Laboratory of Kinetics and Catalysis

Background

The Laboratory of Kinetics and Catalysis at the Chemistry Department of Moscow State University was founded in 1929 to expand education at undergraduate and graduate levels in the general areas of physical chemistry and specifically of catalysis as well as to develop research in surface science and kinetics of heterogeneous catalytic reactions.

Now, its activity lies mainly in the field of zeolites, oxides, metallocomplex and enzymatic catalysis. It aims at performing high-level fundamental research capable of industrial integration and development.

Staff

• Boris V. Romanovsky, Professor, Head of the Laboratory
  
• Oles M. Poltorak, Professor
  
• Alexei A. Kubasov, Associate Professor
  
• Leonid E. Kitaev, Associate Professor
  
• Elena S. Chukhrai, Principal Research Associate
  
• Irina F. Moskovskaya, Senior Research Associate
  
• Irina I. Ivanova, Senior Research Associate
  
• Valentina V. Yushchenko, Senior Research Associate
  
• Liudmila N. Burenkova, Senior Research Associate
  
• Alexander Yu. Loginov, Senior Research Associate
  
• Larisa F. Atiaksheva, Senior Research Associate
  
• Galina N. Takhtarova, Senior Research Associate
  et al., total 18 persons of permanent staff, graduate and post-graduate students.

General Research Objectives

• Preparation of new catalysts and other materials (mainly molecular sieves and oxides, zeolite-included metallo-complexes and oxide clusters, immobilized enzymes)
• Characterization of the physico-chemical and catalytic properties of new materials
• Kinetic description of catalytic processes

General Approach

The objective of catalyst research at the Laboratory of Kinetics and Catalysis are to characterize catalyst types by chemical and physical techniques and to clarify the mechanism of catalytic processes at a molecular level, in order to understand and design or tailor the action of catalytic materials.

On the basis of such fundamental insight, it is possible to develop a set of rules applicable to the discovery of new catalysts or to the modification of existing ones so that to achieve special and desired activity and selectivity patterns.

The Laboratory of Kinetics and Catalysis has long-term experience in the synthesis and characterization of oxide- and zeolite-based catalysts. A wide range of physico-chemical characterization tools is used for these purposes and applied to both finished catalysts and intermediate forms involved in their preparation.

A thorough understanding of the chemistry and reactivity of solids and the ability to identify molecule-catalyst relationship at a molecular level form the basis for the competitive edge of the laboratory in the design of new catalytic materials and the evaluation and improvement of existing catalysts and catalytic processes.

Current Research Topics

1. Synthesis, characterization and evaluation of the catalytic potential of zeolite-included transition metal complexes and oxide clusters.

   A variety of techniques for the preparation of metal complexes as well as oxide clusters topologically included into the host Y zeolite lattice were developed. These materials constitute a new family of catalysts which combines advantages of both homogeneous and heterogeneous catalytic systems. Also, they can be interesting from the standpoint of nanoscale chemistry since spatially separated metallocomplex species immobilized within zeolite cavities represent a sort of quantum dots.

   Zeolite-included phthalocyanines were tested in more than two tens of reactions, namely, oxidation of alkanes, alkenes, aromatics, mercaptanes, carbon monoxide etc., reduction of NO with carbon monoxide and hydrogen that is the key reaction for emission control.

   These systems exhibit regio and shape selectivity due to specific effects of zeolite matrix on metallocomplex or oxide cluster active sites situated inside the large cages of the matrix.

2. Alkylation of benzene with propylene.

   Kinetics and mechanism of gas phase alkylation of benzene with propylene was studied using pentasil type and zeolite-like molecular sieves with isomorphous substitutions of Al by B and Ga as catalysts. At 573 K and atmospheric pressure, molar ratio benzene:olefin of 9:1 and LHSV of c.a. 10, Ga pentasil catalyst produces 8 wt.% of cumene (c.a. 70% of theory) and less than 0.01 wt.% of n.-propylbenzene in liquid products. About 10% of these latter was found to form by direct alkylation of benzene with propylene.

3. Alkylation of phenol with methanol.

   A number of molecular sieves ranging from amorphous silica-aluminas to aluminophosphates were tested as catalysts for phenol alkylation with methanol. Requirements for the acidity of a catalyst surface as well as the reaction conditions in order to obtain maximum yield of desired product, i.e., anysole or methylphenols were established.

4. Alkylation of styrene with methanol.

   A technique for modification of high-silica zeolites by different agents including phosphorous acid, metal chlorides and tetraethoxysilane aimed to improve the paraselectivity was developed. Steamed zeolite modified with La and tetraethoxysilane exhibits the paraselectivity to methylstyrene of 88% at 783 K, LHWV of 6 and methanol:styrene:nitrogen=1:2:2, conversions of styrene and methanol being of 10% and 62% correspondingly. Paraselectivity to methylstyrene was of 87.3% at 873 K, LHWV of 1 and methanol:styrene:nitrogen=1:2:12 using phosphorus and magnesium containing zeolite catalyst, conversions of styrene and methanol being of 22% and 92%.

5. Alkylation of toluene with bioethanol.

   One-step process for producing ethyltoluenes with 100% selectivity (97% of para-isomer) was proposed. A method of attaining this selectivity is based on the use of bioethanol with 10 wt.% of alcohol as an alkylating agent and high-silica zeolites as catalysts. At 623 K and LHWV of 4 for toluene, the catalyst gave 1.4 g of ethyltoluenes/ g.hr.

6. Environmentally-related reactions.

   The effects of strong metal-support (Pd and Ni upon oxides of Y, La and Zr) and oxide-support (Mn and Cr oxides upon yttrium oxide) as catalysts for hydrocarbon oxidation and denoxification were studied using XPS, ESR and temperature-programmed reaction techniques. Ionic forms of transition metals were found to effect on the formation of reactive oxygen species on the catalyst surface. For high-temperature methane conversion, carbonaceous deposits may strongly modify not only the composition of the catalyst surface but also its morphology.

Equipment

Extensive equipment facilities for the characterization of catalysts include:

• IR, ESR, unique ammonia and hydrocarbon TPD technique and adsorption measurements;
• fixed-bed integral and gradientless systems, pulse and micro-flow reactors, batch systems.

• SEM, STEM, AFM, XPS and NMR techniques.

References

More than 200 publications for the last decade including some important reviews were appeared.

Participation in five national research programs. The Laboratory of Kinetics and Catalysis also participates in three bi- and multilateral international programs. The current joint research projects are as follows:

• two INTAS (EC) projects on selective preparation of cumene and on zeolite-catalyzed alkylation of aromatics.
• one NATO project on synthesis and characterization of new types of micro-porous solids.

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