活化气氛对钼基合成醇催化剂的结构和性能的影响

Activated carbon supported Mo-based catalysts were prepared and reduced under different activation atmospheres, including pure H₂, syngas (H₂/CO=2/1), and pure CO. The catalysts structures were characterized by X-ray diffraction, X-ray absorption fine structure, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The catalytic performance for the higher alcohol synthesis from syngas was tested. The pure H₂ treatment showed a high reduction capacity. The presence of a large amount of metallic Co⁰. and low valence state Mo^φ+ (0<φ<2) on the surface suggested a super activity for the CO dissociation and hydrogenation, which promoted hydrocarbons formation and reduced the alcohol selectivity. In contrast, the pure CO-reduced catalyst had a low reduction degree. The Mo and Co species at the catalyst mainly existed in the form of Mo⁴⁺ and Co²⁺. The syngas-reduced catalyst showed the highest activity and selectivity for the higher alcohols synthesis. We suggest that the syngas treatment had an appropriate reduction capacity that is between those of pure H₂ and pure CO and led to the coexistence of multivalent Co species as well as the enrichment of Mo^δ+ on the catalyst''s surface. The synergistic effects between these active species provided a better cooperativity and equilibrium between the CO dissociation, hydrogenation and CO insertion and thus contributed beneficially to the formation of higher alcohols.     

活性炭担载的Rh-M0-K合成醇催化剂

采用XRD、EXAFS等技术研究向微量贵金属Rh对活性炭担载的Rh-Mo-K合成醇催化剂结构的影响,并关联其催化性能。氧化态Rh-Mo-K／AC样品中Rh与Mo有着较强的相互作用,使得K2Mo2O7向MoO2转化。硫化还原后,Mo主要以MoS2微晶形式存在,其有序结构尺度随Rh含量的增加而减小。经Rh助剂修饰后,催化剂的合成醇催化性能有明显的提高。     

活性炭担载的Rh—Mo—K合成醇催化剂

采用XRD、EXAFS等技术研究微量贵金属Rh对活性炭担载的Rh-Mo-K合成醇催化剂结构的影响,并关联其催化性能。氧化态Rh-Mo-K／AC样品中Rh与Mo有着较强的相互作用,使得K2Mo2O7向MoO2转化。硫化还原后,Mo主要以MoS2微晶形式存在,其有序结构尺度随Rh含量的增加而减小。经Rh助剂修饰后,催化剂的合成醇催化性能有明显的提高。     

Mn助剂对K-Co-Mo催化剂结构及CO加氢合成低碳醇性能的影响

通过溶胶-凝胶法合成了一系列Mn掺杂K-Co-Mo催化剂,并利用X射线衍射、N₂吸脱附、NH₃程序升温脱附、原位漫反射红外光谱以及X射线吸收谱等技术对催化剂的结构进行了表征.活性测试结果显示Mn掺杂催化剂比未掺杂催化剂表现更高的合成低碳醇的催化活性,尤其是C₂₊醇的选择性得到了明显的提高.醇产物分布偏离了ASF分布规律,甲醇的含量显著减少,乙醇成为主要醇产物.表征结果表明Mn助剂的加入增强了Co和Mo之间的相互作用,促进了醇生成活性中心Co-Mo-O物种的生成.显著减少了催化剂强酸性位的数量,促进了弱酸性位的产生,有利于醇产物的生成.助剂的加入有利于催化剂对CO的线性和桥式吸附,促进了醇产物的生成和碳链的增长,提高了催化剂对C₂₊醇的选择性.     

粘土担载的钼基催化剂的制备、结构及CO加氢合成醇性能

采用溶胶凝胶法与等体积浸渍相结合制备了一系列以粘土为载体的K-Co-Mo催化剂. 采用XRD、N₂等温吸脱附、H_{26+的还原,但对Mo⁴⁺和Co²⁺的还原没有明显的影响. 催化剂经还原后,在其表面生成了一种更低价态的Mo^δ+(1<δ<4)物种,被认为是合成醇的活性中心. 与非负载催化剂相比,粘土担载的K-Co-Mo具有更高的合成醇性能. 负载型催化剂具有较高的活性物种分散度,并且其介孔结构在一定程度上延长了合成醇反应中间体的滞留时间,从而促进了低碳醇的生成. 经773 K还原的催化剂具有较高的活性,其原因可为催化剂表面具有较高含量的Mo^δ+物种.}     

硫化态Co—Mo—K／AC合成醇催化剂的EXAES研究

采用XRD、EXAFS等手段考察了Co载量对催化剂结构的影响,并关联其合成醇活性。活性炭担载的硫化态Co-Mo-K样品中,Mo主要以MoS2物种形式存在于活性炭的表面上,而Co在低Co载量时主要形成“Co-Mo-S”相,在高Co负载量会有部分类CO9S8的物相出现。经Co助剂修饰后的催化剂显示出良好的合成醇催化性能,Co助剂有利于合成C2醇。Co/Mo原于比为0．5时．表面“Co-Mo-S”相可能达到饱和,合成醇的收率也最高。Co物种是和MoS2物相以协同的方式起作用的。     

An XPS Study of the Effect of La2O3 Dopant on the Dispersion and Thermal Stability of Pt/Al2O3 Catalysts

The Pt(4d)/Al(2s) XPS intensity ratio for Pt/Al₂O₃ catalysts increases with the addition of La₂O₃ as a dopant. The Pt(311) line in the X-ray diffraction pattern also broadens with the addition of La₂O₃. These data imply that doping the Pt/Al₂O₃ catalyst with La₂O₃ increases the dispersion of the platinum which in turn would be expected to increase the activity and thermal stability of the catalyst.     

表面活性剂修饰的CuCoMn催化剂催化合成低碳醇

分别采用阳离子(十六烷基三甲基溴化铵,CTAB)、阴离子(十二烷基硫酸钠,SDS)、非离子(三嵌段共聚物,P123)三种不同类型的表面活性剂对CuCoMn基催化剂进行改性,利用N₂吸脱附、XRD、XPS、IR手段表征了催化剂的微观结构．在生物质基合成气合成高醇中的应用研究结果表明,SDS修饰的CuCoMn催化剂表现出较高的CO转化率(29.7%),而CTAB修饰的CuCoMn催化剂具有优良的高醇选择性(41.2%)．同时,三种表面活性剂修饰的催化剂均不同程度地提高了高醇产率及其在醇产     

Au/Al2O3催化剂的UV-Vis谱研究

研究了十六烷基三甲基溴化铵 (CTAB) /正己醇 /水体系的W/O微乳体系中 ,几种主要实验参数对用NaBH4还原氯金酸溶液制得的金纳米粒子大小的影响。实验结果表明 :微乳体系中水与表面活性剂的摩尔比rw 在所研究的范围内对金粒子大小影响不大 ,而氯金酸溶液的浓度对金粒子大小影响较大。通过优化制备条件 ,用两种不同的方法制备了Au/Al2 O3 催化剂 ,并用紫外 可见光谱、透射电镜 (TEM)和X射线衍射(XRD)对其进行表征 ,初步考察了不同制备方法对催化剂中活性组分Au粒大小的影响     

CuO/Al2O3、CuO/CeO2-Al2O3和CuO/La2O3-Al2O3催化剂中CuO物种被CO氧化的比较

用浸渍法制备了CuO/Al2O3 (Cu/Al)、CuO/CeO2- Al2O3 (Cu/CeAl)和CuO/La2O3-Al2O3(Cu/LaAl)催化剂. 通过原位XRD、Raman和H2-TPR方法， 对催化剂中的CuO物种以及CuO-Al2O3的固-固相反应进行了表征. 结果表明，对于Cu/Al催化剂，CuAl2O4存在于CuO与Al2O3层之间，CuO以高分散和晶相两种相态存在于催化剂的表层；对于Cu/CeAl催化剂，除了少量高分散和晶相的CuO存在于表层外，大部分CuO迁移到了CeO2的内层，     

Pt/CeO2-ZrO2/Al2O3催化剂的光谱表征

利用拉曼光谱表征了不同方法添加ＣｅＯ２－ＺｒＯ２混合氧化物对Ｐｔ／Ａｌ２Ｏ３催化剂的影响,并采用了ＸＲＤ,Ｈ２化学吸附,ＢＥＴ表征了相应的分散度影响。结果表明：Ｃｅ、Ｚｒ、与金属Ｐｔ存在着强的相互作用,而ＣｅＯ２－ＺｒＯ２以盐的形式加入时,高度分散在Ａｌ２Ｏ３载体上,提高贵金属Ｐｔ的分散度,进而提高了反应的活性。     

Rapid,Microwave‐Assisted,and One‐Pot Synthesis of Magnetic Palladium–CoFe2O4–Graphene Composite Nanosheets and Their Applications as Recyclable Catalysts

Here, a microwave‐assisted approach has been demonstrated to rapidly prepare magnetic Pd–CoFe₂O₄–graphene (GE) composite nanosheets in ethylene glycol (EG) solvent. The generation of both Pd and CoFe₂O₄ nanoparticles is accompanied with the reduction process of graphene oxide (GO) by EG. The surface morphologies and chemical composition of the composite nanosheets are characterized by transmission electron microscopy (TEM), energy‐dispersive X‐ray spectrometer (EDS), powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR) measurements. The as‐prepared Pd–CoFe₂O₄–GE composite nanosheets exhibit a remarkable catalytic activity towards the reduction of 4‐nitrophenol by sodium borohydride (NaBH₄) at room temperature. The apparent kinetic rate constant (K _app) of this catalytic reaction could reach about 11.0 × 10^?3 s^?1. Moreover, the CoFe₂O₄ component exhibits a magnetic property, which could make the Pd–CoFe₂O₄–GE composite nanocatalysts separated from the suspension system. The catalytic conversion of the 4‐nitrophenol to 4‐aminophenol could reach 87.2% after four cycles. This work presents a simple, rapid, and versatile method to fabricate both metal and spinel‐type complex oxides on GE nanosheets, providing a new opportunity for their applications in the recyclable catalytic reaction.     

Structural and Magnetic Properties of the Al2O3/Ge-p/Al2O3/Co System

Technical Physics - The Al2O3/Ge-p/Al2O3/Co system with an Al2O3 buffer layer deposited by ion-plasma sputtering has been experimentally investigated. The dependences of the magnetic properties of...     

Co-Mo/Al2O3加氢脱硫催化剂的CO吸附原位红外光谱表征及应用研究

燃油的无硫化成为车用燃料发展的必然趋势.为开发高性能的柴油超深度加氢脱硫催化剂,文章采用CO吸附原位红外光谱法对系列还原态Co-Mo/Al2O3催化剂和高活性工业剂进行了表征,并将表征结果与微反加氢脱硫活性评价结果进行了关联分析.结果表明:随金属负载量的变化CO吸附的光谱特征发生变化,当MoO3负载量达20%、助剂CoO量为4.16%时,在2 179 cm-1出现一个新的CO特征吸收峰,该活性中心的出现明显有利于加氢脱硫(HYD)的反应.在相同金属负载量的情况下,与采用化学处理法制备的催化剂相比较,后者对应的2179 cm-1的特征吸收明显增强,微反评价显示该催化剂的催化活性特别是HYD反应活性明显提高.