催化学报 ›› 2025, Vol. 71: 5-24.DOI: 10.1016/S1872-2067(24)60274-3
陈瑶a, 戈钧a,b,c,*(
)
收稿日期:2024-11-05
接受日期:2025-01-20
出版日期:2025-04-18
发布日期:2025-04-13
通讯作者:
* 电子信箱: junge@mail.tsinghua.edu.cn (戈钧).基金资助:
Yao Chena, Jun Gea,b,c,*()
Received:2024-11-05
Accepted:2025-01-20
Online:2025-04-18
Published:2025-04-13
Contact:
* 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:摘要：
5-羟甲基糠醛(HMF)及其氧化衍生物已被公认为是连接生物质资源和未来能源行业的桥梁. 这些宝贵的可再生生物质资源可以转化为许多高附加值的化学品, 能够有效解决化石资源日益减少和环境污染等问题. 固定化催化剂技术作为一种绿色高效合成HMF及其氧化衍生物的策略, 不仅可以提高产物的产率和选择性, 还可以通过设计载体来调控固定化催化剂的催化性能. 本文综述了近年来固定化催化剂在HMF及其氧化衍生物合成中的应用, 重点探讨了不同固定化催化剂的制备方法及其催化性能. 通过系统全面的介绍, 本文作为固定化催化剂技术在HMF及其氧化衍生物的合成提供了新思路.
本文从固定化酶、细胞和化学催化剂三方面展开, 分析了不同类型固定化技术在合成HMF及其氧化衍生物中的应用. 针对温度和pH值的波动导致酶和细胞的失活, 可重复使用性较差以及难以与反应体系分离的问题, 总结了不同载体结构包括水凝胶、碳基材料、硅基材料、共价有机框架和金属有机框架(MOF)等对酶的固定化方法, 考察这些固定化酶在HMF及其氧化衍生物中的催化效率、选择性和重复使用性能, 并总结了不同固定化方法的制备条件及催化反应条件, 并对重复使用性降低的原因进行了分析. 介绍了固定化细胞在HMF及其氧化衍生物合成中的应用, 由于细胞的特殊性, 常采用壳聚糖、海藻酸钙等生物相容性较好的物质作为固定化载体, 并分析了这些固定化细胞的催化效率以及重复使用性能. 化学催化剂金属纳米颗粒的聚集会降低其催化活性, 将金属纳米颗粒固定在多孔材料中, 通过相互作用和空间限制效应促进了其稳定, 从而防止催化剂制备和催化过程中的聚集. 介绍了多种载体, 如传统沸石咪唑, 二氧化硅, MOF载体, 聚合物载体固定化学催化剂用于合成HMF及其氧化衍生物方面的催化效率、选择性以及重复使用性能, 并对不同固定化化学催化剂的制备方法进行了描述. 最后, 展望了固定化催化剂未来的发展方向, 包括高性能固定化催化剂的制备、固定化催化剂的制备和催化机理等.
综上, 本文综述了固定化催化剂在HMF及其氧化衍生物合成中的应用, 阐述了多种体系的固定化方法及催化性能, 为绿色可持续的催化技术在生物质资源应用方面提供了参考.
陈瑶, 戈钧. 固定化催化剂合成5-羟甲基糠醛及其氧化衍生物: 高效的绿色可持续技术[J]. 催化学报, 2025, 71: 5-24.
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.
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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