Citation: Jiahan Xie, Junfang Nie, Haichao Liu. Aqueous-phase selective aerobic oxidation of 5-hydroxymethylfurfural on Ru/C in the presence of base[J]. Chinese Journal of Catalysis, ;2014, 35(6): 937-944. doi: 10.1016/S1872-2067(14)60136-4 shu

Aqueous-phase selective aerobic oxidation of 5-hydroxymethylfurfural on Ru/C in the presence of base

1.
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Stable and Unstable Species, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Corresponding author: Haichao Liu,
Received Date: 28 April 2014
Available Online: 30 April 2014
Fund Project: This work was supported by the National Basic Research Program of China (973 Program, 2011CB201400, 2011CB808700) (973 Program, 2011CB201400, 2011CB808700)the National Natural Science Foundation of China (21373019, 21173008). (21373019, 21173008)

The aerobic oxidation of 5-hydroxymethylfurfural (HMF) was performed on an activated carbon-supported ruthenium (Ru/C) catalyst in water. The presence of Mg-Al hydrotalcite (HT, Mg/Al molar ratio=3/1) as a base afforded higher selective oxidation of HMF to 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA) than with the bases MgO, Ca(OH)₂ and NaOH owing to its appropriate strength of basicity. X-ray photoelectron spectroscopy characterization confirmed that metallic Ru⁰ species were the active sites for HMF oxidation. Isotopic tracer experiments conducted with ¹⁸O₂ and ¹⁶O₂ indicated that H₂O rather than O₂ provided the oxygen atom for the oxidation of HMF to FFCA and FDCA via hydration of the formyl group. These results and kinetic studies of the oxidation of HMF and 2,5-diformylfuran (DFF) led to the proposition that the aerobic oxidation of HMF to FFCA follows a Langmuir-Hinshelwood mechanism. The oxidation involved dissociative adsorption of HMF and O₂ to form adsorbed alcoholate and atomic oxygen species followed by kinetically relevant abstraction of β-H from the alcoholate species via the atomic oxygen species to adsorbed DFF species on the Ru surface, which then underwent hydration and oxidation to FFCA under basic conditions.
- 5-Hydroxymethylfurfural,
- Aerobic oxidation,
- 2,5-Diformylfuran,
- 5-Formyl-2-furancarboxylic acid,
- Hydrotalcite,
- Ruthenium catalyst,
- Reaction mechanism
1. [1]
  [1] Corma A, Iborra S, Velty A. Chem Rev, 2007, 107: 2411
2. [2]
  [2] Romen-Leshkov Y, Chheda J N, Dumesic J A. Science, 2006, 312: 1933
3. [3]
  [3] Rosatella A A, Simeonov S P, Frade R F M, Afonso C A M. Green Chem, 2011, 13: 754
4. [4]
  [4] Binder J B, Raines R T. J Am Chem Soc, 2009, 131: 1979
5. [5]
  [5] Lewkowski J. Arkivoc, 2001, (1): 17
6. [6]
  [6] Amarasekara A S, Green D, Williams L D. Eur Polym J, 2009, 45: 595
7. [7]
  [7] Hopkins K T, Wilson W D, Bender B C, McCurdy D R, Hall J E, Tidwell R R, Kumar A, Bajic M, Boykin D W. J Med Chem, 1998, 41: 3872
8. [8]
  [8] Del Poeta M, Schell W A, Dykstra C C, Jones S, Tidwell R R, Czarny A, Bajic M, Kumar A, Boykin D, Perfect J R. Antimicrob Agents Chemother, 1998, 42: 2495
9. [9]
  [9] Gandini A, Silvestre A J D, Pascoal Neto C, Sousa A F, Gomes M. J Polym Sci Part A, 2008, 47: 295
10. [10]
  [10] Moreau C, Durand R, Pourcheron C, Tichit D. Stud Surf Sci Catal, 1997, 108: 399
11. [11]
  [11] Navarro O C, Canós A C, Chornet S I. Top Catal, 2009, 52: 304
12. [12]
  [12] Sádaba I, Gorbanev Y Y, Kegnæs S, Putluru S S R, Berg R W, Riisager A. ChemCatChem, 2013, 5: 284
13. [13]
  [13] Nie J F, Liu H C. Pure Appl Chem, 2012, 84: 765
14. [14]
  [14] Yang Z Z, Deng J, Pan T, Guo Q X, Fu Y. Green Chem, 2012, 14: 2986
15. [15]
  [15] Vinke P, van Dam H E, van Bekkum H. Stud Surf Sci Catal, 1990, 55: 147
16. [16]
  [16] Gorbanev Y Y, Klitgaard S K, Woodley J M, Christensen C H, Riisager A. ChemSusChem, 2009,2: 672
17. [17]
  [17] Casanova O, Iborra S, Corma A. ChemSusChem, 2009, 2: 1138
18. [18]
  [18] Gupta N K, Nishimura S, Takagaki A, Ebitani K. Green Chem, 2011, 13: 824
19. [19]
  [19] Gorbanev Y, Kegnaes S, Riisager A. Catal Lett, 2011, 141: 1752
20. [20]
  [20] Gorbanev Y Y, Kegnaes S, Riisager A. Top Catal, 2011, 54: 1318
21. [21]
  [21] Verdeguer P, Merat N, Gaset A. J Mol Catal, 1993, 85: 327
22. [22]
  [22] Lilga M, Hallen R, Gray M. Top Catal, 2010, 53: 1264
23. [23]
  [23] Nie J F, Xie J H, Liu H C. Chin J Catal (聂俊芳，解佳翰，刘海超，催化学报) 2013, 34: 871
24. [24]
  [24] Takagaki A, Takahashi M, Nishimura S, Ebitani K. ACS Catal, 2011,1: 1562
25. [25]
  [25] Nie J F, Xie J H, Liu H C. J Catal, 2013, 301: 83
26. [26]
  [26] Sun J, Liu H. Green Chem, 2011, 13: 135
27. [27]
  [27] Lopez Nieto J M, Dejoz A, Vazquez M I. Appl Catal A, 1995, 132: 41
28. [28]
  [28] Davis S E, Zope B N, Davis R J. Green Chem, 2012, 14: 143
29. [29]
  [29] Zope B N, Hibbitts D D, Neurock M, Davis R J. Science, 2010, 330: 74
1. [1]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
2. [2]
  Hongting Yan , Aili Feng , Rongxiu Zhu , Lei Liu , Dongju Zhang . Reexamination of the Iodine-Catalyzed Chlorination Reaction of Chlorobenzene Using Computational Chemistry Methods. University Chemistry, 2025, 40(3): 16-22. doi: 10.12461/PKU.DXHX202403010
3. [3]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
4. [4]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
5. [5]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
6. [6]
  Ling Fan , Meili Pang , Yeyun Zhang , Yanmei Wang , Zhenfeng Shang . Quantum Chemistry Calculation Research on the Diels-Alder Reaction of Anthracene and Maleic Anhydride: Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 133-139. doi: 10.3866/PKU.DXHX202309024
7. [7]
  Jiabo Huang , Quanxin Li , Zhongyan Cao , Li Dang , Shaofei Ni . Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations. University Chemistry, 2025, 40(3): 153-159. doi: 10.12461/PKU.DXHX202405172
8. [8]
  Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
9. [9]
  Chuanming GUO , Kaiyang ZHANG , Yun WU , Rui YAO , Qiang ZHAO , Jinping LI , Guang LIU . Performance of MnO₂-0.39IrO_x composite oxides for water oxidation reaction in acidic media. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1135-1142. doi: 10.11862/CJIC.20230459
10. [10]
  Wen YANG , Didi WANG , Ziyi HUANG , Yaping ZHOU , Yanyan FENG . La promoted hydrotalcite derived Ni-based catalysts: In situ preparation and CO₂ methanation performance. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 561-570. doi: 10.11862/CJIC.20230276
11. [11]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . 层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响. Acta Physico-Chimica Sinica, 2025, 41(1): 2309002-. doi: 10.3866/PKU.WHXB202309002
12. [12]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029
13. [13]
  Qian Huang , Zhaowei Li , Jianing Zhao , Ao Yu . Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon. University Chemistry, 2024, 39(3): 395-400. doi: 10.3866/PKU.DXHX202309018
14. [14]
  Yong Wang , Yingying Zhao , Boshun Wan . Analysis of Organic Questions in the 37th Chinese Chemistry Olympiad (Preliminary). University Chemistry, 2024, 39(11): 406-416. doi: 10.12461/PKU.DXHX202403009
15. [15]
  Mingyang Men , Jinghua Wu , Gaozhan Liu , Jing Zhang , Nini Zhang , Xiayin Yao . 液相法制备硫化物固体电解质及其在全固态锂电池中的应用. Acta Physico-Chimica Sinica, 2025, 41(1): 2309019-. doi: 10.3866/PKU.WHXB202309019
16. [16]
  Zihan Lin , Wanzhen Lin , Fa-Jie Chen . Electrochemical Modifications of Native Peptides. University Chemistry, 2025, 40(3): 318-327. doi: 10.12461/PKU.DXHX202406089
17. [17]
  Zhuoyan Lv , Yangming Ding , Leilei Kang , Lin Li , Xiao Yan Liu , Aiqin Wang , Tao Zhang . Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst. Acta Physico-Chimica Sinica, 2025, 41(4): 100038-. doi: 10.3866/PKU.WHXB202408015
18. [18]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
19. [19]
  Jingzhao Cheng , Shiyu Gao , Bei Cheng , Kai Yang , Wang Wang , Shaowen Cao . 4-氨基-1H-咪唑-5-甲腈修饰供体-受体型氮化碳光催化剂的构建及其高效光催化产氢研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406026-. doi: 10.3866/PKU.WHXB202406026
20. [20]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(731)
HTML views(91)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142