Abstract
In this paper, we have described a novel route to produce 5-hydroxymethylfurfural (HMF), a valuable platform molecule obtained from biomass. Metal-exchanged Keggin heteropolyacid salts were used as catalysts, in microwave-assisted reactions carried out in a water-ethyl acetate biphasic system. To avoid the use of homogenous Brønsted acid catalysts, which are corrosive and difficult to be reused, we have exchanged the protons of the Keggin heteropolyacids with transition metal cations. These salts were evaluated in the fructose dehydration, being the Cu3/2PW12O40 the most active and selective catalyst, achieving 81% of HMF yield, after 15 min reaction at 413 K under microwave irradiation. The effects of metal cation, anion or heteropolyanion present in the catalyst were evaluated. The greatest efficiency of the Cu3/2PW12O40 was attributed to its high Lewis acidic strength which allows its coordinates with the water molecules, consequently generating H3O+ ions in the reaction medium. In addition, after assessing reactions of fructose dehydration in the presence of other Copper salts [i.e., CuCl2 or Cu(NO3)2], we conclude the anion plays too a key role. The higher softness of phosphotungstic anion should stabilize protonate intermediates better than chloride or nitrate anions, favouring this way the reaction. Finally, although the catalyst has been soluble, it was easily reused by removing the aqueous phase and adding a new load of the substrate dissolved in ethyl acetate. The runs were successfully repeated without the loss of activity of the catalyst.
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Abdelaziz OY, Al-Rabiah AA, El-Halwagi MM, Hulteberg CP (2020) Conceptual design of a kraft lignin biorefinery for the production of valuable chemicals via oxidative depolymerization. ACS Sustain Chem Eng 8:8823–8829. https://doi.org/10.1021/acssuschemeng.0c02945
Batalha DC, Ferreira SO, da Silva RC, da Silva MJ (2020) Cesium-exchanged lacunar keggin heteropolyacid salts: efficient solid catalysts for the green oxidation of terpenic alcohols with hydrogen peroxide. ChemSelect 5:1976–1986. https://doi.org/10.1002/slct.201903437
Besson M, Gallezot P, Pinel C (2014) Conversion of biomass into chemicals over metal catalysts. Chem Rev 114:1827–1870. https://doi.org/10.1021/cr4002269
Brar SK, Dhillon GS, Soccol CR (2014) Biotransformation of waste biomass into high value biochemical. Springer, New York. https://doi.org/10.1007/978-1-4614-8005-1
Cao Q, Guo X, Yao S, Guan J, Wang X, Mu X, Zhang D (2011) Conversion of hexose into 5-hydroxymethylfurfural in imidazolium ionic liquids with and without a catalyst. Carbohydr Res 346:956–959. https://doi.org/10.1016/j.carres.2011.03.015
Castro GAD, Fernandes SA (2021) Microwave-assisted green synthesis of levulinate esters as biofuel precursors using calix[4]arene as an organocatalyst under solvent-free conditions. Sustain Energy Fuels 5:108–111. https://doi.org/10.1039/d0se01257b
Chaves DM, Ferreira SO, Chagas Da Silva R, Natalino R, José Da Silva M (2019) Glycerol esterification over Sn(II)-exchanged Keggin heteropoly salt catalysts: effect of thermal treatment temperature. Energy Fuels 33:7705–7716. https://doi.org/10.1021/acs.energyfuels.9b01583
Combs-Walker LA, Hill CL (1991) Stabilization of the defect (“lacunary”) complex PMo11O397− isolation, purification, stability characteristics, and metalation chemistry. Inorg Chem 30:4016–4026. https://doi.org/10.1021/ic00021a010
Corma Canos A, Iborra S, Velty A (2007) Chemical routes for the transformation of biomass into chemicals. Chem Rev 107:2411–2502. https://doi.org/10.1021/cr050989d
Da Silva MJ, Liberto NA (2016) Soluble and solid supported Keggin heteropolyacids as catalysts in reactions for biodiesel production: challenges and recent advances. Curr Org Chem 20:1263–1283. https://doi.org/10.1002/chin.201636258
Da Silva MJ, Julio AA, Dorigetto FCS (2015) Solvent-free heteropolyacid-catalyzed glycerol ketalization at room temperature. RSC Adv 5:44499–44506. https://doi.org/10.1039/c4ra17090c
Da Silva MJ, Liberto NA, De Andrade Leles LC, Pereira UA (2016) Fe4(SiW12O40)3-catalyzed glycerol acetylation: synthesis of bioadditives by using highly active Lewis acid catalyst. J Mol Catal A Chem 422:69–83. https://doi.org/10.1016/j.molcata.2016.03.003
Da Silva MJ, Vilanculo CB, Teixeira MG, Julio AA (2017) Catalysis of vegetable oil transesterification by Sn(II)-exchanged Keggin heteropolyacids: bifunctional solid acid catalysts. React Kinet Mech Catal 122:1011–1030. https://doi.org/10.1007/s11144-017-1258-z
Da Silva MJ, Julio AA, Ferreira SO, Da Silva RC, Chaves DM (2019a) Tin(II) phosphotungstate heteropoly salt: an efficient solid catalyst to synthesize bioadditives ethers from glycerol. Fuel 254:115607–115618. https://doi.org/10.1016/j.fuel.2019.06.015
da Silva MJ, Oliveira CM (2018) Catalysis by hetropolyacid salts. Curr Catal 29:26–34. https://doi.org/10.2174/2211544707666171219161414
da Silva MJ, Rodrigues AA (2020) Metal silicotungstate salts as catalysts in furfural oxidation reactions with hydrogen peroxide. Mol Catal 493:111104–111114. https://doi.org/10.1016/j.mcat.2020.111104
da Silva MJ, da Silva Andrade PH, Ferreira SO, Vilanculo CB, Oliveira CM (2018) Monolacunary K8SiW11O39-catalyzed terpenic alcohols oxidation with hydrogen peroxide. Catal Lett 148:2516–2527. https://doi.org/10.1007/s10562-018-2434-0
da Silva MJ, de Andrade-Leles LC, Ferreira SO, da Silva RC, de Viveiros K, Chaves DM, Pinheiro PF (2019) A rare carbon skeletal oxidative rearrangement of camphene catalyzed by Al-exchanged keggin heteropolyacid salts. ChemistrySelect. 4:7665–7672. https://doi.org/10.1002/slct.201901025
da Silva MJ, Lopes NPG, Ferreira SO, da Silva RC, Natalino R, Chaves DM, Texeira MG (2020) Monoterpenes etherification reactions with alkyl alcohols over Cesium partially exchanged Keggin heteropoly salts: effects of the catalyst composition. Chem Pap. https://doi.org/10.1007/s11696-020-01288-x
David GF, Ríos-Ríos AM, de Fátima Â, Perez VH, Fernandes SA (2019) The use of p-sulfonic acid calix[4]arene as organocatalyst for pretreatment of sugarcane bagasse increased the production of levoglucosan. Ind Crops Prod 134:382–387. https://doi.org/10.1016/j.indcrop.2019.02.034
de Paiva Silva S, Pereira JO, de Santana Varejão Â, Fátima SAF (2019) p-Sulfonic acid calix[4]arene: a highly efficient organocatalyst for dehydration of fructose to 5-hydroxymethylfurfural. Ind Crops Prod 138:111492. https://doi.org/10.1016/j.indcrop.2019.111492
Deng F, Amarasekara AS (2021) Catalytic upgrading of biomass derived furans. Ind Crops Prod 159:113055. https://doi.org/10.1016/j.indcrop.2020.113055
Desai ML, Eisen EO (1966) Salt effects in liquid-liquid equilibria. J Chem Eng Data 11:480–484. https://doi.org/10.1021/je60049a021
Despax S, Maurer C, Estrine B, Le Bras J, Hoffmann N, Marinkovic S, Muzart J (2014) Fast and efficient DMSO-mediated dehydration of carbohydrates into 5-hydroxymethylfurfural. Catal Commun 51:5–9. https://doi.org/10.1016/j.catcom.2014.03.009
Esteban J, Vorholt AJ, Leitner W (2020) An overview of the biphasic dehydration of sugars to 5-hydroxymethylfurfural and furfural: a rational selection of solvents using COSMO-RS and selection guides. Green Chem 22:2097–2128. https://doi.org/10.1039/c9gc04208c
Fang X, Wang Z, Yuan B, Song W, Li S, Lin W (2018) Efficient conversion of cellulose to 5-hydroxymethylfurfural in NaHSO4/ZrO2/H2O-THF biphasic system. ChemSelect 3:12243–12249. https://doi.org/10.1002/slct.201802029
Gomes FNDC, Mendes FMT, Souza MMVM (2017) Synthesis of 5-hydroxymethylfurfural from fructose catalyzed by phosphotungstic acid. Catal Today 279:296–304. https://doi.org/10.1016/j.cattod.2016.02.018
Gonçalves CE, Laier LO, Cardoso AL, Da Silva MJ (2012) Bioadditive synthesis from H3PW12O40-catalyzed glycerol esterification with HOAc under mild reaction conditions. Fuel Process Technol 102:46–52. https://doi.org/10.1016/j.fuproc.2012.04.027
Görgényi M, Dewulf J, Van Langenhove H, Héberger K (2006) Aqueous salting-out effect of inorganic cations and anions on non-electrolytes. Chemosphere 65:802–810. https://doi.org/10.1016/j.chemosphere.2006.03.029
Guo X, Guo F, Li Y, Zheng Z, Xing Z, Zhu Z, Liu T, Zhang X, Jin Y (2018) Dehydration of D-xylose into furfural over bimetallic salts of heteropolyacid in DMSO/H2O mixture. Appl Catal A Gen 558:18–25. https://doi.org/10.1016/j.apcata.2018.03.027
Hassan A, Ilyas SZ, Jalil A, Ullah Z (2021) Monetization of the environmental damage caused by fossil fuels. Environ Sci Pollut Res 28:21204–21211. https://doi.org/10.1007/s11356-020-12205-w
Holclajtner-Antunović I, Mioč UB, Todorović M, Jovanović Z, Davidović M, Bajuk-Bogdanović D, Laušević Z (2010) Characterization of potassium salts of 12-tungstophosphoric acid. Mater Res Bull 45:1679–1684. https://doi.org/10.1016/j.materresbull.2010.06.064
Huang F, Su Y, Tao Y, Sun W, Wang W (2018) Preparation of 5-hydroxymethylfurfural from glucose catalyzed by silica-supported phosphotungstic acid heterogeneous catalyst. Fuel 226:417–422. https://doi.org/10.1016/j.fuel.2018.03.193
Kong QS, Li XL, Xu HJ, Fu Y (2020) Conversion of 5-hydroxymethylfurfural to chemicals: a review of catalytic routes and product applications. Fuel Process Technol 209:106528. https://doi.org/10.1016/j.fuproc.2020.106528
Kumari PK, Rao BS, Padmakar D, Pasha N, Lingaiah N (2018) Lewis acidity induced heteropoly tungustate catalysts for the synthesis of 5-ethoxymethyl furfural from fructose and 5-hydroxymethylfurfural. Mol Catal 448:108–115. https://doi.org/10.1016/j.mcat.2018.01.034
Kurajica S, Popović J, Tkalčec E, Gržeta B, Mandić V (2012) The effect of annealing temperature on the structure and optical properties of sol-gel derived nanocrystalline cobalt aluminate spinel. Mater Chem Phys 135:587–593. https://doi.org/10.1016/j.matchemphys.2012.05.030
Lai F, Yan F, Wang Y, Li C, Cai J, Zhang Z (2021) Tungstophosphoric acid supported on metal/Si-pillared montmorillonite for conversion of biomass-derived carbohydrates into methyl levulinate. J Clean Prod 314:128072. https://doi.org/10.1016/j.jclepro.2021.128072
Li Y, Zhang Y, Wu P, Feng C, Xue G (2018) Catalytic oxidative/extractive desulfurization of model oil using transition metal substituted phosphomolybdates-based ionic liquids. Catalysts 8:639–652. https://doi.org/10.3390/catal8120639
Liu A, Zhang Z, Fang Z, Liu B, Huang K (2014) Synthesis of 5-ethoxymethylfurfural from 5-hydroxymethylfurfural and fructose in ethanol catalyzed by MCM-41 supported phosphotungstic acid. J Ind Eng Chem 20:1977–1984. https://doi.org/10.1016/j.jiec.2013.09.020
Liu CG, Zheng T, Liu S, Zhang HY (2016) Photodegradation of malachite green dye catalyzed by Keggin-type polyoxometalates under visible-light irradiation: transition metal substituted effects. J Mol Struct 1110:44–52. https://doi.org/10.1016/j.molstruc.2016.01.015
Lucas N, Nagpure AS, Gurrala L, Gogoi P, Chilukuri S (2020) Efficacy of clay catalysts for the dehydration of fructose to 5-hydroxymethyl furfural in biphasic medium. J Porous Mater 27:1691–1700. https://doi.org/10.1007/s10934-020-00943-8
Mandal S, Selvakannan PR, Pasricha R, Sastry M (2003) Keggin ions as UV-switchable reducing agents in the synthesis of Au core-Ag shell nanoparticles. J Am Chem Soc 125:8440–8441. https://doi.org/10.1021/ja034972t
Mazari T, Marchal CR, Hocine S, Salhi N, Rabia C (2010) Oxidation of propane over ammonium-transition metal mixed keggin phosphomolybdate salts. J Nat Gas Chem 19:54–60. https://doi.org/10.1016/S1003-9953(09)60035-9
Méndez L, Torviso R, Pizzio L, Blanco M (2011) 2-Methoxynaphthalene acylation using aluminum or copper salts of tungstophosphoric and tungstosilicic acids as catalysts. Catal Today 173:32–37. https://doi.org/10.1016/j.cattod.2011.03.028
Mika LT, Cséfalvay E, Németh Á (2018) Catalytic conversion of carbohydrates to initial platform chemicals: chemistry and sustainability. Chem Rev 118:505–613. https://doi.org/10.1021/acs.chemrev.7b00395
Patel A, Patel J (2020) Nickel salt of phosphomolybdic acid as a bi-functional homogeneous recyclable catalyst for base free transformation of aldehyde into ester. RSC Adv 10:22146–22155. https://doi.org/10.1039/d0ra04119j
Pinheiro PF, Chaves DM, da Silva MJ (2019) One-pot synthesis of alkyl levulinates from biomass derivative carbohydrates in tin(II) exchanged silicotungstates-catalyzed reactions. Cellulose 26:7953–7969. https://doi.org/10.1007/s10570-019-02665-w
Pizzio LR, Vázquez PG, Cáceres CV, Blanco MN (2003) Supported Keggin type heteropolycompounds for ecofriendly reactions. Appl Catal A Gen 256:125–139. https://doi.org/10.1016/S0926-860X(03)00394-6
Román-Leshkov Y, Chheda JN, Dumesic JA (2006) Phase modifiers promote efficient production of hydroxymethylfurfural from fructose. Science 312:1933–1937. https://doi.org/10.1126/science.1126337
Rosatella AA, Simeonov SP, Frade RFM, Afonso CAM (2011) 5-Hydroxymethylfurfural (HMF) as a building block platform: biological properties, synthesis and synthetic applications. Green Chem 13:754–793. https://doi.org/10.1039/c0gc00401d
Saha B, Abu-Omar MM (2014) Advances in 5-hydroxymethylfurfural production from biomass in biphasic solvents. Green Chem 16:24–38. https://doi.org/10.1039/c3gc41324a
Sheldon RA (2017) The E factor 25 years on: The rise of green chemistry and sustainability. Green Chem 19:18–43. https://doi.org/10.1039/c6gc02157c
Srinivas M, Raveendra G, Parameswaram G, Prasad PSS, Lingaiah N (2016) Cesium exchanged tungstophosphoric acid supported on tin oxide: an efficient solid acid catalyst for etherification of glycerol with tert-butanol to synthesize biofuel additives. J Mol Catal A Chem 413:7–14. https://doi.org/10.1016/j.molcata.2015.10.005
Takagaki A, Nishimura S, Ebitani K (2012) Catalytic transformations of biomass-derived materials into value-added chemicals. Catal Surv Asia 16:164–182. https://doi.org/10.1007/s10563-012-9142-3
Tang J, Zhu L, Fu X, Dai J, Guo X, Hu C (2017) Insights into the kinetics and reaction network of aluminum chloride-catalyzed conversion of glucose in NaCl-H2O/THF biphasic system. ACS Catal 7:256–266. https://doi.org/10.1021/acscatal.6b02515
Tang Y, Cheng Y, Xu H, Wang Y, Ke L, Huang X, Liao X, Shi B (2019) Binary oxide nanofiber bundle supported Keggin-type phosphotungstic acid for the synthesis of 5-hydroxymethylfurfural. Catal Commun 123:96–99. https://doi.org/10.1016/j.catcom.2019.02.015
Teixeira MG, Natalino R, da Silva MJ (2020) A kinetic study of heteropolyacid-catalyzed furfural acetalization with methanol at room temperature via ultraviolet spectroscopy. Catal Today 344:143–149. https://doi.org/10.1016/j.cattod.2018.11.071
van Putten R-J, de Vries JG, van der Waal JC, de Jong E, Rasrendra CB, Heeres HJ (2013) Hydroxymethylfurfural, a versatile platform chemical made from renewable resources. Chem Rev 113:1499–1597. https://doi.org/10.1021/cr300182k
Vilanculo CB (2021) Can Brønsted acids catalyze the epoxidation of allylic alcohols with H2O2 ? With a little help from the proton, the H3PMo12O40 acid did it and well. Mol Catal 512:111780–111789. https://doi.org/10.1016/j.mcat.2021.111780
Vilanculo CB, de Andrade Leles LC, da Silva MJ (2020) H4SiW12O40-catalyzed levulinic acid esterification at room temperature for production of fuel bioadditives. Waste Biomass Valoriz 11:1895–1904. https://doi.org/10.1007/s12649-018-00549-x
Wrigstedt P, Keskiväli J, Repo T (2016) Microwave-enhanced aqueous biphasic dehydration of carbohydrates to 5-hydroxymethylfurfural. RSC Adv 6:18973–18979. https://doi.org/10.1039/x0xx00000x
Yang Y, Abu-Omar MM, Hu C (2012) Heteropolyacid catalyzed conversion of fructose, sucrose, and inulin to 5-ethoxymethylfurfural, a liquid biofuel candidate. Appl Energy 99:80–84. https://doi.org/10.1016/j.apenergy.2012.04.049
Youn MH, Kim H, Song IK, Barteau KP, Barteau MA (2005) UV-visible spectroscopic study of solid state 12-molybdophosphoricacid catalyst. React Kinet Catal Lett 87:85–91. https://doi.org/10.1007/s11144-006-0012-8
Yu IKM, Tsang DCW (2017) Conversion of biomass to hydroxymethylfurfural: a review of catalytic systems and underlying mechanisms. Bioresour Technol 238:716–732. https://doi.org/10.1016/j.biortech.2017.04.026
Acknowledgments
The authors are grateful Fundação de Amparo à Pesquisa do Estado de Minas Gerais —Brazil (FAPEMIG), Conselho Nacional de Desenvolvimento Científico e Tecnológico—Brazil (CNPq) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil (CAPES—Finance Code 001). MJS and SAF are supported by Research Fellowships from CNPq.
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Castro, G.A.D., Lopes, N.P.G., Fernandes, S.A. et al. Copper phosphotungstate-catalyzed microwave-assisted synthesis of 5-hydroxymethylfurfural in a biphasic system. Cellulose 29, 5529–5545 (2022). https://doi.org/10.1007/s10570-022-04623-5
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DOI: https://doi.org/10.1007/s10570-022-04623-5