Journal of Materials Science

, Volume 51, Issue 1, pp 603–614 | Cite as

Pd-based nanoflowers catalysts: controlling size, composition, and structures for the 4-nitrophenol reduction and BTX oxidation reactions

  • Anderson G. M. da Silva
  • Thenner S. Rodrigues
  • Laís S. K. Taguchi
  • Humberto V. Fajardo
  • Rosana Balzer
  • Luiz F. D. Probst
  • Pedro H. C. CamargoEmail author
50th Anniversary


We describe herein the synthesis of solid Au@Pd and hollow AgPd nanoflowers displaying controlled sizes and compositions in order to investigate how their size, composition, and the presence of Au in the core of the nanoparticles influence their catalytic performance toward both liquid and gas-phase transformations. While the size and composition of Au@Pd and AgPd the nanoflowers could be controlled as function of growth time, their structure (solid or hollow) was dependent on the nature of the seeds employed for the synthesis, i.e., Au or Ag nanoparticles. Moreover, Au@Pd and AgPd nanoflowers were successfully supported onto commercial silica displaying truly uniform dispersion. The catalytic activities of Au@Pd and AgPd nanoflowers were investigated toward the 4-nitrophenol reduction and the benzene, toluene, and o-xylene (BTX) oxidation. The catalytic activities for the reduction of 4-nitrophenol decreased as follows: Au58@Pd42 > Au27@Pd73 > Ag20Pd80 and Ag8Pd92 > Au12@Pd88 > Ag38Pd62, suggesting that the Au core enhanced the catalytic activity relative to the hollow material when for Pd at.% was up to 80. Regarding the BTX oxidation, supported Au@Pd displayed higher catalytic activities than AgPd nanoflowers, also illustrating the role of the Au cores in the nanoflowers for improving catalytic performance. We believe these results may serve as a platform for the synthesis of Pd-based bimetallic nanomaterials that enable the correlation between these physical/chemical parameters and properties and thus optimized catalytic activities.


Sodium Borohydride Flame Atomic Absorption Spectrometry Flame Atomic Absorption Spectrometry AgPd Hollow Interior 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



This work was supported by the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) (Grant Number 2013/19861-6), the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) (Grant Number 471245/2012-7). P. H. C. C. and H. V. F. thank the CNPq for the research fellowships. A. G. M. S., L. S. K. T., and T. S. R thank CNPq and CAPES for the fellowships.

Compliance with ethical standards

Conflict of Interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2015_9315_MOESM1_ESM.pdf (4 mb)
Supplementary material 1 (PDF 4143 kb)


  1. 1.
    Cheong S, Watt JD, Tilley RD (2010) Shape control of platinum and palladium nanoparticles for catalysis. Nanoscale 2:2045–2053CrossRefGoogle Scholar
  2. 2.
    Yin Liebscher J (2006) Carbon–carbon coupling reactions catalyzed by heterogeneous palladium catalysts. Chem Rev 107:133–173CrossRefGoogle Scholar
  3. 3.
    Long R, Mao K, Ye X et al (2013) Surface facet of palladium nanocrystals: a key parameter to the activation of molecular oxygen for organic catalysis and cancer treatment. J Am Chem Soc 135:3200–3207CrossRefGoogle Scholar
  4. 4.
    Speziali MG, da Silva AGM, de Miranda DMV et al (2013) Air stable ligandless heterogeneous catalyst systems based on Pd and Au supported in SiO2 and MCM-41 for Suzuki–Miyaura cross-coupling in aqueous medium. Appl Catal A 462–463:39–45CrossRefGoogle Scholar
  5. 5.
    Saldan I, Semenyuk Y, Marchuk I, Reshetnyak O (2015) Chemical synthesis and application of palladium nanoparticles. J Mater Sci 50:2337–2354CrossRefGoogle Scholar
  6. 6.
    Da Silva AM, Robles-Dutenhefner P, Dias A et al (2013) Gold, palladium and gold–palladium supported on silica catalysts prepared by sol–gel method: synthesis, characterization and catalytic behavior in the ethanol steam reforming. J Sol-Gel Sci Technol 67:273–281CrossRefGoogle Scholar
  7. 7.
    Crespo-Quesada M, Yarulin A, Jin M et al (2011) Structure sensitivity of alkynol hydrogenation on shape- and size-controlled palladium nanocrystals: which sites are most active and selective? J Am Chem Soc 133:12787–12794CrossRefGoogle Scholar
  8. 8.
    Jin M, Zhang H, Xie Z, Xia Y (2012) Palladium nanocrystals enclosed by 100 and 111 facets in controlled proportions and their catalytic activities for formic acid oxidation. Energy Environ Sci 5:6352–6357CrossRefGoogle Scholar
  9. 9.
    Slater TJA, Macedo A, Schroeder SLM et al (2014) Correlating catalytic activity of Ag–Au nanoparticles with 3D compositional variations. Nano Lett 14:1921–1926CrossRefGoogle Scholar
  10. 10.
    Bai S, Wang X, Hu C et al (2014) Two-dimensional g-C3N4: an ideal platform for examining facet selectivity of metal co-catalysts in photocatalysis. Chem Commun 50:6094–6097CrossRefGoogle Scholar
  11. 11.
    Long R, Zhou S, Wiley BJ, Xiong Y (2014) Oxidative etching for controlled synthesis of metal nanocrystals: atomic addition and subtraction. Chem Soc Rev 43:6288–6310CrossRefGoogle Scholar
  12. 12.
    Rodrigues T, da Silva AM, Macedo A et al (2015) Probing the catalytic activity of bimetallic versus trimetallic nanoshells. J Mater Sci 50:5620–5629CrossRefGoogle Scholar
  13. 13.
    Wang X, Fu J, Wang M et al (2014) Facile synthesis of Au nanoparticles supported on polyphosphazene functionalized carbon nanotubes for catalytic reduction of 4-nitrophenol. J Mater Sci 49:5056–5065CrossRefGoogle Scholar
  14. 14.
    Lou XWD, Archer LA, Yang Z (2008) Hollow micro-/nanostructures: synthesis and applications. Adv Mater 20:3987–4019CrossRefGoogle Scholar
  15. 15.
    Scott RWJ, Datye AK, Crooks RM (2003) Bimetallic palladium–platinum dendrimer-encapsulated catalysts. J Am Chem Soc 125:3708–3709CrossRefGoogle Scholar
  16. 16.
    Wang D, Villa A, Porta F et al (2008) Bimetallic gold/palladium catalysts: correlation between nanostructure and synergistic effects. J Phys Chem C 112:8617–8622CrossRefGoogle Scholar
  17. 17.
    Song HM, Anjum DH, Sougrat R et al (2012) Hollow Au@Pd and Au@Pt core-shell nanoparticles as electrocatalysts for ethanol oxidation reactions. J Mater Chem 22:25003–25010CrossRefGoogle Scholar
  18. 18.
    Zhang S, Metin Ö, Su D, Sun S (2013) Monodisperse AgPd alloy nanoparticles and their superior catalysis for the dehydrogenation of formic acid. Angew Chem Int Ed 52:3681–3684CrossRefGoogle Scholar
  19. 19.
    Xu J, Wilson AR, Rathmell AR et al (2011) Synthesis and catalytic properties of Au–Pd nanoflowers. ACS Nano 5:6119–6127CrossRefGoogle Scholar
  20. 20.
    Kuai L, Yu X, Wang S et al (2012) Au–Pd alloy and core-shell nanostructures: one-pot coreduction preparation, formation mechanism, and electrochemical properties. Langmuir 28:7168–7173CrossRefGoogle Scholar
  21. 21.
    Xiong Y, Xia Y (2007) Shape-controlled synthesis of metal nanostructures: the case of palladium. Adv Mater 19:3385–3391CrossRefGoogle Scholar
  22. 22.
    Phan NTS, Van Der Sluys M, Jones CW (2006) On the nature of the active species in palladium catalyzed mizoroki-heck and suzuki-miyaura couplings—homogeneous or heterogeneous catalysis, a critical review. Adv Synth Catal 348:609–679CrossRefGoogle Scholar
  23. 23.
    Da Silva AGM, Fajardo HV, Balzer R et al (2015) Versatile and efficient catalysts for energy and environmental processes: mesoporous silica containing Au, Pd and Au–Pd. J Power Sources 285:460–468CrossRefGoogle Scholar
  24. 24.
    Lim B, Jiang M, Tao J et al (2009) Shape-controlled synthesis of Pd nanocrystals in aqueous solutions. Adv Funct Mater 19:189–200CrossRefGoogle Scholar
  25. 25.
    Xia Y, Xiong Y, Lim B, Skrabalak SE (2009) Shape-controlled synthesis of metal nanocrystals: simple chemistry meets complex physics? Angew Chem Int Ed 48:60–103CrossRefGoogle Scholar
  26. 26.
    Fu G, Wu K, Lin J et al (2013) One-pot water-based synthesis of Pt–Pd alloy nanoflowers and their superior electrocatalytic activity for the oxygen reduction reaction and remarkable methanol-tolerant ability in acid media. J Phys Chem C 117:9826–9834CrossRefGoogle Scholar
  27. 27.
    Yin Z, Zheng H, Ma D, Bao X (2008) Porous palladium nanoflowers that have enhanced methanol electro-oxidation activity. J Phys Chem C 113:1001–1005CrossRefGoogle Scholar
  28. 28.
    Mohanty A, Garg N, Jin R (2010) A universal approach to the synthesis of noble metal nanodendrites and their catalytic properties. Angew Chem Int Ed 49:4962–4966CrossRefGoogle Scholar
  29. 29.
    Gao Q, Gao M-R, Liu J-W et al (2013) One-pot synthesis of branched palladium nanodendrites with superior electrocatalytic performance. Nanoscale 5:3202–3207CrossRefGoogle Scholar
  30. 30.
    Damato TC, de Oliveira CCS, Ando RA, Camargo PHC (2013) A facile approach to TiO2 colloidal spheres decorated with Au nanoparticles displaying well-defined sizes and uniform dispersion. Langmuir 29:1642–1649CrossRefGoogle Scholar
  31. 31.
    Saha S, Pal A, Kundu S et al (2009) Photochemical green synthesis of calcium–alginate–stabilized Ag and Au nanoparticles and their catalytic application to 4-nitrophenol reduction. Langmuir 26:2885–2893CrossRefGoogle Scholar
  32. 32.
    Khan FI, Ghoshal AK (2000) Removal of volatile organic compounds from polluted air. J Loss Prev Process Ind 13:527–545CrossRefGoogle Scholar
  33. 33.
    Iranpour R, Cox HHJ, Deshusses MA, Schroeder ED (2005) Literature review of air pollution control biofilters and biotrickling filters for odor and volatile organic compound removal. Environ Prog 24:254–267CrossRefGoogle Scholar
  34. 34.
    Everaert K, Baeyens J (2004) Catalytic combustion of volatile organic compounds. J Hazard Mater 109:113–139CrossRefGoogle Scholar
  35. 35.
    Rezlescu N, Rezlescu E, Popa PD et al (2013) Nanostructured GdAlO3 perovskite, a new possible catalyst for combustion of volatile organic compounds. J Mater Sci 48:4297–4304CrossRefGoogle Scholar
  36. 36.
    Gennequin C, Lamallem M, Cousin R et al (2009) Total oxidation of volatile organic compounds on Au/Ce–Ti–O and Au/Ce–Ti–Zr–O mesoporous catalysts. J Mater Sci 44:6654–6662CrossRefGoogle Scholar
  37. 37.
    da Silva AGM, Rodrigues TS, Macedo A et al (2014) An undergraduate level experiment on the synthesis of Au nanoparticles and their size-dependent optical and catalytic properties. Quím Nova 37:1716–1720Google Scholar
  38. 38.
    Silvert P-Y, Herrera-Urbina R, Duvauchelle N et al (1996) Preparation of colloidal silver dispersions by the polyol process. Part 1-synthesis and characterization. J Mater Chem 6:573–577CrossRefGoogle Scholar
  39. 39.
    Boudart M (1995) Turnover rates in heterogeneous catalysis. Chem Rev 95:661–666CrossRefGoogle Scholar
  40. 40.
    Jiang SP (2006) A review of wet impregnation—an alternative method for the fabrication of high performance and nano-structured electrodes of solid oxide fuel cells. Mater Sci Eng, A 418:199–210CrossRefGoogle Scholar
  41. 41.
    da Silva AGM, de Souza ML, Rodrigues TS et al (2014) Rapid synthesis of hollow Ag–Au nanodendrites in 15 seconds by combining galvanic replacement and precursor reduction reactions. Chem Eur J 20:15040–15046CrossRefGoogle Scholar
  42. 42.
    Wang S, Zhang J, Yuan P et al (2015) Au nanoparticle decorated N-containing polymer spheres: additive-free synthesis and remarkable catalytic behavior for reduction of 4-nitrophenol. J Mater Sci 50:1323–1332CrossRefGoogle Scholar
  43. 43.
    Esumi K, Isono R, Yoshimura T (2003) Preparation of PAMAM- and PPI-metal (silver, platinum, and palladium) nanocomposites and their catalytic activities for reduction of 4-nitrophenol. Langmuir 20:237–243CrossRefGoogle Scholar
  44. 44.
    Oh S-D, Kim M-R, Choi S-H et al (2008) Radiolytic synthesis of Pd–M (M = Ag, Au, Cu, Ni and Pt) alloy nanoparticles and their use in reduction of 4-nitrophenol. J Ind Eng Chem 14:687–692CrossRefGoogle Scholar
  45. 45.
    Endo T, Kuno T, Yoshimura T, Esumi K (2005) Preparation and catalytic activity of Au–Pd, Au–Pt, and Pt–Pd binary metal dendrimer nanocomposites. J Nanosci Nanotechnol 5:1875–1882CrossRefGoogle Scholar
  46. 46.
    Abbasi Z, Haghighi M, Fatehifar E, Saedy S (2011) Synthesis and physicochemical characterizations of nanostructured Pt/Al2O3–CeO2 catalysts for total oxidation of VOCs. J Hazard Mater 186:1445–1454CrossRefGoogle Scholar
  47. 47.
    Liotta LF (2010) Catalytic oxidation of volatile organic compounds on supported noble metals. Appl Catal B Environ 100:403–412CrossRefGoogle Scholar
  48. 48.
    Hosseini M, Barakat T, Cousin R et al (2012) Catalytic performance of core–shell and alloy Pd–Au nanoparticles for total oxidation of VOC: the effect of metal deposition. Appl Catal B Environ 111–112:218–224CrossRefGoogle Scholar
  49. 49.
    Enache DI, Barker D, Edwards JK et al (2007) Solvent-free oxidation of benzyl alcohol using titania-supported gold–palladium catalysts: effect of Au–Pd ratio on catalytic performance. Catal Today 122:407–411CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Anderson G. M. da Silva
    • 1
  • Thenner S. Rodrigues
    • 1
  • Laís S. K. Taguchi
    • 1
  • Humberto V. Fajardo
    • 2
  • Rosana Balzer
    • 3
  • Luiz F. D. Probst
    • 3
  • Pedro H. C. Camargo
    • 1
    Email author
  1. 1.Departamento de Química Fundamental, Instituto de QuímicaUniversidade de São PauloSão PauloBrazil
  2. 2.Departamento de QuímicaUniversidade Federal de Ouro PretoOuro PretoBrazil
  3. 3.Departamento de QuímicaUniversidade Federal de Santa CatarinaFlorianópolisBrazil

Personalised recommendations