测定Cu—Al—O复合物催化剂表面酸碱性的微量热法

以NH3－CO2作探针分子,采用微量热法测定Cu-Al－O复合物催化剂的表面酸碱性,实验结果表明,样品的酸中心强度顺序是：0．5CAO＞CAO＞2CAO（0．5CAO,CAO,2CAO分别表示复合物中n(Cu)/n(Al)为0．5,1和2）,而碱中心强度顺序是,0．5CAO＜CAO＜2CAO。该法测定Cu-Al-O复合物表面酸碱中心的强度和密度,不受样品颜色限制,操作方便,准确度高,是用于测定固体催化剂表面酸碱性的一种较理想的定量方法。     

测定Cu-Al-O复合物催化剂表面酸碱性的微量热法

以NH3 -CO2 作探针分子,采用微量热法测定Cu -Al -O复合物催化剂的表面酸碱性。实验结果表明,样品的酸中心强度顺序是:0.5CAO>CAO>2CAO(0.5CAO、CAO、2CAO分别表示复合物中n(Cu)/n(Al)为0.5、1和2),而碱中心强度顺序是:0.5CAO相似文献   

焙烧温度对Mg(Al)O复合物结构和表面酸碱性质影响的研究

分别在673、873和1073K分解Mg/Al摩尔比为3的水滑石生成Mg(Al)O复合物.XRD测定均显示MgO物相.873K以上焙烧的样品同时存在MgAl2O4尖晶石物相.微量吸附量热测定其表面酸碱中心的强度和密度,发现碱中心强度和密度顺序为:MAO-2＞MAO-3≈MAO-1,而酸中心强度和密度顺序是:MAO-1＞MAO-3≈MAO-2.红外光谱表明,Mg(Al)O复合物表面酸碱中心主要存在L酸,碱中心是氧阴离子.焙烧温度对表面碱中心类型几乎没有影响.固态MAS27Al核磁共振结果展示,这些样品呈现出显著的Al3+配位情况的变化.     

Cu-Al-O氧化物催化剂酸碱性质的量热表征

由共沉淀法合成了Cu/Al物质的量比分别为0.5、1和2的Cu-Al水滑石.经400℃焙烧,水滑石前体转化生成Cu-Al-O氧化物样品.XRD测定样品仅显示CuO物相,表明组成成分较均一.用CO2和NH3作探针分子,量热结果展现,Cu-Al-O氧化物的表面碱中心强度和数量顺序是0.5CuAlO<CuAlO<2CuAlO,而酸位的强度和数量顺序是0.5CuAlO>CuAlO>2CuAlO.研究表明,样品的CO2和NH3起始吸附热与其Sanderson电负性存在较好的线性关系.     

二氧化碳氧化丙烷制丙烯催化反应的研究铬镁铝复合氧化物催化剂的制备、表面微量吸附量热及催化性能

以共沉淀法合成的铬镁铝类水滑石为前体,制备了一系列不同原子比的铬镁铝复合氧化物,研究了其对二氧化碳氧化丙烷制丙烯反应的催化性能.采用微量吸附量热技术,以CO2和NH3为探针分子定量地表征了样品表面酸碱中心的强度和数量,并与其催化性能进行了关联.结果表明,Cr:Mg:Al原子比为1:1:1的催化剂具有较大的比表面积(94.5m2/g),样品中Mg(Al1.5Cr05)O4物相的含量最多.样品表面存在数量较多强度较强的酸性中心和数量最少强度较弱的碱性中心,对NH3吸附,它的吸附热为145 kJ/mol,吸附覆盖度为3.55μmol/m2;对CO2吸附,它的吸附热为115kJ/mol,吸附覆盖度为0.063μmol/m2.该样品的催化活性最高,在温度为650℃,CO2/C3H8摩尔比为3.6,GHSV(C3H8)为3000 h-1时,C3H8的转化率为22.8%,C3H6的选择性为83.5%,收率为19.1%.     

CO和NO在CuO及Cu2O(110)表面吸附选择规律研究

采用离散变分Xα方法分别计算了CO和NO以C（或N）端顶位吸附在CuO（110）及Cu2O（110）表面上的基态势能曲线,结果表明：CO在Cu2O表面上的吸附强,而在CuO表面上的吸附弱;NO则在CuO表面上吸附强,在Cu2O表面上吸附弱．它们的吸附能的大小顺序为：CuO－NO＞Cu2O－CO＞Cu2O－NO＞CuO－CO．对于CuO－NO（或CO）吸附体系,主要是Cu的3d轨道与吸附分子的2π轨道间的相互作用;对于Cu2O－CO（或NO）吸附体系,则主要是吸附质分子的5σ及2π分子轨道与其顶位Cu1的4s及4p轨道和侧位Cu2的3d轨道相互作用．本文通过吸附势能曲线、态密度分析、成键分析及电荷转移量和方向等方面对实验现象做了合理的解释．     

B-P-O系催化剂表面酸性的吸附量热研究

制备了不同P／B比的W-P-O系催化剂，XRD和Raman光谱表明各样品中P和B都处于四面体结构中，但Raman光谱显示P／B＜1的样品表面有B的三配位物相B2O3。存在．用吸附量热法考察了NH3、H2O及二甲醚（DME）等探针分子的吸附行为，研究了样品的表面酸性，NH3在P／B＞1的样品上发生解离吸附，而在P／B＜1的样品上，其起始吸附热与在γ-Al2O3上的相似．进一步的研究表明，二甲醚可以作为合适的探针分子表征B-P-O系催化剂的表面酸性．     

铝硼复合氧化物负载Pt-Sn催化剂的丙烷脱氢性能研究

采用蒸发自组装法制备铝硼复合氧化物（(AlxBy)2O3）,真空络合浸渍法制备PtSn双金属催化剂,并应用于丙烷脱氢制丙烯。采用N2物理吸附、SEM、X射线粉末衍射、H2-TPR、NH3-TPD和TG对催化剂进行表征。掺入B可大幅增加载体的总酸量和酸中心密度,降低酸强度。当B掺入量为10%时,Cat-A0.9B0.1的总酸量是Cat-AB0总酸量的2.45倍,且只有弱酸中心。当B掺入量为50%时,Cat-A0.5B0.5的酸中心密度是Cat-AB0的4.3倍。以铝硼复合氧化物负载的催化剂均优于纯氧化铝负载的催化剂,催化剂的脱氢活性和稳定性与载体的硼铝摩尔比之间存在如下规律：A0.9B0.1＞A0.7B0.3＞A0.5B0.5＞AB0。 关键词：铝硼复合氧化物;PtSn/ (AlxBy)2O3催化剂;丙烷脱氢     

K_2O助剂对合成碳酸二甲酯用Cu-Ni/MoO_3-SiO_2催化剂吸附和反应性能的影响

用等体积浸渍法制备了MoO3 SiO2 (MoSiO)表面复合氧化物负载的Cu Ni K2 O催化剂。利用IR ,TPR ,TPD以及微反技术研究了K2 O助剂对CO2 和CH3OH在Cu Ni MoSiO催化剂表面上吸附和合成DMC(碳酸二甲酯 )反应性能的影响。结果表明 :K2 O助剂的加入 ,使CO2 在催化剂表面吸附强度增加 ,当K2 O含量达Cu Ni总量的 15 %时 ,CO2 在催化剂表面上吸附后生成K2 CO3;CH3OH在催化剂表面上的解离吸附态 (CH3O- H )的吸附强度减弱 ;CO2 和CH3OH在Cu Ni K2 O MoSiO催化剂表面反应主要产物为DMC ,H2 O ,CO和CH2 O。随着K2 O助剂的加入 ,反应转化率在 10 %之前增加 ,之后下降 ,DMC选择性稍有提高。副产物 (CO和CH2 O)的选择性下降。根据实验结果探讨了K2 O对催化剂表面活性中心的电荷分布的影响。     

CO2和CH3OH直接合成碳酸二甲酯用Cu-Ni/ZrO2-SiO2催化剂

 采用表面反应改性法制备了ZrO2－SiO2（ZrSiO）表面复合物,用等体积浸渍法制备了ZrSiO担载的Cu－Ni双金属催化剂,并用IR,TPD,TPSR和微反技术考察了CO2和CH3OH在催化剂表面上的化学吸附及反应性能．实验结果表明：在Cu－Ni／ZrSiO催化剂上存在着Cu－Ni金属位M,Lewis酸位Zrn＋和Lewis碱位Zr－O－三类活性中心;CO2在金属位和Lewis酸位的协同作用下可形成CO2卧式吸附态,此吸附态在142℃左右可解离成M－CO和Zr－O－;CH3OH在Lewis酸位和Lewis碱位的协同作用下可形成解离吸附态Zr－OCH3和Zr－OH;CO2和CH3OH在Cu－Ni／ZrSiO催化剂表面上的主要反应产物为碳酸二甲酯（选择性在85％以上）,另有少量的CH2O,CO和H2O．     

Microcalorimetric Studies of Zn—Al Mixed Oxides Obtained From Hydrotalcite-type Precursors

A series of Zn–Al hydrotalcites with Zn/Al molar ratios of 1, 2, 3 and 6 were prepared by co-precipitation method. TG-DTG results showed that the hydrotalcites decompose in two stages, corresponding to the two endothermic peaks around 180 and 220°C. After calcination at 400°C, the samples were converted into Zn–Al mixed oxides with the only XRD pattern of ZnO, except for the sample with the ratio of 6. The Zn–Al mixed oxides possess similar surface acidity revealed by microcalorimetric adsorption of NH₃. The basicity of the samples increases with the order: ZnO>6Zn/Al>1Zn/Al>Al₂O₃.This revised version was published online in November 2005 with corrections to the Cover Date.     

铜锰铝水滑石的合成、表征及衍生复合氧化物酸碱催化活性研究

采用低过饱和共沉淀法合成了铜锰铝不同摩尔投料比的碳酸根型水滑石,通过XRD、IR、TG-DTA等手段对样品进行测试和表征。X-衍射结果显示,其M2 /M3 摩尔投料比为2-4得到的水滑石为较满意构型。红外的结果进一步证实了碳酸根离子柱撑CuMnA l水滑石的成功合成,热重-差热分析结果显示随M2 /M3 比的增加,水滑石热稳定性减弱。经焙烧后,发现其复合氧化物催化活性随着Cu含量的增加而增大,随着Mn含量的增加对乙醛的选择性增大,可达到91.6%。     

TiO2–ZrO2的表征及其异丙醇催化转化性能

用共沉淀法制备了TiO2-ZrO2复合氧化物. 采用N2吸附、XRD、TEM、NH3和CO2吸附量热、NH3吸附红外对TiO2-ZrO2体系的结构及酸碱性等进行了表征. 结果表明: 与单纯的氧化物相比, 形成的复合氧化物为无定形物相, 有介孔结构, 表面积明显提高, 可达218 m2·g-1; 初始吸附热差别不大, 但具有更多的表面B酸位; 随着TiO2掺入量的增大, 复合氧化物表面碱位减少. 异丙醇催化转化, 在无氧条件下, ZrO2、TiO2和TiO2-ZrO2复合氧化物上丙烯的选择性大于90%, 说明这些氧化物具有强的表面酸性; 在有氧条件下, ZrO2和TiO2丙酮的选择性达到70%～85%, 主要体现为氧化还原性; 而在复合氧化物上丙烯选择性增大到70％左右, 丙酮的选择性下降为30%左右, 表明生成的复合氧化物表面上的氧化还原性削弱, 酸性增强.     

Dispersion and reactivity of copper catalysts supported on Al2O3-ZrO2

A series of CuO/Al(2)O(3)-ZrO(2) catalysts with Cu loadings varying from 1.0 to 20 wt % were prepared and characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), temperature-programmed desorption (TPD) of CO(2) and NH(3), electron spin resonance (ESR), and Brunauer-Emmett-Teller surface area measurements. The dispersion and metal area of copper were determined by the N(2)O decomposition method. XRD results suggest that the copper oxide is present in a highly dispersed amorphous state at copper loadings < 10 wt % and as a crystalline CuO phase at higher Cu loadings. ESR results suggest the presence of two types of copper species on the Al(2)O(3)-ZrO(2) support. TPR results suggest well-dispersed copper oxide species at low Cu loadings and crystalline copper oxide species at high Cu loadings. Well-dispersed copper oxide species were reduced more easily than large copper oxide species by H(2). The results of CO(2) TPD suggest that the basicity of the catalysts was found to increase with an increase of copper loading up to 5.0 wt % and decreases with a further increase of copper loading. The results of NH(3) TPD suggest that the acidity of the catalysts was found to decrease with an increase of copper loading up to 5.0 wt % and increases with a further increase of copper loading. The catalytic properties were evaluated for the vapor-phase dehydrogenation of cyclohexanol to cyclohexanone and correlated with the results of CO(2) TPD measurements and the dispersion of Cu on the Al(2)O(3)-ZrO(2) support.     

Structure and base properties of calcined hydrotalcites

Five hydrotalcites with Mg/Al molar ratio range of 3-15 were prepared. The structure and basicity of Mg-Al mixed oxides (Mg(Al)O) transformed from hydrotalcites were investigated by TPD, XPS, XRD, FT-IR and NMR techniques. The results of elemental analysis and XPS indicate that Al is enriched in the surface regions of Mg(Al)0, and its amount increases with the Mg/Al molar ratio and the calcination temperature. 27Al-MAS-NMR results show that Al exists in two chemical environments: tetrahedral aluminium (Al(t)) and octahedral aluminium (Al(o)) in Mg(Al)O. The amount of Al(t) increases with the Mg/Al molar ratio and the calcination temperature. It is assumed that Al(t) may be mainly from the surface Al. Temperature-programmed desorption (TPD) of CO2 shows that the number of basic sites of Mg(Al)O samples increases with the Mg/Al molar ratio, and the maximum number of basic sites is obtained for hydrotalcite calcined at 773 K. Infrared spectra of adsorbed CO2 and B(OCH3)3 reveal that there are two kinds of     

阳离子掺杂水滑石的制备及其性质研究

研究了掺杂阳离子水滑石的制备及阳离子对水滑石性质的影响. 分别制备了掺杂Zn2+、Ni2+、Fe3+型的水滑石, 考察了掺杂阳离子对水滑石晶相结构、层间距、层间阴离子含量、水滑石表面形态、水滑石碱性的影响, 结果表明, 由于阳离子的引入, 导致水滑石层间距减小及层间阴离子结合量降低, 且使水滑石培烧产物电负性提高, 并最终降低其碱性. 以上述水滑石培烧产物作为固体碱催化剂促进苯甲醛和丙醛缩合, 合成α-甲基肉桂醛, 关联了水滑石培烧产物碱性与反应活性的关系.     

ZrxTixAl1-2xO2的制备及其在三效催化剂上的应用

Zr_0.5Ti_0.5O₂(ZT) and Zr_0.25Ti_0.25Al_0.5O₂(ZTA) mixed oxides were prepared by co-precipitation method and characterized by low temperature adsorption-desorption， XRD and NH₃-TPD. The activity of Pt/Zr_0.5Ti_0.5O₂ and Pt/ Zr_0.5Ti_0.5Al_0.5O₂ catalysts was evaluated using the simulated gases. The results show that ZTA samples exhibit higher specific surface area， larger pore volume and proper surface acidic amount and acidity in comparison with ZT. The results of the catalytic test indicate that Pt/ZT and Pt/ZTA catalysts exhibit excellent low-temperature catalytic activity and lower light-off temperatures of hydrocarbon， carbon monoxide and nitrogen oxides， especially better conversion for nitrogen oxides (NO_x). The addition of Al₂O₃ into ZT enhanced the anti-aging property of Pt/ ZTA catalysts due to the excellent textural， structural， surface acidity and thermal stability.