Abstract
Carbon-based solid acids (CSA) have grown in popularity in recent years owing to their strong catalytic activity, thermal stability, and reusability. The size effect has a significant influence on the catalytic activity of carbon-based solid acids in heterogeneous catalysts. The impacts of raw material size on the shape, sulfonation degree, and catalytic activity of produced carbon-based solid acids were examined in this article. Various sizes of microcrystalline cellulose (MCC), cellulose nanocrystals (CNCs), and cotton fiber pulp (CP) were used as carbon sources in a simple carbon-sulphonation method to synthesize carbon-based solid acids. The produced CSA has a high concentration of sulphonic acid groups, as well as hydroxyl and carboxyl groups, and exhibits remarkable catalytic activity for the conversion of xylan to xylose. The solid acids generated from MCC have the most homogeneous shape, the greatest degree of sulphonation, and the highest catalytic activity. The conversion rate of xylan hydrolysis to xylose was up to 58.8% under ideal reaction conditions (150 °C, 4 h), and the catalyst retained almost its initial level of activity after five cycles with no appreciable deactivation.
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References
Busca G (2010) ChemInform abstract: acid catalysts in industrial hydrocarbon chemistry. ChemInform 39:5366–5410. https://doi.org/10.1002/chin.200804274
Caes BR, Teixeira RE, Knapp KG, Raines RT (2015) Biomass to furanics: renewable routes to chemicals and fuels. ACS Sustain Chem 3:2591–2605. https://doi.org/10.1021/acssuschemeng.5b00473
Cao Q, Guan J, Peng G, Hou T, Zhou J, Mu X (2015) Solid acid-catalyzed conversion of furfuryl alcohol to alkyl tetrahydrofurfuryl ether. Catal Commun 58:76–79. https://doi.org/10.1016/j.catcom.2014.08.030
Chen CL, Wang XK, Nagatsu M (2009) Europium adsorption on multiwall carbon nanotube/iron oxide magnetic composite in the presence of polyacrylic acid. Environ Sci Technol 43:2362–2367. https://doi.org/10.1021/es803018a
Chen N, Tong Z, Yang W, Brennan AB (2015) Biocomposites with tunable properties from poly(lactic acid)-based copolymers and carboxymethyl cellulose via ionic assembly. Carbohyd Polym 128:122–129. https://doi.org/10.1016/j.carbpol.2015.04.015
Chen T, Peng L, Yu X, He L (2018) Magnetically recyclable cellulose-derived carbonaceous solid acid catalyzed the biofuel 5-ethoxymethylfurfural synthesis from renewable carbohydrates. Fuel 219:344–352. https://doi.org/10.1016/j.fuel.2018.01.129
Clark JH (2002) Solid acids for green chemistry. Acc Chem Res 35:791–797. https://doi.org/10.1021/ar010072a
Emeis CA (1993) Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts. J Catal 141:347–354. https://doi.org/10.1002/chin.199338056
Fu Z, Wan H, Hu X, Cui Q, Guan G (2012) Preparation and catalytic performance of a carbon-based solid acid catalyst with high specific surface area. React Kinet Mech Catal 107:203–213. https://doi.org/10.1007/s11144-012-0466-9
Geng L, Wang Y, Yu G, Zhu Y (2011) Efficient carbon-based solid acid catalysts for the esterification of oleic acid. Catal Commun 13:26–30. https://doi.org/10.1016/j.catcom.2011.06.014
Hara M (2010) Biomass conversion by a solid acid catalyst. Energy Environ Sci 3:601–607. https://doi.org/10.1039/b922917e
Hu L, Li Z, Wu Z, Lin L, Zhou S (2016) Catalytic hydrolysis of microcrystalline and rice straw-derived cellulose over a chlorine-doped magnetic carbonaceous solid acid. Ind Crops Prod 84:408–417. https://doi.org/10.1016/j.indcrop.2016.02.039
Huang YB, Yao F (2013) Hydrolysis of cellulose to glucose by solid acid catalysts. Green Chem 15:1095–1111. https://doi.org/10.1039/C3GC40136G
Jae J et al (2010) Depolymerization of lignocellulosic biomass to fuel precursors: maximizing carbon efficiency by combining hydrolysis with pyrolysis. Energy Environ Sci 3:358–365. https://doi.org/10.1039/B924621P
John A, Yadav P, Palaniappan S (2006) Clean synthesis of 1,8-dioxo-dodecahydroxanthene derivatives catalyzed by polyaniline-p-toluenesulfonate salt in aqueous media. J Mol Catal a: Chem 248:121–125. https://doi.org/10.1016/j.molcata.2005.12.017
Khan A, Wen Y, Huq T, Ni Y (2017) Cellulosic nanomaterials in food and nutraceutical applications: a review. J Agric Food Chem 66:8–19. https://doi.org/10.1021/acs.jafc.7b04204
Kiichi et al (2011) Structure and catalysis of cellulose-derived amorphous carbon bearing SO3H groups. Chemsuschem 4:778–784. https://doi.org/10.1002/cssc.201000431
Konwar LJ et al (2014) Biodiesel production from acid oils using sulfonated carbon catalyst derived from oil-cake waste. J Mol Catal a: Chem 388–389:167–176. https://doi.org/10.1016/j.molcata.2013.09.031
Konwar LJ, Mki-Arvela P, Mikkola JP (2019) SO3H-containing functional carbon materials: synthesis, structure, and acid catalysis. Chem Rev 119:11576–11630. https://doi.org/10.1021/acs.chemrev.9b00199
Kozhevniko IV (2009) Heterogeneous acid catalysis by heteropoly acids: approaches to catalyst deactivation. J Mol Catal a: Chem 305:104–111
Li X, Jiang Y, Shuai L, Wang L, Meng L, Mu X (2012) Sulfonated copolymers with SO3H and COOH groups for the hydrolysis of polysaccharides. J Mater Chem 22:1283–1289. https://doi.org/10.1039/C1JM12954F
Li H, Ren J, Zhong L, Sun R, Liang L (2015) Production of furfural from xylose, water-insoluble hemicelluloses and water-soluble fraction of corncob via a tin-loaded montmorillonite solid acid catalyst. Biores Technol 176:242–248. https://doi.org/10.1016/j.biortech.2014.11.044
Lin QX et al (2018) Impact of activation on properties of carbon-based solid acid catalysts for the hydrothermal conversion of xylose and hemicelluloses. Catal Today 319:31–40. https://doi.org/10.1016/j.cattod.2018.03.070
Liu WJ, Ke T, Hong J, Yu HQ (2013) Facile synthesis of highly efficient and recyclable magnetic solid acid from biomass waste. Sci Rep 3:2419–2425. https://doi.org/10.1038/srep02419
Margolese D, Melero JA, Christiansen SC, Chmelka BF, Stucky GD (2000) Direct syntheses of ordered SBA-15 mesoporous silica containing sulfonic acid groups. Chem Mater 12:2448–2459. https://doi.org/10.1021/cm0010304
Masaaki et al (2009) Adsorption-enhanced hydrolysis of β-1,4-glucan on graphene-based amorphous carbon bearing SO3H, COOH, and OH groups. Langmuir 25:5068–5075. https://doi.org/10.1021/la8040506
Nakajima K, Hara M, Hayashi S (2010) Environmentally benign production of chemicals and energy using a carbon-based strong solid acid. J Am Ceram Soc 90:3725–3734. https://doi.org/10.1111/j.1551-2916.2007.02082.x
Ogaki Y, Shinozuka Y, Hatakeyama M, Hara T, Ichikuni N, Shimazu S (2009) Selective production of xylose and xylo-oligosaccharides from bamboo biomass by sulfonated allophane solid acid catalyst. Rep Chiba Ind Technol Res Inst 38:1176–1177. https://doi.org/10.1246/cl.2009.1176
Okuhara T (2002) Water-tolerant solid acid catalysts. Chem Rev 102:3641–3665. https://doi.org/10.1002/chin.200303268
Okuhara T, Mizuno N, Misono M (2001) Catalysis by heteropoly compounds—recent developments. Appl Catal A 222:63–77. https://doi.org/10.1016/S0926-860X(01)00830-4
Olah GA, Iyer PS, Prakash GK (1986) Perfluorinated resinsulfonic acid (Nafion-H) catalysis in synthesis. Synthesis 1986:513–531. https://doi.org/10.1055/s-1986-31692
Qi W et al (2018) Carbon-based solid acid pretreatment in corncob saccharification: specific xylose production and efficient enzymatic hydrolysis. ACS Sustain Chem Eng 6:3640–3648. https://doi.org/10.1021/acssuschemeng.7b03959
Rinaldi R, Schüth F (2010) Acid hydrolysis of cellulose as the entry point into biorefinery schemes. Chemsuschem 2:1057–1057. https://doi.org/10.1002/cssc.201090010
Shu Q, Gao J, Nawaz Z, Liao Y, Wang D, Wang J (2010) Synthesis of biodiesel from waste vegetable oil with large amounts of free fatty acids using a carbon-based solid acid catalyst. Appl Energy 87:2589–2596. https://doi.org/10.1016/j.apenergy.2010.03.024
Su F, Poh CK, Chen JS, Xu G, Wang D, Li Q, Lin J, Lou XW (2011) Nitrogen-containing microporous carbon nanospheres with improved capacitive properties. Energy Environ Sci 4:717–724. https://doi.org/10.1039/c0ee00277a
Suganuma S, Nakajima K, Kitano M, Yamaguchi D, Kato H, Hayashi S, Hara M (2010) Synthesis and acid catalysis of cellulose-derived carbon-based solid acid. Solid State Sci 12:1029–1034. https://doi.org/10.1016/j.solidstatesciences.2010.02.03
Tang LR, Huang B, Wen O, Chen XR, Chen YD (2011) Manufacture of cellulose nanocrystals by cation exchange resin-catalyzed hydrolysis of cellulose. Bioresour Technol 102:10973–10977. https://doi.org/10.1016/j.biortech.2011.09.070
Thoi VS, Usiskin RE, Haile SM (2015) Platinum-decorated carbon nanotubes for hydrogen oxidation and proton reduction in solid acid electrochemical cells. Chem Sci 6:1570–1577. https://doi.org/10.1039/c4sc03003f
Toda M, Takagaki A, Okamura M, Kondo JN, Hayashi S, Domen K, Hara M (2005) Biodiesel made with sugar catalyst. Nature 438:178–178. https://doi.org/10.1038/438178a
Wada M, Chanzy H, Nishiyama Y, Langan P (2004) Cellulose IIII crystal structure and hydrogen bonding by synchrotron X-ray and neutron fiber diffraction. Macromolecules 37:8548–8555. https://doi.org/10.1021/ma0485585
Wilson K, Lee A, Macquarrie DJ, Clark JH (2002) Structure and reactivity of sol–gel sulphonic acid silicas. Appl Catal A 228:127–133. https://doi.org/10.1016/S0926-860X(01)00956-5
Xu Y, Li X, Zhang X, Wang W, Liu S, Qi W, Zhuang X, Luo Y, Yuan Z (2016) Hydrolysis of corncob using a modified carbon-based solid acid catalyst. BioResources 11:10469–10482. https://doi.org/10.15376/biores.11.4.10469-10482
Yu X, Peng L, Gao X, He L, Chen K (2018) One-step fabrication of carbonaceous solid acid derived from lignosulfonate for the synthesis of biobased furan derivatives. RSC Adv 8:15762–15772. https://doi.org/10.1039/C8RA02056F
Zhang X, Tan X, Xu Y, Wang W, Ma L, Qi W (2016) Preparation of core–shell structure magnetic carbon-based solid acid and its catalytic performance on hemicellulose in corncobs. Bio Resources 11:10014–10029. https://doi.org/10.15376/biores.11.4.10014-10029
Zhao K, Liu S, Li K, Hu Z, Yuan Y, Yan L, Guo H (2017) Fabrication of SO3H functionalized aromatic carbon microspheres directly from waste Camellia oleifera shells and their application on heterogeneous acid catalysis. Mol Catal 433:193–201. https://doi.org/10.1016/j.mcat.2017.02.032
Zheng F, Song L, Basit A, Liu J, Miao T, Wen J, Cao Y, Jiang W (2020) An endoxylanase rapidly hydrolyzes xylan into major product xylobiose via transglycosylation of xylose to xylotriose or xylotetraose. Carbohyd Polym 237:116–121. https://doi.org/10.1016/j.carbpol.2020.116121
Funding
This work was funded by National Natural Science Foundation of China (Nos. 21908014), Liaoning Education Department Project (No. J2020038), Liaoning University Innovation Talent Program in 2020, Liaoning province central government guides local science and technology development special project (No. 2022JH6/100100046) and the Foundation of Guangxi Key Laboratory of Clean Pulp & Papermaking and Pollution Control, College of Light Industry and Food Engineering, Guangxi University (No. 2021KF01)
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ZQ: writing—original draft and writing—review and editing. YH: project administration and supervision. ZM: formal analysis and revised the manuscript. QW: data curation and supervision. XW: Conceptualization. YL: resources. GS: formal analysis.
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Qu, Z., Han, Y., Ma, Z. et al. Controlling cellulose feedstock size allows for modification of cellulose-based carbon-based solid acid size. Cellulose 30, 2323–2335 (2023). https://doi.org/10.1007/s10570-022-05028-0
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DOI: https://doi.org/10.1007/s10570-022-05028-0