Skip to main content
SpringerLink
Log in

Surface structural, morphological, and catalytic studies of homogeneously dispersed anisotropic Ag nanostructures within mesoporous silica

  • Research Paper
  • Published:
Journal of Nanoparticle Research Aims and scope Submit manuscript

Abstract

Highly dispersed anisotropic Ag nanostructures were synthesized within the channels of 3-aminopropyltrimethoxysilane (APTMS)-modified mesoporous SBA-15 for catalyzing the reduction of p-dinitrobenzene, p-nitrophenol, and p-nitroacetophenone, respectively. A green templating process without involving any reducing agent, by varying the amount (1–10 wt.%) of Ag loading followed by calcination at 350 °C under H2 led to change in the morphology of Ag nanoparticles from nanospheres (~7–8 nm) to nanorods (aspect ratio ~12–30 nm) without any deformation in mesoporous sieves. In comparison to white bare SBA-15, gray-colored samples were formed with Ag impregnation exhibiting absorption bands at 484 and 840 nm indicating the formation of anisotropic Ag nanostructures within mesoporous matrix. TEM and FE-SEM micrographs confirmed the presence of evenly dispersed Ag nanostructures within as well as on the surface of mesoporous matrix. AFM studies indicated a small decrease in the average roughness of SBA-15 from 20.59 to 19.21 nm for 4 wt.% Ag/m-SBA-15, illustrating the encapsulation of majority of Ag nanoparticles in the siliceous matrix and presence of small amount of Ag nanoparticles on the mesoporous support. Moreover, due to plugging of mesopores with Ag, a significant decrease in surface area from 680 m2/g of SBA-15 to 385 m2/g was observed. The Ag-impregnated SBA-15 catalyst displayed superior catalytic activity than did bare SBA-15 with 4 wt.% Ag-loaded catalyst exhibiting optimum activity for selective reduction of p-nitrophenol to p-aminophenol (100 %), p-nitroacetophenone to p-aminoacetophenone (100 %), and p-dinitrobenzene to p-nitroaniline (87 %), with a small amount of p-phenylenediamine formation.

This paper demonstrates the spontaneous formation of uniformly dispersed Ag nanospecies of various morphologies (nanospheres, size ~7–8 nm and nanorods, aspect ratio ~12–30 nm), both within as well as on the surface of the mesoporous SBA-15, as a function of increased Ag loading. Surface structural and other physiochemical properties of Ag/m-SBA-15 nanocomposites were considerably influenced w.r.t change in Ag loading. Ag/m-SBA-15 nanocomposites with 4 wt.% Ag loading exhibited the highest selectivity (87 %) for the selective reduction of p-dinitrobenzene to p-nitroaniline and 100 % selectivity for p-nitrophenol to p-aminophenol and p-nitroacetophenone to p-aminoacetophenone, respectively.

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

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Scheme 2
Scheme 3
Scheme 4

Similar content being viewed by others

References

  • Alwash AH, Abdullah AZ, Ismail N (2013) Investigation on the catalytic behavior of Fe loaded on encapsulated titanium for sonocatalytic degradation of amaranth: characterization and reusability study

  • Anand N, Reddy KHP, Prasad GVS, Rao KSR, Burri DR (2012) Selective benzylic oxidation of alkyl substituted aromatics to ketones over Ag/SBA-15 catalysts. Catal Commun 23:5–9

    Article  Google Scholar 

  • Cárdenas-Lizana F, de Pedro ZM, Gómez-Quero S, Keane MA (2010) Gas phase hydrogenation of nitroarenes: a comparison of the catalytic action of titania supported gold and silver. J Mol Catal A Chem 326:48–54

    Article  Google Scholar 

  • Chaudhuri H, Dash S, Sarkar A (2016) SBA-15 functionalised with high loading of amino or carboxylate groups as selective adsorbent for enhanced removal of toxic dyes from aqueous solution. New J Chem 40:3622–3634

    Article  Google Scholar 

  • Chen X, Schluesener H (2008) Nanosilver: a nanoproduct in medical application. Toxicol Lett 176:1–12

    Article  Google Scholar 

  • Chen CW, Chen MQ, Serizawa T, Akashi M (1998) In-situ formation of silver nanoparticles on poly (N-isopropylacrylamide)-coated polystyrene microspheres. Adv Mater 10:1122–1126

    Article  Google Scholar 

  • Chen D et al (2011) Comparative studies of silver based catalysts supported on different supports for the oxidation of formaldehyde. Catal Today 175:338–345

    Article  Google Scholar 

  • Cheng D, Yang J, Zhao Y (2004) Antibacterial materials of silver nanoparticles application in medical appliances and appliances for daily use. Chin Med Equip J 4:26–32

    Google Scholar 

  • Chi Y, Yuan Q, Li Y, Tu J, Zhao L, Li N, Li X (2012) Synthesis of Fe 3 O 4@ SiO 2–Ag magnetic nanocomposite based on small-sized and highly dispersed silver nanoparticles for catalytic reduction of 4-nitrophenol. J Colloid Interface Sci 383:96–102

    Article  Google Scholar 

  • El-Sheikh S, Ismail AA, Al-Sharab JF (2013) Catalytic reduction of p-nitrophenol over precious metals/highly ordered mesoporous silica. New J Chem 37:2399–2407

    Article  Google Scholar 

  • Frederix F et al (2003) Biosensing based on light absorption of nanoscaled gold and silver particles. Anal Chem 75:6894–6900

    Article  Google Scholar 

  • Galletto P, Brevet P, Girault H, Antoine R, Broyer M (1999) Enhancement of the second harmonic response by adsorbates on gold colloids: the effect of aggregation. J Phys Chem B 103:8706–8710

    Article  Google Scholar 

  • Gao C, Zhang Q, Lu Z, Yin Y (2011) Templated synthesis of metal nanorods in silica nanotubes. J Am Chem Soc 133:19706–19709

    Article  Google Scholar 

  • Han J, Fang P, Jiang W, Li L, Guo R (2012) Ag-nanoparticle-loaded mesoporous silica: spontaneous formation of Ag nanoparticles and mesoporous silica SBA-15 by a one-pot strategy and their catalytic applications. Langmuir 28:4768–4775

    Article  Google Scholar 

  • Huang M-H, Rust RT (2011) Sustainability and consumption. J Acad Mark Sci 39:40–54

    Article  Google Scholar 

  • Jana NR, Sau TK, Pal T (1999) Growing small silver particle as redox catalyst. J Phys Chem B 103:115–121

    Article  Google Scholar 

  • Jeong S, Song HC, Lee WW, Choi Y, Lee SS, Ryu B-H (2010) Combined role of well-dispersed aqueous Ag ink and the molecular adhesive layer in inkjet printing the narrow and highly conductive Ag features on a glass substrate. J Phys Chem C 114:22277–22283

    Article  Google Scholar 

  • Jiang L, Gu H, Xu X, Yan X (2009) Selective hydrogenation of o-chloronitrobenzene (o-CNB) over supported Pt and Pd catalysts obtained by laser vaporization deposition of bulk metals. J Mol Catal A Chem 310:144–149

    Article  Google Scholar 

  • Kjellman T, Asahina S, Schmitt J, Impéror-Clerc M, Terasaki O, Alfredsson V (2013) Direct observation of plugs and intrawall pores in SBA-15 using low voltage high resolution scanning electron microscopy and the influence of solvent properties on plug-formation. Chem Mater 25:4105–4112

    Article  Google Scholar 

  • Kundu S, Lau S, Liang H (2009) Shape-controlled catalysis by cetyltrimethylammonium bromide terminated gold nanospheres, nanorods, and nanoprisms. J Phys Chem C 113:5150–5156

    Article  Google Scholar 

  • Li S, Shen Y, Xie A, Yu X, Qiu L, Zhang L, Zhang Q (2007) Green synthesis of silver nanoparticles using Capsicum annuum L. extract. Green Chem 9:852–858

    Article  Google Scholar 

  • Lin J, Wang C (1996) Effects of surfactant treatment of silver powder on the rheology of its thick-film paste. Mater Chem Phys 45:136–144

    Article  Google Scholar 

  • Liu Y, Wei Z, Zhang J (2006) Synthesis of m-phenylenediamine from m-dinitrobenzene over silica-supported nickel catalyst. Korean J Chem Eng 23:902–907

    Article  Google Scholar 

  • Maria Chong A, Zhao X (2003) Functionalization of SBA-15 with APTES and characterization of functionalized materials. J Phys Chem B 107:12650–12657

    Article  Google Scholar 

  • Mazali I, Souza Filho A, Viana B, Mendes Filho J, Alves O (2006) Size-controllable synthesis of nanosized-TiO2 anatase using porous Vycor glass as template. J Nanopart Res 8:141–148

    Article  Google Scholar 

  • Murray CB, Kagan C, Bawendi M (2000) Synthesis and characterization of monodisperse nanocrystals and close-packed nanocrystal assemblies. Annu Rev Mater Sci 30:545–610

    Article  Google Scholar 

  • Naik B, Hazra S, Prasad VS, Ghosh NN (2011) Synthesis of Ag nanoparticles within the pores of SBA-15: an efficient catalyst for reduction of 4-nitrophenol. Catal Commun 12:1104–1108

    Article  Google Scholar 

  • Panigrahi S et al (2007) Synthesis and size-selective catalysis by supported gold nanoparticles: study on heterogeneous and homogeneous catalytic process. J Phys Chem C 111:4596–4605

    Article  Google Scholar 

  • Patel A, Rufford TE, Rudolph V, Zhu Z (2011) Selective catalytic reduction of NO by CO over CuO supported on SBA-15: effect of CuO loading on the activity of catalysts. Catal Today 166:188–193

    Article  Google Scholar 

  • Petkov N, Stock N, Bein T (2005) Gold electroless reduction in nanosized channels of thiol-modified SBA-15 material. J Phys Chem B 109:10737–10743

    Article  Google Scholar 

  • Pradhan N, Pal A, Pal T (2002) Silver nanoparticle catalyzed reduction of aromatic nitro compounds. Colloids Surf A Physicochem Eng Asp 196:247–257

    Article  Google Scholar 

  • Rioux R, Song H, Hoefelmeyer J, Yang P, Somorjai G (2005) High-surface-area catalyst design: synthesis, characterization, and reaction studies of platinum nanoparticles in mesoporous SBA-15 silica. J Phys Chem B 109:2192–2202

    Article  Google Scholar 

  • Sareen S, Mutreja V, Singh S, Pal B (2015) Highly dispersed Au, Ag and Cu nanoparticles in mesoporous SBA-15 for highly selective catalytic reduction of nitroaromatics. RSC Adv 5:184–190

    Article  Google Scholar 

  • Sareen S, Mutreja V, Singh S, Pal B (2016) Fine CuO anisotropic nanoparticles supported on mesoporous SBA-15 for selective hydrogenation of nitroaromatics. J Colloid Interface Sci 461:203–210

    Article  Google Scholar 

  • Songping W, Shuyuan M (2005) Preparation of ultrafine silver powder using ascorbic acid as reducing agent and its application in MLCI. Mater Chem Phys 89:423–427

    Article  Google Scholar 

  • Szegedi Á et al (2014) Comparison of silver nanoparticles confined in nanoporous silica prepared by chemical synthesis and by ultra-short pulsed laser ablation in liquid. Applied Physics A 117:55–62

    Article  Google Scholar 

  • Taghavimoghaddam J, Knowles GP, Chaffee AL (2012) Preparation and characterization of mesoporous silica supported cobalt oxide as a catalyst for the oxidation of cyclohexanol. J Mol Catal A Chem 358:79–88

    Article  Google Scholar 

  • Tian Z-Q, Ren B, Wu D-Y (2002) Surface-enhanced Raman scattering: from noble to transition metals and from rough surfaces to ordered nanostructures. J Phys Chem B 106:9463–9483

    Article  Google Scholar 

  • Tüysüz H, Lehmann CW, Bongard H, Tesche B, Schmidt R, Schüth F (2008) Direct imaging of surface topology and pore system of ordered mesoporous silica (MCM-41, SBA-15, and KIT-6) and nanocast metal oxides by high resolution scanning electron microscopy. J Am Chem Soc 130:11510–11517

    Article  Google Scholar 

  • Wang X, Lin KS, Chan JC, Cheng S (2005) Direct synthesis and catalytic applications of ordered large pore aminopropyl-functionalized SBA-15 mesoporous materials. J Phys Chem B 109:1763–1769

    Article  Google Scholar 

  • Wang Y, Hou B, Chen J, Sun Y (2010) Influence of pore regularity on Fischer–Tropsch synthesis with Co/SiO2 catalysts. React Kinet Mech Catal 102:155–164

    Article  Google Scholar 

  • Xie Y, Quinlivan S, Asefa T (2008) Tuning metal nanostructures in mesoporous silica by a simple change of metal complexes and by reduction with grafted imines and hemiaminals. J Phys Chem C 112:9996–10003

    Article  Google Scholar 

  • Xu L et al (2016) Efficient hydrogen generation from formic acid using AgPd nanoparticles immobilized on carbon nitride-functionalized SBA-15. RSC Adv 6:46908–46914

    Article  Google Scholar 

  • Yang CM, Sheu HS, Chao KJ (2002) Templated synthesis and structural study of densely packed metal nanostructures in MCM-41 and MCM-48. Adv Funct Mater 12:143–148

    Article  Google Scholar 

  • Yin A, Wen C, Dai W-L, Fan K (2011) Ag/MCM-41 as a highly efficient mesostructured catalyst for the chemoselective synthesis of methyl glycolate and ethylene glycol. Appl Catal B Environ 108:90–99

    Article  Google Scholar 

  • Yong G-P, Tian D, Tong H-W, Liu S-M (2010) Mesoporous SBA-15 supported silver nanoparticles as environmentally friendly catalysts for three-component reaction of aldehydes, alkynes and amines with glycol as a “green” solvent. J Mol Catal A Chem 323:40–44

    Article  Google Scholar 

  • Zhang X, Qu Z, Li X, Zhao Q, Wang Y, Quan X (2011) Low temperature CO oxidation over Ag/SBA-15 nanocomposites prepared via in-situ “pH-adjusting” method. Catal Commun 16:11–14

    Article  Google Scholar 

  • Zhang H, Tang C, Lv Y, Sun C, Gao F, Dong L, Chen Y (2012) Synthesis, characterization, and catalytic performance of copper-containing SBA-15 in the phenol hydroxylation. J Colloid Interface Sci 380:16–24

    Article  Google Scholar 

  • Zhang Q, Du Q, Jiao T, Zhang Z, Wang S, Sun Q, Gao F (2013) Rationally designed porous polystyrene encapsulated zirconium phosphate nanocomposite for highly efficient fluoride uptake in waters. Sci Rep 3

  • Zhao D, Feng J, Huo Q, Melosh N, Fredrickson GH, Chmelka BF, Stucky GD (1998) Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 279:548–552

    Article  Google Scholar 

  • Zhao Y, Qi Y, Wei Y, Zhang Y, Zhang S, Yang Y, Liu Z (2008) Incorporation of Ag nanostructures into channels of nitrided mesoporous silica. Microporous Mesoporous Mater 111:300–306

    Article  Google Scholar 

  • Zhu Y, Li H, Zheng Q, Xu J, Li X (2012) Amine-functionalized SBA-15 with uniform morphology and well-defined mesostructure for highly sensitive chemosensors to detect formaldehyde vapor. Langmuir 28:7843–7850

    Article  Google Scholar 

  • Zhu Y, Morisato K, Li W, Kanamori K, Nakanishi K (2013) Synthesis of silver nanoparticles confined in hierarchically porous monolithic silica: a new function in aromatic hydrocarbon separations. ACS Appl Mater Interfaces 5:2118–2125

    Article  Google Scholar 

  • Zienkiewicz-Strzałka M, Pasieczna-Patkowska S, Kozak M, Pikus S (2013) Silver nanoparticles incorporated onto ordered mesoporous silica from Tollen’s reagent. Appl Surf Sci 266:337–343

    Article  Google Scholar 

Download references

Acknowledgments

The authors acknowledge the Department of Science and Technology (DST) for providing funding under women scientist scheme (File No. SR/WOS-A/CS-09/2012), Sophisticated Analytical Instruments Facility, CIL, P.U. for TEM, FE-SEM studies, and Institute Instrumentation Centre, IIT Roorkee for AFM studies.

Author information

Authors and Affiliations

  1. School of Chemistry and Biochemistry, Thapar University, Patiala, Punjab, 147004, India

    Shweta Sareen, Bonamali Pal & Satnam Singh

  2. Department of Chemistry, Maharishi Markandeshwar University, Mullana, Haryana, 133207, India

    Vishal Mutreja

Authors
  1. Shweta Sareen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Vishal Mutreja
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Bonamali Pal
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Satnam Singh
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Satnam Singh.

Electronic supplementary material

ESM 1

(DOCX 849 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sareen, S., Mutreja, V., Pal, B. et al. Surface structural, morphological, and catalytic studies of homogeneously dispersed anisotropic Ag nanostructures within mesoporous silica. J Nanopart Res 18, 332 (2016). https://doi.org/10.1007/s11051-016-3634-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11051-016-3634-4

Keywords

Search

Navigation