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Frontiers of Chemical Science and Engineering

Front. Chem. Sci. Eng.    2019, Vol. 13 Issue (3) : 574-585
Magnetic-porous microspheres with synergistic catalytic activity of small-sized gold nanoparticles and titania matrix
Kadriye Özlem Hamaloğlu1, Ebru Sağ2, Çiğdem Kip1, Erhan Şenlik1, Berna Saraçoğlu Kaya2, Ali Tuncel1()
1. Hacettepe University, Chemical Engineering Department, Ankara, Turkey
2. Cumhuriyet University, Chemical Engineering Department, Sivas, Turkey
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Fe3O4 nanoparticles immobilized on porous titania in micron-size range were decorated with small-sized gold nanoparticles and used as a plasmonic catalyst for the reduction of 4-nitrophenol. Monodisperse-porous magnetic titania microspheres were synthesized with bimodal pore-size distribution by the sol-gel templating method. Small-sized gold nanoparticles obtained by the Martin method were attached onto the aminated form of the magnetic titania microspheres. A significant enhancement in the catalytic activity was observed using the gold nanoparticle-decorated magnetic titania microspheres compared to gold nanoparticle-decorated magnetic silica microspheres because of the synergistic effect between small-sized gold nanoparticles and titania. The synergistic effect for gold nanoparticle-attached magnetic titania microspheres could be explained by surface plasmon resonance-induced transfer of hot electrons from gold nanoparticles to the conduction band of titania. Using the proposed catalyst, 4-nitrophenol could be converted to 4-aminophenol in an aqueous solution within 0.5 min. The 4-nitrophenol reduction rates were 2.5–79.3 times higher than those obtained with similar plasmonic catalysts. The selection of micron-size, magnetic, and porous titania microspheres as a support material for the immobilization of small-sized gold nanoparticles provided a recoverable plasmonic catalyst with high reduction ability.

Keywords small-sized gold nanoparticles      magnetic titania microspheres      sol-gel template synthesis      plasmonic catalysis      4-nitrophenol     
Corresponding Authors: Ali Tuncel   
Online First Date: 16 April 2019    Issue Date: 22 August 2019
 Cite this article:   
Kadriye Özlem Hamaloğlu,Ebru Sağ,Çiğdem Kip, et al. Magnetic-porous microspheres with synergistic catalytic activity of small-sized gold nanoparticles and titania matrix[J]. Front. Chem. Sci. Eng., 2019, 13(3): 574-585.
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Kadriye Özlem Hamaloğlu
Ebru Sağ
Çiğdem Kip
Erhan Şenlik
Berna Saraçoğlu Kaya
Ali Tuncel
Fig.1  Synthesis of monodisperse porous (a) Mag-TiO2 and(b) Mag-SiO2 microspheres by a staged-shape template hydrolysis and condensation protocol
Fig.2  (a) SEM photographs of MAuNP@Mag-TiO2 microspheres, (b) SEM photographs of MAuNP@Mag-SiO2 microspheres. Magnification: 20000X and 200000X, Magnification in the SEM photos showing size distribution: 2000X, (c) EDX spectrum of MAuNP@Mag-TiO2 microspheres, (d) EDX spectrum of MAuNP@Mag-SiO2 microspheres
Fig.3  XRD patterns of (a) MAuNP@Mag-SiO2 and (b) MAuNP@Mag-TiO2 microspheres
Fig.4  UV-Vis spectra at different times during the plasmonic reduction of 4-NP with TAuNP@Mag-TiO2 microspheres. Inset: Variation of 4-NP and 4-AP concentrations with the time. Calcination temperature: 450°C, AuNP loading: 5% w/w; catalyst amount: 1 mg, 4-NP concentration: 7.5 mg?L?1, 26.5 mL, temperature: 20°C
Fig.5  Variation of 4-NP concentration with time using TAuNP@Mag-TiO2, MAuNP@Mag-TiO2, and MAuNP@Mag-SiO2 microspheres as plasmonic catalysts and reference materials (i.e., TiO2, Mag-TiO2, and Mag-SiO2). Calcination temperature: 450°C; AuNP loading: 5% w/w; catalyst amount: 1 mg; 4-NP concentration: 7.5 mg?L?1, 26.5 mL; temperature: 20°C
Fig.6  Effect of the initial 4-NP concentration on the plasmonic reduction rate of 4-NP with (a) TAuNP@Mag-TiO2 and (b) MAuNP@Mag-TiO2 microspheres. Calcination temperature: 450°C; AuNP loading: 5% w/w; catalyst amount: 1 mg; temperature: 20°C
Catalyst type 4-NP Initial concentration /(mg?L?1) kapp /(min?1·mgcatalyst?1)
TAuNP@Mag-TiO2 microspheres 5.0 0.353
7.5 0.133
15.0 0.024
MAuNP@Mag-TiO2 microspheres 5.0 5.852
7.5 2.589
15.0 2.927
Tab.1  First-order apparent rate constants for 4-NP reduction by AuNP@Mag-TiO2 microspheres as plasmonic catalyst for different initial concentrations of 4-NP a)
Fig.7  Effect of AuNP loading on the reduction rate of 4-NP with MAuNP@Mag-TiO2 microspheres. Calcination temperature: 450°C; catalyst amount: 1 mg; 4-NP concentration: 7.5 mg?L?1, 26.5 mL; Temperature: 20°C
Fig.8  Effect of catalyst amount on the plasmonic reduction rate of 4-NP with MAuNP@Mag-TiO2 microspheres. Calcination temperature: 450°C, AuNP loading: 5% w/w; 4-NP concentration: 7.5 mg?L?1, 26.5 mL, temperature: 20°C
MAuNP@Mag-TiO2 concentration /(mg?mL?1) kapp /min?1 kapp /(min?1·mgcatalyst?1)
0.019 (0.5)b) 1.834 3.668
0.038 (1.0)b) 2.589 2.589
0.076 (2.0)b) 9.492 4.746
0.152 (4.0)b) 14.532 3.633
Tab.2  First-order apparent rate constants for 4-NP reduction for different MAuNP@Mag-TiO2 concentrationsa)
Fig.9  Possible mechanisms for 4-NP reduction with (a) MAuNP@Mag-TiO2 and (b) MAuNP@Mag-SiO2 microspheres
Fig.10  Reusability of MAuNP@Mag-TiO2 microspheres for plasmonic reduction of 4-NP. Calcination temperature: 450°C; AuNP loading: 5% w/w; catalyst amount: 1 mg; 4-NP concentration: 7.5 mg?L?1, 26.5 mL; temperature: 20°C.
1 G J Hutchings, M Haruta. A golden age of catalysis: A perspective. Applied Catalysis A, General, 2005, 291(1-2): 2–5
2 M Haruta. Catalysis: Gold rush. Nature, 2005, 437(1): 1098–1099
3 A Wittstock, V Zielasek, J Biener, C M Friend, M Bäumer. Nanoporous gold catalysts for selective gas-phase oxidative coupling of methanol at low temperature. Science, 2010, 327(5963): 319–322
4 A Didier, L Feng, R A Jaime. Nanoparticles as recyclable catalysts: The frontier between homogeneous and heterogeneous catalysis. Angewandte Chemie International Edition, 2005, 44(1): 7852–7872
5 L Maolin, C Guofang. Revisiting catalytic model reaction p-nitrophenol/NaBH4 using metallic nanoparticles coated on polymeric spheres. Nanoscale, 2013, 5(23): 11919–11927
6 K Kyoko, I Tamao, H Masatake. Reduction of 4-nitrophenol to 4-aminophenol over Au nanoparticles deposited on PMMA. Journal of Molecular Catalysis A Chemical, 2009, 298(1-2): 7–11
7 D Wang, A Villa, D Su, L Prati, R Schlögl. Carbon-supported gold nanocatalysts: Shape effect in the selective glycerol oxidation. ChemCatChem, 2013, 5(9): 2717–2723
8 C Wang, L Chen, Z Qi. One-pot synthesis of gold nanoparticles embedded in silica for cyclohexane oxidation. Catalysis Science & Technology, 2013, 3(4): 1123–1128
9 B G Donoeva, D S Ovoshchnikov, V B Golovko. Establishing Au nanoparticle size effect in the oxidation of cyclohexene using gradually changing Au catalysts. ACS Catalysis, 2013, 3(12): 2986–2991
10 Y Wang, S Van de Vyver, K Sharma, Y Román-Leshkov. Insights into the stability of gold nanoparticles supported on metal oxides for the base-free oxidation of glucose to gluconic acid. Green Chemistry, 2014, 16(2): 719–726
11 F Cardenas Lizana, S Gomez Quero, H Idriss, M A Keanne. Gold particle size effects in the gas-phase hydrogenation of m-dinitrobenzene over Au/TiO2. Journal of Catalysis, 2009, 268(2): 223–234
12 L Q Nguyen, C Salim, H Hinode. Performance of nano-sized Au/TiO2 for selective catalytic reduction of NOx by propene. Applied Catalysis A, General, 2008, 347(1): 94–99
13 L Q Nguyen, C Salim, H Hinode. Promotive effect of MOx (M= Ce, Mn) mechanically mixed with Au/TiO2 on the catalytic activity for nitrogen monoxide reduction by propene. Topics in Catalysis, 2009, 52(6-7): 779–783
14 Y C Chang, D H Chen. Catalytic reduction of 4-nitrophenol by magnetically recoverable Au nanocatalyst. Journal of Hazardous Materials, 2009, 165(1-3): 664–669
15 T C Damato, C S Oliveira, R A Ando, P H C Camargo. A facile approach to TiO2 colloidal spheres decorated with Au nanoparticles displaying well-defined sizes and uniform dispersion. Langmuir, 2013, 29(5): 1642–1649
16 H Yazid, R Adnan, M A Farrukh. Gold nanoparticles supported on titania for the reduction of p-nitrophenol. Indian Journal of Chemistry, 2013, 52A(2): 184–191
17 K Hyuntae, K Miran, K H Park. Effective immobilization of gold nanoparticles on core-shell thiol-functionalized GO coated TiO2 and their catalytic application in the reduction of 4-nitrophenol. Applied Catalysis A, General, 2015, 502(1): 239–245
18 C Kip, B Maras, O Evirgen, A Tuncel. A new type of monodisperse porous, hydrophilic microspheres with reactive chloroalkyl functionality: Synthesis and derivatization properties. Colloid & Polymer Science, 2013, 292(1): 219–228
19 G Günal, Ç Kip, S E Öğüt, H İlhan, G Kibar, A Tuncel. Comparative DNA isolation behaviours of silica and polymer based sorbents in batch fashion: Monodisperse silica microspheres with bimodal pore size distribution as a new sorbent for DNA isolation. Artificial Cells, Nanomedicine, and Biotechnology, 2018, 46(1): 178–184
20 K Ö Hamaloğlu, E Sağ, A Tuncel. Bare, gold and silver nanoparticle decorated, monodisperse-porous titania microbeads for photocatalytic dye degradation in a newly constructed microfluidic, photocatalytic packed-bed reactor. Journal of Photochemistry and Photobiology A Chemistry, 2017, 332(1): 60–65
21 T Camli, M Tuncel, S Senel, A Tuncel. Functional, uniform, and macroporous latex particles: Preparation, electron microscopic characterization, and nonspecific protein adsorption properties. Journal of Applied Polymer Science, 2002, 84(2): 414–429
22 A Tuncel. Electron microscopic observation of uniform macroporous particles. II. Effect of DVB concentration. Journal of Applied Polymer Science, 1999, 71(14): 2291–2302<2291::AID-APP2>3.0.CO;2-T
23 Z Ma, Y Guan, H Liu. Synthesis and characterization of micron-sized monodisperse superparamagnetic polymer particles with amino groups. Journal of Polymer Science Part A, 2005, 43(15): 3433–3439
24 K Ö Hamaloğlu, E Sağ, A Tuncel. Magnetic, monodisperse titania microspheres with bimodal pore size distribution by a new sol-gel templating method and their photocatalytic activity. Journal of Porous Materials, 2018,
25 K Salimi, D D Usta, O Celikbicak, A Pinar, B Salih, A Tuncel. Ti(IV) carrying polydopamine-coated, monodisperse-porous SiO2 microspheres with stable magnetic properties for highly selective enrichment of phosphopeptides. Colloids and Surfaces. B, Biointerfaces, 2017, 153(1): 280–290
26 J Jiao, Y Wei, Y Zhao, Z Zhao, A Duan, J Liu, Y Pang, J Li, G Jiang, Y Wang. AuPd/3DOM-TiO2 catalysts for photocatalytic reduction of CO2: High efficient separation of photogenerated charge carriers. Applied Catalysis B: Environmental, 2017, 209(1): 228–239
27 Y Wei, X Wu, Y Zhao, L Wang, Z Zhao, X Huang, J Liu, J Li. Efficient photocatalysts of TiO2 nanocrystals-supported PtRu alloy nanoparticles for CO2 reduction with H2O: Synergistic effect of Pt-Ru. Applied Catalysis B: Environmental, 2018, 236(1): 445–457
28 Y Wei, J Jiao, Z Zhao, J Liu, J Li, G Jiang, Y Wang, A Duan. Fabrication of inverse opal TiO2-supported Au@CdS core-shell nanoparticles for efficient photocatalytic CO2 conversion. Applied Catalysis B: Environmental, 2015, 179(1): 422–432
29 Y Zhou, Y Zhu, X Yang, J Huang, W Chen, X Lv, C Lia, C Li. Au decorated Fe3O4@TiO2 magnetic composites with visible light-assisted enhanced catalytic reduction of 4-nitrophenol. RSC Advances, 2015, 5(62): 50454–50461
30 J Zheng, Y Wu, Q Zhang, Y Li, C Wang, Y Zhou. Direct liquid phase deposition fabrication of waxberry-like magnetic Fe3O4@TiO2 core-shell microspheres. Materials Chemistry and Physics, 2016, 181(1): 391–396
31 Y Zhao, Y Wei, X Wu, H Zheng, Z Zhao, J Liu, J Lia. Graphene-wrapped Pt/TiO2 photocatalysts with enhanced photogenerated charges separation and reactant adsorption for high selective photoreduction of CO2 to CH4. Applied Catalysis B: Environmental, 2018, 226(1): 360–372
32 S Majumder, S Dey, K Bagani, S K Dey, S Banerjee, S Kumar. A comparative study on the structural, optical and magnetic properties of Fe3O4 and Fe3O4@SiO2 core-shell microspheres along with an assessment of their potentiality as electrochemical double layer capacitors. Dalton Transactions (Cambridge, England), 2015, 44(1): 7190–7202
33 K Tahir, S Nazir, A Ahmad, B Li, S A A Shah, A U Khan, G M Khan, Q U Khan, Z U H Khan, F U Khan. Biodirected synthesis of palladium nanoparticles using Phoenix dactylifera leaves extract and their size dependent biomedical and catalytic applications. RSC Advances, 2016, 6(89): 85903–85916
34 A Dawson, P V Kamat. Semiconductor-metal nanocomposites. Photoinduced fusion and photocatalysis of gold-capped TiO2 (TiO2/gold) nanoparticles. Journal of Physical Chemistry B, 2001, 105(5): 960–966
35 P V Kamat. Photophysical, photochemical and photo-catalytic aspects of metal nanoparticles. Journal of Physical Chemistry B, 2002, 106(32): 7729–7744
36 A Pandikumar, S Murugesan, R Ramaraj. Functionalized silicate sol-gel-supported TiO2-Au core-shell nanomaterials and their photoelectrocatalytic activity. ACS Applied Materials & Interfaces, 2010, 2(7): 1912–1917
37 Q Wang, Y Li, B Liu, Q Dong, G Xu, L Zhang, J Zhang. Novel recyclable dual-heterostructured Fe3O4@CeO2/M (M 1/4 Pt, Pd and Pt-Pd) catalysts: Synergetic and redox effects for superior catalytic performance. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2015, 3(1): 139–147
38 Q Zhang, X Jin, Z Xu, J Zhang, U F Rendón, L Razzari, M Chaker, D Ma. Plasmonic Au-loaded hierarchical hollow porous TiO2 spheres: Synergistic catalysts for nitroaromatic reduction. Journal of Physical Chemistry Letters, 2018, 9(1): 5317–5326
39 S Linic, P Christopher, D B Ingram. Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy. Nature Materials, 2011, 10(12): 911–921
40 Z F Bian, T Tachikawa, P Zhang, M Fujitsuka, T Majima. Au/TiO2 superstructure-based plasmonic photocatalysts exhibiting efficient charge separation and unprecedented activity. Journal of the American Chemical Society, 2014, 136(1): 458–465
41 M W Knight, H Sobhani, P Nordlander, N J Halas. Photodetection with active optical antennas. Science, 2011, 332(1): 702–704
42 J B Priebe, M Karnahl, H Junge, M Beller, D Hollmann, A Bruckner. Water reduction with visible light: Synergy between optical transitions and electron transfer in Au-TiO2 catalysts visualized by in situ EPR spectroscopy. Angewandte Chemie International Edition, 2013, 52(1): 11420–11424
43 B Y Zheng, H Q Zhao, A Manjavacas, M McClain, P Nordlander, N J Halas. Distinguishing between plasmon-induced and photoexcited carriers in a device geometry. Nature Communications, 2015, 7797(6): 1–7
44 B Mu, W Wang, J Zhang, A Wang. Superparamagnetic sandwich structured silver/halloysite nanotubes/Fe3O4 nanocomposites for 4-nitrophenol reduction. RSC Advances, 2014, 4(1): 39439–39445
45 S Jana, S K Ghosh, S Nath, S Pande, S Praharaj, S Panigrahi, S Basu, T Endo, T Pal. Synthesis of silver nanoshell-coated cationic polystyrene beads: A solid phase catalyst for the reduction of 4-nitrophenol. Applied Catalysis A, 2006, 313(1): 41–48
46 P Veerakumar, M Velayudham, K L Lub, S Rajagopal. Polyelectrolyte encapsulated gold nanoparticles as efficient active catalyst for reduction of nitro compounds by kinetic method. Applied Catalysis A, 2012, 439-440(1): 197–205
47 S Sarkar, A K Guria, N Pradhan. Influence of doping on semiconductor nanocrystals mediated charge transfer and photocatalytic organic reaction. Chemical Communications, 2013, 49(1): 6018–6020
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