Citation: Pingbo Zhang, Yan Zhou, Mingming Fan, Pingping Jiang. Catalytic synthesis of diethyl carbonate with supported Pd-Cu bimetallic nanoparticle catalysts: Cu(I) as the active species[J]. Chinese Journal of Catalysis, ;2015, 36(11): 2036-2043. doi: 10.1016/S1872-2067(15)60973-1 shu

Catalytic synthesis of diethyl carbonate with supported Pd-Cu bimetallic nanoparticle catalysts: Cu(I) as the active species

1.
The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu, China

Corresponding author: Mingming Fan,
Received Date: 29 August 2015
Available Online: 16 September 2015
Fund Project: 国家自然科学基金(21106054). (21106054)

Cupric oxide (CuO) and copper-cuprous oxide (Cu-Cu₂O) nanoparticles were prepared by a simple hydrothermal method for the synthesis of diethyl carbonate (DEC) from ethanol. During these syntheses, varying NaOH and glucose concentrations were applied to explore and pinpoint the active species. It was found that PdCl₂/CuO and PdCl₂/Cu-Cu₂O both catalysts exhibited good thermal stability and morphology. The results of catalytic tests showed that the catalysts prepared with 5 mol/L NaOH show superior catalytic performances because of their lower extent of agglomeration. It is noteworthy that the PdCl₂/Cu-Cu₂O catalysts were the most active, especially the PdCl₂/Cu-Cu₂O catalyst prepared with 10 mmol glucose and having a higher Cu₂O concentration. In Pd(II)-Cu(II) (PdCl₂/CuO) catalysts, there is an induction period, during which Pd(II) is reduced to Pd(0), that must occur prior to electron transfer between Pd and Cu, and this can slow the catalytic reaction. To further pinpoint the active species, PdCl₂/Cu-Cu₂O catalysts with different Cu₂O contents were prepared by controlling the dosages of glucose. The maximum DEC yield obtained with these catalysts was 151.9 mg·g^-1·h^-1, corresponding to an ethanol conversion of 7.2% and 97.9% DEC selectivity on an ethanol basis. Therefore, it was concluded that Cu⁺ was the active species in this catalytic system, possibly because a higher proportion of Cu⁺ reduces the Pd²⁺ concentration and limits the CO oxidation side reaction, thus increasing DEC selectivity. In addition, Cu⁺ promotes electron transfer between Pd and Cu without an induction period, which could also promote the catalytic activity.
- Cupric oxide,
- Copper-cuprous oxide,
- Diethyl carbonate,
- Sodium hydroxide concentration,
- Dosages of glucose,
- Active species
1. [1]
  [1] Pacheco M A, Marshall C L. Energy Fuels, 1997, 11: 2
2. [2]
  [2] Horvath I T. Green Chem, 2008, 10: 1024
3. [3]
  [3] Moumouzias G, Ritzoulis G, Siapkas D, Terzidis D. J Power Sources, 2003, 122: 57
4. [4]
  [4] Herstedt M, Stjerndahl M, Gustafsson T, Edstrom K. Electrochem Commun, 2003, 5: 467
5. [5]
  [5] Muskat I E, Strain F. US Patent 2379250. 1945
6. [6]
  [6] Mo W L, Li G X, Zhu Y Q, Xiong H, Mei F M. Chin J Catal (莫婉玲, 李光兴, 朱永强, 熊辉, 梅付名. 催化学报), 2003, 24: 3
7. [7]
  [7] Zielinska-Nadolska I, Warmuzinski K, Richter J. Catal Today, 2006, 114: 226
8. [8]
  [8] Zhang Z, Ma X B, Zhang J, He F, Wang S P. J Mol Catal A, 2005, 227: 141
9. [9]
  [9] Gao X C, Ma X B, Wang S P, Li Z H. Chin J Catal (高晓晨, 马新宾, 王胜平, 李振花. 催化学报), 2007, 28: 720
10. [10]
  [10] Ryu J Y. US Patent 5902894. 1999
11. [11]
  [11] Tomishige K, Sakaihori T, Ikeda Y, Fujimoto K. Catal Lett, 1999, 58: 225
12. [12]
  [12] Dunn B C, Guenneau C, Hilton S A, Pahnke J, Eyring E M, Dworzanski J, Meuzelaar H L C, Hu J Z, Solum M S, Pugmire R J. Energy Fuels, 2002, 16: 177
13. [13]
  [13] Briggs D N, Lawrence K H, Bell A T. Appl Catal A, 2009, 366: 71
14. [14]
  [14] Briggs D N, Bong G, Leong E, Oei K, Lestari G, Bell A T. J Catal, 2010, 276: 215
15. [15]
  [15] Zhang P B, Huang S Y, Wang S P, Ma X B. Chem Eng J, 2011, 172: 526
16. [16]
  [16] Zhang P B, Ma X B. Chem Eng J, 2010, 163: 93
17. [17]
  [17] Huang S Y, Wang Y, Wang Z Z, Yan B, Wang S P, Gong J L, Ma X B. Appl Catal A, 2012, 417-418: 236
18. [18]
  [18] Zhang P B, Zhang Z, Wang S P, Ma X B. Catal Commun, 2007, 8: 21
19. [19]
  [19] Zheng H Y, Ren J, Zhou Y, Niu Y Y, Li Z. J Fuel Chem Technol, 2011, 39: 282
20. [20]
  [20] Richter M, Fait M J G, Eckelt R, Schreier E, Schneider M, Pohl M M, Fricke R. Appl Catal B, 2007, 73: 269
21. [21]
  [21] Huang S Y, Chen P Z, Yan B, Wang S P, Shen Y L, Ma X B. Ind Eng Chem Res, 2013, 52: 6349
22. [22]
  [22] Huang S Y, Zhang J J, Wang Y, Chen P Z, Wang S P, Ma X B. Ind Eng Chem Res, 2014, 53: 5838
23. [23]
  [23] Zhang Y H, Drake I J, Briggs D N, Bell A T. J Catal, 2006, 244: 219
24. [24]
  [24] Li Z, Wen C M, Zheng H Y, Xie K C. Chem J Chin Univ, 2010, 31: 145
25. [25]
  [25] Ding X S, Dong X M, Kuang D T, Wang S F, Zhao X Q, Wang Y J. Chem Eng J, 2014, 240: 221
26. [26]
  [26] Zhang R G, Liu H Y, Zheng H Y, Ling L X, Li Z, Wang B J. Appl Surf Sci, 2011, 257: 4787
27. [27]
  [27] Zhang R G, Zheng H Y, Wang B J, Li Z. Chem J Chin Univ, 2010, 31: 1246
28. [28]
  [28] King S T. Catal Today, 1997, 33: 173
29. [29]
  [29] Yan B, Huang S Y, Wang S P, Ma X B. ChemCatChem, 2014, 6: 2671
30. [30]
  [30] Chen Z W, Jiao Z, Pan D Y, Li Z, Wu M H, Shek C H, Wu C M L, Lai J K L. Chem Rev, 2012, 112: 3833
31. [31]
  [31] Lignier P, Bellabarba R, Tooze R P. Chem Soc Rev, 2012, 41: 1708
32. [32]
  [32] Park J C, Kim J, Kwon H, Song H. Adv Mater, 2009, 21: 803
33. [33]
  [33] Chanda K, Rej S, Huang M H. Chem Eur J, 2013, 19: 16036
34. [34]
  [34] Li L L, Nan C Y, Peng Q, Li Y D. Chem Eur J, 2012, 18: 10491
35. [35]
  [35] Zhong Z Y, Ng V, Luo J Z, Teh S P, Teo J, Gedanken A. Langmuir, 2007, 23: 5971
36. [36]
  [36] Neupane M P, Kim Y K, Park I S, Kim K A, Lee M H, Bae T S. Surf Interface Anal, 2009, 41: 259
37. [37]
  [37] Cao M H, Hu C W, Wang Y H, Guo Y H, Guo C X, Wang E B. Chem Commun, 2003: 1884
38. [38]
  [38] Zhang Z, Ma X B, Zhang P B, Li Y M, Wang S P. J Mol Catal A, 2007, 266: 202
39. [39]
  [39] Zheng X B, Bell A T. J Phys Chem C, 2008, 112: 5043
40. [40]
  [40] Engeldinger J, Domke C, Richter M, Bentrup U. Appl Catal A, 2010, 382: 303
41. [41]
  [41] Radi A, Pradhan D, Sohn Y, Leung K T. ACS Nano, 2010, 4: 1553
42. [42]
  [42] Ghodselahi T, Vesaghi M A, Shafiekhani A, Baghizadeh A, Lameii M. Appl Surf Sci, 2008, 255: 2730
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