Chemistry, Physics and Technology of Surface

ISSN 2518-1238 (Online), ISSN 2079-1704 (Print)

Search for the “structure-reactivity” correlations of the thermally stimulated reactions of cinnamic acids on the surface of catalysts is important for the development of pyrolytic conversion methods of lignocellulosic biomass components into products with high added value, in particular, into styrene.

Therefore, in this work, the kinetics of pyrolysis of the reaction series of para-substituted derivatives of trans-cinnamic acid (Н, -СН₃, -С(СН₃)₃, -ОСН₃, -F) on the surface of nanosized silica by the method of thermoprogrammed desorption mass spectrometry (TPD MS) was investigated. The products of pyrolytic reactions on the surface are identified ‒ the corresponding, para-substituted vinylbenzenes, phenylacetylenes, and phenylketenes. The kinetic parameters of the decarboxylation, ketenization, and decarbonylation reactions were calculated. The correlations "structure-reactivity" between the kinetic parameters (activation energy) and thermodynamic parameters (Hammett substituents constants) have been obtained, which indicate that electron-donor substituents reduce the activation energy of these three reactions while the electron-acceptor substituents increase it. That is, in the transitional state of the rate-limiting step, a decrease in the electron density is observed at the reaction center. The calculated values of the reaction constants ρ show that the studied reactions dependent on the sensitivity to the effect of the substituents are placed in a sequence: decarbonylation> decarboxylation> ketenization. The formation of phenylacetylenes is the most sensitive to structural changes in the molecule and proceeds through the most polar transition state.

1. Ralph J. Hydroxycinnamates in lignification. Phytochem. Rev. 2010. 9(1): 65. https://doi.org/10.1007/s11101-009-9141-9

2. Menshchikova E.B., Lankin V.Z., Kandalintseva N.V. Phenolic antioxidants in biology and medicine. (Saarbrücken: LAP LAMBERT Academic Publishing, 2012).

3. Tsao R. Chemistry and biochemistry of dietary polyphenols. Nutrients. 2010. 2(12): 1231. https://doi.org/10.3390/nu2121231

4. Simon V., Thuret A. Candy L., Bassil S., Duthen S., Raynaud C., Masseron A. Recovery of hydroxycinnamic acids from renewable resources by adsorption on zeolites. Chem. Eng. J. 2015. 280(15): 748. https://doi.org/10.1016/j.cej.2015.06.009

5. Pazo V., Kulik T., Nastasiienko N., Palianytsia B., Aspromonte S., Alonso E. Interaction of bio-derived ferulic acid from wheat bran with zeolites seen by TPD MS and FT-IR spectroscopy. In: Chemistry, Physics and Technology of Surface. (Proc. Int. Conf.). & Metal-Based Biocompatible Nanoparticles: Synthesis and Applications. Proc. Workshop. (15-17 May, 2019, Kyiv, Ukraine). P.140.

6. Gollakota A.R.K., Kishore N., Gu S. A review on hydrothermal liquefaction of biomass. Renewable Sustainable Energy Rev. 2018. 81(1): 1378. https://doi.org/10.1016/j.rser.2017.05.178

7. Ferracane R., Pellegrini N., Visconti A., Graziani G., Chiavaro E., Miglio C., Fogliano V. Effects of different cooking methods on antioxidant profile, antioxidant capacity, and physical characteristics of artichoke. J. Agric. Food Chem. 2008. 56(18): 8601. https://doi.org/10.1021/jf800408w

8. Zakzeski J., Bruijnincx P.C.A., Jongerius A.L., Weckhuysen B.M. The Catalytic Valorization of Lignin for the Production of Renewable Chemicals. Chem. Rev. 2010. 110(6): 3552. https://doi.org/10.1021/cr900354u

9. Isikgor F.H., Becer C.R. Lignocellulosic biomass: a sustainable platform for production of bio-based chemicals and polymers. Polym. Chem. 2015. 6(25): 4497. https://doi.org/10.1039/C5PY00263J

10. Mathers R.T. How well can renewable resources mimic commodity monomers and polymers. Polym. Chem. 2012. 50(1): 1. https://doi.org/10.1002/pola.24939

11. Mandal S., Bandyopadhyay R., Das A.K. Thermo-catalytic process for conversion of lignocellulosic biomass to fuels and chemicals: a review. Int. J. Petrochem. Sci. Eng. 2018. 3(2): 58. https://doi.org/10.15406/ipcse.2018.03.00077

12. Kulik T.V., Lipkovska N.O., Barvinchenko V.M., Palyanytsya B.B., Kazakova O.A., Dudik O.O., Menyhárd A., László K. Thermal transformation of bioactive caffeic acid on fumed silica seen by UV-spectroscopy, thermogtavimetric analisis, temperature programmed desorption mass spectrometry and quantum chemical methods. J. Colloid. Interface Sci. 2016. 470: 132. https://doi.org/10.1016/j.jcis.2016.02.039

13. Kulik T.V., Palyanytsya B.B., Barvinchenko V.M., Lipkovska N.A., Dudik O.O. Thermal transformations of biologically active derivatives of cinnamic acid by TPD MS investigation. J. Anal. Appl. Pyrolysis. 2011. 90(2): 219. https://doi.org/10.1016/j.jaap.2010.12.012

14. Kulik T.V., Lipkovska N.A., Barvinchenko V.N., Palyanytsya B.B., Kazakova O.A., Dovbiy O.A., Pogorelyi V.K. Interactions between bioactive ferulic acid and fumed silica by UV-vis spectroscopy, FT-IR, TPD MS investigation and quantum chemical methods. J. Colloid Interface Sci. 2009. 339(1): 60. https://doi.org/10.1016/j.jcis.2009.07.055

15. Kulik T.V., Barvinchenko V.N., Palyanitsa B.B., Smirnova O.V., Pogorelyi V.K., Chuiko A.A. A desorption mass spectrometry study of the interaction of cinnamic acid with a silica surface. Russ. J. Phys. Chem. 2007. 81(1): 83. https://doi.org/10.1134/S0036024407010165

16. Kulik T.V., Barvinchenko V.M., Palyanitsa B.B. Adsorption and chemical transformation of cinnamic acid on the surface of highly dispersed silica. Reports of the National Academy of Sciences of Ukraine. 2006. 6: 138. [in Ukranian].

17. Stepanenko B.N. Organic chemistry. 6th ed. (Moscow: Medicine, 1980). [in Russian].

18. Shorygina N.V. Styrene, its polymers and copolymers. (Moscow - Leningrad: Goskhimizdat, 1960). [in Russian].

19. New Process for Producing Styrene Cuts Costs, Saves Energy, and Reduces Greenhouse Gas Emissions Archived 21 April 2013 at the Wayback Machine, U.S. Department of Energy. https://www1.eere.energy.gov/office_eere/pdfs/exelus_case_study.pdf

20. Harmsen P., Hackmann M. Green building blocks for biobased plastics. Biobased processes and market development. (Wageningen: Propress, 2013).

21. Cheng Y.T., Huber G.W. Chemistry of furan conversion into aromatics and olefins over HZSM-5: A model biomass conversion reaction. ACS Catal. 2011.6: 611. https://doi.org/10.1021/cs200103j

22. Matlack A. Introduction to Green Chemistry. 2nd edn. (Boca Raton-London-New York: CRC Press, 2011).

23. McKenna R., Nielsen D.R. Styrene biosynthesis from glucose by engineered E. coli. Metab Eng. 2011. 13(5): 544. https://doi.org/10.1016/j.ymben.2011.06.005

24. Singha A., Rana R.K. Preparation and properties of Agave fiber-reinforced polystyrene composites. J. Thermoplast. Compos. Mater. 2013. 26: 513. https://doi.org/10.1177/0892705711425848

25. Semenov P.V. Industrial technologies for styrene production. Young scientist. 2016. 5: 168. [in Russian].

26. Timofeev V.S, Serafimov L.A. Principles of technology of basic organic and petrochemical synthesis. Train. Allowance for universities. (Moscow: Vysshaya Shkola, 2003). [in Russian].

27. Abramov A.G. The formation of 2-phenylethanol in the process of joint production of styrene and propylene oxide. Bulletin of Kazan Technological University. 2008. 3: 50. [in Russian].

28. Sykes P. A Guidebook to Mechanism in Organic Chemistry. 6th Ed. (New York: Pearson, 1986).

29. Kulik T.V. Use of TPD-MS and linear free energy relationships for assessing the reactivity of aliphatic carboxylic acids on a silica surface. J. Phys. Chem. C. 2012. 116(1): 570. https://doi.org/10.1021/jp204266c

30. Kulyk K., Palianytsia B., Alexander J.D., Azizova L., Borysenko M., Kartel M., Larsson M., Kulik T. Kinetics of valeric acid ketonization and ketenization in catalytic pyrolysis on nanosized SiO₂, γ-Al₂O₃, CeO₂/SiO₂, Al₂O₃/SiO₂ and TiO₂/SiO₂. Chem. Phys. Chem. 2017. 18(14): 1943. https://doi.org/10.1002/cphc.201601370

31. Nicholl S.I., Talley J.W. Development of thermal programmed desorption mass spectrometry methods for environmental applications. Chemosphere. 2006. 63(1): 132. https://doi.org/10.1016/j.chemosphere.2005.07.015

32. Rudziński W., Borowiecki T., Dominko A., Pańczyk T. A New Quantitative interpretation of temperature-programmed desorption spectra from heterogeneous solid Surfaces, based on statistical rate theory of interfacial transport:  the effects of simultaneous readsorption. Langmuir. 1999. 15(19): 6386. https://doi.org/10.1021/la9800147

33. Taft R.W., Grob C.A. Separation of polar and resonance effects in the ionization of 4-substituted pyridinium ions. J. Am. Chem. Soc. 1974. 96(4): 1236. https://doi.org/10.1021/ja00811a054

34. Young R.P. Infrared spectroscopic studies of adsorption and catalysis. Part 3. Carboxylic acids and their derivatives adsorbed on silica. Canadian J. Chem. 1969. 47(12): 2237. https://doi.org/10.1139/v69-362

35. Marshall K., Rochester C.H., Marshall K., Rochester C.H. Infrared study of the adsorption of oleic and linolenic acids onto the surface of silica immersed in carbon tetrachloride. J. Chem. Soc. Faraday Trans. 1. 1975. 71: 1754. https://doi.org/10.1039/f19757101754

36. Brei V.V., Gun'ko V.M., Dudnik V.V., Chuiko A.A. Study of kinetics and mechanisms of some unimolecular reactions on silica surfaces. Langmuir. 1992. 8(8): 1968. https://doi.org/10.1021/la00044a015

37. Brei V.V., Brichka A.V. A Study of the Brönsted Site Acidity of Crystalline and Amorphous Aluminosilicates: 2. Thermal Decomposition of Grafted Acetyl Groups. Adsorp. Sci. Technol. 1996. 14(6): 359. https://doi.org/10.1177/026361749601400603

38. Basyuk V.A. Infrared spectra of carboxylic compounds on silica surfaces at 1500-1800 cm-1. J. Appl. Spectrosc. 1994. 60: 29. https://doi.org/10.1007/BF02606071

39. Martinez R., Huff M. C., Barteau M. A. Synthesis of ketenes from carboxylic acids on functionalized silica monoliths at short contact times. Appl. Catal. A. 2000. 200(1-2): 79. https://doi.org/10.1016/S0926-860X(00)00649-9

40. Libby M.C., Watson P.C., Barteau M.A. Synthesis of Ketenes with oxide catalysts. Ind. Eng. Chem. Res. 1994. 33(12): 2904. https://doi.org/10.1021/ie00036a003

41. Azizova L.R., Kulik T.V., Palyanytsya B.B., Lipkovska N.A. Thermal and hydrolytic stability of grafted ester groups of carboxylic acids on the silica surface. J. Therm. Anal. Calorim. 2015. 122(2): 517. https://doi.org/10.1007/s10973-015-4828-1

42. Redhead P.A. Thermal desorption of gases. Vacuum. 1962. 12(4): 203. https://doi.org/10.1016/0042-207X(62)90978-8

43. Woodruff D.P., Delchar T.A. Modern Techniques of Surface Science. (London: Cambridge University Press, 1986).

44. Kislyuk M.U., Rozanov V.V. Temperature-programmed desorption and temperature-programmed reaction - methods of studying of kinetics and mechanisms of catalytic processes. Kinet. Katal. 1995. 36: 89.

45. Carter G. Thermal resolution of desorption energy spectra. Vacuum. 1962. 12(5): 245. https://doi.org/10.1016/0042-207X(62)90526-2

46. Gridneva T.V., Soroka P.I., Tertyshny O.A. Physical and chemical bases of the process of obtaining silica from rice husk. Bull. National Techn. Univer. "KhPI". 2010. 10: 124. [in Ukrainian].

47. Soukup M., Martinka M., Bosnić D., Čaplovičová M., Elbaum R., Lux A. Formation of silica aggregates in sorghum root endodermis is predetermined by cell wall architecture and development. Ann. Bot. 2017. 120(5): 739. https://doi.org/10.1093/aob/mcx060