Chinese Journal of Catalysis ›› 2025, Vol. 71: 5-24.DOI: 10.1016/S1872-2067(24)60274-3
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Yao Chena, Jun Gea,b,c,*(
)
Received:2024-11-05
Accepted:2025-01-20
Online:2025-04-18
Published:2025-04-13
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* E-mail: About author:Dr. Jun Ge is a professor at Department of Chemical Engineering Tsinghua University. He received his B.Sc. and Ph.D. from the Department of Chemical Engineering, Tsinghua University in 2004 and 2009. From 2009 to 2012, He did his postdoc in the Department of Chemistry, Stanford University. Prof. Ge specializes in enzymatic catalysis, synthetic biology, nanobiotechnology and biomedicine. He has been carrying out scientific research projects from government and industry, including the Distinguished Young Scholars Fund from NSFC, the Excellent Young Scientists Fund from NSFC, the Program of National Key Research and Development Plan of China, and the Distinguished Young Scholars of Beijing National Science Foundation. Prof. Ge has published over 100 papers in journals such as Nature Nanotechnology, Nature Catalysis, Nature Communications, Science Advances, JACS etc. He was selected as the member of MIT Technology Review’s World 35 Innovators Under 35 and was awarded as the young scholar of Yangzi River Scholarship and the Future Chemical Engineering Scholar of the Global Academy of Chinese Chemical Engineers.
Supported by:Yao Chen, Jun Ge. Synthesis of 5-hydroxymethylfurfural and its oxidation derivatives by immobilized catalysts: An efficient green sustainable technology[J]. Chinese Journal of Catalysis, 2025, 71: 5-24.
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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60274-3
Fig. 1. Synthesis of HMF and its oxidation derivatives.
Fig. 2. Immobilization of enzymes, cells and chemical catalysts and the carriers.
Fig. 3. The immobilization of enzymes in the synthesis of HMF. (A) SEM images of conventional cross-linked enzymes aggregates (CLEAs) and porous CLEAs. (B) The reusability of the immobilized biocatalysts, specifically CLEAs and porous CLEAs (pCLEAs) of Candida antarctica lipase B (CaLB). This process included hydration, isomerization and dehydration reactions. Reproduced with permission from Ref. [59]. Copyright 2021, Elsevier. (C) Cascade catalytic reactions of thermophilic glucose isomerase and solid acid catalysts in functionalized silica. This process included isomerization and dehydration reactions. Reproduced with permission from Ref. [64]. Copyright 2014, American Chemical Society. (D) Schematic representation of the cascaded enzymatic and chemical steps for IL pretreated cellulose into HMF. This process included hydration, isomerization and dehydration reactions. Reproduced with permission from Ref. [66]. Copyright 2017, Wiley.
Fig. 4. The immobilization of enzymes in the synthesis of HMF oxidation derivatives. (A) An enzymatic nanoreactor exhibiting enhanced catalytic performance was developed by integrating CALB within the pores of a methylated β-cyclodextrin-derived silica matrix. (B) The catalytic recyclability of the biocatalysts, specifically RaMeβCD-SiO2@CAG@CALB@P4VP. This process included oxidative dehydrogenation and oxidation reactions. Reproduced with permission from Ref. [70]. Copyright 2021, Elsevier. (C) A schematic representation illustrated the immobilization process of Fe3O4-CotA-TJ102. (D) The time course for the biosynthesis of FFCA from the selective oxidation of HMF using free CotA-TJ102 under optimal conditions. This process included oxidative dehydrogenation and oxidation reactions. Reproduced with permission from Ref. [72]. Copyright 2019, Elsevier. (E) Images depicting SEM and confocal microscopy for GO0.05@NECu(II)8 were included. Reproduced with permission from Ref. [74]. Copyright 2022, Elsevier. (F) The conversion of HMF by GO&Hem@Cu(II) in aqueous conditions was reported. This process was oxidative dehydrogenation reaction. Reproduced with permission from Ref. [75]. Copyright 2023, Elsevier.
| Substrate | Enzymes | Immobilization method | Reaction condition | Product | Yield (%) | Selectivity (%) | Stability | Ref. |
|---|---|---|---|---|---|---|---|---|
| starch | lipase B | TPP method promotes the formation of CLEAs by Eupergit and lipase B with 3:1. | 50 °C, pH = 8.0, no oxidant | HMF | 61.3 | — | 44% residual activity after 8 cycles | [ |
| glucose | glucose isomerase | Gensweet®IGI | 50 °C, pH = 4.8 no oxidant | HMF | >80 | >80 | 3 cycles without any significant yield loss | [ |
| glucose | glucose isomerase | IGI with citrate buffer at 100mmol/L | 70 °C, pH = 3.0 no oxidant | HMF | 20 | — | — | [ |
| glucose | glucose isomerase | H2O/[bmim][Cl]0.5[BF4]0.5 1:3 w/w ternary mixture added in glucose isomerase | 50 °C, pH = 7-8 no oxidant | HMF | 50 | — | 5 cycles without any significant activity loss | [ |
| glucose | thermophilic glucose isomerase | −NH2 functionalized mesoporous silica protect the enzyme in a monophasic solvent system composed of tetrahydrofuran (THF) and H2O (4:1 v/v) | 90 °C, pH = 7.0 no oxidant | HMF | 30 | — | this enzyme could not be recycled in the organic solvent | [ |
| cellulose | cellulase and isomerase | Fe3O4@MSN/(cellulase and isomerase = 4:1, v/v | 60 °C, pH = 7.4 no oxidant | HMF | 45.6 | — | the yield of HMF was reduced by 7% after 5 cycles | [ |
| cellulose | cellulase | SBA-15 support/cellulose = 25:1, w: w | 60 °C, pH = 4.8 no oxidant | HMF | 43.6 | — | the yield of HMF was reduced by 1.6% after 5 cycles | [ |
| fructose | heparin | PEI@PDA@MWCNT/heparin = 3:10, w:w | 25 °C, pH = 6.2 no oxidant | HMF | 46.2 | 82.2 | negligible loss in activity after 5 cycles | [ |
| high fructose corn syrup | glucose oxidase, catalase | GA-modified amino resin/ enzymes=1:25 | 150 °C, pH = 1.07 no oxidant | HMF | 85 | 85 | 10 cycles without any significant activity loss | [ |
| glucose | glucose-isomerase, lipase | glucose-isomerase/Novozym 435 = 1:1, DMSO/dioxane = 9:1 | 60 °C, pH = 7 no oxidant | HMF | 15 | — | 5 cycles without any significant activity loss | [ |
| DFF | lipase | Stober process EtOAc/tBuOH (1:1, v/v) | 40 °C, pH > 7 oxidant: O2 | FDCA | >99 | — | 5 cycles retaining more than 90% initial activity | [ |
| DFF | lipase | supramolecular hydrogels @CTMS0.33@APTMS0.16-GAH@ CALB2 (9.6 wt%) | 40 °C, pH = 7.5 oxidant: O2 | FDCA | 100 | 100 | yield reduced from 100% to 25% after 3 cycles | [ |
| HMF | CotA-TJ102 | 50 mg Fe3O4-NH2 microspheres was added to 2 mL 3% v/v glutaraldehyde solution and then added 12.5 mg CotA-TJ102 | 55 °C, pH = 5.5 oxidant: O2 | FFCA | 98.55 | 98.6 | the yield remained 83.28% for 10 cycles | [ |
| DFF | lipase | 0.1 g biocatalyst with 5 mL reaction mixture | 40 °C, pH > 7 oxidant: O2 | FDCA | 60 | — | — | [ |
| HMF | galactose oxidase | 400 μL CuSO4 (80mmol/L) was added to 4 mL of PBS (10 mmol/L) containing GO (0.05 mg/mL) | 37 °C, pH = 7.4 oxidant: O2 | DFF | 98.1 | — | — | [ |
| HMF | galactose oxidase | 120 μL hematin (10 mmol/L) in dimethyl sulfoxide, 80 mL of GO solution (2.5 mg/mL) and 400 μL CuSO4 (80 mmol/L) | 37 °C, pH = 7.4 oxidant: O2 | DFF | 99.5 | — | — | [ |
| HMF | laccase | 50 mL laccase with 100 mg magnetic mesoporous silica nanoparticles | 35 °C, pH = 5.5 oxidant: O2 | FDCA | 90.2 | — | retained 84.8% original activity after 6 cycles | [ |
Table 1 Detailed information of the reactions of immobilization of enzymes.
| Substrate | Enzymes | Immobilization method | Reaction condition | Product | Yield (%) | Selectivity (%) | Stability | Ref. |
|---|---|---|---|---|---|---|---|---|
| starch | lipase B | TPP method promotes the formation of CLEAs by Eupergit and lipase B with 3:1. | 50 °C, pH = 8.0, no oxidant | HMF | 61.3 | — | 44% residual activity after 8 cycles | [ |
| glucose | glucose isomerase | Gensweet®IGI | 50 °C, pH = 4.8 no oxidant | HMF | >80 | >80 | 3 cycles without any significant yield loss | [ |
| glucose | glucose isomerase | IGI with citrate buffer at 100mmol/L | 70 °C, pH = 3.0 no oxidant | HMF | 20 | — | — | [ |
| glucose | glucose isomerase | H2O/[bmim][Cl]0.5[BF4]0.5 1:3 w/w ternary mixture added in glucose isomerase | 50 °C, pH = 7-8 no oxidant | HMF | 50 | — | 5 cycles without any significant activity loss | [ |
| glucose | thermophilic glucose isomerase | −NH2 functionalized mesoporous silica protect the enzyme in a monophasic solvent system composed of tetrahydrofuran (THF) and H2O (4:1 v/v) | 90 °C, pH = 7.0 no oxidant | HMF | 30 | — | this enzyme could not be recycled in the organic solvent | [ |
| cellulose | cellulase and isomerase | Fe3O4@MSN/(cellulase and isomerase = 4:1, v/v | 60 °C, pH = 7.4 no oxidant | HMF | 45.6 | — | the yield of HMF was reduced by 7% after 5 cycles | [ |
| cellulose | cellulase | SBA-15 support/cellulose = 25:1, w: w | 60 °C, pH = 4.8 no oxidant | HMF | 43.6 | — | the yield of HMF was reduced by 1.6% after 5 cycles | [ |
| fructose | heparin | PEI@PDA@MWCNT/heparin = 3:10, w:w | 25 °C, pH = 6.2 no oxidant | HMF | 46.2 | 82.2 | negligible loss in activity after 5 cycles | [ |
| high fructose corn syrup | glucose oxidase, catalase | GA-modified amino resin/ enzymes=1:25 | 150 °C, pH = 1.07 no oxidant | HMF | 85 | 85 | 10 cycles without any significant activity loss | [ |
| glucose | glucose-isomerase, lipase | glucose-isomerase/Novozym 435 = 1:1, DMSO/dioxane = 9:1 | 60 °C, pH = 7 no oxidant | HMF | 15 | — | 5 cycles without any significant activity loss | [ |
| DFF | lipase | Stober process EtOAc/tBuOH (1:1, v/v) | 40 °C, pH > 7 oxidant: O2 | FDCA | >99 | — | 5 cycles retaining more than 90% initial activity | [ |
| DFF | lipase | supramolecular hydrogels @CTMS0.33@APTMS0.16-GAH@ CALB2 (9.6 wt%) | 40 °C, pH = 7.5 oxidant: O2 | FDCA | 100 | 100 | yield reduced from 100% to 25% after 3 cycles | [ |
| HMF | CotA-TJ102 | 50 mg Fe3O4-NH2 microspheres was added to 2 mL 3% v/v glutaraldehyde solution and then added 12.5 mg CotA-TJ102 | 55 °C, pH = 5.5 oxidant: O2 | FFCA | 98.55 | 98.6 | the yield remained 83.28% for 10 cycles | [ |
| DFF | lipase | 0.1 g biocatalyst with 5 mL reaction mixture | 40 °C, pH > 7 oxidant: O2 | FDCA | 60 | — | — | [ |
| HMF | galactose oxidase | 400 μL CuSO4 (80mmol/L) was added to 4 mL of PBS (10 mmol/L) containing GO (0.05 mg/mL) | 37 °C, pH = 7.4 oxidant: O2 | DFF | 98.1 | — | — | [ |
| HMF | galactose oxidase | 120 μL hematin (10 mmol/L) in dimethyl sulfoxide, 80 mL of GO solution (2.5 mg/mL) and 400 μL CuSO4 (80 mmol/L) | 37 °C, pH = 7.4 oxidant: O2 | DFF | 99.5 | — | — | [ |
| HMF | laccase | 50 mL laccase with 100 mg magnetic mesoporous silica nanoparticles | 35 °C, pH = 5.5 oxidant: O2 | FDCA | 90.2 | — | retained 84.8% original activity after 6 cycles | [ |
Fig. 5. The immobilization of cells in the synthesis of HMF and its oxidation derivatives. (A) The SEM imaged depict various aspects of chitosan beads. (B) The influence of initial pH on the degradation of HMF and furfural from a simulated hydrolysate in a free cells culture of Bordetella sp. Continuous lines represent HMF and discontinuous lines represent furfural. This process included hydration, isomerization and dehydration reactions. Reproduced with permission from Ref. [81]. Copyright 2019, Elsevier. (C) HMF was synthesized from pineapple peel utilizing Cr(III) chloride (CrCl3) at a temperature of 100 °C. (D) A scale-up process for the production of FDCA via APLS-1. This process included oxidative dehydrogenation and oxidation reactions. Reproduced with permission from Ref. [83]. Copyright 2023, Elsevier.
| Substrate | Cells | Immobilization method | Reaction condition | Product | Yield (%) | Selectivity (%) | Stability | Ref. |
|---|---|---|---|---|---|---|---|---|
| glucose | Streptomyces coelicolor | commercial immobilization | 37 °C, pH = 7.4 no oxidant | HMF | 74 | low selectivity at high temperature | yield changed from 74% to 67% after 5 cycles | [ |
| lignin | Bordetella BTIITR | 2.5-20 mg cell add in 50 mL 2 wt% chitosan barrier | 40 °C, pH = 8.0 no oxidant | HMF | >90 | — | 7 cycles without any significant activity loss | [ |
| HMF | Raoultella ornithinolytica BF60 | sodium alginate/strain = 3:1 v/v, with 15 g/L Ca2+ | 30 °C, pH = 9.0 oxidant: O2 | FDCA | 42 | — | after 3 cycles without any activity loss | [ |
| pineapple peel | A. flavus APLS-1 | 1 × 106 spores/ml A. flavus APLS-1 inoculate with 1 g 250 ml polyurethane foam cubes | 100 °C, pH > 7 oxidant: O2 | FDCA | 47.6 | — | obtained FDCA dropped sharply after 2 d | [ |
Table 2 Detailed information of the reactions of immobilization of cells.
| Substrate | Cells | Immobilization method | Reaction condition | Product | Yield (%) | Selectivity (%) | Stability | Ref. |
|---|---|---|---|---|---|---|---|---|
| glucose | Streptomyces coelicolor | commercial immobilization | 37 °C, pH = 7.4 no oxidant | HMF | 74 | low selectivity at high temperature | yield changed from 74% to 67% after 5 cycles | [ |
| lignin | Bordetella BTIITR | 2.5-20 mg cell add in 50 mL 2 wt% chitosan barrier | 40 °C, pH = 8.0 no oxidant | HMF | >90 | — | 7 cycles without any significant activity loss | [ |
| HMF | Raoultella ornithinolytica BF60 | sodium alginate/strain = 3:1 v/v, with 15 g/L Ca2+ | 30 °C, pH = 9.0 oxidant: O2 | FDCA | 42 | — | after 3 cycles without any activity loss | [ |
| pineapple peel | A. flavus APLS-1 | 1 × 106 spores/ml A. flavus APLS-1 inoculate with 1 g 250 ml polyurethane foam cubes | 100 °C, pH > 7 oxidant: O2 | FDCA | 47.6 | — | obtained FDCA dropped sharply after 2 d | [ |
Fig. 6. (A) SEM images of ligand-grafted expanded HACS, Fe-NHC expanded HACS, ligand-grafted Starbon 350 and Fe-NHC/S350. Reproduced with permission from Ref. [95]. Copyright 2018, Wiley. (B) Illustration of the employed synthetic procedure for the preparation of heteropolyacids immobilized on ILs-modified organosilica hollow nanospheres. Reproduced with permission from Ref. [108]. Copyright 2019, Wiley. (C) Influence of different catalysts on the conversion of glucose to HMF. (D) Glucose transformation into HMF in the presence of Cr-IM-HSO4-MCM-41. This process included isomerization and dehydration reactions. Reproduced with permission from Ref. [109]. Copyright 2015, RSC. (E) Schematic illustration for the synthesis of composite solid acid catalyst and dehydration of fructose to HMF. This process was dehydration reaction. (F) The yield of HMF in different temperature conditions. This process was dehydration reaction. Reproduced with permission from Ref. [116]. Copyright 2017, Wiley. (G) Glucose conversion and HMF yield with various catalysts. This process included isomerization and dehydration reactions. Reproduced with permission from Ref. [113]. Copyright 2024, Elsevier.
Fig. 7. (A) Schematic illustration for the preparation of g-C3N4 supported chemically functional UiO-66-type MOFs catalysts in a one-pot MHT manner. (B) SEM images of UiO-66-NH2-SO3H-3/C3N4@PDA. (C) HMF yields obtained from glucose conversion catalyzed by UiO-66-NH2-SO3H-2/C3N4@PDA. This process included isomerization and dehydration reactions. Reproduced with permission from Ref. [117]. Copyright 2015, Elsevier. (D) The formation of HMF from fructose catalyzed by MSnPTA. This reaction was dehydration reaction. Reproduced with permission from Ref. [118]. Copyright 2023, Elsevier. (E) Catalytic fructose conversion to HMF. This reaction was dehydration reactions. Reproduced with permission from Ref. [120]. Copyright 2023, Royal Society of Chemistry.
| Substrate | Active component | Immobilization method | Reaction condition | Yield (%) | Selectivity (%) | Stability | Ref. |
|---|---|---|---|---|---|---|---|
| fructose | Fe-NHC | immobilized on mesoporous expanded starch and Starbon™ 350 | 100 °C no oxidant | 87 | 99 | yield from 87% to 81% after 5 cycles | [ |
| glucose | Cr3(CH3COO)7(OH)2 | Fe3O4-NH2-SAL particles (1.0 g, 20 mL) add in Cr3(CH3COO)7(OH)2 (1.04 g, 10 mL), at 80 °C for 12 h | 80 °C no oxidant | 57 | — | 6 cycles without any significant activity loss | [ |
| fructose | ionic liquid | 1 g SBA-16/SH mix with 2 mmol 1-vinylimidazole in 30 mL DMF, using click chemistry method | 120 °C no oxidant | 98 | — | yield from 98% to 88% after 5 cycles | [ |
| fructose | silicotungstic acid | impregnation method, 1 g Hal add in 30 wt% Keggin-type HPA desired in deionized water | 125 °C no oxidant | 99.5 | — | yield from 99.5% to 87% after 5 cycles | [ |
| fructose | IL-HSO4 | 1.4 g of SiO2 NPs add in 0.7 g IL-HSO4 with 0.5 mL DMSO | 130 °C no oxidant | 63 | 63 | yield from 63% to 60% after 7 cycles | [ |
| fructose | Aquivion PFSA | sol-gel method, 10g Aquivion water-dispersion add to the 15 g TEOS solution | 90 °C, pH = 7.0 no oxidant | 85 | 85 | 4 cycles without any significant activity loss, | [ |
| fructose | phosphotungstic acid | (0.086 mmol, 12.7 mL) P123, (28.8 mmol, 2.4 mL) HCl, (9.02 mmol, 1.3 mL) TMB with (2.34 mmol, 0.6 mL) BTMSE and 0.21 g (EtO)3Si-ILs-C4 and 0.75 g H3PW12O40 mix together | 100 °C no oxidant | 93.7 | — | yield from 93.7% to 91.2% after 6 cycles | [ |
| glucose | Cr(III) Schiff | 0.5 g MCM-41 with a mixture of 10 mmol Cr(salen) and 5mmol (3-aminopropyl) triethoxysilane | 140 °C no oxidant | 43.5 | 43.5 | 4 cycles with a little activity loss | [ |
| glucose | SnCl4 | 10 g SiO2, 5 g Al2O3, 5 g Na2SiO3, 1 g MgO, 1 g CaO with metal hydroxide precipitation at a certain precipitation | 170 °C, pH = 7.0 | 63.9 | — | 5 cycles with 53.7% yield | [ |
| glucose | B-L-ILs | 200 mg SiO2@Fe3O4-NH2@DDMAT and 10 mL methanol with 20 mg initiator of AIBN and 20 mg B-L-ILs, crosslinker CL8, SP, DDMAT. introduced into ultrasound | 150 °C no oxidant | 86.7 | 90.0 | 5 cycles without any significant activity loss | [ |
| fructose | UiO-66-SO3HX | dissolve 0.04 g ZrCl4, 0.046 g monosodium 2-sulfoterephthalate and 25 mg PVP-HNTs in 20 mL DMF | 120 °C no oxidant | 92.4 | — | 5 cycles without any significant activity loss | [ |
| glucose | UiO-66-NH2- SO3H-2 | 0.24 mmol ZrOCl2 8H2O (80 mg), 0.12 mmol BDC-SO3Na (30 mg) and 0.12 mmol BDC-NH2 (20 mg) are added in 5.0 mL CH3COOH/deionized water (2/3, v/v) mixture that containing 30mg C3N4@PDA carrier. | 120 °C no oxidant | 54.9 | 59.7 | 5 cycles with 8.2% yield loss | [ |
| fructose | phosphotungstic acid | 1.01 g, 80 mL Pluronic P123, 2.256 g, 5 mL SnCl2. 2H2O add in 0.576 g, 10 mL PTA | 120 °C no oxidant | 95 | — | 3 cycles with 10% yield loss | [ |
| fructose | Cr-IL | from 0.5 to 25 wt% nitrate salts with 50 mL distilled water and then 2.5g activated carbon | 120 °C no oxidant | 54.76 | — | 7 cycles with near half yield loss | [ |
| fructose | sulfonic acid groups | 2 mmol 1,3-propanesultone with 1 g ImIL @MWCNTs in 20 mL anhydrous toluene. Then mix with 30 mL of diluted H2SO4 | 100 °C no oxidant | 95 | — | yield from 95% to 91% after 5 cycles | [ |
| mannose | Cr(NO3)3·9H2O/SnCl4·5H2O | 10 mmol Cr(NO3)3·9H2O/SnCl4·5H2O and LS (20 g, 10 mmol) are dissolved in 70 mL water | 140 °C no oxidant | 68.8 | 70.6 | 5 cycles without any significant activity loss | [ |
| glucose | Nb2O5·nH2O | cellulose concentration of 4.0% (w/w) mix with 1 g NbCl5 | 140-160 °C no oxidant | 27.8 | 28.4 | 4 cycles with 5% yield loss | [ |
Table 3 Detailed information of the reactions of immobilized chemical catalysts for HMF synthesis.
| Substrate | Active component | Immobilization method | Reaction condition | Yield (%) | Selectivity (%) | Stability | Ref. |
|---|---|---|---|---|---|---|---|
| fructose | Fe-NHC | immobilized on mesoporous expanded starch and Starbon™ 350 | 100 °C no oxidant | 87 | 99 | yield from 87% to 81% after 5 cycles | [ |
| glucose | Cr3(CH3COO)7(OH)2 | Fe3O4-NH2-SAL particles (1.0 g, 20 mL) add in Cr3(CH3COO)7(OH)2 (1.04 g, 10 mL), at 80 °C for 12 h | 80 °C no oxidant | 57 | — | 6 cycles without any significant activity loss | [ |
| fructose | ionic liquid | 1 g SBA-16/SH mix with 2 mmol 1-vinylimidazole in 30 mL DMF, using click chemistry method | 120 °C no oxidant | 98 | — | yield from 98% to 88% after 5 cycles | [ |
| fructose | silicotungstic acid | impregnation method, 1 g Hal add in 30 wt% Keggin-type HPA desired in deionized water | 125 °C no oxidant | 99.5 | — | yield from 99.5% to 87% after 5 cycles | [ |
| fructose | IL-HSO4 | 1.4 g of SiO2 NPs add in 0.7 g IL-HSO4 with 0.5 mL DMSO | 130 °C no oxidant | 63 | 63 | yield from 63% to 60% after 7 cycles | [ |
| fructose | Aquivion PFSA | sol-gel method, 10g Aquivion water-dispersion add to the 15 g TEOS solution | 90 °C, pH = 7.0 no oxidant | 85 | 85 | 4 cycles without any significant activity loss, | [ |
| fructose | phosphotungstic acid | (0.086 mmol, 12.7 mL) P123, (28.8 mmol, 2.4 mL) HCl, (9.02 mmol, 1.3 mL) TMB with (2.34 mmol, 0.6 mL) BTMSE and 0.21 g (EtO)3Si-ILs-C4 and 0.75 g H3PW12O40 mix together | 100 °C no oxidant | 93.7 | — | yield from 93.7% to 91.2% after 6 cycles | [ |
| glucose | Cr(III) Schiff | 0.5 g MCM-41 with a mixture of 10 mmol Cr(salen) and 5mmol (3-aminopropyl) triethoxysilane | 140 °C no oxidant | 43.5 | 43.5 | 4 cycles with a little activity loss | [ |
| glucose | SnCl4 | 10 g SiO2, 5 g Al2O3, 5 g Na2SiO3, 1 g MgO, 1 g CaO with metal hydroxide precipitation at a certain precipitation | 170 °C, pH = 7.0 | 63.9 | — | 5 cycles with 53.7% yield | [ |
| glucose | B-L-ILs | 200 mg SiO2@Fe3O4-NH2@DDMAT and 10 mL methanol with 20 mg initiator of AIBN and 20 mg B-L-ILs, crosslinker CL8, SP, DDMAT. introduced into ultrasound | 150 °C no oxidant | 86.7 | 90.0 | 5 cycles without any significant activity loss | [ |
| fructose | UiO-66-SO3HX | dissolve 0.04 g ZrCl4, 0.046 g monosodium 2-sulfoterephthalate and 25 mg PVP-HNTs in 20 mL DMF | 120 °C no oxidant | 92.4 | — | 5 cycles without any significant activity loss | [ |
| glucose | UiO-66-NH2- SO3H-2 | 0.24 mmol ZrOCl2 8H2O (80 mg), 0.12 mmol BDC-SO3Na (30 mg) and 0.12 mmol BDC-NH2 (20 mg) are added in 5.0 mL CH3COOH/deionized water (2/3, v/v) mixture that containing 30mg C3N4@PDA carrier. | 120 °C no oxidant | 54.9 | 59.7 | 5 cycles with 8.2% yield loss | [ |
| fructose | phosphotungstic acid | 1.01 g, 80 mL Pluronic P123, 2.256 g, 5 mL SnCl2. 2H2O add in 0.576 g, 10 mL PTA | 120 °C no oxidant | 95 | — | 3 cycles with 10% yield loss | [ |
| fructose | Cr-IL | from 0.5 to 25 wt% nitrate salts with 50 mL distilled water and then 2.5g activated carbon | 120 °C no oxidant | 54.76 | — | 7 cycles with near half yield loss | [ |
| fructose | sulfonic acid groups | 2 mmol 1,3-propanesultone with 1 g ImIL @MWCNTs in 20 mL anhydrous toluene. Then mix with 30 mL of diluted H2SO4 | 100 °C no oxidant | 95 | — | yield from 95% to 91% after 5 cycles | [ |
| mannose | Cr(NO3)3·9H2O/SnCl4·5H2O | 10 mmol Cr(NO3)3·9H2O/SnCl4·5H2O and LS (20 g, 10 mmol) are dissolved in 70 mL water | 140 °C no oxidant | 68.8 | 70.6 | 5 cycles without any significant activity loss | [ |
| glucose | Nb2O5·nH2O | cellulose concentration of 4.0% (w/w) mix with 1 g NbCl5 | 140-160 °C no oxidant | 27.8 | 28.4 | 4 cycles with 5% yield loss | [ |
Fig. 8. Immobilization of chemical catalysts in synthesis of DFF. (A,B) Ru (III)/Pal TEM images. (C) STEM image. (D) HMF content. This reaction was oxidative dehydrogenation reaction. Reproduced with permission from Ref. [129] Copyright 2023, Elsevier. (E) Selective aerobic oxidation of HMF to DFF over VO2-PANI/CNT. (F) Catalyst recycling. This reaction was oxidative dehydrogenation reaction. Reproduced with permission from Ref. [133]. Copyright 2015, Wiley.
Fig. 9. Immobilization of chemical catalysts in synthesis of FDCA and HMFCA. Time-resolved (A) and recyclability (B) for the oxidation of HMF into FDCA. (C) Schematic representation of the synthesis of Au NPs supported on MgSi-ZSM-12. This process included oxidative dehydrogenation and oxidation reactions. Reproduced with permission from Ref. [138]. Copyright 2021, Elsevier. (D) TEM images of the samples. K-10 clay and K-10 clay-Mo; Reproduced with permission from Ref. [149]. Copyright 2014, Royal Society of Chemistry. (E) Highly efficient Nb-based homogeneous and heterogeneous catalysts were developed for the efficient synthesis of HMFCA. This reaction was oxidation reaction. Reproduced with permission from Ref. [150]. Copyright 2022, Wiley.
| Active component | Immobilization method | Reaction conditions | Product | Yield (%) | Selectivity (%) | Stability | Ref. |
|---|---|---|---|---|---|---|---|
| Al(NO3)3 | 1.12 g, 10 mL of Al(NO3)3·9H2O with 1 g ECS-IL | 50 °C oxidant: O2 | DFF | 98 | 99 | 6 cycles without any significant activity loss | [ |
| RuCl3·3H2O | 0.5 g, 50 mL palygorskite with 4 mg/mL RuCl3 solution, and then 5 mL, 100 mg/mL NaBH4 solution to reduce Ru3+ | 110 °C, 10 bar O2 oxidant: O2 | DFF | 98 | 98 | 5 cycles without any significant activity loss | [ |
| RuCl3 | 2.2 wt% of Ru immobilize on PVP/CNT | 120 °C oxidant: O2 | DFF | 94 | 95 | leach 13.6% Ru | [ |
| VO2 | 400 mg PANI/CNT submerg into 6 mL, 70 °C NH4VO3 | 120 °C, 2.75 bar O2, pH = 3 oxidant: O2 | DFF | 96 | 96 | 5 cycles with 21% yield loss and 30% VO2 leached | [ |
| TEMPO | 2 g SBA-15 with 1.53 mmol PTES-TEMPO in 90 mL toluene | 40 °C oxidant: O2, BAIB, acetic acid | DFF | 73 | — | 5 cycles without any significant activity loss | [ |
| Cu(NO3)2, VOSO4 | 0.5 g VOSO4/Cu(NO3)2 with 1 g MCM-NH2 into 50 mL methanol | 120 °C, 0.28 MPa O2 oxidant: O2 | DFF | 61.2 | 62.4 | 4 cycles without any significant activity loss | [ |
| Cu(NO3)2, VOSO4 | 0.5 g VOSO4/Cu(NO3)2 with 1 g Fe3O4@SiO2-NH2 into 50 mL methanol | 110 °C, 0.28MPa O2 oxidant: O2 | DFF | 85.5 | 86.6 | yield from 85.5% to 81.2% after 4 cycles | [ |
| CuSO4 | 10 g silica support with 1 g CuSO4 in 50 mL water | 160 °C oxidant: pyridine N-oxide | DFF | 54 | 75 | 7 cycles with 5% yield loss | [ |
| HAuCl4 | 0.01 g HAuCl4 with 0.25 g MgSi-ZSM-12 and then NH3⋅H2O solution to adjust the pH ~9 | 90 °C oxidant: O2 | FDCA | 87 | 87 | 5 cycles without any significant activity loss | [ |
| HAuCl4·4H2O, H2PtCl6·6H2O | 1 mL, 4 mg/mL H2PtCl6·6H2O 3.19 mL, 4 mg/mL of HAuCl4·4H2O with 500 mg/5 mL NaBH4 | 95 °C, 10 bar O2 oxidant: O2 | FDCA | 99 | 99 | 6 cycles without any significant activity loss | [ |
| Na2PdCl4 | 30 mg, 10 mL graphite oxide 0.1 g FeCl3·6H2O and 1.2 g NaOAc are added to a mixed solvent of 5 mL water and 10mL ethylene glycol, then mix 4 mg Na2PdCl4 dissolved in 5 mL of N, N-dimethylformamide | 80 °C, 20 mL/min O2 oxidant: O2 | FDCA | 91.8 | 93.5 | 6 cycles without any significant activity loss | [ |
| metalloporphyrins | 0.74 mmol/g metalloporphyrins mix with 1 g chloropropyl functional mesoporous silica in 50 mL DMF | 100 °C 40 bar O2 oxidant: O2 | FDCA | 94.94 | 94.94 | yield from 94.94% to 93.13% after 5 cycles | [ |
| Cu(NO3)2, VOSO4 | 1 g SBA-NH2 with 0.5 g Cu(NO3)2/VOSO4 are added in 50 mL methanol | 110 °C oxidant: O2 | FDCA | 28.9 | 29.3 | 4 cycles without any significant activity loss | [ |
| CoOx, MnOx or FeOx | 10 mL M(II) acetate add in xNb@MNP at pH = 10.5 | 100 °C oxidant: t-BuOOH | FDCA | 93.2 | 96.5 | 5 cycles without any significant activity loss | [ |
| NiFeCe-LDH | 0.4362 g Ni(NO3)2·6H2O, 0.202 g Fe(NO3)3·9H2O, 0.6006 g urea, 0.1852 g NH4F are dispersed into 35 mL deionized water, then transfer to a 50 mL PTFE, and add 0.0434 g Ce(NO3)3·6H2O | 25 °C oxidant: O2 | FDCA | 93.31 | 97.47 | yield from 93.31% to 85.38% after 5 cycles | [ |
| RuCl3·xH2O | 1 g, 5 mL CsPW contain 50 mg RuCl3·xH2O (40 wt% Ru) | 130 °C oxidant: O2 | HMFCA | 72.9 | 75 | 5 cycles with 12.1% yield loss | [ |
| MoO2(acac)2 | 0.6325 g MoO2(acac)2 dissolve in 50 mL dry toluene, then add 1 g K-10 clay | 110 °C oxidant: O2 | HMFCA | 86.9 | 86.9 | yield from 86.9% to 83.9% after 6 cycles | [ |
| Nb(O2)3 | 1.25 mmol, 0.65 g TpNb dissolve in 30% hydrogen peroxide (4 mL, 35.39 mmol), then add 1 g MRG | 60 °C oxidant: H2O2 | HMFCA | 100 | 100 | yield from 100% to 93% after 5 cycles | [ |
Table 4 Detailed information of the reactions of immobilized chemical catalysts for HMF oxidation derivatives synthesis.
| Active component | Immobilization method | Reaction conditions | Product | Yield (%) | Selectivity (%) | Stability | Ref. |
|---|---|---|---|---|---|---|---|
| Al(NO3)3 | 1.12 g, 10 mL of Al(NO3)3·9H2O with 1 g ECS-IL | 50 °C oxidant: O2 | DFF | 98 | 99 | 6 cycles without any significant activity loss | [ |
| RuCl3·3H2O | 0.5 g, 50 mL palygorskite with 4 mg/mL RuCl3 solution, and then 5 mL, 100 mg/mL NaBH4 solution to reduce Ru3+ | 110 °C, 10 bar O2 oxidant: O2 | DFF | 98 | 98 | 5 cycles without any significant activity loss | [ |
| RuCl3 | 2.2 wt% of Ru immobilize on PVP/CNT | 120 °C oxidant: O2 | DFF | 94 | 95 | leach 13.6% Ru | [ |
| VO2 | 400 mg PANI/CNT submerg into 6 mL, 70 °C NH4VO3 | 120 °C, 2.75 bar O2, pH = 3 oxidant: O2 | DFF | 96 | 96 | 5 cycles with 21% yield loss and 30% VO2 leached | [ |
| TEMPO | 2 g SBA-15 with 1.53 mmol PTES-TEMPO in 90 mL toluene | 40 °C oxidant: O2, BAIB, acetic acid | DFF | 73 | — | 5 cycles without any significant activity loss | [ |
| Cu(NO3)2, VOSO4 | 0.5 g VOSO4/Cu(NO3)2 with 1 g MCM-NH2 into 50 mL methanol | 120 °C, 0.28 MPa O2 oxidant: O2 | DFF | 61.2 | 62.4 | 4 cycles without any significant activity loss | [ |
| Cu(NO3)2, VOSO4 | 0.5 g VOSO4/Cu(NO3)2 with 1 g Fe3O4@SiO2-NH2 into 50 mL methanol | 110 °C, 0.28MPa O2 oxidant: O2 | DFF | 85.5 | 86.6 | yield from 85.5% to 81.2% after 4 cycles | [ |
| CuSO4 | 10 g silica support with 1 g CuSO4 in 50 mL water | 160 °C oxidant: pyridine N-oxide | DFF | 54 | 75 | 7 cycles with 5% yield loss | [ |
| HAuCl4 | 0.01 g HAuCl4 with 0.25 g MgSi-ZSM-12 and then NH3⋅H2O solution to adjust the pH ~9 | 90 °C oxidant: O2 | FDCA | 87 | 87 | 5 cycles without any significant activity loss | [ |
| HAuCl4·4H2O, H2PtCl6·6H2O | 1 mL, 4 mg/mL H2PtCl6·6H2O 3.19 mL, 4 mg/mL of HAuCl4·4H2O with 500 mg/5 mL NaBH4 | 95 °C, 10 bar O2 oxidant: O2 | FDCA | 99 | 99 | 6 cycles without any significant activity loss | [ |
| Na2PdCl4 | 30 mg, 10 mL graphite oxide 0.1 g FeCl3·6H2O and 1.2 g NaOAc are added to a mixed solvent of 5 mL water and 10mL ethylene glycol, then mix 4 mg Na2PdCl4 dissolved in 5 mL of N, N-dimethylformamide | 80 °C, 20 mL/min O2 oxidant: O2 | FDCA | 91.8 | 93.5 | 6 cycles without any significant activity loss | [ |
| metalloporphyrins | 0.74 mmol/g metalloporphyrins mix with 1 g chloropropyl functional mesoporous silica in 50 mL DMF | 100 °C 40 bar O2 oxidant: O2 | FDCA | 94.94 | 94.94 | yield from 94.94% to 93.13% after 5 cycles | [ |
| Cu(NO3)2, VOSO4 | 1 g SBA-NH2 with 0.5 g Cu(NO3)2/VOSO4 are added in 50 mL methanol | 110 °C oxidant: O2 | FDCA | 28.9 | 29.3 | 4 cycles without any significant activity loss | [ |
| CoOx, MnOx or FeOx | 10 mL M(II) acetate add in xNb@MNP at pH = 10.5 | 100 °C oxidant: t-BuOOH | FDCA | 93.2 | 96.5 | 5 cycles without any significant activity loss | [ |
| NiFeCe-LDH | 0.4362 g Ni(NO3)2·6H2O, 0.202 g Fe(NO3)3·9H2O, 0.6006 g urea, 0.1852 g NH4F are dispersed into 35 mL deionized water, then transfer to a 50 mL PTFE, and add 0.0434 g Ce(NO3)3·6H2O | 25 °C oxidant: O2 | FDCA | 93.31 | 97.47 | yield from 93.31% to 85.38% after 5 cycles | [ |
| RuCl3·xH2O | 1 g, 5 mL CsPW contain 50 mg RuCl3·xH2O (40 wt% Ru) | 130 °C oxidant: O2 | HMFCA | 72.9 | 75 | 5 cycles with 12.1% yield loss | [ |
| MoO2(acac)2 | 0.6325 g MoO2(acac)2 dissolve in 50 mL dry toluene, then add 1 g K-10 clay | 110 °C oxidant: O2 | HMFCA | 86.9 | 86.9 | yield from 86.9% to 83.9% after 6 cycles | [ |
| Nb(O2)3 | 1.25 mmol, 0.65 g TpNb dissolve in 30% hydrogen peroxide (4 mL, 35.39 mmol), then add 1 g MRG | 60 °C oxidant: H2O2 | HMFCA | 100 | 100 | yield from 100% to 93% after 5 cycles | [ |
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