Citation: Feng Li, Chun-Shan Lu, Xiao-Nian Li. The effect of the amount of ammonia on the Cu⁰/Cu⁺ ratio of Cu/SiO₂ catalyst for the hydrogenation of dimethyl oxalate to ethylene glycol[J]. Chinese Chemical Letters, ;2014, 25(11): 1461-1465. doi: 10.1016/j.cclet.2014.05.050 shu

The effect of the amount of ammonia on the Cu⁰/Cu⁺ ratio of Cu/SiO₂ catalyst for the hydrogenation of dimethyl oxalate to ethylene glycol

1.
Institute of Industrial Catalysis of Zhejiang University of Technology, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Hangzhou 310032, China

Corresponding author: Chun-Shan Lu,
Received Date: 8 April 2014
Available Online: 19 May 2014

The effect of the amount of precipitant ammonia on the Cu⁰/Cu⁺ ratio of Cu/SiO₂ prepared by the deposition-precipitation method is investigated. Species at different preparation stages, resulted from the amount of ammonia used, are identified by the XRD and FTIR techniques. Chrysocolla together with either copper nitrate hydroxide or copper hydroxide coexist in the uncalcined catalysts. Upon calcination, the latter two species are converted to CuO particles while chrysocolla remains. Following reduction, CuO is transformed to metallic Cu and chrysocolla is converted to Cu₂O. The value of Cu⁰/Cu⁺ ratio can be evaluated using the peak areas in their TPR profiles. Hydrogenation of dimethyl oxalate (DMO) to ethylene glycol (EG) shows that the selectivity of EG depends on the Cu⁰/Cu⁺ ratio. Catalyst prepared with the addition of ammonia solution at n(NH₃)/n(Cu²⁺)=0.9 for precipitation-deposition gains a more suitable Cu⁰/Cu⁺ ratio upon reduction and thus has a higher selectivity for EG.
- Amount of ammonia,
- Deposition-precipitation,
- Chrysocolla,
- Copper nitrate hydroxide,
- Copper hydroxide,
- DMO hydrogenation
1. [1]
  [1] L.F. Chen, P.J. Guo, M.H. Qiao, et al., Cu/SiO₂ catalysts prepared by the ammoniaevaporation method: texture, structure, and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol, J. Catal. 257 (2008) 172-180.
2. [2]
  [2] H.R. Yue, Y.J. Zhao, X.B. Ma, et al., Ethylene glycol: properties, synthesis, and applications, Chem. Soc. Rev. 41 (2012) 4218-4244.
3. [3]
  [3] K. Fujii, M. Matsuda, K. Mizutare, et al. Process for continuously preparing ethylene glycol, US 4453026, 1984.
4. [4]
  [4] X.G. Zhao, X.L. Lvy, H.G. Zhao, et al., Study on Pd/a-Al₂O₃ catalyst for vapor-phase coupling reaction of CO with CH₃ONO to (CH₃OOC)2, Chin. J. Catal. 25 (2004) 125-128.
5. [5]
  [5] L.R. Zehner, R. Warren Lenton, Process for the preparation of ethylene glycol, US 4112245 A, 1978.
6. [6]
  [6] U. Matteoli, G. Menchi, M. Bianchi, et al., Selective reduction of dimethyl oxalate by ruthenium carbonyl carboxylates in homogeneous phase Part IV, J. Mol. Catal. 64 (1991) 257-267.
7. [7]
  [7] H.T. Teunissen, C.J. Elsevier, Ruthenium catalysed hydrogenation of dimethyl oxalate to ethylene glycol, Chem. Commun. 12 (1997) 667-668.
8. [8]
  [8] A.Y. Yin, X.Y. Guo, W.L. Dai, et al., High activity and selectivity of Ag/SiO₂ catalyst for hydrogenation of dimethyl oxalate, Chem. Commun. 46 (2010) 4348-4350.
9. [9]
  [9] Z. He, H.Q. Lin, P. He, et al., Effect of boric oxide doping on the stability and activity of a Cu/SiO₂ catalyst for vapor-phase hydrogenation of dimethyl oxalate to ethylene glycol, J. Catal. 277 (2011) 54-63.
10. [10]
  [10] S. Zhao, H.R. Yue, Y.J. Zhao, et al., Chemoselective synthesis of ethanol via hydrogenation of dimethyl oxalate on Cu/SiO₂: enhanced stability with boron dopant, J. Catal. 297 (2013) 142-150.
11. [11]
  [11] A.Y. Yin, C. Wen, X.Y. Guo, et al., Influence of Ni species on the structural evolution of Cu/SiO₂ catalyst for the chemoselective hydrogenation of dimethyl oxalate, J. Catal. 280 (2011) 77-88.
12. [12]
  [12] B.W.Wang, Q. Xu, H. Song, G.H. Xu, Synthesis of methyl glycolate by hydrogenation of dimethyl oxalate over Cu-Ag/SiO₂ catalyst, J. Nat. Gas Chem. 16 (2007) 78-80.
13. [13]
  [13] B.W. Wang, X. Zhao, Q. Xu, G.H. Xu, Preparation and characterization of Cu/SiO₂ catalyst and its catalytic activity for hydrogenation of diethyl oxalate to ethylene glycol, Chin. J. Catal. 29 (2008) 275-280.
14. [14]
  [14] A.Y. Yin, X.Y. Guo, K.N. Fan, W.L. Dai, Ion-exchange temperature effect on Cu/HMS catalysts for the hydrogenation of dimethyl oxalate to ethylene glycol, Chem- CatChem 2 (2010) 206-213.
15. [15]
  [15] A.Y. Yin, X.Y. Guo, K.N. Fan, et al., Influence of copper precursors on the structure evolution and catalytic performance of Cu/HMS catalysts in the hydrogenation of dimethyl oxalate to ethylene glycol, Appl. Catal. A 377 (2010) 128-133.
16. [16]
  [16] C. Wen, A.Y. Yin, Y.Y. Cui, et al., Enhanced catalytic performance for SiO₂-TiO2 binary oxide supported Cu-based catalyst in the hydrogenation of dimethyloxalate, Appl. Catal. A 458 (2013) 82-89.
17. [17]
  [17] X.B. Ma, H.W. Chi, H.R. Yue, et al., Hydrogenation of dimethyl oxalate to ethylene glycol over mesoporous Cu/MCM-41 catalysts, AIChE J. 59 (2013) 2530-2539.
18. [18]
  [18] J.L. Gong, H.R. Yue, Y.J. Zhao, et al., Synthesis of ethanol via syngas on Cu/SiO₂ catalysts with balanced Cu⁰-Cu⁺ sites, J. Am. Chem. Soc. 134 (2012) 13922-13925.
19. [19]
  [19] S.R. Wang, X.B. Li, Q.Q. Yin, et al., Highly active and selective Cu/SiO₂ catalysts prepared by the urea hydrolysis method in dimethyl oxalate hydrogenation, Catal. Commun. 12 (2011) 1246-1250.
20. [20]
  [20] L.M. He, X.C. Chen, J.S. Ma, et al., Characterization and catalytic performance of sol-gel derived Cu/SiO₂ catalysts for hydrogenolysis of diethyl oxalate to ethylene glycol, J. Sol-Gel Sci. Technol. 55 (2010) 285-292.
21. [21]
  [21] X.Y. Guo, A.Y. Yin, W.L. Dai, et al., One pot synthesis of ultra-high copper contented Cu/SBA-15 material as excellent catalyst in the hydrogenation of dimethyl oxalate to ethylene glycol, Catal. Lett. 132 (2009) 22-27.
22. [22]
  [22] S.R. Wang, Q.Q. Yin, X.B. Li, Catalytic performance and texture of TEOS based Cu/ SiO₂ catalysts for hydrogenation of dimethyl oxalate to ethylene glycol, Chem. Res. Chin. Univ. 28 (2012) 119-123.
23. [23]
  [23] C. Carlini, D.G. Marco, M. Mario, et al., Selective synthesis of isobutanol by means of the Guerbet reaction: Part 2. Reaction of methanol/ethanol and methanol/ ethanol/n-propanol mixtures over copper based/MeONa catalytic systems, J. Mol. Catal. A: Chem. 200 (2003) 137-146.
24. [24]
  [24] S. Veibel, J.I. Nielsen, On the mechanism of the Guerbet reaction, Tetrahedron 23 (1967) 1723-1733.
25. [25]
  [25] A.Y. Yin, X.Y. Guo, W.L. Dai, et al., The nature of active copper species in Cu/HMS catalyst for hydrogenation of dimethyl oxalate to ethylene glycol: new insights on the synergetic effect between Cu⁰ and Cu⁺, J. Phys. Chem. C 113 (2009) 11003-11013.
26. [26]
  [26] M.A. Kohler, H.E. Curry-Hyde, A.E. Hughes, et al., The structure of Cu/SiO₂ catalysts prepared by the ion-exchange technique, J. Catal. 108 (1987) 323-333.
27. [27]
  [27] B. Zhang, S.G. Hui, S.H. Zhang, et al., Effect of copper loading on texture, structure and catalytic performance of Cu/SiO₂ catalyst for hydrogenation of dimethyl oxalate to ethylene glycol, J. Nat. Gas Chem. 21 (2012) 563-570.
28. [28]
  [28] T. Toupance, M. Kermarec, C. Louis, Metal particle size in silica-supported copper catalysts. Influence of the conditions of preparation and of thermal pretreatments, J. Phys. Chem. B 104 (2000) 965-972.
29. [29]
  [29] T. Toupance, M. Kermarec, J.F. Lambert, et al., Conditions of formation of copper phyllosilicates in silica-supported copper catalysts prepared by selective adsorption, J. Phys. Chem. B 106 (2002) 2277-2286.
30. [30]
  [30] L. Trouillet, T. Toupance, F. Villain, et al., In situ characterization of the coordination sphere of Cu(Ⅱ) complexes supported on silica during the preparation of Cu/SiO₂ catalysts by cation exchange, PCCP 2 (2000) 2005-2014.
31. [31]
  [31] H. Tominaga, M. Kaneko, Y. Ono, Cation exchange of surface protons on silica gel with cupric ions, J. Catal. 50 (1977) 400-406.
32. [32]
  [32] Y.K. Leong, Yield stress and zeta potential of nanoparticulate silica dispersions under the influence of adsorbed hydrolysis products of metal ions-Cu(Ⅱ), Al(Ⅲ) and Th(IV), J. Colloid Interface Sci. 292 (2005) 557-566.
33. [33]
  [33] C.J.G. Van Der Grift, P.A. Elberse, A. Mulder, et al., Preparation of silica-supported copper catalysts by means of deposition-precipitation, Appl. Catal. 59 (1990) 275-289.
34. [34]
  [34] M.A. Kohler, J.C. Lee, D.L. Trimm, et al., Preparation of Cu/SiO₂ catalysts by the ionexchange technique, Appl. Catal. 31 (1987) 309-321.
1. [1]
  Lu Qi , Zhaoyang Chen , Xiaoyu Luan , Zhiqiang Zheng , Yurui Xue , Yuliang Li . Atomically dispersed Mn enhanced catalytic performance for overall water splitting on graphdiyne-coated copper hydroxide nanowire. Chinese Journal of Structural Chemistry, 2024, 43(1): 100197-100197. doi: 10.1016/j.cjsc.2023.100197
2. [2]
  Xue Zhao , Mengshan Chen , Dan Wang , Haoran Zhang , Guangzhi Hu , Yingtang Zhou . Ultrafine nano-copper derived from dopamine polymerization & synchronous adsorption achieve electrochemical purification of nitrate to ammonia in complex water environments. Chinese Chemical Letters, 2024, 35(8): 109327-. doi: 10.1016/j.cclet.2023.109327
3. [3]
  Ling Fang , Sha Wang , Shun Lu , Fengjun Yin , Yujie Dai , Lin Chang , Hong Liu . Efficient electroreduction of nitrate via enriched active phases on copper-cobalt oxides. Chinese Chemical Letters, 2024, 35(4): 108864-. doi: 10.1016/j.cclet.2023.108864
4. [4]
  Ting Hu , Yuxuan Guo , Yixuan Meng , Ze Zhang , Ji Yu , Jianxin Cai , Zhenyu Yang . Uniform lithium deposition induced by copper phthalocyanine additive for durable lithium anode in lithium-sulfur batteries. Chinese Chemical Letters, 2024, 35(5): 108603-. doi: 10.1016/j.cclet.2023.108603
5. [5]
  Yuxin Wang , Zhengxuan Song , Yutao Liu , Yang Chen , Jinping Li , Libo Li , Jia Yao . Methyl functionalization of trimesic acid in copper-based metal-organic framework for ammonia colorimetric sensing at high relative humidity. Chinese Chemical Letters, 2024, 35(6): 108779-. doi: 10.1016/j.cclet.2023.108779
6. [6]
  Jinglin CHENG , Xiaoming GUO , Tao MENG , Xu HU , Liang LI , Yanzhe WANG , Wenzhu HUANG . NiAlNd catalysts for CO₂ methanation derived from the layered double hydroxide precursor. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1592-1602. doi: 10.11862/CJIC.20240152
7. [7]
  Yuchen Wang , Zhenhao Xu , Kai Yan . Rational design of metal-metal hydroxide interface for efficient electrocatalytic oxidation of biomass-derived platform molecules. Chinese Journal of Structural Chemistry, 2025, 44(1): 100418-100418. doi: 10.1016/j.cjsc.2024.100418
8. [8]
  Shaonan Tian , Yu Zhang , Qing Zeng , Junyu Zhong , Hui Liu , Lin Xu , Jun Yang . Core-shell gold-copper nanoparticles: Evolution of copper shells on gold cores at different gold/copper precursor ratios. Chinese Journal of Structural Chemistry, 2023, 42(11): 100160-100160. doi: 10.1016/j.cjsc.2023.100160
9. [9]
  Ying Chen , Xingyuan Xia , Lei Tian , Mengying Yin , Ling-Ling Zheng , Qian Fu , Daishe Wu , Jian-Ping Zou . Constructing built-in electric field via CuO/NiO heterojunction for electrocatalytic reduction of nitrate at low concentrations to ammonia. Chinese Chemical Letters, 2024, 35(12): 109789-. doi: 10.1016/j.cclet.2024.109789
10. [10]
  Ting Xie , Xun He , Lang He , Kai Dong , Yongchao Yao , Zhengwei Cai , Xuwei Liu , Xiaoya Fan , Tengyue Li , Dongdong Zheng , Shengjun Sun , Luming Li , Wei Chu , Asmaa Farouk , Mohamed S. Hamdy , Chenggang Xu , Qingquan Kong , Xuping Sun . CoSe₂ nanowire array enabled highly efficient electrocatalytic reduction of nitrate for ammonia synthesis. Chinese Chemical Letters, 2024, 35(11): 110005-. doi: 10.1016/j.cclet.2024.110005
11. [11]
  Hong-Rui Li , Xia Kang , Rui Gao , Miao-Miao Shi , Bo Bi , Ze-Yu Chen , Jun-Min Yan . Interfacial interactions of Cu/MnOOH enhance ammonia synthesis from electrochemical nitrate reduction. Chinese Chemical Letters, 2025, 36(2): 109958-. doi: 10.1016/j.cclet.2024.109958
12. [12]
  Jinqiang Gao , Haifeng Yuan , Xinjuan Du , Feng Dong , Yu Zhou , Shengnan Na , Yanpeng Chen , Mingyu Hu , Mei Hong , Shihe Yang . Methanol steam mediated corrosion engineering towards high-entropy NiFe layered double hydroxide for ultra-stable oxygen evolution. Chinese Chemical Letters, 2025, 36(1): 110232-. doi: 10.1016/j.cclet.2024.110232
13. [13]
  Xianzheng Zhang , Yana Chen , Zhiyong Ye , Huilin Hu , Ling Lei , Feng You , Junlong Yao , Huan Yang , Xueliang Jiang . Magnetic field-assisted microbial corrosion construction iron sulfides incorporated nickel-iron hydroxide towards efficient oxygen evolution. Chinese Journal of Structural Chemistry, 2024, 43(1): 100200-100200. doi: 10.1016/j.cjsc.2023.100200
14. [14]
  Guoliang Liu , Zhiqiang Liu , Anmin Zheng . Modulation of zeolite surface realizes dynamic copper species redispersion. Chinese Journal of Structural Chemistry, 2024, 43(6): 100308-100308. doi: 10.1016/j.cjsc.2024.100308
15. [15]
  Luyao Lu , Chen Zhu , Fei Li , Pu Wang , Xi Kang , Yong Pei , Manzhou Zhu . Ligand effects on geometric structures and catalytic activities of atomically precise copper nanoclusters. Chinese Journal of Structural Chemistry, 2024, 43(10): 100411-100411. doi: 10.1016/j.cjsc.2024.100411
16. [16]
  Hanqing Zhang , Xiaoxia Wang , Chen Chen , Xianfeng Yang , Chungli Dong , Yucheng Huang , Xiaoliang Zhao , Dongjiang Yang . Selective CO2-to-formic acid electrochemical conversion by modulating electronic environment of copper phthalocyanine with defective graphene. Chinese Journal of Structural Chemistry, 2023, 42(10): 100089-100089. doi: 10.1016/j.cjsc.2023.100089
17. [17]
  Ruilong Geng , Lingzi Peng , Chang Guo . Dynamic kinetic stereodivergent transformations of propargylic ammonium salts via dual nickel and copper catalysis. Chinese Chemical Letters, 2024, 35(8): 109433-. doi: 10.1016/j.cclet.2023.109433
18. [18]
  Jing-Qi Tao , Shuai Liu , Tian-Yu Zhang , Hong Xin , Xu Yang , Xin-Hua Duan , Li-Na Guo . Photoinduced copper-catalyzed alkoxyl radical-triggered ring-expansion/aminocarbonylation cascade. Chinese Chemical Letters, 2024, 35(6): 109263-. doi: 10.1016/j.cclet.2023.109263
19. [19]
  Pingping Wang , Huixian Miao , Kechuan Sheng , Bin Wang , Fan Feng , Xuankun Cai , Wei Huang , Dayu Wu . Efficient blue-light-excitable copper(Ⅰ) coordination network phosphors for high-performance white LEDs. Chinese Chemical Letters, 2024, 35(4): 108600-. doi: 10.1016/j.cclet.2023.108600
20. [20]
  Yu-Yu Tan , Lin-Heng He , Wei-Min He . Copper-mediated assembly of SO₂F group via radical fluorine-atom transfer strategy. Chinese Chemical Letters, 2024, 35(9): 109986-. doi: 10.1016/j.cclet.2024.109986

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(669)
HTML views(14)

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

The effect of the amount of ammonia on the Cu0/Cu+ ratio of Cu/SiO2 catalyst for the hydrogenation of dimethyl oxalate to ethylene glycol

Metrics

通讯作者: 陈斌, bchen63@163.com

The effect of the amount of ammonia on the Cu⁰/Cu⁺ ratio of Cu/SiO₂ catalyst for the hydrogenation of dimethyl oxalate to ethylene glycol