Confeito-like Au/TiO2 nanocomposite: synthesis and plasmon-induced photocatalysis

  • Nasim Kamely
  • Masaki UjiharaEmail author
Research Paper


Nanocomposites of confeito-like Au nanoparticles (CAuNPs) and TiO2 were synthesized under different irradiation conditions (darkness, UV light, and visible light) and time spans by the reaction of a Ti-citrate-peroxo complex with CAuNPs. The TiO2 synthesized under irradiation formed mesoporous films with embedded CAuNPs. The photocatalytic activity of the CAuNP/TiO2 nanocomposites was measured by the degradation of methylene blue (MB) under different irradiation conditions (darkness, UV light, and visible light). The results demonstrated that the bare CAuNPs decomposed MB under visible light and that this activity was enhanced by hybridization with TiO2. The activity of the CAuNPs was associated with the plasmon-induced effect, which the TiO2 enhanced by suppressing electron-hole recombination via acceptance of the hot electrons from the CAuNPs. This synergistic effect of the CAuNP/TiO2 nanocomposite varied with the amount of TiO2, and a thick layer of TiO2 decreased the activity as the surface of the CAuNPs was covered by TiO2. This behavior indicates that to design effective plasmonic devices and catalysts, an optimum balance between the amounts of CAuNPs and TiO2 must be achieved.


Gold nanoparticle Titanium dioxide Citrate-peroxo complex Localized surface plasmon Photocatalyst 



Au nanoparticle


Confeito-like Au nanoparticle


Citric acid


High-resolution transmission electron microscopy


Methylene blue


Scanning electron microscopy


Transmission electron microscopy


Ultraviolet-visible-near infrared



This study was funded by the Ministry of Science and Technology, Taiwan (106-2221-E-011-164-).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11051_2018_4276_MOESM1_ESM.docx (11 mb)
ESM 1 (DOCX 11252 kb)


  1. Bian Z, Tachikawa T, Zhang P, Fujitsuka M, Majisma T (2014) Au/TiO2 superstructure-based plasmonic photocatalysts exhibiting efficient charge separation and unprecedented activity. J Am Chem Soc 136:458–465. CrossRefGoogle Scholar
  2. Butburee T, Bai Y, Pan J, Zong X, Sun C, Liu G, Wang L (2014) Step-wise controlled growth of metal@TiO2 core-shells with plasmonic hot spots and their photocatalytic properties. J Mater Chem A 2:12776–12784. CrossRefGoogle Scholar
  3. Cushing SK, Li J, Meng F, Senty TR, Suri S, Zhi M, Li M, Bristow AD, Wu N (2012) Photocatalytic activity enhanced by plasmonic resonant energy transfer from metal to semiconductor. J Am Chem Soc 134:15033–15041. CrossRefGoogle Scholar
  4. Deng X, Chan CK, Tüysüz H (2016) Spent tea leaf templating of cobalt-based mixed oxide nanocrystals for water oxidation. ACS Appl Mater Interfaces 8:32488–32495. CrossRefGoogle Scholar
  5. Duan G, Cai W, Luo Y, Li Z, Li Y (2006) Electrochemically induced flowerlike gold nanoarchitectures and their strong surface-enhanced Raman scattering effect. Appl Phys Lett 89:211905. CrossRefGoogle Scholar
  6. Hassan M, Haque E, Reddy KR, Minett AI, Chen J, Gomes VG (2014) Edge-enriched graphene quantum dots for enhanced photo-luminescence and supercapacitance. Nanoscale 6:11988–11994. CrossRefGoogle Scholar
  7. Hidalgo MC, Maicu M, Navío JA, Colón G (2009) Effect of sulfate pretreatment on gold-modified TiO2 for photocatalytic applications. J Phys Chem C 113:12840–12847. CrossRefGoogle Scholar
  8. Hidalgo MC, Murcia JJ, Navío JA, Colón G (2011) Photodeposition of gold on titanium dioxide for photocatalytic phenol oxidation. Appl Catal A Gen 397:112–120. CrossRefGoogle Scholar
  9. Jeong GH, Lee YW, Kim M, Han SW (2009) High-yield synthesis of multi-branched gold nanoparticles and their surface-enhanced Raman scattering properties. J Colloid Interface Sci 329:97–102. CrossRefGoogle Scholar
  10. Kakarla Raghava R, Vincent GG, Mahbub H (2014) Carbon functionalized TiO 2 nanofibers for high efficiency photocatalysis. Mater Res Express 1:015012CrossRefGoogle Scholar
  11. Kumar SG, Rao KSRK (2014) Polymorphic phase transition among the titania crystal structures using a solution-based approach: from precursor chemistry to nucleation process. Nanoscale 6:11574–11632. CrossRefGoogle Scholar
  12. Liu E, Fan J, Hu X, Hu Y, Li H, Tang C, Sun L, Wan J (2015) A facile strategy to fabricate plasmonic Au/TiO2 nano-grass films with overlapping visible light-harvesting structures for H2 production from water. J Mater Sci 50:2298–2305. CrossRefGoogle Scholar
  13. Manna A, Imae T, Yogo T, Aoi K, Okazaki M (2002) Synthesis of gold nanoparticles in a Winsor II type microemulsion and their characterization. J Colloid Interface Sci 256:297–303. CrossRefGoogle Scholar
  14. Molla A, Sahu M, Hussain S (2015) Under dark and visible light: fast degradation of methylene blue in the presence of Ag-In-Ni-S nanocomposites. J Mater Chem A 3:15616–15625. CrossRefGoogle Scholar
  15. Nagamatsu D, Nemoto T, Kurata H, Jiu J, Adachi M, Isoda S (2011) Interface structure of gold particles on TiO<SUB>2</SUB> anatase. Mater Trans 52:280–284. CrossRefGoogle Scholar
  16. Ohtani B, Ogawa Y, Nishimoto S-i (1997) Photocatalytic activity of amorphous−anatase mixture of titanium(IV) oxide particles suspended in aqueous solutions. J Phys Chem B 101:3746–3752. CrossRefGoogle Scholar
  17. Panayotov DA, Morris JR (2016) Surface chemistry of au/TiO2: thermally and photolytically activated reactions. Surf Sci Rep 71:77–271. CrossRefGoogle Scholar
  18. Primo A, Corma A, Garcia H (2011) Titania supported gold nanoparticles as photocatalyst. Phys Chem Chem Phys 13:886–910. CrossRefGoogle Scholar
  19. Rauf MA, Meetani MA, Khaleel A, Ahmed A (2010) Photocatalytic degradation of methylene blue using a mixed catalyst and product analysis by LC/MS. Chem Eng J 157:373–378. CrossRefGoogle Scholar
  20. Reddy KR, Hassan M, Gomes VG (2015) Hybrid nanostructures based on titanium dioxide for enhanced photocatalysis. Appl Catal A Gen 489:1–16. CrossRefGoogle Scholar
  21. Reddy KR, Lee K-P, Gopalan AI, Kim MS, Showkat AM, Nho YC (2006) Synthesis of metal (Fe or Pd)/alloy (Fe–Pd)-nanoparticles-embedded multiwall carbon nanotube/sulfonated polyaniline composites by γ irradiation. J Polym Sci A Polym Chem 44:3355–3364. CrossRefGoogle Scholar
  22. Reddy KR, Lee KP, Gopalan AI (2008a) Self-assembly approach for the synthesis of electro-magnetic functionalized Fe3O4/polyaniline nanocomposites: effect of dopant on the properties. Colloids Surf A Physicochem Eng Asp 320:49–56CrossRefGoogle Scholar
  23. Reddy KR, Nakata K, Ochiai T, Murakami T, Tryk DA, Fujishima A (2010) Nanofibrous TiO2-Core/conjugated polymer-sheath composites: synthesis, structural properties and photocatalytic activity. J Nanosci Nanotechnol 10:7951–7957. CrossRefGoogle Scholar
  24. Reddy KR, Sin BC, Yoo CH, Park W, Ryu KS, Lee JS, Sohn D, Lee Y (2008b) A new one-step synthesis method for coating multi-walled carbon nanotubes with cuprous oxide nanoparticles. Scr Mater 58:1010–1013. CrossRefGoogle Scholar
  25. Reddy R, Lee K-S, Iyenger Gopalan A (2007) Self-assembly directed synthesis of poly (ortho-toluidine)-metal (gold and palladium) composite nanospheres 7. doi:
  26. Reddy R, Nakata K, Ochiai T, Murakami T, Tryk D, Fujishima A (2011) Facile fabrication and photocatalytic application of Ag nanoparticles-TiO2 nanofiber composites vol 11. doi:
  27. Sá J, Tagliabue G, Friedli P, Szlachetko J, Rittmann-Frank MH, Santomauro FG, Milne CJ, Sigg H (2013) Direct observation of charge separation on Au localized surface plasmons. Energy Environ Sci 6:3584. CrossRefGoogle Scholar
  28. Sharma J, Tai Y, Imae T (2008) Synthesis of confeito-like gold nanostructures by a solution phase galvanic reaction. J Phys Chem C 112:17033–17037. CrossRefGoogle Scholar
  29. Showkat AM, Y-p Z, Kim MS, Gopalan AI, Reddy KR, Lee K (2007) Analysis of heavy metal toxic ions by adsorption onto amino-functionalized ordered mesoporous silica. Bulletin-Korean Chem Soc 28:1985CrossRefGoogle Scholar
  30. Shown I, Ujihara M, Imae T (2011) Synthesis of β-cyclodextrin-modified water-dispersible Ag-TiO2 core–shell nanoparticles and their photocatalytic activity vol 11. doi:
  31. Shuai J, Ingo L, Katharina L, Rafael M-E, Daniel C (2017) Nanofibrous photocatalysts from electrospun nanocapsules. Nanotechnology 28:405601CrossRefGoogle Scholar
  32. Suzuki M, Niidome Y, Kuwahara Y, Terasaki N, Inoue K, Yamada S (2004) Surface-enhanced nonresonance Raman scattering from size- and morphology-controlled gold nanoparticle films. J Phys Chem B 108:11660–11665. CrossRefGoogle Scholar
  33. Tada M, Yamashita Y, Petrykin V, Osada M, Yoshida K, Kakihana M (2002) A new water-soluble ammonium citratoperoxotitanate as an environmentally beneficial precursor for TiO2 thin films and RuO2/BaTi4O9 photocatalysts. Chem Mater 14:2845–2846. CrossRefGoogle Scholar
  34. Tian Y, Tatsuma T (2005) Mechanisms and applications of plasmon-induced charge separation at TiO2 films loaded with gold nanoparticles. J Am Chem Soc 127:7632–7637. CrossRefGoogle Scholar
  35. Ujihara M, Dang MN, Imae T (2017) Surface-enhanced resonance Raman scattering of rhodamine 6G in dispersions and on films of confeito-like au nanoparticles. Sensors 17.
  36. Ujihara M, Dang NM, Imae T (2014) Fluorescence quenching of uranine on confeito-like au nanoparticles. J Nanosci Nanotechnol 14:4906–4910. CrossRefGoogle Scholar
  37. Ujihara M, Imae T (2013) Versatile one-pot synthesis of confeito-like Au nanoparticles and their surface-enhanced Raman scattering effect. Colloids Surf A Physicochem Eng Asp 436:380–385. CrossRefGoogle Scholar
  38. Wang L, Imura M, Yamauchi Y (2012a) Tailored synthesis of various Au Nanoarchitectures with branched shapes. CrystEngComm 14:7594–7599. CrossRefGoogle Scholar
  39. Wang L, Liu C-H, Nemoto Y, Fukata N, Wu KCW, Yamauchi Y (2012b) Rapid synthesis of biocompatible gold nanoflowers with tailored surface textures with the assistance of amino acid molecules. RSC Adv 2:4608–4611. CrossRefGoogle Scholar
  40. Wenderich K, Mul G (2016) Methods, mechanism, and applications of photodeposition in photocatalysis: a review. Chem Rev 116:14587–14619. CrossRefGoogle Scholar
  41. Wu Y-H, Imae T, Ujihara M (2017) Surface enhanced plasmon effects by gold nanospheres and nanorods in Langmuir-Blodgett films. Colloids Surf A Physicochem Eng Asp 532:213–221. CrossRefGoogle Scholar
  42. Xuming Z, Yu Lim C, Ru-Shi L, Din Ping T (2013) Plasmonic photocatalysis. Rep Prog Phys 76:046401CrossRefGoogle Scholar
  43. Xuzhong L, Toyoko I (2007) Shape-controlled synthesis of gold nanoparticles under UV irradiation in the presence of poly(ethylene glycol). Curr Nanosci 3:195–198CrossRefGoogle Scholar
  44. Yogi C, Kojima K, Wada N, Tokumoto H, Takai T, Mizoguchi T, Tamiaki H (2008) Photocatalytic degradation of methylene blue by TiO2 film and Au particles-TiO2 composite film. Thin Solid Films 516:5881–5884. CrossRefGoogle Scholar
  45. Zhang Y-P, Lee S-H, Reddy KR, Gopalan AI, Lee K-P (2007) Synthesis and characterization of core-shell SiO2 nanoparticles/poly(3-aminophenylboronic acid) composites. J Appl Polym Sci 104:2743–2750. CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Graduate Institute of Applied Science and TechnologyNational Taiwan University of Science and TechnologyTaipeiRepublic of China

Personalised recommendations