本发明涉及一种微孔材料装载金属络合物-离子液体催化剂。该催化剂通过钛酸酯和硅酸酯的溶胶凝胶过程将1，3-二烷基咪唑和烷基吡啶类离子液体及钯络合物 装载于微孔的钛硅复合氧化物中。该催化剂能够在80℃至200℃，氧气与一氧化碳压力比为0∶1至1∶2，总压力比在1.0至7.0MPa的条件下催化含 氮化合物羰化反应制备氨基甲酸酯和二取代脲。该催化剂的特点是催化活性高，离子液体和钯络合物装载或键合于载体之中，活性组分不易流失，可以重复使用，同 时降低了离子液体和钯络合物的用量，有效降低了催化剂的成本，具有良好的工业应用前景。

邓友全,石峰,彭家建,等. 微孔材料装载金属络合物-离子液体催化剂. Cn1389298. 2004.

本发明涉及一种高效清洁的有机胺类化合物催化氧化羰化制二取代脲的方法。本发明中使用树脂类高聚物担载的金催化剂。在初始反应压力为 4.0-6.0MPa，反应温度为100-200℃。反应时间为1-10小时，使用一氧化碳和氧气混合气为氧化羰化剂，高效地催化氧化羰化有机胺制相应二 取代的脲。该催化剂的主要特点是具有高效、组成相对简单和金含量相对较低的同时，容易与反应体系分离、回收及重复使用。并且反应过程中不需要加入任何其它 溶剂。其中，二取代脲的的单程收率可达到48-85%，产品纯度≥99%。属清洁催化反应工艺，具有良好的工业应用前景。

邓友全,石峰. 催化氧化羰化胺制脲衍生物的方法. Cn1327977. 2003.

CO₂/H₂ was successfully employed in alkylation reactions by performing CO₂ reduction and amine N-methylation in one-pot. In the presence of a simple CuAlO_x catalyst, N-methyl or N,N-dimethyl amines with different structures can be selectively synthesized with up to 96% yields by applying amine, nitrobenzene and nitrile as starting materials.

★★★☆☆ Cui XJ,Dai XC,Zhang Y,et al. Methylation Of Amines, Nitrobenzenes And Aromatic Nitriles With Carbon Dioxide And Molecular Hydrogen[J]. Chemical Science,2014,5:649-655.

By applying a simple TiO₂–(NH₄)₂S₂O₈ system and promoted by UV light, the three-component reactions of cyclic ether, aniline and aldehyde can be progressed efficiently. 29 substituted amines with different structures were synthesized with up to 97% isolated yields. Isotope effect study revealed that the ratedetermining step might be the nucleophilic addition step but not radical generation.

Keywords: Amine; Imine; Heterogeneous catalysis; Light

★★★★☆ Lina Zhang,Deng YQ,Shi F. Light Promoted Aqueous Phase Amine Synthesis Via Three-component Coupling Reactions[J]. Tetrahedron Letters,2013,54:5217-5219.

A simple and efficient Pd/Al₂O₃-NR-RD catalyst was prepared by depositing palladium on a shape controllable Al₂O₃-NR support through a two-step process that involves hydrothermal synthesis of Al₂O₃-NR_s followed by reductive-deposition of palladium. This catalyst showed high activity in the catalytic formylation of amines by CO₂–H₂ under mild conditions with up to 96% yield.

★★★★☆ Cui XJ,Zhang Y,Deng YQ,et al. Amine Formylation Via Carbon Dioxide Recycling Catalyzed By A Simple And Efficient Heterogeneous Palladium Catalyst[J]. Chemical Communications,2013,50:189-191.

As the sustainable and promising hydrogen source, here, glycerol was directly used as the hydrogen source for the reductive amination of alcohol using nitrobenzene as the starting material. The amination of alcohols, especially aliphatic alcohols with different structures, was realized, and mono- or disubstituted amines were synthesized with excellent yields. The reaction mechanism was also explored.

KEYWORDS: amines, alcohols, N-alkylation, glycerol, renewable, catalysis

★★★☆☆ xinjiang Cui,Youquan Deng,Feng Shi. Reductive N‑alkylation Of Nitro Compounds To N‑alkyl And N,n‑dialkyl Amines With Glycerol As The Hydrogen Source[J]. Acs Catalysis,2013,3:808-811.

The N-alkylation of amines or ammonia with alcohols is a valuable route for the synthesis of N-alkyl amines. However, as a potentially clean and economic choice for N-alkyl amine synthesis, non-noble metal catalysts with high activity and good selectivity are rarely reported. Normally, they are severely limited due to low activity and poor generality. Herein, a simple NiCu-FeO_x catalyst was designed and prepared for the N-alkylation of ammonia or amines with alcohol or primary amines. N-alkyl amines with various structures were successfully synthesized in moderate to excellent yields in the absence of organic ligands and bases. Typically, primary amines could be efficiently transformed into secondary amines and N-heterocyclic compounds, and secondary amines could be N-alkylated to synthesize tertiary amines. Note that primary and secondary amines could be produced through a one-pot reaction of ammonia and alcohols. In addition to excellent catalytic performance, the catalyst itself possesses outstanding superiority, that is, it is air and moisture stable. Moreover, the magnetic property of this catalyst makes it easily separable from the reaction mixture and it could be recovered and reused for several runs without obvious deactivation.

Keywords: alcohols · amination ·ammonia · heterogeneous catalysis ·non-noble metals

★★★☆☆ Cui XJ,Dai XC,Deng YQ,et al. Development Of A General Non-noble Metal Catalyst For The Benign Amination Of Alcohols With Amines And Ammonia[J]. Chemistry A-europeann Journal,2013,19(11):3665-3675.

★★★☆☆ Yang HM,Cui XJ,Deng YQ,et al. Selective Hydrogenation Of Nitroaromatic Compounds With A Nickel-oxide-supported Nano-palladium Catalyst Under Ambient Reaction Conditions[J]. Chemcatchem,2013,5:1739-1743.

The controllable preparation of nano-gold catalyst maintains a challenge. Except the parameters have been revealed before, here we’d like to show that controllable preparation of active nano-gold catalyst can be achieved using chlorine as an indicator. By tracing the chlorine concentration in the washing step, a series of Au/Fe₂O₃ catalysts were prepared with co-precipitation method. The applying of these catalysts in CO oxidation and reductive nitrobenzene N-alkylation suggested the active catalysts were prepared from solutions containing ～2 ppm chlorine. The catalytic activity dropped dramatically if the chlorine concentration is >4–6 or <<1 ppm. Extensive characterizations revealed that the active catalyst was composed by nano-gold on the edge of Fe₂O₃ particle with 8.92 Au-Au coordination numbers. Although the real role of chlorine in the variation of catalyst structure and activity was still ambiguous, the current results should promote the controllable preparation of active nano-Au catalyst.

★★☆☆☆ Zhang CM,Liu LQ,Cui XJ,et al. Chlorine As An Indicator In The Controllable Preparation Of Active Nano-gold Catalyst[J]. Scientific Reports,2013,3:1503(1-7).

A series of carbon aerogels were prepared with or without using ionic liquids as templates. By varying the structures and contents of ionic liquids, carbon aerogels with different pore size distributions could be obtained. The effect of the ionic liquids on the properties of the final carbon aerogels was explored and the catalytic performance of the carbon aerogels in the selective oxidation of tetralin was studied.

★★★☆☆ Yang HM,Cui XJ,Deng YQ,et al. Ionic Liquid Templated Preparation Of Carbon Aerogels Based On Resorcinol–formaldehyde: Properties And Catalytic Performance[J]. J. Mater. Chem.,2012,22:21852-21856.