Cu(II) ions loaded on magnesium silicate nanofibers for the liquid oxidation of benzyl alcohol

  • Nguyen Tien ThaoEmail author
  • Tran Quyet Thang
Original Paper


Cu(II) ions were precipitated on nanofiberous magnesium silicate support using hydroxide solution. The texture and characterization of the obtained solids have been investigated by physical methods including XRD, SEM, BET, EDS, XPS, and FT-IR. The catalysts showed medium surface area, highly distributed Cu(II) oxide on the sepiolite fibers. In the liquid-phase oxidation of benzyl alcohol at low temperatures, CuO serves as an active component for the selective production of benzaldehyde. The catalytic activity of the prepared CuO/sepiolite was associated with the dispersion and amount of CuO loading, location and oxidation states of active sites, preparation routes, and reaction variables.

Graphic abstract

Cu2+/sepiolite is active for the selective oxidation of benzyl alcohol to benzaldehyde.


Sepiolite T-BuOOH Benzyl alcohol Supported catalysts Solvent-free oxidation 



This research is funded by Vietnam National Foundation for Science and Technology Development (NAFOSTED) under Grant number 104.05-2017.04.

Supplementary material

11696_2019_901_MOESM1_ESM.doc (2.3 mb)
Supplementary material 1 (DOC 2316 kb)


  1. Ahmad JU, Raisanen MT, Leskela M, Repo T (2012) Copper catalyzed oxidation of benzylic alcohols in water with H2O2. Appl Catal A 411–412:180–187. CrossRefGoogle Scholar
  2. Alaa JF, Tarek TA, Sulaiman NB, Katabathini N (2018) Nanosized samarium modified Au–Ce0.5Zr0.5O2 catalysts for oxidation of benzyl alcohol. Mol Catal 456:10–21. CrossRefGoogle Scholar
  3. Bautista FM, Luna D, Luque J, Marinas JM, Sanchez-Royo JF (2009) Gas-phase selective oxidation of chloro- and methoxy-substituted toluenes on TiO2–sepiolite supported vanadium oxides. Appl Catal A 352:251–258. CrossRefGoogle Scholar
  4. Behera GC, Paridam KM (2012) Liquid phase catalytic oxidation of benzyl alcohol to benzaldehyde over vanadium phosphate catalyst. Appl Catal A 413–414:245–253. CrossRefGoogle Scholar
  5. Burange AS, Jayaram RV, Shukla R, Tyagi AK (2013) Oxidation of benzylic alcohols to carbonyls using tert-butyl hydroperoxide over pure phase nanocrystalline CeCrO3. Catal Commun 40:27–31. CrossRefGoogle Scholar
  6. Burange AS, Kale SR, Zboril R, Gawande MB, Jayaram RV (2014) Magnetically retrievable MFe2O4 spinel (M=Mn Co, Cu, Ni, Zn) catalysts for oxidation of benzylic alcohols to carbonyls. RSC Adv 4:6597–6601. CrossRefGoogle Scholar
  7. Cainelli G, Cardillo G (1984) Chromium oxidants in organic chemistry. Springer, Berlin, p 1984CrossRefGoogle Scholar
  8. Chaudhari MP, Sawant SB (2005) Kinetics of heterogeneous oxidation of benzyl alcohol with hydrogen peroxide. Chem Eng J 106:111–118. CrossRefGoogle Scholar
  9. Choudhary VR, Chaudhari PA, Narkhede VS (2003) Solvent-free liquid phase oxidation of benzyl alcohol to benzaldehyde by molecular oxygen using non-noble transition metal containing hydrotalcite-like solid catalysts. Catal Commun 4:171–175. CrossRefGoogle Scholar
  10. Chusuei CC, Brookshier MA, Goodman DW (1999) Correlation of relative X-ray photoelectron spectroscopy shake-up intensity with CuO particle size. Langmuir 15:2806–2808. CrossRefGoogle Scholar
  11. Dasari K, Alirio ER (2008) Liquid phase catalytic oxidation of isophorone with tert-butylhydroperoxide over Cu/Co/Fe–MgAl ternary hydrotalcites. Appl Catal A 345:104–111. CrossRefGoogle Scholar
  12. Dongfang L, Osman AZ, Angaw KA, Qitang H, Xiaoyun Ch, Yushan Z (2019) Synthesis and photocatalytic activities of a CuO/TiO2 composite catalyst using aquatic plants with accumulated copper as a template. RSC Adv 9:2018–2025. CrossRefGoogle Scholar
  13. Elmaci G, Ozer D, Zumreoglu-Karan B (2017) Liquid phase aerobic oxidation of benzyl alcohol by using manganese ferrite supported-manganese oxide nanocomposite catalyst. Catal Commun 89:56–59. CrossRefGoogle Scholar
  14. Figueiredo RT, Martinez-Arias A, Granados ML, Fierro JLG (1998) Spectroscopic evidence of Cu–Al Interactions in Cu–Zn–Al mixed oxide catalysts used in CO hydrogenation. J Catal 178:146–152. CrossRefGoogle Scholar
  15. Forouzani M, Mardani HR, Ziari M, Malekzadeh A, Biparva P (2015) Comparative study of oxidation of benzyl alcohol: influence of Cu-doped metal cation on nano ZnO catalytic activity. Chem Eng J 275:220–226. CrossRefGoogle Scholar
  16. Garcia-Romero E, Suarez M (2013) Sepiolite–palygorskite: textural study and genetic considerations. Appl Clay Sci 86:129–144. CrossRefGoogle Scholar
  17. Guowu Z, Jiale H, Mingming D, Daohua S, Ibrahim AR, Wenshuang L, Yingling H, Qingbiao L (2012) Liquid phase oxidation of benzyl alcohol to benzaldehyde with novel uncalcined bioreduction Au catalysts: high activity and durability. Chem Eng J 187:232–238. CrossRefGoogle Scholar
  18. Hema E, Manikandan A, Karthika P, Durka M, Antony SA, Venkatraman BR (2016) Magneto-optical properties of reusable spinel NixMg1−xFe2O4 (0.0 ≤ x ≤ 1.0) nano-catalysts. J Nanosci Nanotechnol 16(7):7325–7336. CrossRefGoogle Scholar
  19. Jayesh TB, Itika K, Babu GVR, Rama Rao KS, Keri RS, Jadhav AH, Nagaraj BM (2018) Vapour phase selective hydrogenation of benzaldehyde to benzyl alcohol using Cu supported Mg–Al hydrotalicite catalyst. Catal Commun 106:73–77. CrossRefGoogle Scholar
  20. Jie X, Jie-Kun S, Ye C, Yue W, Yong-Xin L (2017) Palladium nanoparticles supported on mesoporous carbon nitride for efficiently selective oxidation of benzyl alcohol with molecular oxygen. Appl Catal A 542:380–388. CrossRefGoogle Scholar
  21. Juanjuan L, Shihui Z, Jiachao W, Hisayoshi K, Hongting Z, Jie F (2018) Green catalytic oxidation of benzyl alcohol over Pt/ZnO in base-free aqueous medium at room temperature. Chin J Catal 9:1081–1089. Google Scholar
  22. Mahdavi V, Hasheminasa HR (2014) Vanadium phosphorus oxide catalyst promoted by cobalt doping for mild oxidation of benzyl alcohol to benzaldehyde in the liquid phase. Appl Catal A 482:189–197. CrossRefGoogle Scholar
  23. Ozturk OF, Zumreoglu-Karan B, Karabulut S (2008) Solvent-free oxidation of benzyl alcohol over chromium orthoborate. Catal Commun 9:1644–1648. CrossRefGoogle Scholar
  24. Prathap MUA, Kaur B, Srivastava R (2012) Hydrothermal synthesis of CuO micro-/nanostructures and their applications in the oxidative degradation of methylene blue and non-enzymatic sensing of glucose/H2O2. J Colloid Interface Sci 370:144–154. CrossRefGoogle Scholar
  25. Premalatha K, Raghavan PS, Viswanathan B (2012) Liquid phase oxidation of benzyl alcohol with molecular oxygen catalyzed by metal chromites. Appl Catal A 419–420:203–209. CrossRefGoogle Scholar
  26. Ragupathi C, Judith Vijaya J, Thinesh Kumar R, John Kennedy L (2015) Selective liquid phase oxidation of benzyl alcohol catalyzed by copper aluminate nanostructures. J Mol Struc 1079:182–188. CrossRefGoogle Scholar
  27. Reis MC, Barros SDT, Lachter ER, Gil RASS, Flores JH, Silva MIP, Onfroy T (2012) Synthesis, characterization and catalytic activity of meso-niobium phosphate in the oxidation of benzyl alcohols. Catal Today 192:117–122. CrossRefGoogle Scholar
  28. Rydel-Ciszek K, Charczuk M, Paczesniak T, Chmielarz P (2017) Manganese(II) complexes with Bn-tpen as powerful catalysts of cyclohexene oxidation. Chem Pap 71:2085–2093. CrossRefGoogle Scholar
  29. Sanaa T, Yun HTY,Tawfi kAS, Abdul HA, Umer R, Mohd IS (2018) Synthesis of bimetallic gold-pallidum loaded on carbon as efficient catalysts for the oxidation of benzyl alcohol into benzaldehyde. J Mol Liquids 271:885–891.
  30. Suareza M, Garcia-Romero E (2012) Variability of the surface properties of sepiolite. Appl Clay Sci 67–68:72–82. CrossRefGoogle Scholar
  31. Sun Z, Li G, Zhang Y, Liu H, Gao X (2015) Ag–Cu–BTC prepared by postsynthetic exchange as effective catalyst for selective oxidation of toluene to benzaldehyde. Catal Commun 59:92–96. CrossRefGoogle Scholar
  32. Tamizhdurai P, Subramanian S, Santhana KP, Ramesh A, Mangesh VL, Abilarasu A, Narayanan S, Shanthi K, Te-Wei C (2019) Catalytic activity of ratio-dependent SBA-15 supported zirconia catalysts for highly selective oxidation of benzyl alcohol to benzaldehyde and environmental pollutant heavy metal ions detection. J Mol Struct 1176:650–661. CrossRefGoogle Scholar
  33. Thao NT, Huyen LTK (2015) Catalytic oxidation of styrene over Cu-doped hydrotalcites. Chem Eng J 279:840–850. CrossRefGoogle Scholar
  34. Thao NT, Nhu NT (2018) Evaluation of catalytic activity of MeOx/sepiolite in benzyl alcohol oxidation. J Sci Adv Mater Dev 3:289–295. Google Scholar
  35. Thao NT, Nhu NT, Kuen-Song L (2018) Liquid phase oxidation of benzyl alcohol to benzaldehyde over sepiolite loaded chromium oxide catalysts. J Taiwan Inst Chem Eng 83:10–12. CrossRefGoogle Scholar
  36. Weng Z, Liao G, Wang J, Jian X (2007) Selective oxidation of benzyl alcohol with hydrogen peroxide over reaction-controlled phase-transfer catalyst. Catal Commun 8:1493–1496. CrossRefGoogle Scholar
  37. Xiaoyuan Y, Shujie W, Jing H, Xiaoran F, Ling P, Qiubin K, Qisheng H, Jingqi G (2016) Highly efficient N-doped magnetic cobalt-graphene composite for selective oxidation of benzyl alcohol. Catal Commun 87:90–93. CrossRefGoogle Scholar
  38. Yadav GD, Mehta PH, Haldavanekar BV (1993) Capsule membrane phase transfer catalysis: selective alkaline hydrolysis and oxidation of benzyl chloride to benzyl alcohol and benzaldehyde. Stud Surf Sci Catal 78:503–512CrossRefGoogle Scholar
  39. Ying M, Gaoke Z (2016) Sepiolite nanofiber-supported platinum nanoparticle catalysts toward the catalytic oxidation of formaldehyde at ambient temperature: efficient and stable performance and mechanism. Chem Eng J 288:70–78. CrossRefGoogle Scholar
  40. Yingying L, Jiale H, Xijun H, Frank LYL, Wenju W, Rafael L (2016) Heterogeneous Pd catalyst for mild solvent-free oxidation of benzyl alcohol. J Mol Catal A 425:61–67. CrossRefGoogle Scholar
  41. Zhou W, Liu J, Pan J, Sun F, He M, Chen Q (2015) Effect of Mg2+ on the catalytic activities of CoMgAl hydrotalcites in the selective oxidation of benzyl alcohol to benzaldehyde. Catal Commun 69:1–4. CrossRefGoogle Scholar
  42. Zhou C, Guoa Z, Daia Y, Jia X, Yu H, Yang Y (2016) Promoting role of bismuth on carbon nanotube supported platinum catalysts in aqueous phase aerobic oxidation of benzyl alcohol. Appl Catal B 181:118–126. CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2019

Authors and Affiliations

  1. 1.Faculty of ChemistryVietnam National University, HanoiHanoiVietnam

Personalised recommendations