Abstract
Utilization of the second-most abundant biopolymer, lignin, in production of fine chemicals is considered as a strategy for environmental conservation and economic feasibility of technologies. Photocatalytic conversion of sodium lignosulfonate to low molecular weight compounds over eco-friendly semiconducting materials under simulated solar light is a perspective eco-innovative approach for “green technology” development. The more efficient depolymerization of lignosulfonate during photolytic reaction occurs at pH 2 as a result of sulfonic groups’ protonation, whereas the re-polymerization of hydrolyzed fragments to more complex structure in solutions at pH 5 and pH 9 is reported. Photo-sensibilization pathway toward polymer fragmentation is low effective process. It is shown that photocatalytic process is also more effective at pH 2 due to an electrostatic interaction of positively charge surface of metal oxides’ films and negatively charged NaLSA molecules. As shown by LDI MS investigation, the destruction of aromatic component of NaLSA molecule can be achieved in the presence of TiO2 film under simulated solar light due to the strong reductive power of superoxide radicals resulting in the benzoic ring-opening route. The mechanism of photocatalytic reaction over iron titanate films is governed by the presence of two semi-conductive crystalline phases, pseudobrookite and landauite, that are characterized by the anodically shifted energy positions of the conduction and valence bands compared to TiO2 providing an effective oxidation by HO• radicals. Nitrogen-doped iron titanate films are considered as a photocatalyst for the processes of low molecular weight aromatic compounds’ synthesis exhibiting activity under both simulated solar and visible light with the phenol yields of 0.96 μg mL−1 and 1.2 μg mL−1, respectively.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Bui TD, Kimura A, Higashida S, Ikeda S, Matsumura M (2011) Two routes for mineralizing benzene by TiO2-photocatalyzed reaction. Appl Catal b: Environ 107:119–127. https://doi.org/10.1016/j.apcatb.2011.07.004
Chakar FS, Ragauskas AJ (2004) Review of current and future softwood kraft lignin process chemistry. Ind Crops Prod 20:131–141. https://doi.org/10.1016/j.indcrop.2004.04.016
Chorna N, Smirnova N, Vorobets V, Kolbasov G, Linnik O (2019) Nitrogen doped iron titanate films: photoelectrochemical, electrocatalytic, photocatalytic and structural features. Appl Surf Sci 473:343–351. https://doi.org/10.1016/j.apsusc.2018.12.154
Cogulet A, Blanchet P, Landry V (2016) Wood degradation under UV irradiation: a lignin characterization. J Photochem Photobiol B 158:184–191. https://doi.org/10.1016/j.jphotobiol.2016.02.030
Gaidai SV, Grynko VS, Zhludenko MG, Dyachenko AG, Tkach VM, Ishchenko OV (2017) Activity of carbon-fiber-supported Fe–Co catalysts in the CO2 methanation reaction. J Superhard Mater 39:122–128. https://doi.org/10.3103/S1063457617020071
Garrido RA, Reckamp JM, Satrio JA (2017) Effects of pretreatments on yields, selectivity and properties of products from pyrolysis of phragmites Australis (common reeds). Environments. https://doi.org/10.3390/environments4040096
Gasson JR, Forchheim D, Sutter T, Hornung U, Kruse A, Barth T (2012) Modeling the lignin degradation kinetics in an ethanol/formic acid solvolysis approach. Part 1. Kinetic model development. Ind Eng Chem Res 51:10595–10606. https://doi.org/10.1021/ie301487v
Granone LI, Sieland F, Zheng N, Dillerta R, Bahnemann DW (2018) Photocatalytic conversion of biomass into valuable products: a meaningful approach? Green Chem 20:1169–1192. https://doi.org/10.1039/C7GC03522E
Hashimoto K, Kawai T, Sakata T (1984) Photocatalytic reactions of hydrocarbons and fossil fuels with water. Hydrogen production and oxidation. J Phys Chem 88:4083–4088. https://doi.org/10.1021/j150662a04610.1021/j150662a046
Hayoz P, Peter W, Rogez D (2003) A new innovative stabilization method for the protection of natural wood. Prog Org Coat 48:297–309. https://doi.org/10.1016/S0300-9440(03)00102-4
Kansal SK, Singh M, Sud D (2008) Studies on TiO2/ZnO photocatalysed degradation of lignin. J Hazard Mater 153:412–417. https://doi.org/10.1016/j.jhazmat.2007.08.091
Khalyavka TA, Shcherban ND, Shymanovska VV, Manuilov EV, Permyakov VV, Shcherbakov SN (2019) Cerium-doped mesoporous BaTiO3/TiO2 nanocomposites: structural, optical and photocatalytic properties. Res Chem Intermed 45:4029–4042. https://doi.org/10.1007/s11164-019-03888-z
Kim KH, Kim CS (2018) Recent efforts to prevent undesirable reactions from fractionation to depolymerization of lignin: toward maximizing the value from lignin. Front Energy Res. https://doi.org/10.3389/fenrg.2018.00092
Kisch H (2015) Semiconductor photocatalysis principles and application. Wiley-VCH, Weinheim
Ksibi M, Amor SB, Cherif S, Elalouia E, Houasa A, Elalouia M (2003) Photodegradation of lignin from black liquor using a UV/TiO2 system. J Photochem Photobiol A 154:211–218. https://doi.org/10.1016/S1010-6030(02)00316-7
Kumar A, Raizada P, Singh P, Saini RV, Saini AK, Hosseini-Bandegharaei A (2020) Perspective and status of polymeric graphitic carbon nitride-based Z-scheme photocatalytic systems for sustainable photocatalytic water purification. Chem Eng J 391:123496. https://doi.org/10.1016/j.cej.2019.123496
Linnik O, Kisch H (2006) On the mechanism of nitrogen fixation at nanostructured iron titanate films. Photochem Photobiol Sci 5:938–942. https://doi.org/10.1039/b608396j
Linnik O, Petrik I, Smirnova N, Kandyba V, Korduban O, Eremenko A, Socol G, Stefan N, Ristoscu C, Mihailescu IN, Sutan C, Malinovski V, Djokic V, Janakovic D (2012) TiO2/ZrO2 thin films synthesized by PLD in low pressure N–, C– and/or O–containing gases: structural, optical and photocatalytic properties. Digest J Nanomater Biostruct 7:1343–1352
Linnik O, Chorna N, Smirnova N (2017) Nonporous iron titanate thin films doped with nitrogen: optical, structural and photocatalytic properties. Nanoscale Res Lett 12:249–258. https://doi.org/10.1186/s11671-017-2027-7
Lundquist K, Lundgren R (1972) Acid degradation of lignin. Part VII. The cleavage of ether bonds. Acta Chem Scand 26:2005–2023
mMass—Open Source Mass Spectrometry Tool. Available online. http://www.mmass.org/ Accessed on 07 Nov 2021
Roberts VM, Stein V, Reiner T, Lemonidou A, Li X, Lercher JA (2011) Towards quantitative catalytic lignin depolymerization. Chemistry 17:5939–5948. https://doi.org/10.1002/chem.201002438
Schmidt JA (1995) Heitner C Light-induced yellowing of mechanical and ultra-high pulps. Part 3. Comparison of solfwood TMP, softwood CTMP and aspen CTMP. J Wood Chem Technol 15:223–245. https://doi.org/10.1080/02773819508009509
Sharma S, Dutta V, Singh P, Raizada P, Rahmani-Sani A, Hosseini-Bandegharaei A (2019) Thakur VK Carbon quantum dot supported semiconductor photocatalysts for efficient degradation of organic pollutants in water: a review. J Clean Prod 228:755–769. https://doi.org/10.1016/j.jclepro.2019.04.292
Sheldon RA (2014) Green and sustainable manufacture of chemicals from biomass: state of the art. Green Chem 11:950–963. https://doi.org/10.1039/C3GC41935E
Song Q, Wang F, Cai J, Wang Y, Zhang J, Yua W, Xu J (2013) Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation hydrogenolysis process. Energy Environ Sci 6:994–1007. https://doi.org/10.1039/C2EE23741E
Toledano A, Serrano L, Pineda A, Romero AA, Luque R, Labidi J (2012) Microwave-assisted depolymerisation of organosolv lignin via mild hydrogen-free hydrogenolysis: catalyst screening. Appl Catal B Environ 145:43–55. https://doi.org/10.1016/j.apcatb.2012.10.015
Verma S, Nadagouda MN, Varma SR (2019) Visible light-mediated and water-assisted selective hydrodeoxygenation of lignin-derived guaiacol to cyclohexanol. Green Chem 21:1253–1257. https://doi.org/10.1039/C8GC03951H
Xiaoqing L, Xiaoguang D, Wei W, Shaobin W, Bing-Jie N (2019) Photocatalytic conversion of lignocellulosic biomass to valuable products. Green Chem 21:4266–4289. https://doi.org/10.1039/C9GC01728C
Yan M, Yang D, Deng Y, Chen P, Zhou H, Qiu X (2010) Influence of pH on the behavior of lignosulfonate macromolecules in aqueous solution. Colloids Surf A Physicochem Eng Asp 371:50–58. https://doi.org/10.1016/j.colsurfa.2010.08.062
Ye Y, Zhang Y, Fan J, Chang J (2012) Selective production of 4-ethylphenolics from lignin via mild hydrolysis. Bioresour Technol 118:648–651. https://doi.org/10.1016/j.biortech.2012.05.127
Yoshikawa T, Yagi T, Shinohara S, Fukunagab T, Nakasakaa Y, Tagoa T, Masudaa T (2012) Production of phenols from lignin via depolymerization and catalytic cracking. Fuel Process Technol 108:69–75. https://doi.org/10.1016/j.fuproc.2012.05.003
Acknowledgements
This research was funded by National Research Foundation of Ukraine (Project No 2020.01/0136 “Efficient use of renewable plant resources and photocatalytic conversion of biomass as eco-innovative approaches for environmental protection and human biosafety”). The authors are thankful the brave defenders of Ukraine who provided the possibility to finalize this publication.
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Kramar, A., Anishchenko, V., Kuzema, P. et al. Features of lignosulfonate depolymerization and photocatalytic transformation to low-molecular-weight compounds over nano-sized semiconductive films. Appl Nanosci 12, 2345–2355 (2022). https://doi.org/10.1007/s13204-022-02492-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13204-022-02492-9