCl 4 with Ce(NO 3) 3 and then loaded with different amounts of CuO. The effects of CuO on NO+CO reaction were investigated, and the structure and reductive properties of various CuO/Ce x Ti 1- x O 2 were characterized by the methodologies of BET, TPR and XRD. The results show that different Ce/Ti mole ratios and calcination temperatures induce changes of structure and reductive properties of the Ce x Ti 1- x O 2 mixed oxides. When x =0.1～0.5, amorphous CeTi 2O 6 phase mainly forms at 650 ℃ compared to the formation of CeTi 2O 6 which crystallizes at 800 ℃. When x >0.6, some TiO 2 enters the CeO 2 lattice and a CeO 2 TiO 2 solid solution is formed. The activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 650 ℃ is largely affected by the x values, which is the highest when x =0.3, 0.4 and 0.9. The NO conversion reaches 70% at a reaction temperature of 150 ℃. By comparison, the x values have little effect on the activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 800 ℃ . There are strong interactions between CuO and CeTi 2O 6, i.e., formation of the CeTi 2O 6 phase shifts the CuO reduction peak temperature from 380 to 200 ℃, and CuO, in turn, shifts the CeTi 2O 6 reduction peak temperature from 600 to 300 ℃.

Study on Catalysts with Rhodium Loading on Different Cerium-Zirconium Mixed Oxides

The catalysts with Rh loading on different cerium-zirconium mixed oxides were characterized by BET, H2-TPR and OSC. The effects of different cerium-zirconium mixed oxides on catalytic performance and thermal stability of Rh loaded catalyst were studied. The results show that: (1) Rh can enhance cerium-zirconium mixed oxides OSC and catalytic reaction rates; (2) cerium-zirconium mixed oxides with high Ce contents and low Zr contents are more favorable to the stability of catalysts. Moreover, the contents of CeO2 have important effect on catalysts characteristics, and the addition of some rare earth components, such as La, Pr and Nd also have some influences.

A rationale for the development of thermally stable nanostructured CeO_2-ZrO_2-containing mixed oxides

CeO2-ZeO2 solid solutions are extensively used as oxygen storage promoters in the current automotive three-way catalysts. High thermal stability of the textural properties is one of the most important requirements for practical application since temperatures up to 1273 K are easily experienced by these materials under real working conditions. In the present paper, we investigated how hydrothermal treatments applied to cakes of doped and undoped ZrO2-rich CeO2-ZrO2 precursors might improve the thermal stability of the final CeO2-ZrO2 solid solution. A rationale was developed that allowed to correlate the morphology of the hydrothermaUy treated cake with the thermal stability at 1273 K of the final product, which did not depend on the composition of the mixed oxides.

Effect of Different Dopant in the Mo-V-Te-O Catalyst on the Performance of Selective Oxidation Propane to Acrolein

Several Mo-V-Te-O mixed metal oxides catalysts with different dopant were prepared and used for catalytic oxidation propane to acrolein. It was revealed that the addition of P could greatly improve the performance of the Mo-V-Te-O catalyst. The catalysts were examined by XRD and H2-TPR. The XRD characteristic of the Mo-V-Te-P-O showed that the addition of P could aggrandize the (V0.07Mo0.93)5O14 phase. H2-TPR illuminated that the MoV0.3Te0.23P0.15On catalyst took on the best redox ability.

Effect of diluent and reaction parameter on selective oxidation of propane over MoVTeNb catalyst using nanoflow catalytic reactor

The selective oxidation of propane to acrylic acid over an MoVTeNb mixed oxide catalyst, dried and calcined before reaction has been studied using high-throughput instrumentation, which is called nanoflow catalytic reactor. The effects of catalyst dilution on the catalytic performance of the MoVTeNb mixed oxide catalyst in selective oxidation of propane to acrylic acid were also investigated. The effects of some reaction parameters, such as gas hourly space velocity （GHSV） and reaction temperature, for selective oxidation of propane to acrylic acid over diluted MoVTeNb catalyst have also been studied. The configuration of the nanoflow is shown to be suitable for screen catalytic performance, and its operating conditions were mimicked closely to conventional laboratory as well as to industrial conditions. The results obtained provided very good reproducibility and it showed that preparation methods as well as reaction parameters can play significant roles in catalytic performance of these catalysts.

Effect of loading content of copper oxides on performance of Mn-Cu mixed oxide catalysts for catalytic combustion of benzene

A series of Mn-Cu mixed oxide catalysts were prepared by precipitation method. The catalysts were characterized by N2 adsorp- tion-desorption, H2-TPR and XPS. When the loading ratio of manganese oxides to copper oxides was 8：2 or 7：3, the catalysts possessed better catalytic activity, and benzene was converted completely at 558 K. Results of H2-TPR showed that the loading of a small amount of copper oxides decreased the reduction temperature of catalysts. Results of XPS showed that the loading of a small amount of copper oxides increased the proportion of manganese and defective oxygen on the surface of catalysts, and stabilized manganese at higher oxidation state. And the catalyst with the loading ratio 7：3 was a little worse than 8：2, since the interaction between manganese oxides and copper oxides is too strong, copper oxides migrate to the surface of catalysts and manganese oxides in excess are immerged.

催化超临界水氧化法处理焦化废水的试验研究

焦化废水是在煤气净化、煤制焦炭和回收焦化产品的过程中产生的,其成分复杂,危害性大,常规的处理方法很难达到理想的效果。本次试验采用超临界水氧化技术对焦化废水进行处理研究,对废水中COD,NH_(3)-N等污染指标进行检测,通过采用新型混合催化剂,降低超临界水氧化所需反应条件,使出水效果满足GB 16171-2012炼焦化学工业污染物排放标准。

Sol-gel derived oxides and mixed oxides catalysts with narrow mesoporous distribution

A novel sol-gel process for preparing oxides and mixed oxides sols from precipitation and peptization process is reported in this article. Inorganic salts are used as raw materials in this study. It is found that the amount of acid has great influence on the stability and particle diameter distribution of the precursor sols. Ultrasonic treatment is used to prepare alumina sol at room temperature. The result of27Al NMR shows that there exist Al13 7+ species in the sol. By controlling the sol particles with narrow particle diameter distribution, alumina, titania and silica-alumina (SA) materials with narrow mesoporous distribution are formed by regular packing of sol particles during gelation without using any templates. The results also show that the structure and particle diameter distribution of precursor sol determine the final materials’ texture.

Catalytic behavior of Mo-Bi-Fe-Co-K-M-O(M=Ce,Gd,CeGd)catalysts for selective oxidation of isobutene

The further improvement of methacrolein(MAL)selectivity from isobutene(IB)oxidation is crucial and challenging.In this study,based on the typical Mo-Bi-Fe-Co-K-O mixed metal oxide,the rare earth element Gd-doped,Ce-doped and CeGd co-doped catalysts were prepared by co-precipitation strategy to increase the selectivity of MAL from 47.9%to 49.8%,64.2% and 68.6%,respectively.In order to elucidate in-depth the promoting effect of Ce and/or Gd,various characterizations were utilized including X-ray diffraction patterns(XRD),Raman,X-ray fluorescence spectrometry(XRF),X-ray photoelectron spectroscopy(XPS),O_(2)-temperature programmed desorption(O_(2)-TPD),H2-temperature programmed reduction(H2-TPR),CO_(2)-temperature programmed desorption(CO_(2)-TPD),IB-temperature programmed desorption(i-C4-TPD)and in-situ IB-Fourier transform infrared spectroscopy(IB-FTIR).Both Ce and Gd finely regulate the bulk and surface structure of the catalyst,thus altering the redox ability,oxygen mobility and storage ability and basicity.Compared with Ce,Gd addition slightly regulates the variation of Co^(2+)/Co^(3+)redox couples,greatly enhances the interaction among the components on the catalyst,thus only increases the content of surface oxygen species and has little effect on their mobility.While Cecontaining catalyst performs stronger oxygen storage and migration ability,thus leading to the overproduction of surface Odefectspecies,which are proposed to be the active sites for the production of MAL and COx.The CeGd co-doped catalyst possesses the proper content of surface Odefectspecies,thus exhibits much higher MAL selectivity.Moreover,the promoting mechanism of Ce and/or Gd over IB oxidation is proposed.Therefore,this work is helpful for understanding the influence of rare earth elements on the structure of mixed metal oxides and the olefin selective oxidation reaction.

Zn-Mg复合氧化物催化大豆油甘油解合成单甘酯

采用共沉淀法制备了一系列不同Zn、Mg物质的量比的Zn-Mg复合氧化物,将其用于催化大豆油甘油解合成单甘酯（MG）,采用XRD、氮气吸附-脱附仪、SEM、TEM对Zn-Mg复合氧化物结构与性能进行了表征,并测定了催化剂的表面碱强和碱量。优化了合成单甘酯的工艺条件,并考察了Zn-Mg复合氧化物的重复使用性能。结果表明,改变Zn、Mg物质的量比不仅可以调控Zn-Mg复合氧化物的碱强与碱量,还可以调控其比表面积、孔容等结构参数;不同Zn、Mg物质的量比复合氧化物的催化活性变化趋势与其碱强度（H）在15.0〈H〈17．2间碱量变化趋势相一致；n（Zn）／n（Mg）=0．1时，复合氧化物（ZM0．1）具有最好的催化甘油解反应活性；使用该催化剂合成单甘酯的适宜条件为：n（甘油）：n（大豆油）=3：1，反应温度210℃，反应时间2h，催化剂用量为大豆油质量的0．6％，该条件下大豆油转化率达95．6％，单甘酯收率为58．5％。ZM0．1催化剂重复使用4次时大豆油转化率仍达80．9％。

Influences of (Ce-Zr-La-Pr)O Contents on Three-Way Catalyst Performances

A series of catalysts with (Ce-Zr-La-Pr)O contents range from 0 to 50% in coating and single-palladium loads on substrates were prepared to study effects of (Ce-Zr-La-Pr)O contents on catalytic activities and durability by contrasting the characteristics of light-off, A/F and catalytic conversions of the fresh catalysts with that of the aged catalysts. The results show that (Ce-Zr-La-Pr)O can enhance the catalysts light-off characteristics, widen A/F windows and increase catalytic conversions at a certain extent through optimizing physical structural and chemical property of the mixed coating. However, (Ce-Zr-La-Pr)O contents influence greatly on the catalysts activities and durability, and the catalysts with contents ranging from 10% to 30% exhibited better integrative properties in all samples, and 10% was the optical content to make the catalyst performance highest in this thesis. It is indicated that an suitable content of (Ce-Zr-La-Pr)O plays an important role in assisting catalysis, enhancing durability and increasing oxygen storage capability.

Enhancing the activity of MoS_(2)/SiO_(2)-Al_(2)O_(3) bifunctional catalysts for suspended-bed hydrocracking of heavy oils by doping with Zr atoms

Developing catalysts with not only hydrogenation activity but also cracking activity is very important for the advancement of suspended-bed hydrocracking technology.Within this respect,MoS_(2)/SiO_(2)-Al_(2)O_(3)bifunctional catalyst is a kind of typical catalysts with both hydrogenation and cracking activity.Herein,a series of Zr-doped SiO_(2)-Al_(2)O_(3)mixed oxides were synthesized by a sol-gel coupled with hydrothermal method.The synthesized mixed oxides were characterized for chemical structures and acidic properties.It is found that doping SiO_(2)-Al_(2)O_(3)with Zr atoms significantly increases the numbers of acidic sites.The Zr-doped SiO_(2)-Al_(2)O_(3)mixed oxides were then combined with dispersed MoS_(2),which was in-situ produced from oil-soluble Mo precursors,to fabricate a novel kind of bifunctional catalysts for suspended-bed hydrocracking of heavy oils.Owing to the significantly increased numbers of acidic sites in Zr-doped SiO_(2)-Al_(2)O_(3)mixed oxides,corresponding bifunctional catalysts demonstrate much enhanced activity for suspended-bed hydrocracking of heavy oils in relative to MoS_(2)/SiO_(2)-Al_(2)O_(3)bifunctional catalysts.

Influences of Platinum Precursors and Solution Acidities on REO-Based Catalysts Performances

Important effects exist between precious metals and rare earths oxides in three-way catalyst, especially the coordinated effects. These effects were studied by using H2PtCl6, Pt(NH3)2(NO2)2 and Pt(OH)2(C2H5ONH2)2 as Pt precursors, and the mixed oxide of (Ce-Zr-La-Pr)O as base material to prepare a series of catalysts, and their performances of the catalysts were studied by TPR and CO pulse titration technologies. The results shown that Pt precursors and their solutions pH values influenced the oxygen storage capabilities, the active metal distribution degrees of the catalysts obviously, and every catalyst prepared by different precursors had an optimal pH values. It indicates that the active metals precursors and their solutions acidities have outstanding influences on the catalysts performances for the mutual effects existing between the active metals and the Rare Earth metal oxides, which results from the mate groups of the precursors and the solution acidity.

Effect of hydration on the surface basicity and catalytic activity of Mg-rare earth mixed oxides for aldol condensation

Magnesium and rare earth mixed oxides（Mg3 REOx（RE=La, Y. Ce）） were prepared and characterized by Xray diffraction（XRD）, N_2 adsorption-desorption, infrared spectra and microcalorimetry of CO_2. The results reveal that the Mg_3 CeO_x catalyst is present in the form of Mg-Ce-O solid solution,while the Mg3 LaOx and Mg_3 YO_x catalysts are probably rare earth oxides dispersed on MgO surface. As a result, among the calcined Mg_3 REO_x catalysts, the Mg_3 CeO_x catalyst presents the highest rate constant for acetone aldolization, which is well correlated to its more homogeneous distribution of basic sites. In contrary, the Mg_3 YO_x catalyst exhibit the lowest catalytic activity for acetone aldolization. Upon hydration pre-treatment, the basic properties on the surface of the Mg_3 REO_x catalysts were changed markedly. The Mg_3 YO_x catalyst after hydration treatment shows the highest amount of basic sites on catalyst surface, and then exhibits the highest activity among the hydrated Mg_3 REO_x catalysts. These results make it possible to fine-tune basic sites for acetone aldolization.

Multicomponent transition metal oxides and(oxy)hydroxides for oxygen evolution

Oxygen evolution reaction(OER)is the core electrode reaction in energy-related technologies,such as electrolytic water,electrocatalytic carbon dioxide reduction,rechargeable metal-air batteries,and renewable fuel cells.Development of well-stocked,cost-effective,and high-performance OER electrocatalysts is the key to the improvement of energy efficiency and the large-scale commercial implementation of these technologies.Multicomponent transition metal oxides and(oxy)hydroxides are the most promising OER catalysts due to their low cost,adjustable structure,high electrocatalytic activity,and outstanding durability.In this review,a brief overview about the mechanisms of OER is first offered,accompanied with the theory and calculation criteria.Then,the latest advances in the rational design of the related OER electrocatalysts and the modulation of the electronic structure of active sites are comprehensively summarized.Specifically,various strategies(including element doping,defect engineering,and fabrication of binderless catalysts)used to improve the OER performance are detailedly discussed,emphasizing the structure–function relationships.Finally,the challenges and perspectives on this promising field are proposed.

富CO_(2)气氛中镨基复合氧化物载金催化CO氧化反应

采用传统水热法制备了一系列不同镨锆摩尔比的镨锆复合氧化物Pr_(a)Zr_(b)O_(x)载体,并考查了富CO_(2)气氛下相应Au/Pr_(a)Zr_(b)O_(x)催化剂催化CO氧化反应的催化性能.研究发现Pr/Zr=0.005为最优摩尔比,其对应的Au/Pr_(0.005)Zr_(1)O_(x)催化剂因较易吸附更多的氧分子而表现出最好的催化活性.结合XRD、CO_(2)-TPD、TEM、XPS等表征手段发现:反应过程中活性物种Au的价态和氧物种组分含量发生变化,是造成催化剂活性差异的关键性因素.此外通过稳定性测试发现无论是Au/ZrO_(2)还是Pr_(a)Zr_(b)O_(x)系列催化剂均不受高浓度CO_(2)的影响.

前驱体盐对铁钛催化剂及其脱硝性能的影响

利用低价态铁前驱体盐(FeSO_(4))对高价铁前驱体盐(Fe(NO_(3))_(3))进行替换,制备一系列新型铁-钛复合氧化物基脱硝催化剂。在该系列催化剂中,Fe_(0.5)Fe_(0.5)TiO_(y)催化剂展现高稳定性、水硫耐受性及优异的低温活性与催化选择性等优点。通过X射线衍射(XRD)、拉曼光谱(Raman)、比表面积测试(BET)、程序升温法(H_(2)-TPR、NH_(3)-TPD、O_(2)-TPD)、X射线光电子能谱(XPS)和原位红外(In situ DRIFTs)等分析手段对催化剂进行表征。结果表明,Fe_(0.5)Fe_(0.5)TiO_(y)催化剂具有较大的比表面积(65.056 7 m^(2)/g),较高的表面可增加还原物种含量、酸性位点数量及表面活性氧浓度。此外,该催化剂表面的NH_(3)-SCR反应过程主要遵循E-R机理。

双金属催化剂催化氧化VOCs的研究进展

挥发性有机物(VOCs)是一类对环境和人体健康产生威胁的有毒有机化合物。催化氧化法因其高效、环保和去除率高等优点被认为是目前最有效的VOCs消除方法之一,负载双金属催化剂由于良好的催化性能被应用于挥发性有机物的去除。综述了近年来负载双贵金属、双非贵金属和混合金属催化剂对VOCs的催化性能,分析典型催化剂对VOCs氧化催化性能的影响,并展望VOCs催化氧化的未来发展趋势。

镓铝固溶体的制备及其COS催化水解性能

工业生产中含硫废气的排放严重污染了大气环境并且危害人体健康,COS的水解脱除是处理含硫废气的有效手段之一。通过水热法合成GaAl(O)催化剂,并且通过XRD、SEM、BET、XPS等技术对其进行系统的表征,结果表明,Ga离子进入了Al_(2)O_(3)晶格内部,催化剂的表面具有碱性。性能测试结果表明,Ga的添加能够极大程度地提升催化剂的水解性能。考察反应温度、空速和水含量对COS催化水解性能的影响,在140℃之后,GaAl(O)催化剂的COS转化率和H 2 S选择性都约保持100%,并且适当的水含量有助于COS转化率的提升,在低于180℃时,COS转化率在高空速下相对较低。在模拟工业生产的反应条件下考察催化剂的稳定性,GaAl(O)催化剂在24 h的测试中保持100%的COS转化率。

Ce_(1-X)Mn_XO_(2-a)复合氧化物催化剂甲烷催化燃烧性能的研究

采用水热法合成了系列Ce1-XMnXO2-a-T(X=0.0,0.1,0.2,0.3,0.5,0.7,0.9,1.0;T表示焙烧温度),T=500,650,800℃)复合氧化物催化剂用于甲烷的催化燃烧。通过XRD、N2吸/脱附、TG-DSC、UV-Vis-DRS和TPR表征手段研究了不同组成催化剂的物理化学性质及其对甲烷催化燃烧活性。结果表明,在500℃焙烧的情况下Mn进入CeO2晶格形成均相固溶体催化剂的最大取代值为0.7,而当Mn继续增加时则出现Mn2O3晶相偏析,同时各催化剂具有较高的比表面积;随着焙烧温度的升高,进入CeO2晶格的Mn最大取代值逐渐减少,650和800℃时分别为0.5和0.3,且比表面积相应降低。Ce1-XMnXO2-a-800催化剂的还原行为大致呈现三阶段,即为Mn2O3→Mn3O4的还原(340～420℃),Mn3O4→MnO的还原(420～480℃)和体相氧化铈的还原(700～900℃),且Mn的引入整体上提高了催化剂的可还原能力。甲烷催化燃烧活性评价结果表明,比表面积并非影响催化剂活性的主要因素,影响催化剂甲烷催化活性的主要因素为催化剂的组成、可还原能力和焙烧温度;而其中以Ce0.3Mn0.7O2-a-800催化剂表现出较高的甲烷催化燃烧活性,在甲烷转化率为10%和90%时的温度分别为430和613℃。进一步考察Ce0.3Mn0.7O2-a在不同温度(500、650、800和1000℃)焙烧后的催化活性表明,随着焙烧温度的提高催化剂催化活性降低。