In situ synthesis and catalytic properties of Cu2O nanoparticles based on clay materials and polyethylene glycol

  • Ainur N. ImangaliyevaEmail author
  • Yitzhak Mastai
  • Gulziya A. Seilkhanova
Research Paper


A novel protocol for in situ synthesis of Cu2O nanoparticles immobilized on natural bentonite and zeolite and functionalized by polyethylene glycol is reported. The NPs were synthesized during the course of the catalytic reduction of 4-nitrophenol in the presence of NaBH4. The synthesized precursors and the catalysts Cu2O/PEG-BT and Cu2O/PEG-ZT were characterized by X-ray diffraction, high-resolution scanning electron microscopy, energy-dispersive X-ray and atomic absorption spectroscopy, surface area analysis, and UV-visible spectroscopy. The diffraction and microscopy data confirmed that in situ copper oxide (I) NPs were synthesized with a size range of 20 to 40 nm. The reduction rate constants at 25 °C for Cu2O/PEG-BT and Cu2O/PEG-ZT were 1.22 × 10−2 and 1.79 × 10−2 s−1, respectively. The synthesized catalysts were found to be highly effective and inexpensive.

Graphical abstract


Bentonite Zeolite PEG Cu2O catalyst Nano-composites 4-Nitrophenol reduction Nanostructured catalysts 


Funding information

This work was supported by the Ministry of Education and Science of Republic of Kazakhstan grant 3444/GF4 “Scientific bases development of phosphorus-containing compounds obtained on the basis of technogenic mineral raw materials”.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11051_2019_4548_MOESM1_ESM.docx (166 kb)
ESM 1 (DOCX 165 kb)


  1. Abd El Maksod IH, Saleh TS, Hegazy EZ (2010) Preparation, characterization and utilization of (Ni:Cu) bimetallic system loaded on zeolites. J Alloys Compd 506:923–927. CrossRefGoogle Scholar
  2. Bawane SP, Sawant SB (2005) Hydrogenation of p-nitrophenol to metol using Raney nickel catalyst: reaction kinetics. Appl Catal A Gen 293:162–170CrossRefGoogle Scholar
  3. Caglar B, Afsin B, Tabak A, Eren E (2009) Characterization of the cation-exchanged bentonites by XRPD, ATR, DTA/TG analyses and BET measurement. Chem Eng J 149:242–248. CrossRefGoogle Scholar
  4. Cárdenas-Lizana F, Gómez-Quero S, Perret N, Keane MA (2011) Gold catalysis at the gas-solid interface: role of the support in determining activity and selectivity in the hydrogenation of m-dinitrobenzene. Catal Sci Technol 1:652–661. CrossRefGoogle Scholar
  5. Clegg F, Breen C, Khairuddin (2014) Synergistic and competitive aspects of the adsorption of poly (ethylene glycol) and poly (vinyl alcohol) onto Na-bentonite. J Phys Chem B 118:13268–13278. CrossRefGoogle Scholar
  6. Deka P, Deka RC, Bharali P (2014) In situ generated copper nanoparticle catalyzed reduction of 4-nitrophenol. New J Chem 38:1789–1793. CrossRefGoogle Scholar
  7. Dong Z, Le X, Dong C et al (2015) Environmental Ni @ Pd core – shell nanoparticles modified fibrous silica nanospheres as highly efficient and recoverable catalyst for reduction of 4-nitrophenol and hydrodechlorination of 4-chlorophenol. Appl Catal B Environ 162:372–380. CrossRefGoogle Scholar
  8. Giri S, Das R, van der Westhuyzen C, Maity A (2017) An efficient selective reduction of nitroarenes catalyzed by reusable silver-adsorbed waste nanocomposite. Appl Catal B Environ 209:669–678. CrossRefGoogle Scholar
  9. Gkizis PL, Stratakis M, Lykakis IN (2013) Catalytic activation of hydrazine hydrate by gold nanoparticles: chemoselective reduction of nitro compounds into amines. Catal Commun 36:48–51. CrossRefGoogle Scholar
  10. Guo XH, Ma JQ, Ge HG (2015) Synthesis and characterization of Cu2O/Au and its application in catalytic reduction of 4-nitrophenol. Russ J Phys Chem A 89:1374–1380. CrossRefGoogle Scholar
  11. He L, Wang LC, Sun H, Ni J, Cao Y, He HY, Fan KN (2009) Efficient and selective room-temperature gold-catalyzed reduction of nitro compounds with CO and H2O as the hydrogen source. Angew Chem Int Ed 48:9538–9541. CrossRefGoogle Scholar
  12. Horáček J, Št’Ávová G, Kelbichová V, Kubička D (2013) Zeolite-beta-supported platinum catalysts for hydrogenation/ hydrodeoxygenation of pyrolysis oil model compounds. Catal Today 204:38–45. CrossRefGoogle Scholar
  13. Kaur B, Tumma M, Srivastava R (2013) Transition-metal-exchanged nanocrystalline ZSM-5 and metal-oxide- incorporated SBA-15 catalyzed reduction of nitroaromatics. Ind Eng Chem Res 52:11479–11487. CrossRefGoogle Scholar
  14. Khalfaoui M, Knani S, Hachicha MA, Lamine AB (2003) New theoretical expressions for the five adsorption type isotherms classified by BET based on statistical physics treatment. J Colloid Interface Sci 263:350–356. CrossRefGoogle Scholar
  15. Khan MN, Bashir O, Khan TA, al-Thabaiti SA, Khan Z (2017) Catalytic activity of cobalt nanoparticles for dye and 4-nitro phenol degradation: a kinetic and mechanistic study. Int J Chem Kinet 49:438–454. CrossRefGoogle Scholar
  16. Kumar A, Saxena A, De A et al (2013) Facile synthesis of size-tunable copper and copper oxide nanoparticles using reverse microemulsions. RSC Adv 3:5015–5021. CrossRefGoogle Scholar
  17. Lawrence SA (2004) Amines: synthesis, properties and applications. Cambridge New YorkGoogle Scholar
  18. Lee J, Park JC, Song H (2008) A nanoreactor framework of a Au@SiO2 yolk/shell structure for catalytic reduction of p-nitrophenol. Adv Mater 20:1523–1528. CrossRefGoogle Scholar
  19. Li S, Guo S, Yang H, Gou G, Ren R, Li J, Dong Z, Jin J, Ma J (2014) Enhancing catalytic performance of Au catalysts by noncovalent functionalized graphene using functional ionic liquids. J Hazard Mater 270:11–17. CrossRefGoogle Scholar
  20. Liu B, Yu S, Wang Q, Hu W, Jing P, Liu Y, Jia W, Liu Y, Liu L, Zhang J (2013) Hollow mesoporous ceria nanoreactors with enhanced activity and stability for catalytic application. Chem Commun (Camb) 49:3757–3759. CrossRefGoogle Scholar
  21. Lu S, Yu J, Cheng Y, Wang Q, Barras A, Xu W, Szunerits S, Cornu D, Boukherroub R (2017) Preparation of silver nanoparticles/polydopamine functionalized polyacrylonitrile fiber paper and its catalytic activity for the reduction 4-nitrophenol. Appl Surf Sci 411:163–169. CrossRefGoogle Scholar
  22. Narváez LE, Rosales-Martínez RI, Narváez-Hernández L, Hernández-Hernández LS (2015) Electrochemical stability of steel reinforced bars embedded in cement mortars containing clinoptilolite as supplementary. Int J Electrochem Sci 10:10003–10016Google Scholar
  23. Natkański P, Białas A, Kuśtrowski P (2012) The synthesis of poly (acrylic acid)-bentonite and polyacrylamide-bentonite composites for adsorption applications. Chemik 746–749Google Scholar
  24. Padervand M, Salari H, Darabi FS, Gholami MR (2013) Kinetic and mechanistic study of p-nitrochlorobenzene photoreduction and Bacillus inactivation over aluminosilicate-based nanocomposites. Monatsh Chem 144:589–596. CrossRefGoogle Scholar
  25. Raghavendra GM, Jung J, Kim D, Seo J (2017) Chitosan-mediated synthesis of flowery-CuO , and its antibacterial and catalytic properties. Carbohydr Polym 172:78–84. CrossRefGoogle Scholar
  26. Rajasekaran P, Kannan H, Das S, Young M (2016) Comparative analysis of copper and zinc based agrichemical biocide products: materials characteristics, phytotoxicity and in vitro antimicrobial efficacy. AIMS Environ Sci 3:439–455. CrossRefGoogle Scholar
  27. Ramdar M, Kazemi F, Kaboudin B (2017) A photocatalytic green system for chemoselective reduction of nitroarenes. Chem Pap 71:1155–1163. CrossRefGoogle Scholar
  28. Rath PC, Saikia D, Mishra M, Kao H (2018) Exceptional catalytic performance of ultrafine Cu2O nanoparticles confined in cubic mesoporous carbon for 4-nitrophenol reduction. Appl Surf Sci 427:1217–1226. CrossRefGoogle Scholar
  29. Rostami-Vartooni A, Alizadeh M, Bagherzadeh M (2015) Green synthesis, characterization and catalytic activity of natural bentonite-supported copper nanoparticles for the solvent-free synthesis of 1-substituted 1H-1,2,3,4-tetrazoles and reduction of 4-nitrophenol. Beilstein J Nanotechnol 6:2300–2309. CrossRefGoogle Scholar
  30. Sahiner N, Ozay H, Ozay O, Aktas N (2010) New catalytic route : hydrogels as templates and reactors for in situ Ni nanoparticle synthesis and usage in the reduction of 2- and 4-nitrophenols. Appl Catal A Gen 385:201–207. CrossRefGoogle Scholar
  31. Schrinner M, Ballauff M, Talmon Y, Kauffmann Y, Thun J, Moller M, Breu J (2009) Single nanocrystals of platinum prepared by partial dissolution of Au-Pt nanoalloys. Science 323:617–620. CrossRefGoogle Scholar
  32. Seilkhanova GA, Imangaliyeva AN, Akbayeva DN (2017) Modified raw materials: synthesis, characterization and application for Cd2+ ions removal. Studia UBB Chemia LXII:35–50. CrossRefGoogle Scholar
  33. Šimáková P, Gautier J, Procházka M, Aubert K, Choupra I (2014) Polyethylene-glycol-stabilized Ag nanoparticles for surface-enhanced Raman scattering spectroscopy: Ag surface accessibility studied using metalation of free-base porphyrins. J Phys Chem 118:7690–7697. CrossRefGoogle Scholar
  34. Singh DP, Singh JAI, Mishra PR, Tiwari RS, Srivastava ON (2008) Synthesis, characterization and application of semiconducting oxide (Cu2O and ZnO) nanostructures. Bull Mater Sci 31:319–325CrossRefGoogle Scholar
  35. Su Y, Fan B, Wang L, Liu Y, Huang B, Fu M, Chen L, Ye D (2013) MnOx supported on carbon nanotubes by different methods for the SCR of NO with NH3. Catal Today 201:115–121. CrossRefGoogle Scholar
  36. Subramanian T, Pitchumani K (2012) Selective reduction of nitroarenes by using zeolite-supported copper nanoparticles with 2-propanol as a sustainable reducing agent. ChemCatChem 4:1917–1921. CrossRefGoogle Scholar
  37. Veerakumar P, Velayudham M, Lu KL, Rajagopal S (2012) Polyelectrolyte encapsulated gold nanoparticles as efficient active catalyst for reduction of nitro compounds by kinetic method. Appl Catal A Gen 439–440:197–205. CrossRefGoogle Scholar
  38. Wang Z, Xu C, Gao G, Li X (2014) Facile synthesis of well-dispersed Pd-graphene nanohybrids and their catalytic properties in 4-nitrophenol reduction. RSC Adv 4:13644–13651. CrossRefGoogle Scholar
  39. Wang F, Ren J, Cai Y, Sun L, Chen C, Liang S, Jiang X (2016) Palladium nanoparticles confined within ZSM-5 zeolite with enhanced stability for hydrogenation of p-nitrophenol to p-aminophenol. Chem Eng J 283:922–928. CrossRefGoogle Scholar
  40. Yoshida A, Mori Y, Ikeda T, Azemoto K, Naito S (2013) Enhancement of catalytic activity of Ir/TiO2by partially reduced titanium oxide in aerobic oxidation of alcohols. Catal Today 203:153–157. CrossRefGoogle Scholar
  41. Zeng J, Zhang Q, Chen J, Xia Y (2010) A comparison study of the catalytic properties of Au-based nanocages, nanoboxes, and nanoparticles. Nano Lett 10:30–35. CrossRefGoogle Scholar
  42. Zhou J, Yang Q (2012) Facile synthesis of monodisperse noble-metal nanoparticles and high catalytic performance for organic reactions in both water and oil systems. Chem Asian J 7:2045–2050. CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Faculty of Chemistry and Chemical TechnologyAl-Farabi Kazakh National UniversityAlmatyKazakhstan
  2. 2.Department of Chemistry and the Institute of NanotechnologyBar-Ilan UniversityRamat-GanIsrael

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