Metal-Carbon Composites Based on Lignosulfonates

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UDС

676.084

DOI:

10.37482/0536-1036-2020-3-159-168

Abstract

The synthesis of the new nanostructured metal-carbon composites (NMCC) based on lignosulfonates was proposed. Obtaining and studying the properties of NMCC is a crucial task of modern materials chemistry due to the use of the materials based on them in various fields of science and technology as ion-selective electrodes and electrochemical cathodes, supercapacitors, magnetic sensors, information recording and storage devices, heterogeneous catalysts. The synthesis method, which allows the formation of particles of a certain shape and size, which subsequently determine the properties of the composite material (sorption, electrochemical, catalytic, magnetic and optical), acquires decisive importance in the production of the new materials. The research purpose is to study the influence of the synthesis conditions of NMCC based on carbon-containing organic raw materials (lignosulfonates, chitosan and polyethylene polyamine) and embedded metal on the structure and physico-chemical properties of the new materials. The feature of the developed approach is the colloid-chemical synthesis with subsequent carbonization, which allows to obtain a highly dispersed NMCC  with the developed micro- and mesoporous structure, specific surface area up to 400 m2/g and a narrow particle size (30–65 nm) distribution. Metal binds to sodium lignosulfonate (LS) at the stage of chelate complex formation, which upon mutual coagulation with chitosan (CT) or polyethylene polyamine (PEPA) forms a water-insoluble compound (polymer metalorganic complex). The degree of extraction of Co(II) ions from aqueous solutions during the formation of the LS–Co–CТ metal complex is 78.6 % (LS : CТ mass ratio is 1 : 0.25) and the LS–Co–PEPA complex is 56.3 % (LS : PEPA mass ratio is 1 : 0.1). Centrifugation and washing with acetone followed by carbonization allow the metal to be fixed in the structure of the NMCC. The synthesis conditions, including the quantitative ratio of polymer components (LS : CT – 1 : 0.25 and LS : PEPA – 1 : 0.1), the duration of the formation of the chelate complex (1 h) and the metal-organic composite (1 h) and pH (4–6), were analyzed. The morphology of the NMCC was studied by electron microscopy, and the parameters of the porous structure were found by the method of low-temperature nitrogen adsorption. Carbon nanomaterials based on cheap starting polymers and obtained in the mild synthesis conditions are promising for practical use as effective sorbents and catalysts, as well as for environmental protection.

Authors

O.S. Brovko, Candidate of Chemistry, Leading Research Scientist, Assoc. Prof.;
ResearcherID: AAF-5387-2019,
ORCID: https://orcid.org/0000-0002-1961-7831
I.A. Palamarchuk, Candidate of Chemistry, Senior Research Scientist; ResearcherID: AAF-5454-2019,
ORCID: https://orcid.org/0000-0002-2947-1370
N.A. Gorshkova, Junior Research Scientist; ResearcherID: AAF-5411-2019,
ORCID: https://orcid.org/0000-0002-2036-2418
A.D. Ivakhnov, Candidate of Chemistry, Senior Research Scientist; ResearcherID: U-4822-2019,
ORCID: https://orcid.org/0000-0003-2822-9192

Affiliation

N. Laverov Federal Center for Integrated Arctic Research, Naberezhnaya Severnoy Dviny, 23, Arkhangelsk, 163000, Russian Federation; e-mail: nat.gorshkova@mail.ru

Keywords

lignosulfonate, chitosan, nanocomposite, carbon material, metal complex, polyethylene polyamine

For citation

Brovko O.S., Palamarchuk I.A., Gorshkova N.A., Ivakhnov A.D. Metal-Carbon Composites Based on Lignosulfonates. Lesnoy Zhurnal [Russian Forestry Journal], 2020, no. 3, pp. 159–168. DOI: 10.37482/0536-1036-2020-3-159-168

References

1. Brovko O.S., Palamarchuk I.A., Vishnyakova A.P. The Effect of the Molecular Weight of Sodium Lignosulfonate on Complex Formation with Polyethylene Polyamine. Khimija Rastitel’nogo Syr’ja [Chemistry of plant raw material], 2011, no. 1, pp. 65–70.
2. Brovko O.S., Palamarchuk I.A., Sysoeva N.V., Val’chuk N.A., Boytsova T.A., Bogolitsyn K.G., Dubovyy V.K. Filter Materials Based on Mineral Fibers with Biopolymer Layer. Lesnoy Zhurnal [Russian Forestry Journal], 2017, no. 1, pp. 186–194. DOI: 10.17238/issn0536-1036.2017.1.186, URL: http://lesnoizhurnal.ru/upload/iblock/e82/brovko.pdf
3. Vishnyakova A.P., Brovko O.S. Application of Ultrafiltration for Clearing, Concentration and Fractionating of Lignosulphonates of Sulfite Lye. Ekologia i promyshlennost Rossii [Ecology and Industry of Russia], 2009, no. 8. pp. 37–39.
4. Gusev A.I. Nanomaterials, Nanostructures, Nanotechnologies. Moscow, Nauka-Fizmatlit Publ., 2007. 416 p.
5. Palamarchuk I.A., Brovko O.S., Boytsova T.A., Vishnyakova A.P., Makarevich N.A. The Ionic Strength Effect of a Solution on the Complex Formation of Sulfonated Biopolymers of Lignin and Chitosan. Khimija Rastitel’nogo Syr’ja [Chemistry of plant raw material], 2011, no. 2, pp. 57–64.
6. Palamarchuk I.A., Makarevich N.A., Brovko O.S., Boitsova T.A. Afanasiev N.I. The Cooperative Interaction in the System of Lignosulfonate – Chitosan. Khimija Rastitel’nogo Syr’ja [Chemistry of plant raw material], 2008, no. 4, pp. 29–34.
7. Prshibil R. Complexones in Chemical Analysis. Ed. by Yu.Yu. Lur’ye. Moscow, Izdatel’stvo inostrannoy literatury, 1960, 580 p.
8. Serov V.A. Afanas’yev N.I., Brovko O.S. Zasukhina L.V. Extraction of Lignin-Containing Compounds from Aqueous Solutions in the Form of Mixed Ligand Complexes with Transition Metals. Khimiya v interesakh ustoichivogo razvitiya [Chemistry for Sustainable Development], 1997, vol. 5, no. 5, pp. 613–618.
9. Serov V.A., Brovko O.S., Palamarchuk I.A. Complex Formation in the System Sodium Lignosulphonate – Polyethylenepolyamin. Khimiya v interesakh ustoichivogo razvitiya [Chemistry for Sustainable Development], 2006, vol. 14, no. 5, pp. 485–489.
10. Sokolov O.M. Determination of Molecular Weights of Lignins Using an Ultracentrifuge and by the Gel Filtration Method. Leningrad, LTA Publ., 1978. 76 p.
11. Teptereva G.A., Shavshukova S.Yu., Konesev V.G. Features of the Complexation Ofneutral Lignosulfonates with the Cations of Variable Valency Metals. Bashkirskii khimicheskii zhurnal [Bashkir chemistry journal], 2017, vol. 24, no. 2, pp. 66–69.
12. Khabarov Yu.G., Veshnyakov V.A., Kuzyakov N.Yu. Preparation and Application of Complexes of Lignosulfonic Acids with Iron Cations. Lesnoy Zhurnal [Russian Forestry Journal], 2019, no. 5, pp. 167–187. DOI: 10.17238/issn0536-1036.2019.5.167, URL: http://lesnoizhurnal.ru/upload/iblock/73e/167_187.pdf
13. Babkin I., Brovko O., Iakovlev M., Khabarov Yu. Ferrofluid Synthesis Using Nitrosated Lignosulfonates. Industrial and Engineering Chemistry Research, 2013, vol. 52, no. 23, pp. 7746–7751. DOI: 10.1021/ie400531f
14. Bhushan B., Luo D., Schricker S.R., Sigmund W., Zauscher S. Handbook of Nanomaterials Properties. Berlin, Springer, 2014. 1463 p. DOI: 10.1007/978-3-642-31107-9
15. Brovko O., Palamarchuk I., Bogdanovich N., Ivakhnov A., Chukhchin D., Malkov A., Volkov A., Arkhilin M., Gorshkova N. Structure and Electrophysical Properties of Carbogels Based on the Interpolyelectrolyte Complex Lignosulfonate – Chitosan with Various Composition. Microporous and Mesoporous Materials, 2019, vol. 282, pp. 211–218. DOI: 10.1016/j.micromeso.2019.03.030
16. Brovko O., Palamarchuk I., Bogolitsyn K., Bogdanovich N., Ivakhnov A., Chukhchin D., Khviuzova K., Valchuk N. Carbon Nanomaterials Based on Interpolyelectrolyte Complex Lignosulfonate Chitosan. Holzforschung, 2019, vol. 73, iss. 2, pp. 181–187. DOI: 10.1515/hf-2017-0221
17. Brovkо O.S., Palamarchuk I.A., Boitsova T.A., Bogolitsyn K.G., Valchuk N.A., Chukhchin D.G. Influence of the Conformation of Biopolyelectrolytes on the Morphological Structure of Their Interpolymer Complexes. Macromolecular Research, 2015, vol. 23, no. 11, pp. 1059–1067. DOI: 10.1007/s13233-015-3140-z
18. Dzidziguri E.L., Sidorova E.N., Bagdasarova K.A., Zemtsov L.M., Karpacheva G.P. Formation of Co Nanoparticles in Metal-Carbon Composites. Crystallography Reports, 2008, vol. 53, pp. 316–319. DOI: 10.1134/S1063774508020223
19. Dzidziguri L., Zemtsov L.M., Karpacheva G.P., Muratov D.G., Sidorova E.N. Preparation and Structure of Metal-Carbon Nanocomposites Cu-C. Nanotechnologies in Russia, 2010, vol. 5, pp. 665–668. DOI: 10.1134/S1995078010090119
20. Gamzazade A.I., Šlimak V.M., Skljar A.M., Štykova E.V., Pavlova S.S.A., Rogožin S.V. Investigation of the Hydrodynamic Properties of Chitosan Solutions. Acta Polymerica, 1985, vol. 36, iss. 8, pp. 420–424. DOI: 10.1002/actp.1985.010360805
21. Gardon J.L., Mason S.G. Physicochemical Studies of Lignosulphonates. II. Behaviour as Polyelectrolytes. Canadian Journal of Chemistry, 1955, vol. 33, no. 10, pp. 1491–1501. DOI: 10.1139/v55-182
22. Lu A.-H., Hao G.-P., Sun Q., Zhang X.-Q., Li W.-C. Chemical Synthesis of Carbon Materials with Intriguing Nanostructure and Morphology. Macromolecular Chemistry and Physics, 2012, vol. 213, iss. 10-11, pp. 1107–1131. DOI: 10.1002/macp.201100606
23. Lu Y., Zhu Z., Liu Z. Carbon-Encapsulated Fe Nanoparticles from Detonation-Induced Pyrolysis of Ferrocene. Carbon, 2005, vol. 43, iss. 2, pp. 369–374. DOI: 10.1016/j.carbon.2004.09.020
24. Rodríguez-Reinoso F. The Role of Carbon Materials in Heterogeneous Catalysis. Carbon, 1998, vol. 36, iss. 3, pp. 159–175. DOI: 10.1016/S0008-6223(97)00173-5
25. Schur D.V., Dubovoy A.G., Zaginaichenko S.Yu., Adejev V.M., Kotko A.V., Bogolepov V.A., Savenko A.F., Zolotarenko A.D. Production of Carbon Nanostructures by Arc Synthesis in the Liquid Phase. Carbon, 2007, vol. 45, iss. 6, pp. 1322–1329. DOI: 10.1016/j.carbon.2007.01.017
26. Velo-Gala I., López-Peñalver J.J., Sánchez-Polo M., Rivera-Utrilla J. Role of Activated Carbon Surface Chemistry in Its Photocatalytic Activity and the Generation of Oxidant Radicals under UV or Solar Radiation. Applied Catalysis B: Environmental, 2017, vol. 207, pp. 412–423. DOI: 10.1016/j.apcatb.2017.02.028
27. Yengejeh S.I., Kazemi S.A., Öchsner A. Carbon Nanotubes as Reinforcement in Composites: A Review of the Analytical, Numerical and Experimental Approaches. Computational Materials Science, 2017, vol. 136, pp. 85–101. DOI: 10.1016/j.commatsci.2017.04.023