Ce1-xNixOy氧载体在化学链甲烷重整耦合CO2还原中的应用

化学链甲烷重整耦合CO₂还原技术既能生产合成气还可以还原CO₂生成CO。采用共沉淀法制备不同Ce/Ni摩尔比的系列Ce_1-xNi_xO_{y（x = 0,0.2,0.4,0.6,0.8,1）氧载体。通过XRD、BET、XPS及CH4-TPR等表征对氧载体的理化性质进行了研究。系统考察了Ce1-xNixOy氧载体在化学链甲烷重整耦合CO2还原反应中的反应性能。与单一金属氧化物NiO和CeO2相比,Ce1-xNixOy复合氧载体在该反应中具有更高的活性和热稳定性。在甲烷部分氧化阶段,Ce0.2Ni0.8Oy和Ce0.4Ni0.6Oy氧载体具有较高的CH4转化率。经历了20次redox循环实验,Ce0.2Ni0.8Oy氧载体的CO2转化率几乎保持不变,表明Ce0.2Ni0.8Oy氧载体具有较高的热稳定性。}     

LaMn1-x-yFexCoyO3-δ钙钛矿载氧体用于化学链部分氧化

采用溶胶-凝胶法制备了B位Fe和Co共取代的LaMn_1-x-yFe_xCo_yO_3-δ钙钛矿型复合氧化物,并用于化学链甲烷部分氧化制合成气。X射线衍射（XRD）结果表明Fe和Co均进入了LaMnO₃的晶格形成钙钛矿晶相,活性和稳定性测试表明LaMn_1/3Fe_1/3Co_1/3O_3-δ载氧体具有最佳的化学链甲烷部分氧化性能。CH₄程序升温还原（CH₄-TPR）表征发现LaMn_1/3Fe_1/3Co_1/3O_3-δ具有比LaBO₃（B=Co, Mn, Fe）更高的甲烷活化能力和晶格氧迁移性能。甲烷恒温脉冲反应（CH₄-pulse reaction）进一步证实了B位离子的协同作用可以提高LaBO₃（B=Co, Mn, Fe）的表面反应速率。程序升温氢气还原（H₂-TPR）表明,LaMn_1/3Fe_1/3Co_1/3O_3-δ中晶格氧具有适中的氧化还原能力,适合用于化学链甲烷部分氧化。     

Ta、Ba共掺杂石榴石型Li7La3Zr2O12电解质的制备及性能研究

传统锂离子电池采用有机电解液体系,能量密度难以进一步提升,同时存在一定的安全隐患。采用无机固体电解质构建全固态锂电池,在提高电池能量密度同时可兼顾安全性问题。在众多无机固体电解质中,Li₇La₃Zr₂O₁₂(LLZO)石榴石电解质具有离子电导率高、与金属锂接触稳定等优势,成为受人关注的材料。为了进一步提高该材料的导电性,采用固相法合成Ta、Ba共掺杂LLZO(Li_7-x+yLa_3-yBa_yZr_2-xTa_xO₁₂)电解质,采用X射线衍射、扫描电子显微镜和电化学阻抗法分析样品的物相结构、微观形貌及离子电导率。结果表明,Ta⁵⁺掺杂能够稳定立方相结构,Ba²⁺作为掺杂剂和烧结剂,促进晶粒生长和陶瓷致密化,从而降低总电阻。其中,Li_6.45La_2.95Ba_0.05Zr_1.4Ta_0.6O₁₂样品在室温下的总电导率为1.07×10^-3 S·cm^-1,活化能为0.378 eV。Ta⁵⁺/Ba²⁺共掺杂有利于制备高致密度和高电导率的石榴石型电解质材料。     

火焰喷雾合成法制备La0.8Sr0.2Mn1-xCuxO3催化氧化CO性能研究

采用火焰喷雾合成法制备了Sr²⁺、Cu²⁺分别取代A、B位的La_0.8Sr_0.2Mn_1-xCu_xO₃ （x=0,0.1,0.2,0.3,0.4）钙钛矿催化剂,并用于CO催化氧化实验,研究了水蒸气和CO₂对催化剂CO氧化活性的影响。对不同取代量La_0.8Sr_0.2Mn_1-xCu_xO₃ 催化剂进行了XRD、SEM、EDS、BET、XPS、H₂-TPR和O₂-TPD等表征测试。结果表明,火焰喷雾合成法制备的钙钛矿催化剂具有良好的钙钛矿相、疏松多孔结构和催化氧化活性。其中,La_0.8Sr_0.2Mn_0.9Cu_0.1O₃分别在119.4℃和133.3℃实现50%和90%的CO转化率。掺杂水蒸气和CO₂会与CO在催化剂表面形成竞争吸附,导致5种催化剂性能衰减,但La_0.8Sr_0.2Mn_0.9Cu_0.1O₃仍能在150.2℃实现90%的CO催化转化,在连续稳定性催化氧化测试中,5种催化剂性能衰减不超过10%。结合上述CO催化氧化实验,火焰喷雾合成法制备的催化剂具有良好的稳定性和催化活性,适合制备高CO催化氧化活性的钙钛矿催化剂。     

Ag/Ce0.75Zr0.25O2催化剂中Ag的负载量对碳烟燃烧活性的影响

开发低温下高催化活性的柴油机碳烟颗粒燃烧催化剂是当前环境催化领域的热点问题。利用共沉淀的方法制备了用于碳烟催化燃烧反应的Ag/Ce_0.75Zr_0.25O₂催化剂。活性评价结果表明,相对于Ce_0.75Zr_0.25O₂催化剂,Ag的引入可显著降低碳烟催化燃烧温度。而且,Ag的负载量存在一个最佳值。以XRD、in-situ XRD、BET、TPR等表征手段探究了该系列催化剂结构性质及其变化产生的影响。结果表明,Ag与Ce物种间的相互作用可显著降低催化剂（特别是CeO₂表面氧）的还原温度。该相互作用使Ag/Ce_0.75Zr_0.25O₂催化剂在一定温度下（>200℃）就表现出Ag⁺的性质。这些性质与该催化剂具有较高的碳烟氧化活性相关。而且,该催化剂也表现出良好的稳定性。     

负载型NiO-La2O3催化剂在CO2甲烷化反应中的研究

将二氧化碳转化为易于储存和运输的高热值燃料——甲烷,不仅可以缓解温室效应,也是解决能源短缺的有效途径。本文采用柠檬酸络合的等体积超声浸渍法制备一系列NiO-La₂O₃/SiO₂催化剂,其中镍和镧的摩尔比为1:1,并采用XRD、H₂-TPR表征技术对NiO-La₂O₃/SiO₂催化剂的结构和物化性质进行了研究。考察了NiO-La₂O₃的负载量对CO₂甲烷化反应性能的影响。结果表明,10%NiO-La₂O₃/SiO₂催化剂表现出最优的CO₂甲烷化反应性能,且在450℃时表现出最佳的反应活性,CO₂转化率和CH₄选择性分别为59.3%和60.8%。     

Si/(Yb1-xYx)2Si2O7/LaMgAl11O19热/环境障涂层的高温性能研究

采用等离子喷涂法在碳化硅纤维增强碳化硅陶瓷基复合材料(SiC_f/SiC-CMCs)表面制备了Si/(Yb_1-xY_x)₂Si₂O₇/LaMgAl₁₁O₁₉(x=0、0.5)热/环境障涂层(T/EBCs)体系。通过SEM、EDS和XRD等测试方法研究了不同组成的T/EBCs体系在1 300 ℃下的热循环性能和抗水氧腐蚀性能,进而探讨了热循环失效和水氧腐蚀失效机理。结果表明,在T/EBCs体系中,Si/Yb₂Si₂O₇/LMA涂层体系的热循环寿命为403次,抗水氧腐蚀性能为50 h,Si/YbYSi₂O₇/LMA体系的热循环寿命降低至277次,而水氧腐蚀性能提高至80 h。YbYSi₂O₇与LMA之间较大的热失配应力以及层间含Al化合物或固溶体的生成是Si/YbYSi₂O₇/LMA热循环寿命降低的主要原因;YbYSi₂O₇-EBCs层较少的杂质氧化物减少了与水反应生成挥发性物质的几率,提高了Si/YbYSi₂O₇/LMA的抗水氧腐蚀能力。     

CeO2助剂对Ni基催化剂甲烷化性能的影响

甲烷化工艺是煤制天然气的关键技术,甲烷化催化剂则是甲烷化技术的核心。Ni基催化剂具有活性高、选择性好和价格低廉等优点,但易积炭,积炭堵塞催化剂孔道,覆盖表面金属活性位,导致催化剂失活。稀土类金属氧化物（如CeO₂、La₂O₃等）对Ni基催化剂的活性、稳定性、抗积炭性能以及活性组分的分散有明显的促进作用。采用共沉淀法制备了CeO₂-La₂O₃复合氧化物载体,负载Ni后用于CO甲烷化反应,利用N2物理吸附、XRD、H₂-TPR、XPS和TG等对催化剂结构进行表征。结果表明,Ni/CeO₂-La₂O₃中CeO₂的添加主要发挥了电子助剂的作用,CeO₂的存在提高了催化剂表面Ni0周围的电子密度,促进Ni物种的还原,同时还能提高催化剂的抗积炭能力,使催化剂表现出更好的甲烷化活性与稳定性。在V（H₂）∶V（CO）=1、反应温度450 ℃、空速24 000 h^-1和常压下,Ni/CeO₂-La₂O₃催化剂的CO转化率达82.7%。     

Ni-Mn/Al2O3催化剂在浆态床中CO甲烷化催化性能

采用共浸渍法制备了Ni-Mn/Al₂O₃催化剂,考察了助剂Mn的含量对催化剂结构及浆态床CO甲烷化性能的影响。采用XRD、H₂-TPR、BET、TEM、H₂-化学吸附等表征对催化剂进行了测试分析,结果表明,Mn助剂的引入能够促进Ni物种在载体表面的分散,减弱Ni物种与载体的相互作用,降低催化剂的还原温度,提高催化剂的比表面积,减小活性金属Ni的晶粒尺寸。随着Mn含量的增加,Ni-Mn/Al₂O₃催化剂的甲烷化性能先升后降,其中以Mn含量为4%（质量分数）时的催化甲烷化性能最佳,添加过量的Mn导致活性组分Ni被部分覆盖,催化甲烷化性能下降。通过对16Ni4Mn/Al₂O₃催化剂样品的浆态床反应温度及反应压力的研究发现,当反应温度为280℃、反应压力为1.5 MPa时,催化剂样品16Ni4Mn/Al₂O₃的CO转化率及CH₄选择性分别达到96.2%和88.8%。     

甲烷二氧化碳重整镍基催化剂的研究

采用浸渍法制备不同组成催化剂Ni-M/γ-Al₂O₃（M=Zr、Co、Mg、Nd）,通过固定床反应装置考察不同助剂、助剂含量和反应温度对催化剂活性的影响,并对催化剂进行X射线衍射表征。结果表明,14Ni-5Mg/γ-Al₂O₃的催化活性较好,随着反应温度的升高,甲烷转化率和CO收率均升高,反应温度升至800 ℃时,甲烷转化率达97.54%。采用共沉淀法制备载体、浸渍法制备的催化剂14Ni/MgO-Al₂O₃,在反应温度800 ℃、压力1.013 kPa、n(CO₂)∶n(CH₄)=1.2和催化剂用量0.5 g条件下,CO收率高于14Ni-5Mg/γ-Al₂O₃催化剂,但甲烷转化率略低。     

Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts for catalytic combustion of methane

A series of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts (x = 0–1) were prepared. The structure of the catalysts was characterized using XRD, SEM and H₂-TPR. The catalytic activity of the catalysts for the combustion of methane was evaluated. The results indicated that in the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts the surface phase structure were the Ce_1−xCu_xO_2−x solid solution, -Al₂O₃ and γ-Al₂O₃. The surface particle shape and size were different with the variety of the molar ratio of Ce to Cu in the Ce_1−xCu_xO_2−x solid solution. The Cu component of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts played an important role to the catalytic activity for the methane combustion. There were the stronger interaction among the Ce_1−xCu_xO_2−x solid solution and the Al₂O₃ washcoats and the FeCrAl support.     

Catalytic reduction of sulfur dioxide using hydrogen or carbon monoxide over Ce1−xZrxO2 catalysts for the recovery of elemental sulfur

This study focuses on the direct sulfur recovery process (DSRP), in which SO₂ can be directly converted into elemental sulfur using a variety of reducing agents over Ce_1−xZr_xO₂ catalysts. Ce_1−xZr_xO₂ catalysts (where x = 0.2, 0.5, and 0.8) were prepared by a citric complexation method. The experimental conditions used for SO₂ reduction were as follow: the space velocity (GHSV) was 30,000 ml/g_-cat h and the ratio of [CO (or H₂, H₂ + CO)]/[SO₂] was 2.0. It was found that the catalyst and reducing agent providing the best performance were the Ce_0.5Zr_0.5O₂ catalyst and CO, respectively. In this case, the SO₂ conversion was about 92% and the sulfur yield was about 90% at 550 °C. Also, a higher efficiency of SO₂ removal and elemental sulfur recovery was achieved in the reduction of SO₂ with CO as a reducing agent than that with H₂. In the reduction of SO₂ by H₂ over the Ce_0.5Zr_0.5O₂ catalyst, SO₂ conversion and sulfur yield were about 92.7% and 73%, respectively, at 800 °C. Also, the reduction of SO₂ using synthetic gas with various [CO]/[H₂] molar ratios over the Ce_0.5Zr_0.5O₂ catalyst was performed, in order to investigate the possibility of using coal-derived gas as a reducing agent in the DSRP. It was found that the reactivity of the SO₂ reduction using the synthetic gas with various [CO]/[H₂] molar ratios was increased with increasing CO content of the synthetic gas. Therefore, it was found that the Ce_1−xZr_xO₂ catalysts are applicable to the DSRP using coal-derived gas, which contains a larger percentage of CO than H₂.     

Catalytic oxidation of VOCs on Au/Ce-Ti-O

Ce_xTi_1−xO₂ oxides have been synthesised by sol–gel method with x varying from 0 to 0.3 and characterised by XRD and TPR. The structure of oxides changes with the Ce/Ti molar ratio. The presence of ceria in Ce-Ti oxides inhibits the phase transition from anatase to rutile. When x = 0.3 (Ce_0.3Ti_0.7O₂ sample), the solid presents an amorphous state. The TPR results indicate that the presence of Ti enhances the reducibility of cerium oxide species. Catalytic oxidation of propene is investigated on Ce-Ti oxides and the better conversion is obtained with Ce_0.3Ti_0.7O₂ but the CO₂ selectivity reaches 63% at 400 °C. Gold is then deposited on theses oxides to improve the catalytic activity. On the basis of characterisation data (H₂ TPR), it has been suggested that gold influences the reduction of the Ce-Ti oxide support and the catalytic activity to the propene oxidation. Thus, Au/Ce-Ti-O system catalysts are promising catalysts for propene oxidation.     

Synthesis, characterization and catalytic activity for NO–CO reaction of Pd–(La, Sr)2MnO4 system

La_xSr_2−xMnO₄ (0 ≤ x ≤ 0.8) oxides were synthesized and single-phase K₂NiF₄-type oxides were obtained in the range of 0.1 ≤ x < 0.5. The catalytic activity of La_xSr_2−xMnO₄ for NO–CO reaction increased with increasing x in the range of solubility limit of La. La_0.5Sr_1.5MnO₄ showed the highest activity among La_xSr_2−xMnO₄ prepared in this study, but its activity was inferior to perovskite-type La_0.5Sr_0.5MnO₃. Among the Pd-loaded catalysts, however, Pd/La_0.8Sr_1.2MnO₄ showed the higher activity and the selectivity to N₂ than Pd/La_0.5Sr_0.5MnO₃ and Pd/γ-Al₂O₃. The excellent catalytic performance of Pd/La_0.2Sr_1.2MnO₄ could be ascribable to the formation of SrPd₃O₄ which was detected by XRD in the catalyst but not in the other two catalysts.     

Methanol decomposition to synthesis gas at low temperature over palladium supported on ceria–zirconia solid solutions

The Ce_xZr_1−xO₂ solid solution was used as a support of a palladium catalyst for methanol decomposition to synthesis gas at low temperature. All Pd-containing catalysts tested in this study showed high selectivity to synthesis gas (over 96%). The Pd supported on the composite oxide with a Ce/Zr molar ratio of 4/1 exhibited the highest activity. Pd/Ce_0.8Zr_0.2O₂ (17 wt.%) (cop) (prepared by coprecipitation method) showed a conversion of 51.2% for the methanol decomposition at 473 K, which was higher than those over 17 wt.% Pd/CeO₂ (cop) (40.7%) and 17 wt.% Pd/ZrO₂ (cop) (24.3%) at 473 K. The 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst showed a higher BET surface area and smaller Pd particles than those of 17 wt.% Pd/CeO₂ (cop). Moreover, a more active Pd^σ+ state could be maintained by Zr⁴⁺ ion modification due to promotion of the oxygen mobility and enhancement of the reductibility and increase in the acid sites of the CeO₂ support. The 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst showed a much higher conversion (51.2%) than that over 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (imp) (prepared by impregnation method) (17.2%) at 473 K. This is due to the 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) possessing many small Pd particles. The 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst showed an initial conversion of 51.2% at 473 K but the conversion decreased to 43.1% after 24 h on stream. This deactivation was attributed to carbonaceous deposit on the catalyst surface. The amounts of coke on the 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst were 0.9 wt.% after 24 h on stream at 473 K and 2.1 wt.% after 1 h on stream at 523 K.     

Methane combustion on Mg-doped LaMnO3 perovskite catalysts

LaMn_1−xMg_xO₃ perovskite catalysts (x=0–0.5) were synthesised by the so-called “citrates method”, characterised (chemical analysis, TEM, BET, XRD, temperature-programmed desorption of oxygen) and tested for their activity towards the catalytic combustion of methane. The role of MgO as a textural promoter, which hinders the sintering of the catalyst crystals by geometrical interposition, has also been assessed. Finally, a kinetics study was performed on the most promising catalysts prepared (LaMnO₃ and LaMn_0.8Mg_0.2O₃). The major results obtained are: (i) Mg substitution in the basic LaMnO₃ perovskite has a positive effect on the catalytic activity only at low x values (x≤0.2); (ii) as opposed to the results of previous studies on the LaCr_1−xMg_xO₃ system, the role of MgO as a textural promoter is not always significant and depends strongly on the calcination temperature of the samples (800–1200°C) and on the value of x; (iii) an Eley–Rideal mechanism could satisfactorily fit the experimental kinetics results for both catalysts, even though, as opposed to LaMnO₃, the catalytic combustion over LaMn_0.8Mg_0.2O₃ seems to involve two different types of adsorbed oxygen species, depending on the operating temperature.     

Ceria-based oxides as supports for LaCoO3 perovskite; catalysts for total oxidation of VOC

Supported LaCoO₃ perovskites with 10 and 20 wt.% loading were obtained by wet impregnation of different Ce_1−xZr_xO₂ (x = 0–0.3) supports with a solution prepared from La and Co nitrates, and citric acid. Supports were also prepared using the “citrate method”. All materials were calcined at 700 °C for 6 h and investigated by N₂ adsorption at −196 °C, XRD and XPS. XRD patterns and XPS measurements evidenced the formation of a pure perovskite phase, preferentially accumulated at the outer surface. These materials were comparatively tested in benzene and toluene total oxidation in the temperature range 100–500 °C. All catalysts showed a lower T₅₀ than the corresponding Ce_1−xZr_xO₂ supports. Twenty weight percent LaCoO₃ catalysts presented lower T₅₀ than bulk LaCoO₃. In terms of reaction rates per mass unit of perovskite calculated at 300 °C, two facts should be noted (i) the activity order is more than 10 times higher for toluene and (ii) the reverse variation with the loading as a function of the reactant, a better activity being observed for low loadings in the case of benzene. For the same loading, the support composition influences drastically the oxidative abilities of LaCoO₃ by the surface area and the oxygen mobility.