Abstract
The one-pot hydrolytic hydrogenation of carbohydrates to sugar alcohols is one of the important value-added transformations of biomass, but the hydrolysis efficiency of carbohydrates in this one-pot conversion is still limited by the high cleavage energy of their β-1,4-glycosidic bonds and the concomitant serious side-reactions. Therefore, it is necessary to develop the new acidic carriers to improve the key first-step hydrolysis. This paper discloses that a forestry processing waste bamboo powder can be converted into the P and Si-containing porous biochar (PSBC) via inserting silica sol, impregnating concentrated phosphoric acid (H3PO4) and heating carbonization. Due to the improved porosity and strong acidity of PSBC and its affinity to β-1,4-glycosidic bonds, this new acid carrier exhibits an outstanding catalysis performance for the hydrolysis of cellulose, cellobiose, especially sucrose and inulin, affording ca. 76.2% glucose yield in cellulose hydrolysis at 150 °C. More importantly, PSBC can efficiently and uniformly load Ru nanometer particles (average size of 1.5 nm) to fabricate 1%Ru/PSBC as an excellent bifunctional catalyst for the one-pot conversion of these carbohydrates to hexitols, affording ca. 85.2% hexitols with 51.7 h−1 turnover frequency in the one-pot conversion of cellulose under 150 °C and 3 MPa H2 pressure. This work not only provides an effective strategy for the preparation of biomass-derived bifunctional catalysts, but also it opens up new voyages for the development of efficient bio-refining.
Graphical abstract
Ru-loaded P and Si-containing porous biochar (1% Ru/PSBC) is an excellent bifunctional catalyst for the hydrolytic hydrogenation of carbohydrates under relatively mild conditions, affording ca. 85.2% hexitols with 51.7 h−1 TOF in the one-pot conversion of cellulose.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Adsuar-García M, Flores-Lasluisa JX (2018) Carbon-black-supported Ru catalysts for the valorization of cellulose through hydrolytic hydrogenation. Catalysts 8:572–586. https://doi.org/10.3390/catal8120572
Alonso DM, Gallo JMR, Mellmer MA, Wettstein SG, Dumesic JA (2013) Direct conversion of cellulose to levulinic acid and gamma-valerolactone using solid acid catalysts. Catal Sci Technol 3:927–931. https://doi.org/10.1039/C2CY20689G
Azar FZ (2020) Mesoporous activated carbon supported Ru catalysts to efficiently convert cellulose into sorbitol by hydrolytic hydrogenation. Energies 13:4394. https://doi.org/10.3390/en13174394
Bedia J, Barrionuevo R, Rodríguez-Mirasol J, Cordero T (2011) Ethanol dehydration to ethylene on acid carbon catalysts. Appl Catal B-Environ 103:302–310. https://doi.org/10.1016/j.apcatb.2011.01.032
Bedia J, Rosas JM, Márquez J, Rodríguez-Mirasol J, Cordero T (2009) Preparation and characterization of carbon based acid catalysts for the dehydration of 2-propanol. Carbon 47:286–294. https://doi.org/10.1016/j.carbon.2008.10.008
Bourbigot S, Le Bras M, Delobel R, Bréant P, Trémillon JM (1995) Carbonization mechanisms resulting from intumescence-part II. Association with an ethylene terpolymer and the ammonium polyphosphate-pentaerythritol fire retardant system. Carbon 33:283–294. https://doi.org/10.1016/0008-6223(94)00131-I
Broekhoff JCP, De Boer JH (1968) Studies on pore systems in catalysts: XI. pore distribution calculations from the adsorption branch of a nitrogen adsorption isotherm in the case of “ink-bottle” type pores. J Catal 10:153–165. https://doi.org/10.1016/0021-9517(68)90168-1
Cao L, Yu IKM, Tsang DCW, Zhang S, Ok YS, Kwon EE, Song H, Poon CS (2018) Phosphoric acid-activated wood biochar for catalytic conversion of starch-rich food waste into glucose and 5-hydroxymethylfurfural. Bioresour Technol 267:242–248. https://doi.org/10.1016/j.biortech.2018.07.048
Chen Z, Huang T, Feng Y, Hu W, Fu Z (2019) Richer and stable interlayer porous bamboo carbon sulfonic acids constructed by silica intercalation as cheap and robust acid catalysts. Bull Chem Soc Jpn 92:1824–1833. https://doi.org/10.1246/bcsj.20190185
Dai Y, Shao C, Piao Y, Hu H, Lu K, Zhang T, Zhang X, Jia S, Wang M, Man S (2017) The mechanism for cleavage of three typical glucosidic bonds induced by hydroxyl free radical. Carbohydr Polym 178:34–40. https://doi.org/10.1016/j.carbpol.2017.09.016
Ding LN, Wang AQ, Zheng MY, Tao Z (2010) Selective Transformation of Cellulose into Sorbitol by Using a Bifunctional Nickel Phosphide Catalyst. Chemsuschem 3:818–821. https://doi.org/10.1002/cssc.201000092
Feng B, Chen C, Yang H, Zhao X, Hua L, Yu Y, Cao T, Shi Y, Hou Z (2012) Ionic liquid-promoted oxidant-free dehydrogenation of alcohols with water-soluble ruthenium nanoparticles in aqueous phase. Adv Synth Catal 354:1559–1565. https://doi.org/10.1002/adsc.201100908
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 Cat 107:203–213. https://doi.org/10.1007/s11144-012-0466-9
Fujiwara M, Kieffer R, Ando H, Souma Y (1995) Development of composite catalysts made of Cu-Zn-Cr oxide/zeolite for the hydrogenation of carbon dioxide. Appl Catal A Gen 121:113–124. https://doi.org/10.1016/0926-860X(95)85014-7
Fukuoka A, Dhepe PL (2006) Catalytic conversion of cellulose into sugar alcohols. Angew Che Int Ed Engl 45:5161–5163. https://doi.org/10.1002/ange.200601921
García-Mateos FJ, Berenguer R, Valero-Romero MJ, Rodríguez-Mirasol J, Cordero T (2018) Phosphorus functionalization for the rapid preparation of highly nanoporous submicron-diameter carbon fibers by electrospinning of lignin solutions. J Mater Chem A 6:1219–1233. https://doi.org/10.1039/C7TA08788H
Geboers J, Van de Vyver S, Carpentier K, de Blochouse K, Jacobs P, Sels B (2010) Efficient catalytic conversion of concentrated cellulose feeds to hexitols with heteropoly acids and Ru on carbon. Chem Commun 46:3577–3579. https://doi.org/10.1039/C001096K
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
George WH (2004) Renewable alkanes by aqueous-phase reforming of biomass-derived oxygenates. Angew Chem 12:1575–1577. https://doi.org/10.1002/ange.200353050
Han JW, Lee H (2012) Direct conversion of cellulose into sorbitol using dual-functionalized catalysts in neutral aqueous solution. Catal Commun 19:115–118. https://doi.org/10.1016/j.catcom.2011.12.032
Huber GW, Corma A (2010) Synergies between bio- and oil refineries for the production of fuels from biomass. Angew Chem 46:7184–7201. https://doi.org/10.1002/anie.200604504
Hubin R (1967) Spectre d’absorption infra-rouge des pyrophosphates et pyroarséniates cubiques d’éléments tétravalents XIVP2O7 et XIVAs2O7. Spectrochim Acta A 23:1815–1829. https://doi.org/10.1016/0584-8539(67)80064-3
Jarvis M (2003) Cellulose stacks up. Nature 426:611–612. https://doi.org/10.1038/426611a
Kobayashi H, Hosaka Y, Hara K, Feng B, Hirosaki Y, Fukuoka A (2014) Control of selectivity, activity and durability of simple supported nickel catalysts for hydrolytic hydrogenation of cellulose. Green Chem 16:637–644. https://doi.org/10.1039/C3GC41357H
Kobayashi H, Ito Y, Komanoya T, Hosaka Y, Dhepe PL, Kasai K, Hara K, Fukuoka A (2011) Synthesis of sugar alcohols by hydrolytic hydrogenation of cellulose over supported metal catalysts. Green Chem 13:326–333. https://doi.org/10.1039/C0GC00666A
Komanoya T, Kobayashi H, Hara K, Chun WJ, Fukuoka A (2014) Kinetic study of catalytic conversion of cellulose to sugar alcohols under low-pressure hydrogen. Chem Cat Chem 6:230–236. https://doi.org/10.1002/cctc.201300731
Kusserow B, Schimpf S, Claus P (2003) Hydrogenation of glucose to sorbitol over nickel and ruthenium catalysts. Adv Synth Catal 345:289–299. https://doi.org/10.1002/adsc.200390024
Li B, Zhou L, Wu D, Peng H, Yan K, Zhou Y, Liu Z (2011) Photochemical chlorination of graphene. ACS Nano 5:5957–5961. https://doi.org/10.1021/nn201731t
Li Z, Liu Y, Liu C, Wu S, Wei W (2019) Direct conversion of cellulose into sorbitol catalyzed by a bifunctional catalyst. Bioresour Technol 274:190–197. https://doi.org/10.1016/j.biortech.2018.11.089
Liang G, Cheng H, Li W, He L, Yu Y, Zhao F (2012) Selective conversion of microcrystalline cellulose into hexitols on nickel particles encapsulated within ZSM-5 zeolite. Green Chem 14:2146–2149. https://doi.org/10.1039/C2GC35685F
Liao Y, Liu Q, Wang T, Long J, Ma L, Zhang Q (2014) Zirconium phosphate combined with Ru/C as a highly efficient catalyst for the direct transformation of cellulose to C6 alditols. Green Chem 16:3305–3312. https://doi.org/10.1039/C3GC42444H
Liu M, Deng W, Zhang Q, Wang Y, Wang Y (2011) Polyoxometalate-supported ruthenium nanoparticles as bifunctional heterogeneous catalysts for the conversions of cellobiose and cellulose into sorbitol under mild conditions. Chem Commun 47:9717–9719. https://doi.org/10.1039/C1CC12506K
Luo C, Wang S, Liu H (2010) Cellulose conversion into polyols catalyzed by reversibly formed acids and supported ruthenium clusters in hot water. Angew Chem 119:7780–7783. https://doi.org/10.1002/ange.200702661
Mao F, Chen S, Zhang Q, Yang L, Wan F, Jiang D, Xiong M, Zhang C, Liu Y, Fu Z (2020) Ru/P-containing porous biochar-efficiently catalyzed cascade conversion of cellulose to sorbitol in water under medium-pressure H2 atmosphere. Bull Chem Soc Jpn 93:1026–1035. https://doi.org/10.1246/bcsj.20200095
Mi L, Deng W, Zhang Q, Wang Y, Ye W (2011) Polyoxometalate-supported ruthenium nanoparticles as bifunctional heterogeneous catalysts for the conversions of cellobiose and cellulose into sorbitol under mild conditions. Chem Commun 47:9717–9719. https://doi.org/10.1039/C1CC12506K
Mok WS, Antal MJ, Varhegyi G (1992) Productive and parasitic pathways in dilute acid-catalyzed hydrolysis of cellulose. Ind Eng Chem Res 31:94–100. https://doi.org/10.1021/ie00001a014
Negoi A, Triantafyllidis K, Parvulescu VI, Coman SM (2014) The hydrolytic hydrogenation of cellulose to sorbitol over M (Ru, Ir, Pd, Rh)-BEA-zeolite catalysts. Cataly Today 223:122–128. https://doi.org/10.1016/j.cattod.2013.07.007
Okamura M, Takagaki A, Toda M, Kondo JN, Domen K, Tatsumi T, Hara M, Hayashi S (2006) Acid-catalyzed reactions on flexible polycyclic aromatic carbon in amorphous carbon. Chem Mater 18:3039–3045. https://doi.org/10.1021/cm0605623
Palkovits R, Tajvidi K, Procelewska J, Rinaldi R, Ruppert A (2010) Hydrogenolysis of cellulose combining mineral acids and hydrogenation catalysts. Green Chem 12:972–978. https://doi.org/10.1039/C000075B
Palomo J, Ternero-Hidalgo JJ, Rosas JM, Rodríguez-Mirasol J, Cordero T (2017) Selective nitrogen functionalization of phosphorus-containing activated carbons. Fuel Process Technol 156:438–445. https://doi.org/10.1016/j.fuproc.2016.10.006
Pang J, Wang A, Zheng M, Zhang Y, Huang Y, Chen X, Zhang T (2012) Catalytic conversion of cellulose to hexitols with mesoporous carbon supported Ni-based bimetallic catalysts. Green Chem 14:614–617. https://doi.org/10.1039/C2GC16364K
Patnukao P, Pavasant P (2008) Activated carbon from Eucalyptus camaldulensis Dehn bark using phosphoric acid activation. Bioresou Technol 99:8540–8543. https://doi.org/10.1016/S0008-6223(97)00149-8
Puziy AM, Poddubnaya OI (1998) The properties of synthetic carbon derived from nitrogen- and phosphorus-containing polymer. Carbon 36:45–50. https://doi.org/10.1016/S0008-6223(97)00149-8
Puziy AM, Poddubnaya OI, Kochkin YN, Vlasenko NV, Tsyba MM (2010) Acid properties of phosphoric acid activated carbons and their catalytic behavior in ethyl-tert-butyl ether synthesis. Carbon 48:706–713. https://doi.org/10.1016/j.carbon.2009.10.015
Puziy AM, Poddubnaya OI, Martínez-Alonso A, Suárez-García F, Tascón JMD (2005) Surface chemistry of phosphorus-containing carbons of lignocellulosic origin. Carbon 43:2857–2868. https://doi.org/10.1016/j.carbon.2005.06.014
Puziy AM, Poddubnaya OI, Martı́nez-Alonso A, Suárez-Garcı́a F, Tascón JMD, (2002) Synthetic carbons activated with phosphoric acid: I. surface chemistry and ion binding properties. Carbon 40:1493–1505. https://doi.org/10.1016/S0008-6223(01)00317-7
Rey-Raap N, Ribeiro LS, Órfão JJdM, Figueiredo JL, Pereira MFR (2019) Catalytic conversion of cellulose to sorbitol over Ru supported on biomass-derived carbon-based materials. Appl Catal B-Environ 256:117826. https://doi.org/10.1016/j.apcatb.2019.117826
Ribeiro LS, Delgado JJ, de Melo Órfão JJ, Pereira MFR (2017a) Direct conversion of cellulose to sorbitol over ruthenium catalysts: influence of the support. Cataly Today 279:244–251. https://doi.org/10.1016/j.cattod.2016.05.028
Ribeiro LS, Delgado JJ, Órfão JJM, Pereira MFR (2017b) Carbon supported Ru-Ni bimetallic catalysts for the enhanced one-pot conversion of cellulose to sorbitol. Appl Catal B-Environ 217:265–274. https://doi.org/10.1016/j.apcatb.2017.04.078
S. Ribeiro L, Órfão JJM, R Pereira MF, (2015) Enhanced direct production of sorbitol by cellulose ball-milling. Green Chem 17:2973–2980. https://doi.org/10.1039/C5GC00039D
Sánchez JA, Hernández DL, Moreno JA, Mondragón F, Fernández JJ (2011) Alternative carbon based acid catalyst for selective esterification of glycerol to acetylglycerols. Appl Catal A Gen 405:55–60. https://doi.org/10.1016/j.apcata.2011.07.027
Suganuma S, Nakajima K, Kitano M, Kato H, Tamura A, Kondo H, Yanagawa S, Hayashi S, Hara M (2011) SO3H-bearing mesoporous carbon with highly selective catalysis. Micr Mesopor Mat 143:443–450. https://doi.org/10.1016/j.micromeso.2011.03.028
Suganuma S, Nakajima K, Kitano M, Yamaguchi D, Kato H, Hayashi S, Hara M (2008) Hydrolysis of cellulose by amorphous carbon bearing SO3H, COOH, and OH groups. J A Chem Soc 130:12787–12793. https://doi.org/10.1021/ja803983h
Valero-Romero MJ, García-Mateos F, Rodríguez-Mirasol J, Cordero T (2017) Role of surface phosphorus complexes on the oxidation of porous carbons. Fuel Process Technol 157:116–126. https://doi.org/10.1016/j.fuproc.2016.11.014
Van de Vyver S, Geboers J, Schutyser W, Dusselier M, Eloy P, Dornez E, Seo JW, Courtin CM, Gaigneaux EM, Jacobs PA et al (2012) Tuning the acid/metal balance of carbon nanofiber-supported nickel catalysts for hydrolytic hydrogenation of cellulose. Chemsuschem 5:1549–1558. https://doi.org/10.1002/cssc.201100782
Deng WP, Tan XS, Fang WH, Zhang QH, Wang Y (2009) Conversion of cellulose into sorbitol over carbon nanotube-supported ruthenium catalyst. Catal Lett 133:167–174. https://doi.org/10.1007/s10562-009-0136-3
Wen L (1994) Active phase of solid phosphoric acid catalyst. Chem J Chin Univ 3:428–430
Wu X, Radovic LR (2006) Inhibition of catalytic oxidation of carbon/carbon composites by phosphorus. Carbon 44:141–151. https://doi.org/10.1016/j.carbon.2005.06.038
Wu Y, Fu Z, YinD XuQ, Liu F, Lu C, Mao L (2010) Microwave-assisted hydrolysis of crystalline cellulose catalyzed by biomass char sulfonic acids. Green Chem 12:696–700. https://doi.org/10.1039/B917807D
Xi J, Zhang Y, Xia Q, Liu X, Ren J, Lu G, Wang Y (2013) Direct conversion of cellulose into sorbitol with high yield by a novel mesoporous niobium phosphate supported ruthenium bifunctional catalyst. Appl Catal A- Gen 459:52–58. https://doi.org/10.1016/j.apcata.2013.03.047
Xie X, Han J, Wang H, Zhu X, Liu X, Niu Y, Song Z, Ge Q (2014) Selective conversion of microcrystalline cellulose into hexitols over a Ru/[Bmim]3PW12O40 catalyst under mild conditions. Cataly Today 233:70–76. https://doi.org/10.1016/j.cattod.2013.09.061
Yang E, Yao C, Liu Y, Zhang C, Jia L, Li D, Fu Z, Sun D, Robert Kirk S, Yin D (2018) Bamboo-derived porous biochar for efficient adsorption removal of dibenzothiophene from model fuel. Fuel 211:121–129. https://doi.org/10.1016/j.fuel.2017.07.099
Yang P, Kobayashi H, Hara K, Fukuoka A (2012) Phase change of nickel phosphide catalysts in the conversion of cellulose into sorbitol. Chemsuschem 5:920–926. https://doi.org/10.1002/cssc.201100498
Zhang C, Fu Z, Liu Y, Dai B, Zou G (2012a) Ionic liquid-functionalized biochar sulfonic acid as a biomimetic catalyst for hydrolysis of cellulose and bamboo under microwave irradiation. Green Chem 14:1928–1934. https://doi.org/10.1039/C3GC41917G
Zhang J, Wu S, Li B, Zhang H (2012b) Direct conversion of cellobiose into sorbitol and catalyst deactivation mechanism. Catal Commun 29:180–184. https://doi.org/10.1016/j.catcom.2012.10.016
Zhang YH, Lynd LR (2004) Toward an aggregated understanding of enzymatic hydrolysis of cellulose: noncomplexed cellulase systems. Biotechnol Bioeng 88:797–824. https://doi.org/10.1002/bit.20282
Zhao S (1981) Structure and catalytic activity of solid phosphoric acid catalysts. Petrol Chem Ind 10:414–421
Zhu W, Yang H, Chen J, Chen C, Guo L, Gan H, Zhao X, Hou Z (2014) Efficient hydrogenolysis of cellulose into sorbitol catalyzed by a bifunctional catalyst. Green Chem 16:1534–1542. https://doi.org/10.1039/C3GC41917G
Acknowledgments
We acknowledge the financial support for this work by the National Natural Science Fund of China (21676079, 21546010, 22008062), the Natural Science Fund of Hunan Province (2018JJ3335, 14JJ2148, 11JJ6008, 10JJ2007), Hunan 2011 Collaborative Innovation Center of Chemical Engineering & Technology with Environmental Benignity and Effective Resource Utilization.
Funding
The authors have not disclosed any funding.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of interests
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
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
Chen, S., Mao, F., Tang, S. et al. One-pot hydrolytic hydrogenation of carbohydrates to hexitols catalyzed by Ru loaded P and Si-containing hierarchical porous biochars with excellent catalytic efficiency. Cellulose 29, 6039–6056 (2022). https://doi.org/10.1007/s10570-022-04650-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-022-04650-2