SiO<sub>2</sub>-AlO(OH) composite-loaded gold nanoparticles catalyze the oxidative esterification reaction of 5-hydroxymethylfurfural

Zhang Hailin; Li Xianjie; Zhang Changcheng; Liu Yaping; Qiu Xiaomin; Xiao Meng; Huang Tingting; Zhu Quanhong; Shang Zhijie; Song Hongbing

doi:null

Your Location：

Home >

Browse articles >

SiO₂-AlO(OH) composite-loaded gold nanoparticles catalyze the oxidative esterification reaction of 5-hydroxymethylfurfural

Updated：2026-09-17

- SiO₂-AlO(OH) composite-loaded gold nanoparticles catalyze the oxidative esterification reaction of 5-hydroxymethylfurfural
- Chinese Journal of Chemical Engineering Vol. 95, Issue 7, Pages: 207-216(2026)
- Affiliations：
  
  College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
- Author bio：
  
  *Corresponding authors. E-mail addresses:shangzhijie1204@outlook.com(Z. Shang)
  *Corresponding authors. E-mail addresses:cehbsong@qust.edu.cn(H. Song).
- Funds：
- DOI：
  CLC：
- Received：28 October 2025，
  
  Revised：2026-01-24，
  
  Accepted：27 January 2026，
  
  Online First：12 April 2026，
  
  Published：2026-07
- Accepted：
Scan QR Code
Zhang Hailin, Li Xianjie, Zhang Changcheng, et al. SiO₂-AlO(OH) composite-loaded gold nanoparticles catalyze the oxidative esterification reaction of 5-hydroxymethylfurfural[J]. Chinese Journal of Chemical Engineering, 2026, 95(7): 207-216.
DOI：

Zhang Hailin, Li Xianjie, Zhang Changcheng, et al. SiO₂-AlO(OH) composite-loaded gold nanoparticles catalyze the oxidative esterification reaction of 5-hydroxymethylfurfural[J]. Chinese Journal of Chemical Engineering, 2026, 95(7): 207-216. DOI：

摘要

Abstract

5-Hydroxymethylfurfural (HMF) is a highly valuable platform compound derived from cellulose

enabling the synthesis of various premium chemical products through oxidative esterification

including dimethyl 2

5-furanedicarboxylate (FDMC). This process finds widespread applications across numerous industries. By adjusting the Si/Al ratio

we prepared diverse catalyst carriers and utilized the urea precipitation method to fabricate various catalysts with a low gold loading of 1% (mass). These catalysts were subsequently characterized by a range of analytical techniques. Notably

the Au/SiO

-AlO(OH)-3 catalyst

characterized by its large specific surface area and abundant pore size

facilitated the highly dispersed presence of gold on the catalyst surface

exhibiting the best catalytic performance. Specifically

the Au/SiO

-AlO(OH)-3 catalyst demonstrated high efficiency

achieving 99.9% HMF conversion and 95.2% FDMC yield at a 0.25 mmol scale of HMF within 6 h under 0.1 equivalent Na

. This study proposes a mechanistic scheme for the conversion of HMF to FDMC

via

Au/SiO

-AlO(OH)-3-catalyzed oxidative esterification. Furthermore

free radical inhibition experiments were conducted

and the results indicated that superoxide anion radicals play a significant role in the HMF oxidativ

e esterification reaction. We also performed a series of substrate extensions

confirming the catalyst's excellent oxidative esterification effect on a wide range of substrates

including aromatic aldehydes and alcohols. These findings are expected to facilitate the development of oxidative esterification reactions of biomass-derived platform compounds.

关键词

Keywords

references

G.Z. Mao, H.Y. Zou, G.Y. Chen, H.B. Du, J. Zuo, Past, current and future of biomass energy research: a bibliometric analysis, Renew. Sustain. Energy Rev. 52 (2015) 1823—1833.

A. Mahdavi-Shakib, J. Sempel, M. Hoffman, A. Oza, E. Bennett, J.S. Owen, A. Rahmani Chokanlu, B.G. Frederick, R.N. Austin, Au/TiO 2 -catalyzed benzyl alcohol oxidation on morphologically precise anatase nanoparticles, ACS Appl. Mater. Interfaces 13 (10) (2021) 11793—11804.

N.L. Panwar, S.C. Kaushik, S. Kothari, Role of renewable energy sources in environmental protection: a review, Renew. Sustain. Energy Rev. 15 (3) (2011) 1513—1524.

A. Barakat, H. de Vries, X. Roua u, Dry fractionation process as an important step in current and future lignocellulose biorefineries: a review, Bioresour. Technol. 134 (2013) 362—373.

S. Saxena, D. Yadaw, K. Tiwari, V. Venkatesh, S. Verma, R.G.S. Pala, S. Sivakumar, Hollow zeolites encapsulating ultra-low noble metal nanoparticles for HMF oxidation, Catal. Lett. 151 (4) (2021) 921—931.

M. El Fergani, N. Candu, P. Granger, S.M. Coman, V.I. Parvulescu, Hierarchically MO x @Nb-zeolites for the selective oxidation of HMF to HMFCA, Catal. Today 405 (2022) 267—276.

A.A. Turkin, E.V. Makshina, B.F. Sels, Catalytic hydroconversion of 5-HMF to value-added chemicals: insights into the role of catalyst properties and feedstock purity, ChemSusChem 15 (13) (2022) e202200412.

B. Pomeroy, M. Grilc, S. Gyergyek, B. Likozar, Catalyst structure-based hydroxymethylfurfural (HMF) hydrogenation mechanisms, activity and selectivity over Ni, Chem. Eng. J. 412 (2021) 127553.

X.Y. Jia, K. Yuan, G.F. Wang, S.H. Zhu, M. Dong, J.M. Wang, X.M. Li, W.B. Fan, Reaction-induced restructuring of partial Pd single atoms to nanoparticles for enhancing HMF selective hydrogenation to BHMTHF, Chem. Eng. J. 487 (2024) 150482.

F. Zaccheria, F. Bossola, N. Scotti, C. Evangelisti, V. Dal Santo, N. Ravasio, On demand production of ethers or alcohols from furfural and HMF by selecting the composition of a Zr/Si catalyst, Catal. Sci. Technol. 10 (22) (2020) 7502—7511.

P. Lanzafame, G. Papanikolaou, K. Barbera, G. Centi, S. Perathoner, Etherification of HMF to biodiesel additives: the role of NH4+confinement in Beta zeolites, J. Energy Chem. 36 (2019) 114—121.

M.C. Allen, A.J. Hoffman, T.W. Liu, M.S. Webber, D. Hibbitts, T.J. Schwartz, Highly selective cross-etherification of 5-hydroxymethylfurfural with ethanol, ACS Catal. 10 (12) (2020) 6771—6785.

E.B. Gilcher, H. Chang, G.W. Huber, J.A. Dumesic, Controlled hydrogenation of a biomass-derived platform chemical formed by aldol-condensation of 5hydroxymethyl furfural (HMF) and acetone over Ru, Pd, and Cu catalysts, Green Chem. 24 (5) (2022) 2146—2159.

M. Kopp, P. Anabalón, M. Larriba, S. Rocha, M.E. González, M. Cea, Green production of 5-hydroxymethylfurfural (HMF) in biphasic continuous microreactor using terpenoid-based solvents, Chem. Eng. J. 516 (2025) 164077.

S.K. Burgess, J.E. Leisen, B.E. Kraftschik, C.R. Mubarak, R.M. Kriegel, W.J. Koros, Chain mobility, thermal, and mechanical properties of Poly(ethylene furanoate) compared to Poly(ethylene terephthalate), Macromolecules 47 (4) (2014) 1383—1391.

K.A.P. Payne, S.A. Marshall, K. Fisher, M.J. Cliff, D.M. Cannas, C.Y. Yan, D.J. Heyes, D.A. Parker, I. Larrosa, D. Leys, Enzymatic carboxylation of 2-furoic acid yields 2, 5-furandicarboxylic acid (FDCA), ACS Catal. 9 (4) (2019) 2854—2865.

F. Li, X.L. Li, C. Li, J. Shi, Y. Fu, Aerobic oxidative esterification of 5hydroxymethylfurfural to dimethyl furan-2, 5-dicarboxylate by using homogeneo us and heterogeneous PdCoBi/C catalysts under atmospheric oxygen, Green Chem. 20 (13) (2018) 3050—3058.

H. Liu, X. Tang, X.H. Zeng, Y. Sun, X.X. Ke, T.Y. Li, J.R. Zhang, L. Lin, Catalyst design strategy toward the efficient heterogeneously-catalyzed selective oxidation of 5-hydroxymethylfurfural, Green Energy Environ. 7 (5) (2022) 900—932.

D.Y. Zhao, T. Su, C. Len, R. Luque, Z.L. Yang, Recent advances in the oxidative esterification of 5-hydroxymethylfurfural to furan-2, 5-dimethylcarboxylate, Green Chem. 24 (18) (2022) 6782—6789.

Y.C. Feng, W.L. Jia, G.H. Yan, X.H. Zeng, J. Sperry, B.B. Xu, Y. Sun, X. Tang, T.Z. Lei, L. Lin, Insights into the active sites and catalytic mechanism of oxidative esterification of 5-hydroxymethylfurfural by metal-organic frameworksderived N-doped carbon, J. Catal. 381 (2020) 570—578.

H. Zhou, S. Hong, H. Zhang, Y.T. Chen, H.H. Xu, X.K. Wang, Z. Jiang, S.L. Chen, Y. Liu, Toward biomass-based single-atom catalysts and plastics: highly active single-atom Co on N-doped carbon for oxidative esterification of primary alcohols, Appl. Catal. B Environ. 256 (2019) 117767.

E.X. Yuan, M.X. Zhou, P.M. Jian, X. Hou, Atomically dispersed Co/C 3 N 4 for boosting aerobic cyclohexane oxidation, Appl. Surf. Sci. 613 (2023) 155886.

O. Ivanez, A. Miro i Rovira, E.A. Blekkan, Impact of the support material on the phosphorus poisoning on Co-based catalysts for Fischer-Tropsch synthesis, Catal. Today 441 (2024) 114866.

H. Yang, C. Li, L.Z. Lü, Z.G. Li, S.Q. Zhang, Z. Huang, R. Ma, S.S. Liu, M. Ge, W. Zhou, X.L. Yuan, Electronegativity- induced cobalt-doped platinum hollow nanospheres with high CO tolerance for efficient methanol oxidation reaction, J. Colloid Interface Sci. 678 (2025) 300—308.

C. Pei, S.J. Chen, R.R. Song, F. Lv, Y. Wan, The self-assembly of gold nanoparticles in large-pore ordered mesoporous carbons, Chin. J. Chem. Eng. 41 (2022) 420—429.

S.R. Docherty, O.V. Safonova, C. Copéret, Surface redox dynamics in gold—zinc CO 2 Hydrogenation catalysts, J. Am. Chem. Soc. 145 (25) (2023) 13526—13530.

P.P. George, A. Gedanken, N. Perkas, Z. Zhong, Selective oxidation of CO in the presence of air over gold-based catalysts Au/TiO 2 /C (sonochemistry) and Au/TiO 2 /C (microwave), Ultrason. Sonochem. 15 (4) (2008) 539—547.

L. Xuan Dien, T. Murayama, N. Tuan Hung, Q. Duc Truong, H. Dang Chinh, M. Yoshimura, M. Haruta, T. Ishida, Efficient non-volatile organogold complex for TiO 2 -supported gold cluster catalysts: preparation and catalytic activity for CO oxidation, J. Catal. 408 (2022) 236—244.

Z.P. Liu, P. Hu, A. Alavi, Catalytic role of gold in gold-based catalysts: a density functional theory study on the CO oxidation on gold, J. Am. Chem. Soc. 124 (49) (2002) 14770—14779.

B.P.C. Hereijgers, B.M. Weckhuysen, Aerobic oxidation of cyclohexane by gold-based catalysts: new mechanistic insight by thorough product analysis, J. Catal. 270 (1) (2010) 16—25.

Q. Huang, Y.X. Cao, K. Satou, H. Murayama, A. Yoshizawa, E. Yamamoto, A. Nakayama, T. Ishida, Y. Kitagawa, Y. Ishimaru, M. Okumura, T. Honma, Y. Suzuki, M. Tokunaga, Active and stable Au/ZrO 2 catalysts for isomerization of allylic esters: a practical application of heterogeneous gold catalysis, Appl. Catal. B Environ. Energy 373 (2025) 125351.

Y.H. Zhou, Z.Q. Wang, B. Ye, X.B. Huang, H. Deng, Ligand effect over gold nanocatalysts towards enhanced gas-phase oxidation of alcohols, J. Catal. 400 (2021) 274—282.

B. Ballarin, D. Barreca, E. Boanini, M.C. Cassani, P. Dambruoso, A. Massi, A. Mignani, D. Nanni, C. Parise, A. Zaghi, Supported gold nanoparticles for alcohols oxidation in continuous-flow heterogeneous systems, ACS Sustainable Chem. Eng. 5 (6) (2017) 4746—4756.

W. Wang, Y. Xie, S.H. Zhang, X. Liu, L.Y. Zhang, B.S. Zhang, M. Haruta, J.H. Huang, Highly efficient base-free aerobic oxidation of alcohols over gold nanoparticles supported on ZnO-CuO mixed oxides, Chin. J. Catal. 40 (12) (2019) 1924—1933.

W. Hong, X.Q. Yan, R.H. Li, J. Fan, Gold nanoparticle stabilization within tailored cubic mesoporous silica: optimizing alcohol oxidation activity, Chin. J. Catal. 38 (3) (2017) 545—553.

M. Li, L. Shi, T. Xie, C. Jing, G.L. Xiu, Y.T. Long, An ultrasensitive plasmonic nanosensor for aldehydes, ACS Sens. 2 (2) (2017) 263—267.

X.X. Qin, M. Chen, X.Y. Chen, J.H. Zh ang, X.X. Wang, J.H. Fang, H. He, C.B. Zhang, Regulating the surface Au sites of Au/TiO 2 catalyst for achieving cooxidation of HCHO and CO at room temperature, Appl. Catal. B Environ. 330 (2023) 122663.

J.J. Luo, S.H. Yang, Y. Ling, W.H. Yang, H.Y. Niu, W.L. Li, H.B. Liu, C.H. Liang, Defective Au nanoparticles manipulated by Au-Mg x Al-LDH interplay for alkali-free oxidation of benzyl alcohol, Chem. Eng. J. 473 (2023) 145171.

X.L. Li, L. Zhao, M. Douthwaite, K. Wang, O. Akdim, I.T. Daniel, R. Oh, L. Liu, Z. Wang, F.H. Meng, S. Pattisson, A. López-Martin, J. Yang, X.J. Huang, R.J. Lewis, G.J. Hutchings, Solvent-free benzyl alcohol oxidation using spatially separated carbon-supported Au and Pd nanoparticles, ACS Catal. 14 (22) (2024) 16551—16561.

E. Taarning, I. Nielsen, K. Egeblad, R. Madsen, C. Christensen, Chemicals from renewables: aerobic oxidation of furfural and hydroxymethylfurfural over gold catalysts, ChemSusChem 1 (1—2) (2008) 75—78.

O. Casanova, S. Iborra, A. Corma, Biomass into chemicals: one pot-base free oxidative esterification of 5-hydroxymethyl-2-furfural into 2, 5dimethylfuroate with gold on nanoparticulated ceria, J. Catal. 265 (1) (2009) 109—116.

T.T. Ge, X.R. Liu, J. Tang, C. Liu, J.H. Huang, Effect of support on oxidative esterification of 2, 5-furandiformaldehyde to dimethyl furan-2, 5dicarboxylate, Catalysts 13 (11) (2023) 1430.

Q. Jiang, Y.F. Liu, T. Dintzer, J.J. Luo, K. Parkhomenko, A.C. Roger, Tuning the highly dispersed metallic Cu species via manipulating Brønsted acid sites of mesoporous aluminosilicate support for CO 2 hydrogenation reactions, Appl. Catal. B Environ. 269 (2020) 118804.

G.X. Yang, X.Y. Zhang, H.L. Yang, Y. Long, J.T. Ma, Sucrose facilitated synthesis of mesoporous silicoaluminophosphate SAPO-11 with different crystalline phases of MoO 3 for highly-efficient oxidative desulfurization, J. Colloid Interface Sci. 532 (2018) 92—102.

L. Zhu, Y.L. Ma, Y.G. Sun, J. Ma, S. Qiao, Y.F. Wu, B.L. Zhao, L. Wang, M. Xu, Y.H. Wu, W.X. Ji, N-doped hollow spherical composite derived from coal gasification fine slag through spatial reconstruction for peroxymonosulfate activation, Sep. Purif. Technol. 354 (2025) 129106.

T. Zhang, F. Qiu, J.H. Li, Design and synthesis of core-shell structured meso-Cu-SSZ-13@mesoporous aluminosilicate catalyst for SCR of NO x with NH 3 :enhancement of activity, hydrothermal stability and propene poisoning resistance, Appl. Catal. B Environ. 195 (2016) 48—58.

Y.T. Zou, Y.Z. Hu, Z.W. Shen, L. Yao, D.Y. Tang, S. Zhang, S.Q. Wang, B.W. Hu, G. X. Zhao, X.K. Wang, Application of aluminosilicate clay mineral-based composites in photocatalysis, J. Environ. Sci. 115 (2022) 190—214.

H. Huang, H.H. Fan, Y.Z. Ge, W.Y. Ye, Y.C. Liu, C.C. Song, H. Lin, X.T. Zhang, B. Li, X.W. Nie, S.F. Zhang, R.W. Lu, Solvent-free oxidation of toluene to benzaldehyde using electron-rich Au clusters confined in Silicalite-1, Chem. Eng. J. 458 (2023) 141446.

D. Liu, F.Y. Hu, Y. Yan, R.P. Ye, X.H. Chen, B.Y. Han, Z.H. Lu, L. Zhou, G. Feng, R.B. Zhang, Promotion of oxygen vacancies and metal-support interaction over 3DOM Au/CeO 2 catalyst for CO oxidation, Appl. Surf. Sci. 629 (2023) 157438.

K. Narasimharao, A. Alshehri, Gold supported yttrium oxide nanorods for catalytic oxidative cracking of n -propane to light olefins, Fuel 278 (2020) 118375.

X.M. Zhong, Y.F. Wei, S. Sadjadi, D. Liu, M.Y. Li, T. Yu, G.Z. Zhuang, P. Yuan, Base-free oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid over palygorskite-supported bimetallic Pt—Pd catalyst, Appl. Clay Sci. 226 (2022) 106574.

H. Zhang, R.Z. Zhang, W.D. Zhang, B. Gu, Q.H. Tang, Q.E. Cao, W.H. Fang, Basefree selective oxidation of 5-hydroxymethylfurfural over Pt nanoparticles on surface Nb-enriched Co-Nb oxide, Appl. Catal. B Environ. 330 (2023) 122670.

S. Sadjadi, M. Akbari, F.G. Kahangi, M.M. Heravi, Pd immobilized on the composite of halloysite and low-cost bio-based eutectic solvent-derived carbon: an efficient catalyst for hydrogenation in the presence of cyclodextrin, Appl. Clay Sci. 192 (2020) 105640.

F. Wang, J. Zhang, C. Liu, J.H. Liu, Pd—palygorskite catalysts: preparation, characterization and catalytic performance for the oxidation of styrene, Appl. Clay Sci. 105 (2015) 150—155.

Y. Wang, L.M. Li, S.G. Wang, X.Y. Dong, C.T. Ding, Y. Mu, M. Cui, T. Hu, C.G. Meng, Y.F. Zhang, Anion structure regulation of cobalt silicate hydroxide endo wing boosted oxygen evolution reaction, Small 20 (36) (2024) 2401394.

D.W. Cho, Y.S. Han, J. Lee, J.Y. Jang, G.J. Yim, S. Cho, J.S. Lee, Y.W. Cheong, Water defluorination using granular composite synthesized via hydrothermal treatment of polyaluminum chloride (PAC) sludge, Chemosphere 247 (2020) 125899.

M. Tsuji, M. Hotta, T. Watanabe, R. Endo, M. Susa, M. Hayashi, Factors affecting microscopic basicity of silicate glasses from the perspective of O1s binding energy, Steel Res. Int. 95 (11) (2024) 2300383.

P.D. Sarvalkar, R.S. Vhatkar, K.K.K. Sharma, Cellulose nanofiber-reinforced γ-AlOOH aerogels for enhanced removal of environmental pollutants, Langmuir 41 (5) (2025) 3475—3489.

S.C. Huang, Y.L. Zhou, L. Duan, D.Z. Luo, B.P. Yang, G. Chen, X.H. Liu, J.G. Tang, N. Zhang, Mn 2+ -doped Co 3 Si 2 O 5 (OH) 4 serpentine nanosheets with tuned dband centers for efficient oxygen evolution in alkaline and neutral electrolytes, Rare Met. 44 (2) (2025) 1042—1052.

W.N. Bao, X.D. Liang, Y.Y. Liu, Y.F. Gao, J.F. Wang, Effects of AC and DC corona on the surface properties of silicone rubber: characterization by contact angle measurements and XPS high resolution scan, IEEE Trans. Dielectr. Electr. Insul. 24 (5) (2017) 2911—2919.

X.S. Guo, Y.X. Si, Y.C. Huang, J.H. Zhang, X.L. Lyu, Y.W. Cheng, X. Li, Base-free oxidative esterification of HMF using Mg—Al hydrotalcite-supported gold catalyst, Ind. Eng. Chem. Res. 62 (40) (2023) 16 309—16318.

H. Wang, X.Y. Liu, W.J. Yang, G.Y. Mao, Z. Meng, Z.K. Wu, H.L. Jiang, Surfaceclean Au25 nanoclusters in modulated microenvironment enabled by metal—organic frameworks for enhanced catalysis, J. Am. Chem. Soc. 144 (48) (2022) 22008—22017.

Y.X. Sun, H. Ma, X.Q. Jia, J.P. Ma, Y. Luo, J. Gao, J. Xu, A high-performance base-metal approach for the oxidative esterification of 5-hydroxymethylfurfural, ChemCatChem 8 (18) (2016) 2907—2911.

H. Weerathunga, S. Sarina, H.Y. Zhu, E.R. Waclawik, Oxidative esterification of 5-hydroxymethylfurfural into dimethyl 2, 5-furandicarboxylate using gamma alumina-supported gold nanoparticles, ACS Omega 6 (7) (2021) 4740—4748.

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Enhanced catalytic performance of lignin-derived carbon supported SnOx via lignin fractionation in the conversion of glucose to 5-hydroxymethylfurfural

Gold nanoparticles on Fe-doped Co3O4 for enhanced low-temperature CO oxidation

Influences of fractional separation on the structure and reactivity of wheat straw cellulose for producing 5-hydroxymethylfurfural

Regulating the oxidation state of Pd to enhance the selective hydrogenation for 5-hydroxymethylfurfural

Postsynthetic acid modification of amino-tagged metal-organic frameworks: Structure-functionrelationship for catalytic 5-hydroxymethylfurfural synthesis

Related Author

Gan Linhuo

Kang Tingting

Wang Yan

Yang Ningwei

Wang Weijie

Yan Sien

Xiang Wang

Yu Li

Related Institution

Fujian Provincial Key Laboratory of Biomass Low-Carbon Conversion, Huaqiao University

College of Chemical Engineering, Huaqiao University

Shanxi Province Key Laboratory of Chemical Process Intensification, School of Chemistry and Chemical Engineering, North University of China

Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University

State Key Laboratory of Organic-Inorganic Composites and College of Chemical Engineering, Beijing University of Chemical Technology

⁰

SiO2-AlO(OH) composite-loaded gold nanoparticles catalyze the oxidative esterification reaction of 5-hydroxymethylfurfural

DOI：

摘要

Abstract

关键词

Keywords

references

SiO₂-AlO(OH) composite-loaded gold nanoparticles catalyze the oxidative esterification reaction of 5-hydroxymethylfurfural