Efficient conversion of chitin to HMF under the co-catalytic system of formic acid and silicotungstic acid

Luxiao ZHOU; Kun GAO; Peng HE; Huahua YU; Ronge XING; Song LIU; Yukun QIN

Your Location：

Home >

Browse articles >

Efficient conversion of chitin to HMF under the co-catalytic system of formic acid and silicotungstic acid

Biology | Updated：2025-02-19

- Efficient conversion of chitin to HMF under the co-catalytic system of formic acid and silicotungstic acid
- Journal of Oceanology and Limnology Vol. 43, Issue 1, Pages: 261-273(2025)
- Affiliations：
  
  1.College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
  2.CAS and Shandong Province Key Laboratory of Experimental Marine Biology, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China
  3.Laboratory for Marine Drugs and Bioproducts, Qingdao Marine Science and Technology Center, Qingdao 266237, China
- Author bio：
  
  hepeng@qust.edu.cn
  ykqin@qdio.ac.cn
- Funds：
- DOI：
  CLC：
- Received：21 March 2024，
  
  Published：01 January 2025
- Accepted：
Scan QR Code
ZHOU Luxiao,GAO Kun,HE Peng,et al.Efficient conversion of chitin to HMF under the co-catalytic system of formic acid and silicotungstic acid[J].Journal of Oceanology and Limnology,2025,43(01):261-273.
DOI：

ZHOU Luxiao,GAO Kun,HE Peng,et al.Efficient conversion of chitin to HMF under the co-catalytic system of formic acid and silicotungstic acid[J].Journal of Oceanology and Limnology,2025,43(01):261-273. DOI：

摘要

Abstract

The conversion process of chitin

one of the abundant biomass resources on the earth

not only follows the principles of green chemistry

but also has significant value in industrial applications. However

it is a great challenge to directly convert insoluble and rigid structured chitin to 5-hydroxymethylfurfural (HMF). To address this issue

we developed a green conversion process combining pretreatment and catalytic system. Chitin was first pretreated by hexafluoro isopropanol (HFIP)

which somewhat disrupted the hydrogen bonding network within the chitin structure. Subsequently

formic acid (FA) and silicotungstic acid (STA) synergistically catalyzed the conversion to HMF in a biphasic system of 2-methyltetrahydrofuran (2-Me-THF)/H

and high yields (40.2%) HMF was obtained under the optimism conditions. The product distribution was analyzed by HPLC-MS and the co-catalysis of FA with STA was evidenced. A dual-function catalytic system with both Lewis and Brønsted acids was created

the catalytic system that significantly improved the efficiency of complex tandem catalytic reactions with chitin. Based on the

experimental results

a possible pathway for chitin conversion was deduced

providing a new catalytic idea for the efficient conversion of chitin to HMF.

关键词

Keywords

references

Bozell J J , Petersen G R . 2010 . Technology development for the production of biobased products from biorefinery carbohydrates—The US Department of Energy’s “Top 10” revisited . Green Chemistry , 12 ( 4 ): 539 - 554 , https://doi.org/10.1039/b922014c https://doi.org/10.1039/b922014c .

Cai Z P , Chen R J , Zhang H et al . 2021 . One-pot production of diethyl maleate via catalytic conversion of raw lignocellulosic biomass . Green Chemistry , 23 ( 24 ): 10116 - 10122 , https://doi.org/10.1039/d1gc03114g https://doi.org/10.1039/d1gc03114g .

Chen X , Gao Y J , Wang L et al . 2015 . Effect of treatment methods on chitin structure and its transformation into nitrogen-containing chemicals . ChemPlusChem , 80 ( 10 ): 1565 - 1572 , https://doi.‍org/10.1002/cplu.201500326 https://doi.‍org/10.1002/cplu.201500326 . https://do 10.1002/cplu.201500326 http://dx.doi.org/10.1002/cplu.201500326

Chen Z , Reznicek W D , Wan C X . 2018 . Aqueous choline chloride: a novel solvent for switchgrass fractionation and subsequent hemicellulose conversion into furfural . ACS Sustainable Chemistry & Engineering , 6 ( 5 ): 6910 - 6919 , https://doi.org/10.1021/acssuschemeng.8b00728 https://doi.org/10.1021/acssuschemeng.8b00728 .

Chheda J N , Román-Leshkov Y , Dumesic J A . 2007 . Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides . Green Chemistry , 9 ( 4 ): 342 - 350 , https://doi.org/10.1039/b611568c https://doi.org/10.1039/b611568c .

De S , Dutta S , Saha B . 2011 . Microwave assisted conversion of carbohydrates and biopolymers to 5-hydroxymethylfurfural with aluminium chloride catalyst in water . Green Chemistry , 13 ( 10 ): 2859 - 2868 , https://doi.org/10.1039/c1gc15550d https://doi.org/10.1039/c1gc15550d .

Deng T S , Cui X J , Qi Y Q et al . 2012 . Conversion of carbohydrates into 5-hydroxymethylfurfural catalyzed by ZnCl 2 in water . Chemical Communications , 48 ( 44 ): 5494 - 5496 , https://doi.org/10.1039/c2cc00122e https://doi.org/10.1039/c2cc00122e .

Dugoni G C , Mezzetta A , Guazzelli L et al . 2020 . Purification of Kraft cellulose under mild conditions using choline acetate based deep eutectic solvents . Green Chemistry , 22 ( 24 ): 8680 - 8691 , https://doi.org/10.1039/d0gc03375h https://doi.org/10.1039/d0gc03375h .

Gallezot P . 2012 . Conversion of biomass to selected chemical products . Chemical Society Reviews , 41 ( 4 ): 1538 - 1558 , https://doi.org/10.1039/c1cs15147a https://doi.org/10.1039/c1cs15147a .

Gao X Y , Zhong H , Yao G D et al . 2016 . Hydrothermal conversion of glucose into organic acids with bentonite as a solid-base catalyst . Catalysis Today , 274 : 49 - 54 , https://doi.org/10.1016/j.cattod.2016.02.008 https://doi.org/10.1016/j.cattod.2016.02.008 .

Gong C X , Ju Z Y , Sheng K C et al . 2023 . Efficient conversion of chitin into 5-hydroxymethylfurfural via a simple formylation step under mild conditions . Green Chemistry , 25 ( 12 ): 4781 - 4792 , https://doi.org/10.1039/d3gc00503h https://doi.org/10.1039/d3gc00503h .

Gounder R , Davis M E . 2013 . Monosaccharide and disaccharide isomerization over Lewis acid sites in hydrophobic and hydrophilic molecular sieves . Journal of Catalysis , 308 : 176 - 188 , https://doi.‍org/10.1016/j.jcat.2013.06.016 https://doi.‍org/10.1016/j.jcat.2013.06.016 . https://do 10.1016/j.jcat.2013.06.016 http://dx.doi.org/10.1016/j.jcat.2013.06.016

He G Y , Zhang J H , Hu Y et al . 2019 . Dual-template synthesis of mesoporous TiO 2 nanotubes with structure-enhanced functional photocatalytic performance . Applied Catalysis B: Environmental , 250 : 301 - 312 , https://doi.‍org/10.1016/j.apcatb.2019.03.027 https://doi.‍org/10.1016/j.apcatb.2019.03.027 . https://do 10.1016/j.apcatb.2019.03.027 http://dx.doi.org/10.1016/j.apcatb.2019.03.027

Hsu W H , Lee Y Y , Peng W H et al . 2011 . Cellulosic conversion in ionic liquids (ILs): effects of H 2 O/cellulose molar ratios, temperatures, times, and different ILs on the production of monosaccharides and 5-hydroxymethylfurfural (HMF) . Catalysis Today , 174 ( 1 ): 65 - 69 , https://doi.org/10.1016/j.cattod.2011.03.020 https://doi.org/10.1016/j.cattod.2011.03.020 .

Hu L , Wu Z , Xu J X et al . 2014 . Zeolite-promoted transformation of glucose into 5-hydroxymethylfurfural in ionic liquid . Chemical Engineering Journal , 244 : 137 - 144 , https://doi.org/10.1016/j.cej.2014.01.057 https://doi.org/10.1016/j.cej.2014.01.057 .

Islam M S , Nakamura M , Rabin N N et al . 2022 . Microwave-assisted catalytic conversion of chitin to 5-hydroxymethylfurfural using polyoxometalate as catalyst . RSC Advances , 12 ( 1 ): 406 - 412 , https://doi.org/10.1039/d1ra08560c https://doi.org/10.1039/d1ra08560c .

Jadhav A H , Chinnappan A , Patil R H et al . 2014 . Deprotection of tert -butyldimethylsilyl (TBDMS) ethers using efficient and recyclable heterogeneous silver salt of silicotungstic acid catalyst under mild reaction condition . Chemical Engineering Journal , 236 : 300 - 305 , https://doi.org/10.1016/j.cej.2013.09.011 https://doi.org/10.1016/j.cej.2013.09.011 .

Jin C D , Xiang N , Zhu X et al . 2021 . Selective 5-hydroxymethylfurfural production from cellulose formate in DMSO-H 2 O media . Applied Catalysis B: Environmental , 285 : 119799 , https://doi.org/10.1016/j.apcatb.2020.119799 https://doi.org/10.1016/j.apcatb.2020.119799 .

Lai F J , Yan F , Wang P J et al . 2021 . Efficient conversion of carbohydrates and biomass into furan compounds by chitin/Ag co-modified H 3 PW 12 O 40 catalysts . Journal of Cleaner Production , 316 : 128243 , https://doi.org/10.1016/j.jclepro.2021.128243 https://doi.org/10.1016/j.jclepro.2021.128243 .

Lee S B , Kim S K , Hong Y K et al . 2016 . Optimization of the production of platform chemicals and sugars from the red macroalga, Kappaphycus alvarezii . Algal Research , 13 : 303 - 310 , https://doi.org/10.1016/j.algal.2015.12.013 https://doi.org/10.1016/j.algal.2015.12.013 .

Li H , Guo H X , Fang Z et al . 2020 . Cycloamination strategies for renewable N-heterocycles . Green Chemistry , 22 ( 3 ): 582 - 611 , https://doi.org/10.1039/c9gc03655e https://doi.org/10.1039/c9gc03655e .

Li M G , Zang H J , Feng J X et al . 2015 . Efficient conversion of chitosan into 5-hydroxymethylfurfural via hydrothermal synthesis in ionic liquids aqueous solution . Polymer Degradation and Stability , 121 : 331 - 339 , https://doi.‍org/10.1016/j.polymdegradstab.2015.09.009 https://doi.‍org/10.1016/j.polymdegradstab.2015.09.009 . https://do 10.1016/j.polymdegradstab.2015.09.009 http://dx.doi.org/10.1016/j.polymdegradstab.2015.09.009

Li Y D , Shuai L , Kim H et al . 2018 . An “ideal lignin” facilitates full biomass utilization . Science Advances , 4 ( 9 ): 10 , https://doi.org/10.1126/sciadv.aau2968 https://doi.org/10.1126/sciadv.aau2968 .

Lin C Q , Chai C Q , Li Y Z et al . 2021 . CaCl 2 molten salt hydrate-promoted conversion of carbohydrates to 5-hydroxymethylfurfural: an experimental and theoretical study . Green Chemistry , 23 ( 5 ): 2058 - 2068 , https://doi.org/10.1039/d0gc04356g https://doi.org/10.1039/d0gc04356g .

Liu Y X , Li C Z , Miao W et al . 2019 . Mild redox-neutral depolymerization of lignin with a binuclear Rh complex in water . ACS Catalysis , 9 ( 5 ): 4441 - 4447 , https://doi.org/10.1021/acscatal.9b00669 https://doi.org/10.1021/acscatal.9b00669 .

Lu Y J , Ma B , Zhao C . 2018 . Integrated production of bio-jet fuel containing lignin-derived arenes via lipid deoxygenation . Chemical Communications , 54 ( 70 ): 9829 - 9832 , https://doi.org/10.1039/c8cc04969f https://doi.org/10.1039/c8cc04969f .

Marianou A A , Michailof C M , Pineda A et al . 2018 . Effect of Lewis and Brønsted acidity on glucose conversion to 5-HMF and lactic acid in aqueous and organic media . Applied Catalysis A: General , 555 : 75 - 87 , https://doi.‍org/10.1016/j.apcata.2018.01.029 https://doi.‍org/10.1016/j.apcata.2018.01.029 . https://do 10.1016/j.apcata.2018.01.029 http://dx.doi.org/10.1016/j.apcata.2018.01.029

Nikoofar K . 2017 . Silicotungstic acid (H 4 SiW 12 O40): an efficient Keggin heteropoly acid catalyst for the synthe sis of oxindole derivatives . Arabian Journal of Chemistry , 10 ( 2 ): 283 - 287 , https://doi.org/10.1016/j.arabjc.2014.07.008 https://doi.org/10.1016/j.arabjc.2014.07.008 .

Qin Y Z , Zong M H , Lou W Y et al . 2016 . Biocatalytic upgrading of 5-hydroxymethylfurfural (HMF) with Levulinic acid to HMF Levulinate in biomass-derived solvents . ACS Sustainable Chemistry & Engineering , 4 ( 7 ): 4050 - 4054 , https://doi.org/10.1021/acssuschemeng.6b00996 https://doi.org/10.1021/acssuschemeng.6b00996 .

Oriez V , Labauze H , Benjelloun-Mlayah B et al . 2023 . Catalyst-free synthesis of 5-hydroxymethylfurfural from fructose by extractive reaction in supercritical CO 2 -subcritical H 2 O two-phase system . The Journal of Supercritical Fluids , 198 : 105904 , https://doi.org/10.1016/j.supflu.2023.105904 https://doi.org/10.1016/j.supflu.2023.105904 .

Ramírez-Wong D G , Ramírez-Cardona M , Sánchez-Leija R J et al . 2016 . Sustainable-solvent-induced polymorphism in chitin films . Green Chemistry , 18 ( 15 ): 4303 - 4311 , https://doi.org/10.1039/c6gc00628k https://doi.org/10.1039/c6gc00628k .

Rodríguez-Padrón D , Zhao D Y , Carrillo-Carrion C et al . 2021 . Exploring the potential of biomass-templated Nb/ZnO nanocatalysts for the sustainable synthesis of N-heterocycles . Catalysis Today , 368 : 243 - 249 , https://doi.org/10.1016/j.cattod.2020.06.076 https://doi.org/10.1016/j.cattod.2020.06.076 .

Saghandali F , Kazemeini M , Sadjadi S . 2024 . Halloysite-supported silicotungstic acid as an efficient catalyst for dehydration of fructose to 5-hydroxymethylfurfural . Journal of Physics and Chemistry of Solids , 184 : 111697 , https://doi.org/10.1016/j.jpcs.2023.111697 https://doi.org/10.1016/j.jpcs.2023.111697 .

Su H , Wang J K , Yan L F . 2019 . Homogeneously synchronous degradation of chitin into carbon dots and organic acids in aqueous solution . ACS Sustainable Chemistry & Engineering , 7 ( 22 ): 18476 - 18482 , https://doi.org/10.1021/acssuschemeng.9b04436 https://doi.org/10.1021/acssuschemeng.9b04436 .

Tajiri R , Mihata A , Yamamoto K et al . 2014 . Facile preparation of chitin gels with calcium bromide dihydrate/methanol media and their efficient conversion into porous chitins . RSC Advances , 4 ( 11 ): 5542 - 5546 , https://doi.org/10.1039/c3ra46285d https://doi.org/10.1039/c3ra46285d .

Takagaki A , Jung J C , Hayashi S . 2014 . Solid Lewis acidity of boehmite γ-AlO(OH) and its catalytic activity for transformation of sugars in water . RSC Advances , 4 ( 82 ): 43785 - 43791 , https://doi.org/10.1039/c4ra08061k https://doi.org/10.1039/c4ra08061k .

Tschirner S , Weingart E , Teevs L et al . 2018 . Catalytic dehydration of fructose to 5-hydroxymethylfurfural (HMF) in low-boiling solvent hexafluoroisopropanol (HFIP) . Molecules , 23 ( 8 ): 1866 , https://doi.org/10.3390/molecules23081866 https://doi.org/10.3390/molecules23081866 .

Van Putten R J , Van Der Waal J C , De Jong E et al . 2013 . Hydroxymethylfurfural, a versatile platform chemical made from renewable resources . Chemical Reviews , 113 ( 3 ): 1499 - 1597 , https://doi.org/10.1021/cr300182k https://doi.org/10.1021/cr300182k .

Wang Y D , Kou J , Wang X W et al . 2023 . Acid hydrolysis of chitin in calcium chloride solutions . Green Chemistry , 25 ( 7 ): 2596 - 2607 , https://doi.org/10.1039/d2gc04246k https://doi.org/10.1039/d2gc04246k .

Xu C P , Nasrollahzadeh M , Selva M et al . 2019 . Waste-to-wealth: biowaste valorization into valuable bio(nano)materials . Chemical Society Reviews , 48 ( 18 ): 4791 - 4822 , https://doi.org/10.1039/c8cs00543e https://doi.org/10.1039/c8cs00543e .

Yang F , Tang J J , Ou R et al . 2019 . Fully catalytic upgrading synthesis of 5-ethoxymethylfurfural from biomass-derived 5-hydroxymethylfurfural over recyclable layered-niobium-molybdate solid acid . Applied Catalysis B: Environmental , 256 : 117786 , https://doi.org/10.1016/j.apcatb.2019.117786 https://doi.org/10.1016/j.apcatb.2019.117786 .

Yuan L , Hu Y C , Guo X et al . 2022 . Biomass-based production of food preservatives . Chem Catalysis , 2 ( 9 ): 2302 - 2311 , https://doi.org/10.1016/j.checat.2022.07.014 https://doi.org/10.1016/j.checat.2022.07.014 .

Zang H J , Lou J , Jiao S L et al . 2021 . Valorization of chitin derived N -acetyl-D-glucosamine into high valuable N-containing 3-acetamido-5-acetylfuran using pyridinium-based ionic liquids . Journal of Molecular Liquids , 330 : 115667 , https://doi.org/10.1016/j.molliq.2021.115667 https://doi.org/10.1016/j.molliq.2021.115667 .

Zhang Z , Lucia L A . 2020 . Efficient green approaches for the preparation of physically crosslinked chitin gel materials by freeze-induced self-assembly . Journal of Molecular Liquids , 320 : 114392 , https://doi.org/10.1016/j.molliq.2020.114392 https://doi.org/10.1016/j.molliq.2020.114392 .

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

No data

Related Author

No data

Related Institution

No data

Address：Editorial Office of JOL, 88 Haijun Rd. Qingdao, 266000, China
Tel：+86-532-82898754 Email：jol@qdio.ac.cn
Technical support is provided by Beijing Founder electronics co., LTD 京ICP备09064830号-19 京公网安备11010802024621
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.

⁰