对氯硝基苯在含镧的镍钼硼奈米触媒上的氢化反应

钼和镧是好的镍硼触媒的促进剂, 对于对氯硝基苯氢化反应有好的效果, 因此同时加入钼和镧在镍硼触媒上应该是有趣的研究题目. 本研究利用化学还原法制备了一系列含有不同量镧的镧钼镍触媒, 醋酸镍、钼酸胺及硝酸镧同时加入含有甲醇的水溶液中. 以X光绕射, 穿透式电子显微镜、高分辨率电子显微镜及X光光电能谱仪鉴定了这些触媒. 对氯硝基苯氢化反应是在批次反应器中于333 K、1.2 MPa氢气压力及500 r/min转速下操作. 即使在镍钼硼中加入很少量的镧, 对提高活性及对氯苯胺的选择性都有显著的效果, 加入适量的镧可以抑制镍钼硼的长范围的结晶排列, 并保持镍钼硼在非结晶状态. 镧以氧化态存在, 其功效为阻隔物, 避免镍钼硼聚集, 但是过量的镧会有相反的效果, 镧和镍的适当比例是0.2.     

负载型纳米Ni催化剂用于对氯硝基苯选择加氢

以TiO2为载体,N iB为诱导剂,粉末化学镀法制备了负载型纳米N i催化剂.通过TEM、HRTEM、XRD和ICP技术对催化剂物性进行了表征.结果表明,碱性镀液可使载体表面均匀负载微晶结构纳米N i团簇,尺度为35nm左右.该负载型纳米N i在对氯硝基苯选择加氢反应中表现出很高催化加氢活性,并能有效抑制脱氯,达到了工业骨架镍水平.由酸性镀液得到的负载型非晶态纳米N i-P合金具有较弱的催化对氯硝基苯加氢活性.反应温度对反应时间和脱氯率有明显影响.     

纳米二氧化锆催化剂上一氧化碳加氢合成异丁烯

 考察了纳米ZrO2的制备方法及Al2O3和KOH助剂的添加对ZrO2催化\r\nCO加氢合成异丁烯反应的影响．纳米ZrO2的制备方法对ZrO2的物理性质\r\n和催化性能有较大的影响．用超临界流体干燥法干燥并在流动N2气氛中\r\n焙烧制得的ZrO2催化剂对异丁烯具有较高的选择性．Al2O3和KOH助剂表\r\n现出非常优良的助剂效应，在大幅度提高催化剂对i－C4烃选择性的同\r\n时保持了和ZrO2同样高的催化活性．催化剂的酸碱性表征结果表明，酸\r\n碱性对催化剂的催化性能影响很大，催化剂上适宜的酸碱数量和酸碱比\r\n例是影响其催化CO加氢合成异丁烯性能的非常重要的因素．     

纳米贵金属插入的粘土用于催化选择性加氢反应

 The use of clay minerals in the synthesis of nanosized noble metal particles to give increased catalytic activity was investigated. Nanosized platinum and ruthenium catalysts intercalated in clay (montmorillonite/hectorite) were synthesised and their catalytic activity was evaluated for the selective hydrogenation of three different α,β-unsaturated aldehydes, namely, crotonaldehyde, cinnamaldehyde, and citral, in a gas phase microreactor. The metal nano-sol was prepared by the chemical reduction of its precursor by the micellar technique in the presence of cetyl trimethyl ammonium bromide (CTAB), and the micelle stabilized metal particles were intercalated in the clay mineral by ion exchange. TEM micrographs of the catalyst particles showed that the metal particles were in the nanometre range. The average diameters of the particles were 1–25 nm. The effects of temperature, metal loading, and hydrogen flow rate on the catalytic activity and selectivity for α,β- unsaturated alcohol were studied. The results were correlated with the structural properties of the catalysts. The products formed in each reaction over the different catalysts showed that the catalysts were very active for hydrogenation, and the selectivity for the desired product, namely, α,β-unsaturated alcohol, was good. The metal catalysts intercalated in montmorillonite showed better selectivity than that in hectorite because of its higher acidity. Increased selectivity for α,β-unsaturated alcohol was observed with increased flow rate of hydrogen.     

Straight and Modified Copper Catalysts for Stereoselective Hydrogenation of 5,17-Docosadiyne

Modified copper catalysts providing high rate of 5,17-docosadiyne hydrogenation with 100% yield of cis,cis-5,17-docosadiene (gypsy moth attractant) were developed.     

手性修饰的介孔树脂材料负载铂催化剂上丙酮酸乙酯的不对称氢化反应

采用氯铂酸和二氯四氨合铂为前体通过浸渍法分别制备了介孔树脂材料FDU-14负载的质量分数为5%的铂催化剂Pt/FDU-14, 并利用XRD, TEM, N₂气吸附和CO化学吸附等手段对催化剂进行了表征. 考察了经过手性分子辛可尼定修饰后的Pt/FDU-14催化剂在丙酮酸乙酯不对称氢化反应中的催化性能. 以氯铂酸为前体制备的Pt/FDU-14催化剂因其具有较小的铂粒子和较高的分散度而表现出较高的活性, 乙酸溶剂中的初始活性(TOF)可以达到21902 mol/(mol?h); 而以二氯四氨合铂为前体制备的Pt/FDU-14催化剂则具有较强的手性诱导能力, 乙酸溶剂中(R)-(+)-乳酸乙酯的光学选择性可以达到81.4% e.e.. 更重要的是, 由于FDU-14具有较强的疏水性, Pt/FDU-14催化剂在水溶剂中也表现出较高的催化性能, 并且还可以重复使用10次以上.     

活性炭负载Pt-Fe双金属催化剂催化对氯硝基苯选择性加氢

采用浸渍还原法制备了活性炭负载Pt-Fe双金属催化剂(Pt-Fe/AC),考察了其催化对氯硝基苯加氢性能。 与Pt/AC催化剂比较,该催化剂对催化对氯硝基苯加氢表现出高活性和优异的抑制脱氯性能,在乙醇为溶剂、催化剂Pt_0.003-Fe_0.04/AC(下标为元素在催化剂中的质量分数)用量为0.02 g/g对氯硝基苯、1 MPa H₂和30 ℃条件下反应150 min,对氯硝基苯完全转化为对氯苯胺,而且即使在较高的反应温度和H₂压力下,脱氯反应也得到了完全抑制。 采用X射线衍射(XRD)、透射电子显微镜(TEM)及X射线光电子能谱(XPS)等技术手段对Pt-Fe/AC催化剂进行了表征。 结果表明,Pt、Fe高度分散在活性炭上,Pt与Fe之间的相互作用对纳米Pt粒子的电子结构有一定的调变作用,使纳米Pt处于缺电子态,减弱了Pt与对氯苯胺苯环之间的电子反馈,这可能是Pt-Fe/AC对催化对氯硝基苯加氢表现出高活性和优异的抑制脱氯性能的主要因素。     

杂多酸盐修饰骨架镍催化剂上肉桂醛的选择加氢

研究了杂多酸盐改性：Raney Ni催化剂上肉桂醛选择加氢制备肉桂醇的反应，考察了杂多酸盐负载量、反荷阳离子、杂多阴离子对RaneyNi催化剂上肉桂醛加氢活性和选择性的影响，结果表明：随着Cu1.5PMo12O40负载量增加，肉桂醛加氢沽性降低而生成肉桂醇的选择性增加，当Cu1.5PMo12O40负载量达到6．3％时，肉桂醇的选择性达到了26．4％，而没有改性的RaneyNi催化剂上肉桂醛加氢生成肉桂醇的选择性为零；在各种不同反荷阳离子的PM012盐中，只有反荷阳离子为Cu2 的Cu1.5PMo12O40改性Raney Ni催化剂具有最高的选择性，在选定的四种杂多阴离子的铜盐中，Cu2SiMo12O40和Cu2SiW12O40改性Raney Ni催化剂的选择性为零，Cul．5PW12O40改性Raney Ni催化剂上肉桂醛加氢生成肉桂醇的选择性也比Cu1.5PMo12O40改性Raney Ni的低的多．     

Adsorption and Hydrogenation Process of p-Chloronitrobenzene on Au_(20) Cluster:a DFT Study

We have systematically investigated the adsorption and hydrogenation process of p-chloronitrobenzene on Au20 cluster using density functional theory-DFT) calculations.The adsorption of two types of all species,vertical adsorption and parallel adsorption,is compared,revealing that former model is more stable than the latter,and all of the species prefer to adsorb at the vertex site.After adsorption,electrons transferred from Au20 cluster to the p-chloronitrobenzene molecule.Almost all hydrogenation processes are exothermic,and the C–Cl bond scissions are considered as the rate-limiting step for both Paths A-p-CNB→p-CAN→AN) and B-p-CNB→NB→AN) with the energy barriers of 2.62 and 2.95 e V,respectively.These suggest that the C–Cl bond scission is not easy to occur on Au20 cluster due to the high energy barrier,especially the path B.The p-chloroaniline is the main hydrogenation product catalyzed by Au20.     

多相不对称催化氢化研究进展*

本文综述了多相不对称催化氢化反应的最新研究进展.特别是对最近几年来两个典型的多相不对称催化氢化体系即酒石酸盐修饰镍催化剂催化β-酮酸酯的不对称氢化反应体系和金鸡纳生物碱修饰铂催化剂催化α-酮酸酯的不对称氢化反应体系进行了详细的介绍和讨论,同时展望了多相不对称催化氢化反应研究的前景.     

Hydrogenation on Granular Palladium-containing Catalysts: II. Hydrogenation of Nitroheterocyclic Compounds

Nitroheterocyclic compounds were reduced in a classical reactor with an agitator equipped with a cell for fixed bed of catalyst. As catalysts were applied granular palladium catalysts (0.5% of Pd on -Al₂O₃ and 2% of Pd on granulated carbon). Anilines and 3-amino-2(1H)-pyridones were obtained in high yield at reduction of the appropriate nitro compounds, and the activity of the catalyst samples only slightly decreased. Yet aminopyrazoles and aminoimidazoles obtained by hydrogenation on palladium were very sensitive to the presence of air even as hydrochlorides. In the course of hydrogenation of nitropyrazoles and nitroimidazoles the activity of the catalyst markedly decreased.     

Hydrogenation of Carbon Dioxide on Iron Manganese Catalysts

The synthesis of hydrocarbons from hydrogenation of carbon dioxide has been studied on a series of coprecipitated iron-manganese catalysts. Kinetic measurements, X-ray diffraction, Mössbauer spectroscopy, and temperature-programmed reaction of adsorbed species were used for activity tests and catalyst characterizations. The results showed that the yields of low-carbon olefins decrease, whereas the amount of methane increases with increasing manganese content in catalysts. The conversion to hydrocarbons is suppressed by the reverse water-gas shift (RWGS) reaction equilibrium. Mössbauer spectra and XRD patterns of catalysts after reaction indicate that catalysts are severely oxidized; it is speculated that the olefin producing surface structure in CO hydrogenation may be destroyed by this oxidation. A pulse-reactor study of the Boudouard reaction showed that manganese has the effect of suppressing CO dissociation and thus decreasing carbon content on catalysts. For CO₂ hydrogenation, the affinity to carbon on catalysts is important; therefore manganese is not a good promoter. Among all catalysts tested, pure iron has the best selectivity to olefinic and long-chain hydrocarbons.     

Colloidal and Nanosized Catalysts in Organic Synthesis: XX. Continuous Hydrogenation of Imines and Enamines Catalyzed by Nickel Nanoparticles

Nickel nanoparticles on the BAU-A active carbon or NaX zeolite catalyze hydrogenation of imines and enamines in a flow reactor in a gas phase or in a gas–liquid–solid catalyst system. The process occurs at atmospheric pressure of hydrogen and gives secondary or tertiary amines in a high yield.     

Hydrogenation on Granular Palladium-containing Catalysts: I. Hydrogenation of Tertiary Acetylene Alcohols

Commercial granular palladium catalyst (0.5% of Pd on -Al₂O₃) was modified by treating with zinc acetate (type 1) or successively with zinc acetate and ammonia (type 2). The treatment significantly increased the hydrogenation selectivity for a triple bond into a double bond: to 85.3-93.1% with the type 1 catalyst and to 96.3-97.8% with the type 2 catalyst. A construction of an autoclave with a fixed bed of the granular catalyst is described.     

助剂改性活性炭担载Pt催化剂催化硝基苯加氢制对氨基苯酚

以改性活性炭担载的Pt为催化剂催化硝基苯经加氢重排一步合成对氨基苯酚，收率54．70％，选择性可达91.40%。     

Conception of Nanosized Membrane Reactors for Hydrogenation with Accumulated Hydrogen

Russian Journal of Physical Chemistry A - Results are summarized from studies to develop the concept of next-generation nanosized membrane reactors (NMRs) in which hydrogenation reactions are run...     

介孔氧化铝复合材料负载铂催化剂上丙酮酸乙酯的不对称氢化反应

采用固相研磨法制备了有序介孔树脂FDU-14孔道限阈分散的Al2O3复合材料Al2O3@FDU-14.以其为载体,采用浸渍法制备了4.0％ Pt/Al2O3@FDU- 14催化剂,并利用X射线衍射、透射电子显微镜和N2吸附等手段对催化剂进行了表征.结果表明,Pt/Al2O3@FDU- 14催化剂保持了FDU-14的介孔...