Abstract
2,5-Furandicarboxylic acid (FDCA) is an important and renewable building block and can serve as an alternative to terephthalic acid in the production of bio-based degradable plastic. In this study, Cu-doped MnO2 nanorods were prepared by a facile hydrothermal redox method and employed as catalysts for the selective oxidation of 5-hydroxymethylfurfural (HMF) to FDCA using tert-butyl hydroperoxide (TBHP) as an oxidant. The catalysts were characterized using X-ray diffraction analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy. The effects of oxidants, solvents, and reaction conditions on the oxidation of HMF were investigated, and a reaction mechanism was proposed. Experimental results demonstrated that 99.4% conversion of HMF and 96.3% selectivity of FDCA were obtained under suitable conditions, and tert-butanol was the most suitable solvent when TBHP was used as an oxidant. More importantly, the Cu-doped MnO2 catalyst can maintain durable catalytic activity after being recycled for more than ten times.
Similar content being viewed by others
References
Wang H L, Yang B, Zhang Q, Zhu W B. Catalytic routes for the conversion of lignocellulosic biomass to aviation fuel range hydrocarbons. Renewable & Sustainable Energy Reviews, 2020, 120: 109612
Zhu S H, Wang J G, Fan W B. Graphene-based catalysis for biomass conversion. Catalysis Science & Technology, 2015, 5: 3845–3858
Wang Y Z, De S, Yan N. Rational control of nano-scale metal-catalysts for biomass conversion. Chemical Communications, 2016, 52: 6210–6224
Abou-Yousef H, Hassan E B. A novel approach to enhance the activity of H-form zeolite catalyst for production of hydroxymethyl-furfural from cellulose. Journal of Industrial and Engineering Chemistry, 2014, 20: 1952–1957
Liu X X, Ding H, Xu Q, Zhong W Z, Yin D L, Su S P. Selective oxidation of biomass derived 5-hydroxymethylfurfural to 2,5-diformylfuran using sodium nitrite. Journal of Energy Chemistry, 2016, 25: 117–121
Liu X X, Xiao J F, Ding H, Zhong W Z, Xu Q, Su S P, Yin D L. Catalytic aerobic oxidation of 5-hydroxymethylfurfural over VO2+ and Cu2+ immobilized on amino functionalized SBA-15. Chemical Engineering Journal, 2016, 283: 1315–1321
Wu B S, Xu Y T, Bu Z Y, Wu L B, Li B G, Dubois P. Biobased poly (butylene 2,5-furandicarboxylate)and poly(butylene adipate-co-butylene 2,5-furandicarboxylate)s: from synthesis using highly purified 2,5-furandicarboxylic acid to thermo-mechanical properties. Polymer, 2014, 55: 3648–3655
Zhu J H, Cai J L, Xie W C, Chen P H, Gazzano M, Scandola M, Gross R A. Poly(butylene 2,5-furan dicarboxylate), a biobased alternative to PBT: synthesis, physical properties, and crystal structure. Macromolecules, 2013, 46: 796–804
Liu B, Ren Y S, Zhang Z H. Aerobic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid in water under mild conditions. Green Chemistry, 2015, 17: 1610–1617
Zhu Y Y, Wang F S, Fan M Y, Zhu Q, Dong Z P. Ultrafine Pd nanoparticles immobilized on N-doped hollow carbon nanospheres with superior catalytic performance for the selective oxidation of 5-hydroxymethylfurfural and hydrogenation of nitroarenes. Journal of Colloid and Interface Science, 2019, 553: 588–597
Li Q Q, Wang H Y, Tian Z P, Weng Y J, Wang C G, Ma J R, Zhu C F, Li W Z, Liu Q Y, Ma L L. Selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over Au/CeO2 catalysts: the morphology effect of CeO2. Catalysis Science & Technology, 2019, 9: 1570–1580
Megías-Sayago C, Lolli A, Ivanova S, Albonetti S, Cavani F, Odriozola J A. Au/Al2O3—efficient catalyst for 5-hydroxymethyl-furfural oxidation to 2,5-furandicarboxylic acid. Catalysis Tadoy, 2019, 333: 169–175
Liu H, Cao X J, Wang T, Wei J N, Tang X, Zeng X H, Sun Y, Lei T Z, Liu S J, Lin L. Efficient synthesis of bio-monomer 2,5-furandicarboxylic acid from concentrated 5-hydroxymethylfurfural or fructose in DMSO/H2O mixed solvent. Journal of Industrial and Engineering Chemistry, 2019, 77: 209–214
Zhou X H, Song K H, Li Z H, Kang W M, Ren H R, Su K M, Zhang M L, Cheng B W. The excellent catalyst support of Al2O3 fibers with needle-like mullite structure and HMF oxidation into FDCA over CuO/Al2O3 fibers. Ceramics International, 2019, 45: 2330–2337
Hayashi E, Yamaguchi Y, Kamata K, Tsunoda N, Kumagai Y, Oba F, Hara M. Effect of MnO2 crystal structure on aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid. Journal of the American Chemical Society, 2019, 141: 890–900
Zhou H, Xu H H, Liu Y. Aerobic oxidation of 5-hydroxymethyl-furfural to 2,5-furandicarboxylic acid over Co/Mn-lignin coordination complexes-derived catalysts. Applied Catalysis B: Environmental, 2019, 244: 965–973
Gawade A B, Nakhate A V, Yadav G D. Selective synthesis of 2,5-furandicarboxylic acid by oxidation of 5-hydroxymethylfurfural over MnFe2O4 catalyst. Catalysis Tadoy, 2018, 309: 119–125
Gao T, Glerup M, Krumeich F, Nesper R, Fjellvag H, Norby P. Microstructures and spectroscopic properties of cryptomelane-type manganese dioxide nanofibers. Journal of Physical Chemistry C, 2008, 112: 13134–13140
Gac W. The influence of silver on the structural, redox and catalytic properties of the cryptomelane-type manganese oxides in the low-temperature CO oxidation reaction. Applied Catalysis B: Environmental, 2007, 75: 107–117
Hayashi E, Komanoya T, Kamata K, Hara M. Heterogeneously-catalyzed aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid with manganese dioxide. ChemSusChem, 2017, 10(4): 815–815
Ding Y S, Shen X F, Sithambaram S, Gomez S, Kumar R, Crisostomo V M B, Suib S L, Aindow M. Synthesis and catalytic activity of cryptomelane-type Manganese dioxide nanomaterials produced by a novel solvent-free method. Chemistry of Materials, 2005, 17: 5382–5389
Yang F, Ding Y, Tang J J, Zhou S J, Wang B B, Kong Y. Oriented surface decoration of (Co-Mn) bimetal oxides on nanospherical porous silica and synergetic effect in biomass-derived 5-hydroxymethylfurfural oxidation. Molecular Catalysis, 2017, 435: 144–155
Duh Y S, Kuo H Y, Kao C S. Characterization on thermal decompositions of tert-butylhydroperoxide (TBHP) by confinement test. Journal of Thermal Analysis and Calorimetry, 2016, 127(1): 1047–1059
Acknowledgements
The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (Grant No. 21606082), Hunan Provincial Natural Science Foundation of China (No. 2018JJ3334), China Postdoctoral Science Foundation (No. 2019M662787), and Hunan Provincial Innovation Foundation for Postgraduate (No. CX20200522).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Cheng, F., Guo, D., Lai, J. et al. Efficient base-free oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over copper-doped manganese oxide nanorods with tert-butanol as solvent. Front. Chem. Sci. Eng. 15, 960–968 (2021). https://doi.org/10.1007/s11705-020-1999-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11705-020-1999-5