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(i) main field: Pyrolysis; Catalysis; Physical Chemistry: Kinetics, Reactions/Mechanisms, Surface chemistry.
(ii) other fields: Investigating processes of heterogeneous catalytic pyrolysis of renewable biomass components for a development of green technologies for production of bio-oils, bio-based chemicals and biofuel.
(iii) current research interest: use of TPD-MS and Linear Free Energy Relationships for assessing the reactivity of organic molecules, biomolecules (fatty and cinnamic acids, coumarins) and biopolymers (Lignin, Cellulose, Chitin/Chitosan, Dextran, Hemicellulose, etc.) on surfaces of nanoscale catalysts.
• Project Manager of the Project “Nanocatalyst-assisted pyrolysis for conversion of lignocellulose waste residues into sustainable biofuels using microwave treatment” FSA3-20-66700-0 from the U.S. Civilian Research & Development Foundation (CRDF Global) with funding from the United States Department of State, 2020-2021.
• Project Manager of the Project “Next generation solid acid fuel cells and electrolyzers for a sustainable energy future” (Science and Technology Center in Ukraine (P 707, STCU)), 2018.
• Team Leader of the Project between Stockholm University and Chuiko Institute of Surface Chemistry “Development of green nanotechnologies for catalytic pyrolysis of biomass” (Swedish Research Council under contract 348-2014-4250), 2016-2018.
• Project Manager of the Project “Pyrolysis with the use of nanocatalysts MexOy/SiO2 the way to get second-generation biofuels via processing of fatty acids, triglycerides and renewable plant biomass” UKC2-7072-KV-12 from the U.S. Civilian Research & Development Foundation (CRDF Global) with funding from the United States Department of State, 2013-2015.
• 2008-12 Hybrid Nanocomposites and their Biomedical Applications, FP7-PEOPLE-IRSES-2008 (UK, Poland, Greece, Hungary, Ukraine).
• 2008-11 STCU (Science and Technology Center in Ukraine) Grant 3832 “Modernization of processing technology for pharmaceutical preparation Silics.”
• Innocentive 4039381, “Pyrolysis of Cellulose”, March 28, 2007.
• 2004-06 STCU (Science and Technology Center in Ukraine).Grant 3103 “High-dispersed compositions: the way to optimization of reproductive cell media”.
Honours, Awards, Fellowships:
• the Swedish Institute for research scholarship for Professor within Visby Programme [03804/2016], the Project “Testing of the important catalytic reactions for green pyrolytic conversion of algae biomass to biofuels and chemicals”, 2016.
• the EMSL User Project #48581 "Mass-selected Ion Deposition and Surface Characterization Techniques for Evaluation of Nanocatalytic Conversion of Biomass Components in Biofuels Production" (Northwest National Laboratory (PNNL), Richland, Washington, USA, 2014.
Institute of Organic Chemistry of NASU, Department of Acetylene Chemistry, Kyiv
August 1984 - September 1988
Chuiko Institute of Surface Chemistry of NASU, Kyiv, Ukraine
September 1988 - Present
Chuiko Institute of Surface Chemistry of NASU
January 2005 - January 2020
Catalytic pyrolysis of renevable biomass components ove nanoscale metal-oxides catalysts
“Systematic relationships in the catalytic pyrolysis of natural compounds on the surface of nanosized oxides of groups III and IV elements”.
Chuiko Institute of Surface Chemistry NAS of Ukraine
January 1992 - January 2020
Desorption Mass Spectrometry of thermal transformations of biomolecules in condesed an adsorbed states
Mass spectrometry of carbohydrate fragments - terminal groups of receptors molecules in condensed state and in adsorbed state on the surface of ultrafine silica
Taras Schevchenko National University, Kyiv, Ukraine, Department of Organic chemistry
January 1981 - January 1984
The annelation of the 2-aminopyran-4-one ring to condensed thiophenes
Synthetic chemistry of heterocyclic compounds
Northwest National Laboratory (PNNL), Richland, Washington, USA
the EMSL User Project #48581 "Mass-selected Ion Deposition and Surface Characterization Techniques for Evaluation of Nanocatalytic Conversion of Biomass Components in Biofuels Production"
Swedish Institute for research scholarship for Professor within Visby Programme [03804/2016
Swedish Institute for research scholarship for Professor within Visby Programme [03804/2016
Kulik, T.; Palianytsia, B.; Larsson, M.
Ketonization is a promising way for upgrading bio-derived carboxylic acids from pyrolysis bio-oils, waste oils, and fats to produce high value-added chemicals and biofuels. Therefore, an understanding of its mechanism can help to carry out the catalytic pyrolysis of biomass more efficiently. Here we show that temperature-programmed desorption mass spectrometry (TPD-MS) together with linear free energy relationships (LFERs) can be used to identify catalytic pyrolysis mechanisms. We report the kinetics of the catalytic pyrolysis of deuterated acetic acid and a reaction series of linear and branched fatty acids into symmetric ketones on the surfaces of ceria-based oxides. A structure–reactivity correlation between Taft’s steric substituent constants Es* and activation energies of ketonization indicates that this reaction is the sterically controlled reaction. Surface D3-n-acetates transform into deuterated acetone isotopomers with different yield, rate, E,, and deuterium kinetic isotope effect (DKIE). The obtained values of inverse DKIE together with the structure–reactivity
correlation support a concerted mechanism over ceria-based catalysts. These results demonstrate that analysis of Taft’s correlations and using simple equation for estimation of DKIE from TPD-MS data are promising approaches for the study of catalytic pyrolysis mechanisms on a semi-quantitative level.
The interaction of acetic, propionic, butyric, isobutyric, valeric, nonanoic, decanoic, and pivalic acids with the surface of fumed silica
was investigated by temperature-programmed desorption mass spectrometry (TPDMS). Mechanisms of the formation of ketenes
from chemisorbed fragments of carboxylic acids on the surface of fumed silica were proposed and the kinetic parameters of the
reaction were calculated. The Taft correlation equation and the reaction parameter F could be obtained by application of the linear
free energy relationship (LFER) principle for this reaction series. The applicability of the LFER method to the study of reactions of
adsorbed organic molecules on mineral surfaces occurring during TPDMS experiments was demonstrated using a series of acids.
6. K.Kulyk B.Palianytsia, J.D.Alexander, L.Azizova, M.Borysenko, M.Kartel, M.Larsson, T.Kulik
Valeric acid is an important renewable platform chemical that can be produced efficiently from lignocellulosic biomass. Upgrading of valeric acid by catalytic pyrolysis has the potential to produce value added biofuels and chemicals on an industrial scale. Understanding the different mechanisms involved in the thermal transformations of valeric acid on the surface of nanometer-sized oxides is important for the development of efficient heterogeneously catalyzed pyrolytic conversion techniques. In this work, the thermal decomposition of valeric acid on the surface of nanoscale SiO2, g-Al2O3, CeO2/SiO2, Al2O3/SiO2 and TiO2/SiO2 has been investigated by temperature-programmed desorption mass spectrometry (TPD MS). Fourier transform infrared spectroscopy (FTIR) has also been used to investigate the structure of valeric acid complexes on the oxide surfaces. Two main products of pyrolytic conversion were observed to be formed depending on the nano-catalyst used—dibutylketone and propylketene. Mechanisms of ketene and ketone formation from chemisorbed fragments of valeric acid are proposed and the kinetic parameters of the corresponding reactions were calculated. It was found that the activation energy of ketenization decreases in the order SiO2> gAl2O3>TiO2/SiO2>Al2O3/SiO2, and the activation energy of ketonization decreases in the order g-Al2O3>CeO2/SiO2. anooxide CeO2/SiO2 was found to selectively catalyze the ketonization reaction.
Nastasiienko, N., Kulik, T., Palianytsia, B., Laskin, J., Cherniavska, T., Kartel, M. and Larsson, M.,
Understanding the mechanisms of thermal transformations of model lignin compounds (MLC) over nanoscale catalysts is important for improving the technologic processes occurring in the pyrolytic conversion of lignocellulose biomass into biofuels and value-added chemicals. Herein, we investigate catalytic pyrolysis of MLC (pyrocatechol (P), guaiacol (G), ferulic (FA), and vanillic acids (VA)) over nanoceria using FT-IR spectroscopy, temperature-programmed desorption mass spectrometry (TPD MS), and thermogravimetric analysis (DTG/DTA/TG). FT-IR spectroscopic studies indicate that the active groups of aromatic rings of P, G, VA, and FA as well as carboxylate groups of VA and FA are involved in the interaction with nanoceria surface. We explore the general transformation mechanisms of different surface complexes and identify their decomposition products. We demonstrate that decomposition of carboxylate acid complexes occurs by decarboxylation. When FA is used as a precursor, this reaction generates 4-vinylguaiacol. Complexes of VA and FA formed through both active groups of the aromatic ring and decompose on the CeO2 surface to generate hydroxybenzene. The formation of alkylated products accompanies catalytic pyrolysis of acids due to processes of transalkylation on the surface.