Skip to main content
SpringerLink
Log in

Palladium nanoparticles supported on fluorine-doped tin oxide as an efficient heterogeneous catalyst for Suzuki coupling and 4-nitrophenol reduction

  • Regular Article
  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

Abstract

Immobilization of palladium nanoparticles onto the fluorine-doped tin oxide (FTO) as support Pd/FTO, resulted in a highly active heterogeneous catalyst for Suzuki-Miyaura cross-coupling reactions and 4-nitrophenol reduction. The Pd/FTO catalyst has been synthesized by immobilization of palladium nanoparticles onto FTO via a simple impregnation method. ICP-MS analysis confirmed that there is 0.11 mmol/g of palladium was loaded successfully on FTO support. The crystallinity, morphologies, compositions and surface properties of Pd/FTO were fully characterized by various techniques. It was further examined for its catalytic activity and robustness in Suzuki coupling reaction with different aryl halides and solvents. The yields obtained from Suzuki coupling reactions were basically over 80%. The prepared catalyst was also tested on mild reaction such as reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). Pd/FTO catalyst exhibited high catalytic activity towards 4-NP reduction with a rate constant of 1.776 min−1 and turnover frequency (TOF) value of 29.1 hr−1. The findings revealed that Pd/FTO also maintained its high stability for five consecutive runs in Suzuki reactions and 4-NP reductions. The catalyst showed excellent catalytic activities by using a small amount of Pd/FTO for the Suzuki coupling reaction and 4-NP reduction.

Graphic abstract

Novel Pd-supported FTO nano-powder catalyst exhibited high activity and selectivity towards C-C Suzuki coupling reaction and nitroarene reduction.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10

Similar content being viewed by others

References

  1. Fareghi-Alamdari R, Golestanzadeh M and Bagheri O 2017 An efficient and recoverable palladium organocatalyst for Suzuki reaction in aqueous media Appl. Organomet. Chem. 31 e3698

    Google Scholar 

  2. Hekmati M, Bonyasi F, Javaheri H and Hemmati S 2017 Green synthesis of palladium nanoparticles using Hibiscus sabdariffa L. flower extract: Heterogeneous and reusable nanocatalyst in Suzuki coupling reactions Appl. Organomet. Chem. 31 e3757

    Google Scholar 

  3. Hajipour A R and Tavangar-Rizi Z 2017 Palladium nanoparticles immobilized on magnetic methionine-functionalized chitosan: A versatile catalyst for Suzuki and copper-free Sonogashira reactions of aryl halides at room temperature in water as only solvent Appl. Organomet. Chem. 31 e3701

    Google Scholar 

  4. Du Q and Li Y 2012 Application of an air-and-moisture-stable diphenylphosphinite cellulose-supported nanopalladium catalyst for a Heck reaction Res. Chem. Intermed. 38 1807

    CAS  Google Scholar 

  5. Geyer F L, Brosius V and Bunz U H 2015 2-bromotetraazapentacene and Its functionalization by Pd (0)-Chemistry J. Org. Chem. 80 12166

    CAS  PubMed  Google Scholar 

  6. Shah D and Kaur H 2016 Supported palladium nanoparticles: A general sustainable catalyst for microwave enhanced carbon-carbon coupling reactions J. Mol. Catal. A: Chem. 424 171

    CAS  Google Scholar 

  7. Zhou P, Wang H, Yang J, Tang J, Sun D and Tang W 2012 Bacteria cellulose nanofibers supported palladium(0) nanocomposite and its catalysis evaluation in Heck reaction Ind. Eng. Chem. Res. 51 5743

    CAS  Google Scholar 

  8. Xing G 2016 Palladium immobilized on aminated polyacrylonitrile nanofiber as an efficient heterogeneous catalyst for Heck reaction Fibers Polym. 17 194

    CAS  Google Scholar 

  9. Lu G, Franzen R, Yu X J and Xu Y J 2006 Synthesis of Flurbiprofen via Suzuki reaction catalyzed by palladium charcoal in water Chin. Chem. Lett. 17 461

    CAS  Google Scholar 

  10. Albani D, Vilé G, Mitchell S, Witte P T, Almora-Barrios N, Verel R, López N and Pérez-Ramírez J 2016 Ligand ordering determines the catalytic response of hybrid palladium nanoparticles in hydrogenation Catal. Sci. Technol. 6 1621

    CAS  Google Scholar 

  11. Monguchi Y, Wakayama F, Ueda S, Ito R, Takada H, Inoue H, Nakamura A, Sawama Y and Sajiki H 2017 Amphipathic monolith-supported palladium catalysts for chemoselective hydrogenation and cross-coupling reactions RSC Adv. 7 1833

    CAS  Google Scholar 

  12. Liu C, Li M, Wang J, Zhou X, Guo Q, Yan J and Li Y 2016 Plasma methods for preparing green catalysts: Current status and perspective Chin. J. Catal. 37 340

    CAS  Google Scholar 

  13. Viswanathan P and Ramaraj R 2018 Gold nanodots self-assembled polyelectrolyte film as reusable catalyst for reduction of nitroaromatics J. Chem. Sci. 130 4

    Google Scholar 

  14. Farooqi Z H, Khalid R, Begum R, Farooq U, Wu Q, Wu W, Ajmal M, Irfan A and Naseem K 2019 Facile synthesis of silver nanoparticles in a crosslinked polymeric system by in situ reduction method for catalytic reduction of 4-nitroaniline Environ. Technol. 40 2027

    CAS  Google Scholar 

  15. Deraedt C, Salmon L and Astruc D 2014 “Click” dendrimer-stabilized palladium nanoparticles as a green catalyst down to parts per million for efficient C-C cross-coupling reactions and reduction of 4-nitrophenol Adv. Synth. Catal. 356 2525

    CAS  Google Scholar 

  16. Nandanwar S U and Chakraborty M 2012 Synthesis of colloidal CuO/γ-Al2O3 by microemulsion and its catalytic reduction of aromatic nitro compounds Chin. J. Catal. 33 1532

    CAS  Google Scholar 

  17. Juttukonda V, Paddock R L, Raymond J E, Denomme D, Richardson A E, Slusher L E and Fahlman B D 2006 Facile synthesis of tin oxide nanoparticles stabilized by dendritic polymers J. Am. Chem. Soc. 128 420

    CAS  PubMed  Google Scholar 

  18. Zhang G and Liu M 2000 Effect of particle size and dopant on properties of SnO2-based gas sensors Sens. Actuat. B 69 144

    CAS  Google Scholar 

  19. Boegeat D, Jousseaume B, Toupance T, Campet G and Fournes L 2000 The first mixed-valence fluorotin alkoxides: new sol− gel precursors of fluorine-doped tin oxide materials Inorg. Chem. 39 3924

    CAS  Google Scholar 

  20. Vannucci A K, Alibabaei L, Losego M D, Concepcion J J, Kalanyan B, Parsons G N and Meyer T J 2013 Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation PNAS USA 110 20918

    CAS  PubMed  Google Scholar 

  21. Han C-H, Han S-D, Gwak J and Khatkar S 2007 Synthesis of indium tin oxide (ITO) and fluorine-doped tin oxide (FTO) nano-powder by sol–gel combustion hybrid method Mater. Lett. 61 1701

    CAS  Google Scholar 

  22. Tran Q-P, Fang J-S and Chin T-S 2015 Properties of fluorine-doped SnO2 thin films by a green sol–gel method Mater. Sci. Semicond. Process. 40 664

    CAS  Google Scholar 

  23. Zhang J and Gao L 2004 Synthesis and characterization of nanocrystalline tin oxide by sol–gel method J. Solid State Chem. 177 1425

    CAS  Google Scholar 

  24. Murakami T N and Grätzel M 2008 Counter electrodes for DSC: application of functional materials as catalysts Inorg. Chim. Acta 361 572

    CAS  Google Scholar 

  25. Kent C A, Concepcion J J, Dares C J, Torelli D A, Rieth A J, Miller A S, Hoertz P G and Meyer T J 2013 Water oxidation and oxygen monitoring by cobalt-modified fluorine-doped tin oxide electrodes J. Am. Chem. Soc. 135 8432

    CAS  PubMed  Google Scholar 

  26. Samad W Z, Isahak W N R W, Liew K H, Nordin N, Yarmo M A and Yusop M R 2014 Ru/FTO: Heterogeneous catalyst for glycerol hydrogenolysis AIP Conf. Proc. pp 269-274

  27. Batzill M and Diebold U 2005 The surface and materials science of tin oxide Prog. Surf. Sci. 79 47

    CAS  Google Scholar 

  28. Varala R, Narayana V, Kulakarni S R, Khan M, Alwarthan A and Adil S F 2016 Sulfated tin oxide (STO)–Structural properties and application in catalysis: A review Arab. J. Chem. 9 550

    CAS  Google Scholar 

  29. Liew K H, Samad W Z, Nordin N, Loh P L, Juan J C, Yarmo M A, Yahaya B H and Yusop R M 2015 Preparation and characterization of HypoGel-supported Pd nanocatalysts for Suzuki reaction under mild conditions Chin. J. Catal. 36 771

    CAS  Google Scholar 

  30. Cho J K, Najman R, Dean T W, Ichihara O, Muller C and Bradley M 2006 Captured and cross-linked palladium nanoparticles J. Am. Chem. Soc. 128 6276

    CAS  PubMed  Google Scholar 

  31. Najman R, Cho J K, Coffey A F, Davies J W and Bradley M 2007 Entangled palladium nanoparticles in resin plugs Chem. Commun. 5031

  32. Liew K H, Loh P L, Juan J C, Yarmo M A and Yusop R M 2014 QuadraPure-supported palladium nanocatalysts for microwave-promoted suzuki cross-coupling reaction under aerobic condition Sci. World J. 2014 7

    Google Scholar 

  33. Liew K H, Rocha M, Pereira C, Pires A L, Pereira A M, Yarmo M A, Juan J C, Yusop R M, Peixoto A F and Freire C 2017 Highly active ruthenium supported on magnetically recyclable chitosan-based nanocatalyst for nitroarenes reduction ChemCatChem 9 3930

    CAS  Google Scholar 

  34. Kumar V, Singh K, Singh K, Kumari S, Kumar A and Thakur A 2016 Effect of solvent on the synthesis of SnO2 nanoparticles AIP Conf. Proc. 1728 020532

    Google Scholar 

  35. Alaf M, Guler M O, Gultekin D, Uysal M, Alp A and Akbulut H 2008 Effect of oxygen partial pressure on the microstructural and physical properties on nanocrystalline tin oxide films grown by plasma oxidation after thermal deposition from pure Sn targets Vacuum 83 292

    CAS  Google Scholar 

  36. Samad W Z, Goto M, Kanda H, Nordin N, Liew K H, Yarmo M A and Yusop M R 2017 Fluorine-doped tin oxide catalyst for glycerol conversion to methanol in sub-critical water J. Supercrit. Fluids 120 366

    CAS  Google Scholar 

  37. Khan Z, Dummer N F and Edwards J K 2018 Silver–palladium catalysts for the direct synthesis of hydrogen peroxide Philos. Trans. R Soc. A 376

    Google Scholar 

  38. Xue N, Yu R-J, Yuan C-Z, Xie X, Jiang Y-F, Zhou H-Y, Cheang T-Y and Xu A-W 2017 In situ redox deposition of palladium nanoparticles on oxygen-deficient tungsten oxide as efficient hydrogenation catalysts RSC Adv. 7 2351

    CAS  Google Scholar 

  39. Guan X, Luo P, Li X, Yu Y, Chen D and Zhang L 2018 One-step facile synthesis of hierarchically porous nitrogen-doped Sno2 nanoparticles with ultrahigh surface area for enhanced lithium storage performance Int. J. Electrochem. Sci. 13 5667

    CAS  Google Scholar 

  40. Zhang H, Sun J, Dagle V L, Halevi B, Datye A K and Wang Y 2014 Influence of ZnO facets on Pd/ZnO catalysts for methanol steam reforming ACS Catal. 4 2379

    CAS  Google Scholar 

  41. Metin Ö, Sun X and Sun S 2013 Monodisperse gold–palladium alloy nanoparticles and their composition-controlled catalysis in formic acid dehydrogenation under mild conditions Nanoscale 5 910

  42. Sengupta D, Saha J, De G and Basu B 2014 Pd/Cu bimetallic nanoparticles embedded in macroporous ion-exchange resins: an excellent heterogeneous catalyst for the Sonogashira reaction J. Mater. Chem. A 2 3986

    CAS  Google Scholar 

  43. Tammina S K, Mandal B K, Ranjan S and Dasgupta N 2017 Cytotoxicity study of Piper nigrum seed mediated synthesized SnO2 nanoparticles towards colorectal (HCT116) and lung cancer (A549) cell lines J. Photochem. Photobiol. B 166 158

    CAS  PubMed  Google Scholar 

  44. Zhi X, Zhao G, Zhu T and Li Y 2008 The morphological, optical and electrical properties of SnO2: F thin films prepared by spray pyrolysis Surf. Interface Anal. 40 67

    CAS  Google Scholar 

  45. Tressaud A, Labrugère C, Durand E, Brigouleix C and Andriessen H 2009 Switchable hydrophobic-hydrophilic layer obtained onto porous alumina by plasma-enhanced fluorination Sci. China Ser. E: Technol. Sci. 52 104

    CAS  Google Scholar 

  46. Babar A, Shinde S, Moholkar A, Bhosale C, Kim J and Rajpure K 2011 Physical properties of sprayed antimony doped tin oxide thin films: The role of thickness J. Semicond. 32 053001

    Google Scholar 

  47. Elazab H A, Moussa S, Siamaki A R, Gupton B F and El-Shall M S 2017 The Effect of graphene on catalytic performance of palladium nanoparticles decorated with Fe3O4, Co3O4, and Ni(OH)2: Potential efficient catalysts used for suzuki cross-coupling Catal. Lett. 147 1510

    CAS  Google Scholar 

  48. Martinez A, Huerta L, de León J O-R, Acosta D, Malik O and Aguilar M 2006 Physicochemical characteristics of fluorine doped tin oxide films J. Phys. D 39 5091

    CAS  Google Scholar 

  49. Noor N and Parkin I P 2013 Enhanced transparent-conducting fluorine-doped tin oxide films formed by aerosol-assisted chemical vapour deposition J. Mater. Chem. C 1 984

    CAS  Google Scholar 

  50. Yu J, Wang C, Xiang L, Xu Y and Pan Y 2018 Enhanced C3H6/C3H8 separation performance in poly (vinyl acetate) membrane blended with ZIF-8 nanocrystals Chem. Eng. Sci. 179 1

    CAS  Google Scholar 

  51. Rathod P V and Jadhav V H 2017 Palladium incorporated on carbonaceous catalyst for Suzuki coupling reaction in water Tetrahedron Lett. 58 1006

    CAS  Google Scholar 

  52. Baran T, Yılmaz Baran N and Menteş A 2018 Sustainable chitosan/starch composite material for stabilization of palladium nanoparticles: Synthesis, characterization and investigation of catalytic behaviour of Pd@chitosan/starch nanocomposite in Suzuki–Miyaura reaction Appl. Organomet. Chem. 32 e4075

    Google Scholar 

  53. Han D, Zhang Z, Bao Z, Xing H and Ren Q 2018 Pd-Ni nanoparticles supported on titanium oxide as effective catalysts for Suzuki-Miyaura coupling reactions Front. Chem. Sci. Eng. 12 24

    CAS  Google Scholar 

  54. Dadras A, Naimi-Jamal M R, Moghaddam F M and Ayati S E 2018 Green and selective oxidation of alcohols by immobilized Pd onto triazole functionalized Fe3O4 magnetic nanoparticles J. Chem. Sci. 130 162

    Google Scholar 

  55. Pourkhosravani M, Dehghanpour S and Farzaneh F 2016 Palladium nanoparticles supported on zirconium metal organic framework as an efficient heterogeneous catalyst for the Suzuki–Miyaura coupling reaction Catal. Lett. 146 499

    CAS  Google Scholar 

  56. Yusop R M, Unciti-Broceta A and Bradley M 2012 A highly sensitive fluorescent viscosity sensor Bioorg. Med. Chem. Lett. 22 5780

    CAS  Google Scholar 

  57. Lamblin M, Nassar-Hardy L, Hierso J-C, Fouquet E and Felpin F-X 2010 Recyclable heterogeneous palladium catalysts in pure water: Sustainable developments in Suzuki, Heck, Sonogashira and Tsuji–Trost Reactions Adv. Synth. Catal. 352 33

    CAS  Google Scholar 

  58. Jabbari A, Tahmasbi B, Nikoorazm M and Ghorbani-Choghamarani A 2018 A new Pd-Schiff-base complex on boehmite nanoparticles: Its application in Suzuki reaction and synthesis of tetrazoles Appl. Organomet. Chem. 32 e4295

    Google Scholar 

  59. Veisi H, Ghadermazi M and Naderi A 2016 Biguanidine-functionalized chitosan to immobilize palladium nanoparticles as a novel, efficient and recyclable heterogeneous nanocatalyst for Suzuki–Miyaura coupling reactions Appl. Organomet. Chem. 30 341

    CAS  Google Scholar 

  60. Farzad E and Veisi H 2018 Fe3O4/SiO2 nanoparticles coated with polydopamine as a novel magnetite reductant and stabilizer sorbent for palladium ions: Synthetic application of Fe3O4/SiO2@ PDA/Pd for reduction of 4-nitrophenol and Suzuki reactions J. Ind. Eng. Chem. 60 114

    CAS  Google Scholar 

  61. Krishna R, Fernandes D M, Ventura J, Freire C and Titus E 2016 Novel synthesis of highly catalytic active Cu@Ni/RGO nanocomposite for efficient hydrogenation of 4-nitrophenol organic pollutant Int. J Hydrog. Energy 41 11608

    CAS  Google Scholar 

  62. Abay A K, Chen X and Kuo D-H 2017 Highly efficient noble metal free copper nickel oxysulfide nanoparticles for catalytic reduction of 4-nitrophenol, methyl blue, and rhodamine-B organic pollutants New J. Chem. 41 5628

    CAS  Google Scholar 

  63. Zhou R, Yang X, Zhang P, Yang L, Liu C, Liu D and Gui J 2018 Insights into catalytic roles of noble-metal-free catalysts CoxSy for reduction of 4-nitrophenol PCCP 20 27730

  64. Morrissey C and He H 2018 Silicene catalyzed reduction of nitrobenzene to aniline: A mechanistic study Chem. Phys. Lett. 695 228

    CAS  Google Scholar 

  65. Rocha M, Fernandes C, Pereira C, Rebelo S L, Pereira M F and Freire C 2015 Gold-supported magnetically recyclable nanocatalysts: a sustainable solution for the reduction of 4-nitrophenol in water RSC Adv. 5 5131

    CAS  Google Scholar 

  66. Sun W, Lu X, Tong Y, Zhang Z, Lei J, Nie G and Wang C 2014 Fabrication of highly dispersed palladium/graphene oxide nanocomposites and their catalytic properties for efficient hydrogenation of p-nitrophenol and hydrogen generation Int. J. Hydrog. Energy 39 9080

    CAS  Google Scholar 

  67. Lv Z-S, Zhu X-Y, Meng H-B, Feng J-J and Wang A-J 2019 One-pot synthesis of highly branched Pt@Ag core-shell nanoparticles as a recyclable catalyst with dramatically boosting the catalytic performance for 4-nitrophenol reduction J. Colloid Interface Sci. 538 349

    CAS  PubMed  Google Scholar 

  68. Barman B K and Nanda K K 2015 Rapid reduction of GO by hydrogen spill-over mechanism by in situ generated nanoparticles at room temperature and their catalytic performance towards 4-nitrophenol reduction and ethanol oxidation Appl. Catal. A 491 45

    CAS  Google Scholar 

  69. Kohantorabi M and Gholami M R 2018 Fabrication of novel ternary Au/CeO2@g-C3N4 nanocomposite: Kinetics and mechanism investigation of 4-nitrophenol reduction, and benzyl alcohol oxidation Appl. Phys. A 124 441

    Google Scholar 

  70. Shi G-M, Li S-T, Shi F-N, Shi X-F, Lv S-H and Cheng X-B 2018 A facile strategy for synthesis of Ni@C(N) nanocapsules with enhanced catalytic activity for 4-nitrophenol reduction Colloid. Surf. A 555 170

    CAS  Google Scholar 

Download references

Acknowledgements

Financial assistance from Universiti Kebangsaan Malaysia (UKM) for a research grant (GUP-2016-063) and Malaysia-Thailand Joint Authority (ST-2018-005) are acknowledged. The authors are gratefully acknowledged to Center for Research and Instrumentation (CRIM) UKM for providing the facilities for the analysis work. Lastly, we are grateful to our lab associates, colleagues and staffs for their knowledge supports and assists during this research.

Author information

Authors and Affiliations

  1. School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM, Bangi, Selangor Darul Ehsan, Malaysia

    Sek Yin Mak, Kin Hong Liew, Chia Chia Chua, Mohd Ambar Yarmo, Mohd Suzeren Md Jamil & Rahimi M Yusop

  2. Regenerative Medicine Cluster, Advanced Medical and Dental Institute, Universiti Sains Malaysia, Bertam, 13200, Kepala Batas, Pulau Pinang, Malaysia

    Badrul H Yahaya & Rahimi M Yusop

  3. Department of Chemistry, Kulliyyah of Science, International Islamic University Malaysia (IIUM Kuantan Campus), Bandar Indera Mahkota, 25200, Kuantan, Pahang, Malaysia

    Wan Zurina Samad

Authors
  1. Sek Yin Mak
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kin Hong Liew
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Chia Chia Chua
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mohd Ambar Yarmo
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Badrul H Yahaya
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Wan Zurina Samad
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Mohd Suzeren Md Jamil
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Rahimi M Yusop
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Kin Hong Liew or Rahimi M Yusop.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (PDF 1949 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mak, S.Y., Liew, K.H., Chua, C.C. et al. Palladium nanoparticles supported on fluorine-doped tin oxide as an efficient heterogeneous catalyst for Suzuki coupling and 4-nitrophenol reduction. J Chem Sci 131, 111 (2019). https://doi.org/10.1007/s12039-019-1685-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s12039-019-1685-7

Keywords

Search

Navigation