Abstract
Background: Cellulose structures are in stable crystalline form. The hydrolysis of cellulose to small reducing sugars is difficult, but essential for its utilization.
Objective: To investigate the effect of graphene oxide (GO) loading on the catalytic performance of phosphotungstic acid (HPW) for the catalyzed hydrolysis of cellulose, with the purpose to get high yield of total reducing sugar (TRS).
Methods: Graphene oxide/phosphotungstic acid (GO/HPW) composites were prepared using a liquid-phase composite method. The materials were applied to catalyze hydrolysis of microcrystalline cellulose in 1-butyl-3-methylimidazole chloride ionic liquid ([Bmim]Cl). The samples were characterized by powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), field emission scanning electron micrographs (FE-SEM), pyridine IR and acid-base chemical titration.
Results: The Brønsted acidic sites were the main source of acidity in the composites and its concentration was determined to be 0.96 mmol/g. With the use of the GO/HPW composite as catalysts for cellulose hydrolysis, high TRS yield of 90.5% was obtained.
Conclusion: GO/HPW composites retained the functional groups of both materials. It was the Brønsted acidic sites in the materials that effectively promoted the cellulose hydrolysis reaction. The structures of GO/HPW with the agglomeration of HPW scattered on GO had high accessibility of acidic sites and fast mass transfer of the reducing sugars to the outside of the catalysts in time to prevent their further conversion into by-products. TRS yield of 90.5% was obtained from the hydrolysis of cellulose catalyzed by the GO/HPW (1:1.5) composites at 115°C for 4 h using catalysts to cellulose 1:1 ratio.
Graphical Abstract
[1]
Goyal HB, Seal D, Saxena RC. Bio-fuels from thermochemical conversion of renewable resources: A review. Renew Sustain Energy Rev 2008; 12(2): 504-17.
[http://dx.doi.org/10.1016/j.rser.2006.07.014]
[http://dx.doi.org/10.1016/j.rser.2006.07.014]
[2]
Serrano DP, Melero JA, Morales G, Iglesias J, Pizarro P. Progress in the design of zeolite catalysts for biomass conversion into biofuels and bio-based chemicals. Catal Rev, Sci Eng 2018; 60(1): 1-70.
[http://dx.doi.org/10.1080/01614940.2017.1389109]
[http://dx.doi.org/10.1080/01614940.2017.1389109]
[3]
Kabir G, Hameed BH. Recent progress on catalytic pyrolysis of lignocellulosic biomass to high-grade bio-oil and bio-chemicals. Renew Sustain Energy Rev 2017; 70: 945-67.
[http://dx.doi.org/10.1016/j.rser.2016.12.001]
[http://dx.doi.org/10.1016/j.rser.2016.12.001]
[4]
De Bhowmick G, Sarmah AK, Sen R. Lignocellulosic biorefinery as a model for sustainable development of biofuels and value added products. Bioresour Technol 2018; 247: 1144-54.
[http://dx.doi.org/10.1016/j.biortech.2017.09.163] [PMID: 28993055]
[http://dx.doi.org/10.1016/j.biortech.2017.09.163] [PMID: 28993055]
[5]
Almeida EL, Andrade CMG, Andreo dos Santos O. Production of biodiesel via catalytic processes: A brief review. Int J Chem React Eng 2018; 16(5): 20170130.
[http://dx.doi.org/10.1515/ijcre-2017-0130]
[http://dx.doi.org/10.1515/ijcre-2017-0130]
[6]
Mika LT, Cséfalvay E, Németh Á. Catalytic conversion of carbohydrates to initial platform chemicals: Chemistry and sustainability. Chem Rev 2018; 118(2): 505-613.
[http://dx.doi.org/10.1021/acs.chemrev.7b00395] [PMID: 29155579]
[http://dx.doi.org/10.1021/acs.chemrev.7b00395] [PMID: 29155579]
[7]
Heinze T. Cellulose: structure and properties Cellulose chemistry and properties: Fibers, nanocelluloses and advanced materials. Springer 2016; pp. 1-52.
[8]
Shrotri A, Kobayashi H, Fukuoka A. Cellulose depolymerization over heterogeneous catalysts. Acc Chem Res 2018; 51(3): 761-8.
[http://dx.doi.org/10.1021/acs.accounts.7b00614] [PMID: 29443505]
[http://dx.doi.org/10.1021/acs.accounts.7b00614] [PMID: 29443505]
[9]
Huang YB, Fu Y. Hydrolysis of cellulose to glucose by solid acid catalysts. Green Chem 2013; 15(5): 1095-111.
[http://dx.doi.org/10.1039/c3gc40136g]
[http://dx.doi.org/10.1039/c3gc40136g]
[10]
Guo F, Shi W, Sun W, et al. Differences in the adsorption of enzymes onto lignins from diverse types of lignocellulosic biomass and the underlying mechanism. Biotechnol Biofuels 2014; 7(1): 38.
[http://dx.doi.org/10.1186/1754-6834-7-38] [PMID: 24624960]
[http://dx.doi.org/10.1186/1754-6834-7-38] [PMID: 24624960]
[11]
Jørgensen H, Pinelo M. Enzyme recycling in lignocellulosic biorefineries. Biofuels Bioprod Biorefin 2017; 11(1): 150-67.
[http://dx.doi.org/10.1002/bbb.1724]
[http://dx.doi.org/10.1002/bbb.1724]
[12]
Yuan Y, Zhai R, Li Y, Chen X, Jin M. Developing fast enzyme recycling strategy through elucidating enzyme adsorption kinetics on alkali and acid pretreated corn stover. Biotechnol Biofuels 2018; 11: 1-12.
[13]
Yin J, Hao L, Yu W, et al. Enzymatic hydrolysis enhancement of corn lignocellulose by supercritical CO2 combined with ultrasound pretreatment. Chin J Catal 2014; 35(5): 763-9.
[http://dx.doi.org/10.1016/S1872-2067(14)60040-1]
[http://dx.doi.org/10.1016/S1872-2067(14)60040-1]
[14]
Cocero MJ, Cabeza Á, Abad N, et al. Understanding biomass fractionation in subcritical & supercritical water. J Supercrit Fluids 2018; 133: 550-65.
[http://dx.doi.org/10.1016/j.supflu.2017.08.012]
[http://dx.doi.org/10.1016/j.supflu.2017.08.012]
[15]
Martínez CM, Adamovic T, Cantero DA, Cocero MJ. Scaling up the production of sugars from agricultural biomass by ultrafast hydrolysis in supercritical water. J Supercrit Fluids 2019; 143: 242-50.
[http://dx.doi.org/10.1016/j.supflu.2018.08.017]
[http://dx.doi.org/10.1016/j.supflu.2018.08.017]
[16]
Sun B, Peng G, Duan L, Xu A, Li X. Pretreatment by NaOH swelling and then HCl regeneration to enhance the acid hydrolysis of cellulose to glucose. Bioresour Technol 2015; 196: 454-8.
[http://dx.doi.org/10.1016/j.biortech.2015.08.009] [PMID: 26280097]
[http://dx.doi.org/10.1016/j.biortech.2015.08.009] [PMID: 26280097]
[17]
Suzuki S, Takeoka Y, Rikukawa M, Yoshizawa-Fujita M. Brønsted acidic ionic liquids for cellulose hydrolysis in an aqueous medium: Structural effects on acidity and glucose yield. RSC Advances 2018; 8(26): 14623-32.
[http://dx.doi.org/10.1039/C8RA01950A] [PMID: 35540788]
[http://dx.doi.org/10.1039/C8RA01950A] [PMID: 35540788]
[18]
Liu F, Huang K, Zheng A, Xiao FS, Dai S. Hydrophobic solid acids and their catalytic applications in green and sustainable chemistry. ACS Catal 2018; 8(1): 372-91.
[http://dx.doi.org/10.1021/acscatal.7b03369]
[http://dx.doi.org/10.1021/acscatal.7b03369]
[19]
Zhong R, Sels BF. Sulfonated mesoporous carbon and silica-carbon nanocomposites for biomass conversion. Appl Catal B 2018; 236: 518-45.
[http://dx.doi.org/10.1016/j.apcatb.2018.05.012]
[http://dx.doi.org/10.1016/j.apcatb.2018.05.012]
[20]
Swatloski RP, Spear SK, Holbrey JD, Rogers RD. Dissolution of cellose with ionic liquids. J Am Chem Soc 2002; 124(18): 4974-5.
[http://dx.doi.org/10.1021/ja025790m] [PMID: 11982358]
[http://dx.doi.org/10.1021/ja025790m] [PMID: 11982358]
[21]
Gromov NV, Medvedeva TB, Taran OP, et al. Hydrothermal solubilization–hydrolysis–dehydration of cellulose to glucose and 5-hydroxymethylfurfural over solid acid carbon catalysts. Top Catal 2018; 61(18-19): 1912-27.
[http://dx.doi.org/10.1007/s11244-018-1049-4]
[http://dx.doi.org/10.1007/s11244-018-1049-4]
[22]
Li OL, Ikura R, Ishizaki T. Hydrolysis of cellulose to glucose over carbon catalysts sulfonated via a plasma process in dilute acids. Green Chem 2017; 19(20): 4774-7.
[http://dx.doi.org/10.1039/C7GC02143G]
[http://dx.doi.org/10.1039/C7GC02143G]
[23]
Tondro H, Zilouei H, Zargoosh K, Bazarganipour M. Nettle leaves-based sulfonated graphene oxide for efficient hydrolysis of microcrystalline cellulose. Fuel 2021; 284: 118975.
[http://dx.doi.org/10.1016/j.fuel.2020.118975]
[http://dx.doi.org/10.1016/j.fuel.2020.118975]
[24]
Huang L, Ye H, Wang S, et al. Enhanced hydrolysis of cellulose by highly dispersed sulfonated graphene oxide. BioResources 2018; 13(4): 8853-70.
[http://dx.doi.org/10.15376/biores.13.4.8853-8870]
[http://dx.doi.org/10.15376/biores.13.4.8853-8870]
[25]
Guo F, Fang Z, Xu CC, Smith RL Jr. Solid acid mediated hydrolysis of biomass for producing biofuels. Pror Energy Combust Sci 2012; 38(5): 672-90.
[http://dx.doi.org/10.1016/j.pecs.2012.04.001]
[http://dx.doi.org/10.1016/j.pecs.2012.04.001]
[26]
Shimizu K, Furukawa H, Kobayashi N, Itaya Y, Satsuma A. Effects of Brønsted and Lewis acidities on activity and selectivity of heteropolyacid-based catalysts for hydrolysis of cellobiose and cellulose. Green Chem 2009; 11(10): 1627-32.
[http://dx.doi.org/10.1039/b913737h]
[http://dx.doi.org/10.1039/b913737h]
[27]
Nakamura M, Islam MS, Rahman MA, et al. Microwave aided conversion of cellulose to glucose using polyoxometalate as catalyst. RSC Advances 2021; 11(55): 34558-63.
[http://dx.doi.org/10.1039/D1RA04426E] [PMID: 35494741]
[http://dx.doi.org/10.1039/D1RA04426E] [PMID: 35494741]
[28]
Miller GL. Use of dinitrosalicylic acid reagent for determination of reducing sugar. Anal Chem 1959; 31(3): 426-8.
[http://dx.doi.org/10.1021/ac60147a030]
[http://dx.doi.org/10.1021/ac60147a030]
[29]
Cao CF, Yu B, Guo BF, et al. Bio-inspired, sustainable and mechanically robust graphene oxide-based hybrid networks for efficient fire protection and warning. Chem Eng J 2022; 439: 134516.
[http://dx.doi.org/10.1016/j.cej.2022.134516]
[http://dx.doi.org/10.1016/j.cej.2022.134516]
[30]
Yang ZJ, Nana Na, Zhang . Syntheis of wells-dawson-typed tungstophosphoric heteropolyacid and its application in the baeyer-villiger oxidation. Chemistry 2014; 77(6): 521-6.
[31]
Sudesh Kumar N, Das S, Bernhard C, Varma GD. Effect of graphene oxide doping on superconducting properties of bulk MgB2. Supercond Sci Technol 2013; 26(9): 095008.
[http://dx.doi.org/10.1088/0953-2048/26/9/095008]
[http://dx.doi.org/10.1088/0953-2048/26/9/095008]
[32]
He D, Peng Z, Gong W, Luo Y, Zhao P, Kong L. Mechanism of a green graphene oxide reduction with reusable potassium carbonate. RSC Advances 2015; 5(16): 11966-72.
[http://dx.doi.org/10.1039/C4RA14511A]
[http://dx.doi.org/10.1039/C4RA14511A]
[33]
Wang Z, Huang B, Dai Y, et al. Crystal facets controlled synthesis of graphene@TiO2 nanocomposites by a one-pot hydrothermal process. CrystEngComm 2012; 14(5): 1687-92.
[http://dx.doi.org/10.1039/C1CE06193C]
[http://dx.doi.org/10.1039/C1CE06193C]
[34]
Ramya AV, Manoj B, Mohan AN. Extraction and characterization of wrinkled graphene nanolayers from commercial graphite. Asian J Chem 2016; 28(5): 1031-4.
[http://dx.doi.org/10.14233/ajchem.2016.19577]
[http://dx.doi.org/10.14233/ajchem.2016.19577]
[35]
Poźniczek J, Micek-Ilnicka A, Lubańska A, Bielański A. Catalytic synthesis of ethyl-tert-butyl ether on Dawson type heteropolyacid. Appl Catal A Gen 2005; 286(1): 52-60.
[http://dx.doi.org/10.1016/j.apcata.2005.02.035]
[http://dx.doi.org/10.1016/j.apcata.2005.02.035]
[36]
Zhang X, Zhang D, Sun Z, Xue L, Wang X, Jiang Z. Highly efficient preparation of HMF from cellulose using temperature-responsive heteropolyacid catalysts in cascade reaction. Appl Catal B 2016; 196: 50-6.
[http://dx.doi.org/10.1016/j.apcatb.2016.05.019]
[http://dx.doi.org/10.1016/j.apcatb.2016.05.019]
[37]
Chen T, Xiong C, Tao Y. Enhanced hydrolysis of cellulose in ionic liquid using mesoporous ZSM-5. Molecules 2018; 23(3): 529.
[http://dx.doi.org/10.3390/molecules23030529] [PMID: 29495459]
[http://dx.doi.org/10.3390/molecules23030529] [PMID: 29495459]
