Head of department – Sergey V. Kolotilov

Doctor of chemical sciences
31 pr. Nauky, Kyiv, 03039, Ukraine

L.V. Pisarzhevskii Institute of physical chemistry

NAS of Ukraine

tel.: +38 (044) 525 66 61 fax: +38 (044) 525 62 16

e-mail: s.v.kolotilov@gmail.com; svk001@mail.ru

General description of the Department

The Department of porous substances and materials was created in November 1957 on the base of adsorption group and laboratory of catalysis department (initial name – department of synthesis and investigation of sorbents, later – department of inorganic sorbents), it was headed by famous scientist, PhD, professor, laureate of state prize of USSR І.О.Neymark. From the beginning of existence main works of department were dedicated to investigations of synthesis of mineral adsorbents, adjustment of their porous structure and chemical nature of surface, determination of particularities and conformities of adsorption and ion exchange on real sorbents, in particular on silicagel, silicon-element-organic sorbents, aerosol, some oxides, zeolites. General results of investigations are extended in monographs: I.O.Neymark, R.Yu.Sheynfayn “Silicagel, its receiving, properties and application” (Kyiv, Naukova dumka, 1973), M.А.Piontkovskaya “Physical-chemical, adsorption and catalytic properties of modified faujasite” (Kyiv, Naukova dumka, 1978), I.O.Neymark “Synthetic mineral adsorbents and catalysts supports” (Kyiv, Naukova dumka, 1982), I.B.Slinyakova, T.I.Denisova “Silicon-organic adsorbents: receiving, properties, application” (Kyiv, Naukova dumka, 1988). Among the next directions of investigations are hydrothermal modification of inorganic sorbents, chemical and structural modification of synthetic and natural zeolites. From the early 90-th, investigations in the department were focused in the field of template synthesis of zeolites, zeolite-like silicates and phosphates of new generation, later – mesoporous molecular sieves etc.

Photo of the Department, July 2015

 Main directions of study:

• physico-chemical principles of molecular and supramolecular template synthesis, as well as chemical and structural modification and functionalization of zeolites and mesoporous molecular sieves (MMS) with different composition and structure, in particular, extrawide-porous element-germanium-silica zeolites (ESiGe-UTL) and MMS based on different oxides, carbon and polymers, etc.;
•  sorption, catalytic, electrocatalytic properties of porous coordination polymers (PCP) of 3d metals with organic bridging ligands; separation of mixtures (in particular, racemates of optical isomers of organic compounds) using coordination polymers;
•  creation of efficient adsorbents, ion-exchangers, catalysts and photocatalysts, elements of sensors,  etc. on the basis of zeolites, MMS and PCPs;
•  sorption, catalytic and electrocatalytic properties of nanosized metals and metal oxides (nanoparticles, nanofoams) and their composites with porous compounds 

The most important results for the recent years

• For the first time zeolites of new generation, in particular zeolite structures with the large elemental cell parameter – up to 2 nm, great adsorption capacity, availability of strong acidic sites.
• New approaches to creation of extra-large porous zeolites – microporous materials with pore diameter 8-12 Å were developed.
• The synthesis pathways were developed and phosphate zeolites (microporous Al- and Si,Al-phosphates with cycles from 12-20 tetrahedrons (SAPO-37, VPI-5, JDF-20, cloverite), element-derivatives VPI-5 with acidic centers of different strong, as well as Mg-, Co-, Mn- Fe-, Ti-, Zn-containing Al- and Si, Al-phosphates MAPO-36, -39, 46, 50, MAPSO-36,  MeAPO-36 types etc.) were obtained.
• New ideas and approaches to structure formation and functionalization of moleular sieves connected with chemistry of templating action, features of nonsilicate isomorphism in phosphate and germanate Zt-formative systems (specifically – group and determinate isomorphism), as well as in ММS (structural isomorphism), with effect of solubilization, etc., were proposed and developed.
• Germanosilicate zeolite IPC-3 with channels formed by 24- membered ring of tetrahedral and also their Si-, Al- and Ti-containing analogs were obtained. The possibility of selective inclusion of elements in the frame, depending on their coordination number defined by oxygen and determined as the structural features of the secondary structural units (SSU) of zeolite was established. A method of obtaining Ge, Si-zeolite IPC-4 (D_pores ~ 11 Å) using spiroazocomounds with different type and position of substituents as templates was developed. The relationship between the nature of the template and the phase composition, morphology, and adsorption characteristics of zeolites was established. It was found that the factor determining formation of Ge, Si-zeolites (unlike Al, Si-zeolites) is not only templating, but a cumulative effect of template and frame-formation elements, wherein precisely Ge promotes the formation of key SSU – dual four-membered rings.

Influence of the SDA cation structure on the selectivity of zeolite-formation in boron- and aluminum-containing germanosilicate reaction medium

• The possibility of 100% selectivity in the reaction of ЕТВЕ synthesis using catalysis based on the B-containing Ge, Si-zeolites and high performance the reaction – near 13,3·10^-6 mol ETBE/(g_cat ∙ s) was shown. These data exceeds the indexes for industrial catalyst Amberlyst-15.

Combination of the two-dimensional system of the channels with extra-large porous channels with Dpor ~1 nm  of the UTL structure is unique for n-decane hydroconversion process, since owing to increase of channels diameter allows obtain bulk products in large quantities, compared to large porous zeolites

• Conditions and features were determinated, optimized and original pathways of template and matrix synthesis of mesoporous materials on base of silica (МСМ-41, -48, SBA-15, -16, KIT-6; in form of spheres, fibers, gyroids, toroids etc.), Al, Ge, Ti, Zr, Sn, W, Mo, etc., as well as carbon and organic polymers (matrix synthesis), titaniumsilicates and silica-organic compounds, some phosphates, nanotubular titanates and vanadium oxide with controlled structural-sorption characteristics, condensation degree, electroconductivity and photocatalytic activity were developed. Bitemplate synthesis method with using of solubilization’s effect were worked and homologous row of MMS with period of change of hexagonal US’ parameter and pore diameter 2-3 Å were obtained.

Phase diagram of the products of structure formation of silicon MMC in system СТАВ – TEOS – NaOH – H₂O

Matrix synthesis of mesoporous carbon molecular sieves CMK-3

• New approach to the synthesis of nanoscale oxide clusters Ni, Cr and Fe in the mesopores of SBA-15 by pre-solubilization of polynuclear complexes corresponding micelles polyalkylene oxide triblock Pluronic-123 was proposed and implemented.
• Novel nanocomposites which combine adsorptive properties of the molecular sieves and magnetic characteristics of the iron oxide nanoparticles were developed.

Scientific collaboration

• Heyrovský Institute of Physical Chemistry, АS of Czech Republic, department of catalysis II, prof. Jiří Čejka, joint research;
• Abo Akademi, Finland, Prof. D.Yu. Murzin, joint research
• N.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, Dr. M. Kiskin
• Equipe Organométalliques Matériaux et Catalyse, Institut des Sciences Chimiques de Rennes, Prof. L. Ouahab, Dr. O. Cador, Dr. S. Golhen
• Standad Bio, Telemark, Norway, Dr. N. Kasyan

Scientific staff of the department

Oleksiy V. Shvets, candidate of chemical sciences; senior research scientist;  Tel.:+38(044)5254196; e-mail: alexshvets@ukr.net

Natalia D. Shcerban (Lysenko), candidate of chemical sciences; senior research scientist; Tel.:+38(044)5256771; e-mail: nataliyalisenko@ukr.net 

Anton S. Lytvynenko, candidate of chemical sciences; research scientist; Tel.:+38(044)5256771; e-mail: anton.s.lytvynenko@gmail.com

Roman Yu. Barakov, candidate of chemical sciences; junior research scientist; Tel.:+38(044)5256771; e-mail: barakov.r.yu@gmail.com

Pavlo S. Yaremov, junior research scientist; tel.: +38 (044) 5256771; e-mail: yaremovp@ukr.net

Tetiana M. Boichuk, PhD (Chemical Kinetics and Catalysis); tel.: +38(044)525-62-22; e-mail: boichuk_tm@ukr.net

Kurmach Mykhailo, Candidate of chemicals science, researcher; tel.: +38 (044) 525-41-96; e-mail: mazinator3710@ukr.net

Some recent papers

• O.V. Shvets, N.V. Kasian, V.G. Ilyin. Selective isomorphism of silicon, aluminum and titanium in extra-large-pore zeolite-like germanate IPC-3.// Adsorption Science and Technology – 2008. – Vol. 26, N1-2 – P. 29-35.
• O. Shvets, A. Zukal, N. Kasian, N. Žilková, J. Čejka The Role of Crystallization Parameters for the Synthesis of Germanosilicate with UTL Topology. // Chemistry – A European Journal – 2008. – Vol. 14, N 32 – P. 10134-10140.
• O.V.Shvets, A. Zukal, N. Kasian, J. Pinkas, J. Čejka. The Role of Template Structure and  Synergism between Inorganic and Organic Structure Directing Agents in the Synthesis of UTL Zeolite. // Chem. Mater. – 2010 – V. 22, N11, p. 3482-3495.
• N. Kasian, T. I. Koranyi, G. Vanbutsele, K. Houthoofd, J. A. Martens, C. E. A. Kirschhock. Decane hydroisomerization test probing catalytic activity and selectivity of aluminum and boron substituted extra-large pore UTL zeolite. // Topics in Catalysis – 2010. – V. 53, N. 19-20, P. 1374 – 1380.
• М. R. Кullіsh, V. L. Struzhko, V. P. Bryksa, А.V. Мurаshkо, V. G.Іlyin. Hydrotermal synthesis and properties of titania nanotubes doped with Fe, Ni, Zn, Cd, Mn. // Semicond. Phys. Quant. Electron. Optoelectron. – 2011. – V.14, N 1. – P.21-30.
• O.V. Shvets, M.V. Shamzhy, P.S. Yaremov, Z. Musilová, D. Procházková, J. Čejka. Isomorphous Introduction of Boron in Germanosilicate Zeolites with UTL Topology. // Chem. Mater. – 2011– V. 23, N10 – p. 2573-2585.
• N. D. Lysenko, P. S. Yaremov, M. V. Ovcharova, V. G. Ilyin. Conditions and features of matrix and bulk carbonization of the organic precursors // J. Mater. Sci. – 2012. – V. 46, N13. –  P. 4465-4470.
• N. Kasian, G. Vanbutsele, K. Houthoofd, T. I. Koranyi, J. A. Martens, C. E. A. Kirschhock. Catalytic Activity and Extra-Large Pores of Germanosilicate UTL Zeolite Demonstrated with Decane Test Reaction // Catalysis Sci. Techn. – 2011. – V. 1, N2 – P. 246 – 254.
• W.J. Roth, O.V. Shvets, M.V. Shamzhy, P. Chlubná, M. Kubů, P. Nachtigall, J.Čejka. The first post-synthesis transformation of 3-dimensional framework into a lamellar zeolite with modifiable architecture // J. Amer. Chem. Soc. – 2011 – V. 133, N16 – p. 6130 – 6133.
• N.D. Lysenko, P..S. Yaremov, M.V. Ovcharova, V.G. Ilyin. Highly acidic phosphorus-containing porous carbons: synthesis and physicochemical properties. // J. Mater. Sci. – 2012. – V. 47, N7. –  P. 3089-3095.

The list of developments that may present potential interest

• methods of preparation, modification and functionalization of different by the composition, spatial organization, structure and properties micro- and mesoporous molecular sieves, adsorbents, ion exchangers, storage media, catalysts and photocatalysts for practically important processes and also compounds of inclusion for different functional purposes and nanocomposites based on them, including:
• zeolites, zeolite-like silica, phosphate and germanate
• silica and titanium-silica mesoporous molecular sieves (MMS), MMS based on the oxides of Al, Sn, oxides and phosphates of some transition metals (Ti, V, Zr, Mo, W, etc.);
• methods of preparation of functionalized organic silica MMS;
• methods of obtaining different morphology mezostructured and mesoporous types of silica (fiber, hydroids, toroid, sphere);
• methods of preparation and modification of nanotubes based on vanadium oxide with high and stable charger capacity, and also titanates;
• matrix methods of production and modification of carbon and polymer molecular sieves;
• flow sheet of complex processing, enrichment and modification of natural zeolite of Transcarpathian;
• methods of enrichment and modification of the natural zeolites of clinoptilolite and mordenite type, obtained on the basis of effective eko-sorbents and catalysts, including process of hydroizomerization of n-hexane;
• methods of separation of gas mixtures consisting of hydrogen and methane.