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Erschienen in: Journal of Sol-Gel Science and Technology 2/2017

25.05.2017 | Original Paper: Sol-gel and hybrid materials for catalytic, photoelectrochemical and sensor applications

Synthesis and characterization of tungstophosphoric acid-modified mesoporous silica nanoparticles with tuneable diameter and pore size distribution

verfasst von: Alexis A. Sosa, Marina N. Gorsd, Mirta N. Blanco, Luis R. Pizzio

Erschienen in: Journal of Sol-Gel Science and Technology | Ausgabe 2/2017

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Abstract

Mesoporous silica nanoparticles were prepared in aqueous/organic phase using cetyltrimethylammonium bromide and polystyrene as organic templates. The morphology and crystalline phase of the products were characterized by scanning electron microcopy, transmission electron microscopy, X-ray diffraction, small angle X-ray scattering, and N2 adsorption/desorption isotherm analysis. The octane/water ratio influenced the pore size distribution, the morphology and size of the nanospheres obtained. Transmission electron microscopy revealed that mesoporous silica nanoparticles with “blackberry-like structure” (MSN3, MSN4, MSN5, and MSN6 samples) were obtained using octane/water ratios in the range 0.007–0.35. They present small (in the range 5–6 nm) and large (in the range 28–34 nm) mesopores. Large mesopores were mainly generated by polystyrene, and their volume contribution was clearly higher than in the MSN1 and MSN2 samples. The structure and morphology of mesoporous silica nanoparticles solids impregnated with tungstophosphoric acid were similar to those of the mesoporous silica nanospheres used as support. In addition, the characterization of all the solids impregnated with tungstophosphoric acid by Fourier transform infrared and 31P nuclear magnetic resonance indicated the presence of undegraded [PW12O40]3− and [H3−X PW12O40](3−X)− species interacting electrostatically with the ≡Si–OH2 + groups, and by potentiometric titration the solids presented very strong acid sites. In summary, they are good candidates to be used in reactions catalyzed by acids, especially to obtain quinoxaline derivatives.

Graphical Abstract

https://static-content.springer.com/image/art%3A10.1007%2Fs10971-017-4428-6/MediaObjects/10971_2017_4428_Figa_HTML.gif

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Literatur
1.
Zurück zum Zitat Rivera TS, Sosa A, Romanelli GP, Blanco MN, Pizzio LR (2012) Tungstophosphoric acid/zirconia composites prepared by the sol–gel method: an efficient and recyclable green catalyst for the one-pot synthesis of 14-aryl-14H-dibenzo[a,j] xanthenes. Appl Catal A 443–444:207–213CrossRef Rivera TS, Sosa A, Romanelli GP, Blanco MN, Pizzio LR (2012) Tungstophosphoric acid/zirconia composites prepared by the sol–gel method: an efficient and recyclable green catalyst for the one-pot synthesis of 14-aryl-14H-dibenzo[a,j] xanthenes. Appl Catal A 443–444:207–213CrossRef
2.
Zurück zum Zitat Rengifo-Herrera JA, Frenzel RA, Blanco MN, Pizzio LR (2014) Visible-light-absorbing mesoporous TiO2 modified with tungstosilicicacid as photocatalyst in the photodegradation of 4-chlorophenol. J Photochem Photobiol A 289:22–30CrossRef Rengifo-Herrera JA, Frenzel RA, Blanco MN, Pizzio LR (2014) Visible-light-absorbing mesoporous TiO2 modified with tungstosilicicacid as photocatalyst in the photodegradation of 4-chlorophenol. J Photochem Photobiol A 289:22–30CrossRef
3.
Zurück zum Zitat Nandiyanto ABD, Hagura N, Iskandar F, Okuyama K (2010) Design of a highly ordered and uniform porous structure with multisized pores in film and particle forms using a template-driven self-assembly technique. Acta Mater 58:282–289CrossRef Nandiyanto ABD, Hagura N, Iskandar F, Okuyama K (2010) Design of a highly ordered and uniform porous structure with multisized pores in film and particle forms using a template-driven self-assembly technique. Acta Mater 58:282–289CrossRef
4.
Zurück zum Zitat Sosa A, Rivera TS, Blanco MN, Pizzio LR, Romanelli GP (2013) Tungstophosphoric acid supported on zirconia: a recyclable catalyst for the green synthesis on quinoxaline derivatives under solvent-free conditions. Phosphorus Sulfur Silicon Relat Elem 188:1071–1079CrossRef Sosa A, Rivera TS, Blanco MN, Pizzio LR, Romanelli GP (2013) Tungstophosphoric acid supported on zirconia: a recyclable catalyst for the green synthesis on quinoxaline derivatives under solvent-free conditions. Phosphorus Sulfur Silicon Relat Elem 188:1071–1079CrossRef
5.
Zurück zum Zitat Iskandar F, Lenggoro IW, Kim TO, Nakao N, Shimada M, Okuyama K (2001) Fabrication and characterization of SiO2 particles generated by spray method for standards aerosol. J Chem Eng Jpn 34:1285–1292CrossRef Iskandar F, Lenggoro IW, Kim TO, Nakao N, Shimada M, Okuyama K (2001) Fabrication and characterization of SiO2 particles generated by spray method for standards aerosol. J Chem Eng Jpn 34:1285–1292CrossRef
6.
Zurück zum Zitat Ray S, Bhaumik A, Pramanik M, Butcher RJ, Yildirim SO, Mukhopadhyay C (2014) Binary conjugate Brønsted–Lewis acid supported on mesoporous silica nanoparticles for the domino addition/elimination/addition and addition/elimination/addition/cyclization cascade. Catal Commun 43:173–178CrossRef Ray S, Bhaumik A, Pramanik M, Butcher RJ, Yildirim SO, Mukhopadhyay C (2014) Binary conjugate Brønsted–Lewis acid supported on mesoporous silica nanoparticles for the domino addition/elimination/addition and addition/elimination/addition/cyclization cascade. Catal Commun 43:173–178CrossRef
7.
Zurück zum Zitat Tu J, Wang T, Shi W, Wu G, Tian X, Wang Y, Ge D, Ren L (2012) Multifunctional ZnPc-loaded mesoporous silica nanoparticles for enhancement of photodynamic therapy efficacy by endolysosomal escape. Biomaterials 33:7903–7914CrossRef Tu J, Wang T, Shi W, Wu G, Tian X, Wang Y, Ge D, Ren L (2012) Multifunctional ZnPc-loaded mesoporous silica nanoparticles for enhancement of photodynamic therapy efficacy by endolysosomal escape. Biomaterials 33:7903–7914CrossRef
8.
Zurück zum Zitat Mehraban Z, Farzaneh F (2006) MCM-41 as selective separator of chlorophyll-a from b-carotene and chlorophyll-a mixture. Microporous Mesoporous Mater 88:84–90CrossRef Mehraban Z, Farzaneh F (2006) MCM-41 as selective separator of chlorophyll-a from b-carotene and chlorophyll-a mixture. Microporous Mesoporous Mater 88:84–90CrossRef
9.
Zurück zum Zitat Hosseini M, Ganjali MR, Aboufazeli F, Faridbod F, Goldooz H, Badiei A, Norouzi P (2013) A selective fluorescent bulk sensor for lutetium based on hexagonal mesoporous structures. Sens Actuators B 184:93–99CrossRef Hosseini M, Ganjali MR, Aboufazeli F, Faridbod F, Goldooz H, Badiei A, Norouzi P (2013) A selective fluorescent bulk sensor for lutetium based on hexagonal mesoporous structures. Sens Actuators B 184:93–99CrossRef
10.
Zurück zum Zitat Kamyshny A, Magdassi S (2000) Fluorescence immunoassay based on fluorescer microparticles. Colloids Surf B 18:13–17CrossRef Kamyshny A, Magdassi S (2000) Fluorescence immunoassay based on fluorescer microparticles. Colloids Surf B 18:13–17CrossRef
11.
Zurück zum Zitat Yu J, Shi JL, Chen HR, Yan JN, Yan DS (2001) Effect of inorganic salt addition during synthesis on pore structure and hydrothermal stability of mesoporous silica. Microporous Mesoporous Mater 46:153–162CrossRef Yu J, Shi JL, Chen HR, Yan JN, Yan DS (2001) Effect of inorganic salt addition during synthesis on pore structure and hydrothermal stability of mesoporous silica. Microporous Mesoporous Mater 46:153–162CrossRef
12.
Zurück zum Zitat Nandiyanto ABD, Kim SG, Iskandar F, Okuyama K (2009) Synthesis of spherical mesoporous silica nanoparticles with nanometer-size controllable pores and outer diameters. Microporous Mesoporous Mater 120:447–453CrossRef Nandiyanto ABD, Kim SG, Iskandar F, Okuyama K (2009) Synthesis of spherical mesoporous silica nanoparticles with nanometer-size controllable pores and outer diameters. Microporous Mesoporous Mater 120:447–453CrossRef
13.
Zurück zum Zitat Rossi LM, Shi L, Quina FH, Rosenzweig Z (2005) Stöber synthesis of monodispersed luminescent silica nanoparticles for bioanalytical assays. Langmuir 21:4277–4280CrossRef Rossi LM, Shi L, Quina FH, Rosenzweig Z (2005) Stöber synthesis of monodispersed luminescent silica nanoparticles for bioanalytical assays. Langmuir 21:4277–4280CrossRef
14.
Zurück zum Zitat Burns A, Vider J, Ow H, Herz E, Penate-Medina O, Baumgart M, Larson SM, Wiesner U, Bradbury M (2009) Fluorescent silica nanoparticles with efficient urinary excretion for nanomedicine. Nano Lett. 9:442–448CrossRef Burns A, Vider J, Ow H, Herz E, Penate-Medina O, Baumgart M, Larson SM, Wiesner U, Bradbury M (2009) Fluorescent silica nanoparticles with efficient urinary excretion for nanomedicine. Nano Lett. 9:442–448CrossRef
15.
Zurück zum Zitat Heikkila T, Salonen J, Tuura J, Hamdy MS, Mul G, Kumar N, Salmi T, Yu D, Murzin D, Laitinen L, Kaukonen AM, Hirvonen J, Lehto VP (2007) Mesoporous silica material TUD-1 as a drug delivery system. Int J Pharm 331:133–138CrossRef Heikkila T, Salonen J, Tuura J, Hamdy MS, Mul G, Kumar N, Salmi T, Yu D, Murzin D, Laitinen L, Kaukonen AM, Hirvonen J, Lehto VP (2007) Mesoporous silica material TUD-1 as a drug delivery system. Int J Pharm 331:133–138CrossRef
16.
Zurück zum Zitat Keggin JF (1934) The structure and formula of 12- phosphotungstic acid. Proc R Soc London Ser A 144:75–100CrossRef Keggin JF (1934) The structure and formula of 12- phosphotungstic acid. Proc R Soc London Ser A 144:75–100CrossRef
17.
Zurück zum Zitat Rao KM, Gobetto R, Iannibello A, Zecchina A (1989) Solid state NMR and IR studies of phosphomolybdenum and phosphotungsten heteropoly acids supported on SiO2, α-Al2O3, and SiO2–Al2O3. J Catal 119:512–516CrossRef Rao KM, Gobetto R, Iannibello A, Zecchina A (1989) Solid state NMR and IR studies of phosphomolybdenum and phosphotungsten heteropoly acids supported on SiO2, α-Al2O3, and SiO2–Al2O3. J Catal 119:512–516CrossRef
18.
Zurück zum Zitat Kapustin GI, Brueva TR, Klyachkov AL, Timofeeva MN, Kulikov SM, Kozhevnikov IV (1991) Study of the acidity of heteropolyacids. Kinet Catal 31:1017–1020 Kapustin GI, Brueva TR, Klyachkov AL, Timofeeva MN, Kulikov SM, Kozhevnikov IV (1991) Study of the acidity of heteropolyacids. Kinet Catal 31:1017–1020
19.
Zurück zum Zitat Moffat JB, Kasztelan S (1988) The oxidation of methane on heteropolyoxometalates II. Nature and stability of the supported species. J Catal 109:206–211CrossRef Moffat JB, Kasztelan S (1988) The oxidation of methane on heteropolyoxometalates II. Nature and stability of the supported species. J Catal 109:206–211CrossRef
20.
Zurück zum Zitat Kasztelan S, Payen E, Moffat JB (1988) The formation of molybdosilicic acid on Mo/SiO2 catalysts and its relevance to methane oxidation. J Catal 112:320–324CrossRef Kasztelan S, Payen E, Moffat JB (1988) The formation of molybdosilicic acid on Mo/SiO2 catalysts and its relevance to methane oxidation. J Catal 112:320–324CrossRef
21.
Zurück zum Zitat Lefebvre F (1992) 31P MAS NMR study of H3PW12O40 supported on silica: formation of (≡SiOH2 +)(H2PW12O40 –). J Chem Soc Chem Commun (10): 756–757 Lefebvre F (1992) 31P MAS NMR study of H3PW12O40 supported on silica: formation of (≡SiOH2 +)(H2PW12O40 ). J Chem Soc Chem Commun (10): 756–757
22.
Zurück zum Zitat Legagneux N, Basset JM, Thomas A, Lefebvre F, Goguet A, Sa J, Hardacre Ch (2009) Characterization of silica-supported dodecatungstic heteropolyacids as a function of their dehydroxylation temperature. Dalton Trans (12): 2235–2240 Legagneux N, Basset JM, Thomas A, Lefebvre F, Goguet A, Sa J, Hardacre Ch (2009) Characterization of silica-supported dodecatungstic heteropolyacids as a function of their dehydroxylation temperature. Dalton Trans (12): 2235–2240
23.
Zurück zum Zitat Pizzio LR, Cáceres CV, Blanco MN (1998) Acid catalysts prepared by impregnation of tungstophosphoric acid solutions on different supports. Appl Catal A 167:283–294CrossRef Pizzio LR, Cáceres CV, Blanco MN (1998) Acid catalysts prepared by impregnation of tungstophosphoric acid solutions on different supports. Appl Catal A 167:283–294CrossRef
24.
Zurück zum Zitat Okuhara T, Mizuno N, Misono M (1996) Catalytic chemistry of heteropoly compounds. Adv Catal 41:113–252 Okuhara T, Mizuno N, Misono M (1996) Catalytic chemistry of heteropoly compounds. Adv Catal 41:113–252
25.
Zurück zum Zitat Jeannin YP (1998) The nomenclature of polyoxometalates: how to connect a name and a structure. Chem Rev 98:51–76CrossRef Jeannin YP (1998) The nomenclature of polyoxometalates: how to connect a name and a structure. Chem Rev 98:51–76CrossRef
26.
Zurück zum Zitat Kozhevnikov IV (1998) Catalysis by heteropoly acids and multicomponent polyoxometalates in liquid-phase reactions. Chem Rev 98:171–198CrossRef Kozhevnikov IV (1998) Catalysis by heteropoly acids and multicomponent polyoxometalates in liquid-phase reactions. Chem Rev 98:171–198CrossRef
27.
Zurück zum Zitat Misono M (2001) Unique acid catalysis of heteropoly compounds (heteropolyoxometalates) in the solid state. Chem Commun (13): 1141–1152. Misono M (2001) Unique acid catalysis of heteropoly compounds (heteropolyoxometalates) in the solid state. Chem Commun (13): 1141–1152.
28.
Zurück zum Zitat Anastas PT, Warner JC (1998) Green chemistry: theory and practice. Oxford University Press, Oxford Anastas PT, Warner JC (1998) Green chemistry: theory and practice. Oxford University Press, Oxford
29.
Zurück zum Zitat Ajaikumar S, Pandurangan A (2007) Esterification of alkyl acids with alkanols over MCM-41 molecular sieves: influence of hydrophobic surface on condensation reaction. J Mol Catal A 266:1–10CrossRef Ajaikumar S, Pandurangan A (2007) Esterification of alkyl acids with alkanols over MCM-41 molecular sieves: influence of hydrophobic surface on condensation reaction. J Mol Catal A 266:1–10CrossRef
30.
Zurück zum Zitat Rocchiccioli-Deltcheff C, Thouvenot R, Franck R (1976) Spectres i.r. et Raman d’hétéropolyanions α-XM12O40 n- de structure de type Keggin (X = BIII, SiIV, GeIV, PV, AsV et M = WVI et MoVI). Spectrochim Acta Part A 32:587–597CrossRef Rocchiccioli-Deltcheff C, Thouvenot R, Franck R (1976) Spectres i.r. et Raman d’hétéropolyanions α-XM12O40 n- de structure de type Keggin (X = BIII, SiIV, GeIV, PV, AsV et M = WVI et MoVI). Spectrochim Acta Part A 32:587–597CrossRef
31.
Zurück zum Zitat Essayem N, Tong YY, Jobic H, Vedrine JC (2000) Characterization of protonic sites in H3PW12O40 and Cs1.9H1.1PW12O40: a solid-state 1H, 2H, 31P MAS-NMR and inelastic neutron scattering study on samples prepared under standard reaction conditions. Appl Catal A 194–195:109–122CrossRef Essayem N, Tong YY, Jobic H, Vedrine JC (2000) Characterization of protonic sites in H3PW12O40 and Cs1.9H1.1PW12O40: a solid-state 1H, 2H, 31P MAS-NMR and inelastic neutron scattering study on samples prepared under standard reaction conditions. Appl Catal A 194–195:109–122CrossRef
32.
Zurück zum Zitat Okuhara T, Nishimura T, Watanabe H, Na K, Misono M (1994) 4.8 novel catalysis of cesium salt of heteropoly acid and its characterization by solid-state NMR. Stud Surf Sci Catal 90:419–428CrossRef Okuhara T, Nishimura T, Watanabe H, Na K, Misono M (1994) 4.8 novel catalysis of cesium salt of heteropoly acid and its characterization by solid-state NMR. Stud Surf Sci Catal 90:419–428CrossRef
33.
Zurück zum Zitat Massart R, Contant R, Fruchart J, Ciabrini J, Fournier M (1977) Phosphorus-31 NMR studies on molybdic and tungstic heteropolyanions. Correlation between structure and chemical shift. Inorg Chem 16:2916–2921CrossRef Massart R, Contant R, Fruchart J, Ciabrini J, Fournier M (1977) Phosphorus-31 NMR studies on molybdic and tungstic heteropolyanions. Correlation between structure and chemical shift. Inorg Chem 16:2916–2921CrossRef
34.
Zurück zum Zitat Rengifo-Herrera JA, Blanco MN, Wist J, Florian P, Pizzio LR (2016) TiO2 modified with polyoxotungstates should induce visible-light absorption and high photocatalytic activity through the formation of surface complexes. App Catal A 189:99–109CrossRef Rengifo-Herrera JA, Blanco MN, Wist J, Florian P, Pizzio LR (2016) TiO2 modified with polyoxotungstates should induce visible-light absorption and high photocatalytic activity through the formation of surface complexes. App Catal A 189:99–109CrossRef
35.
Zurück zum Zitat Rengifo-Herrera JA, Blanco MN, Fidalgo de Cortalezzi MM, Pizzio LR (2016) Visible-light-absorbing Evonik P-25 nanoparticles modified with tungstophosphoric acid and their photocatalytic activity on different wavelengths. Mater Res Bull 83:360–368CrossRef Rengifo-Herrera JA, Blanco MN, Fidalgo de Cortalezzi MM, Pizzio LR (2016) Visible-light-absorbing Evonik P-25 nanoparticles modified with tungstophosphoric acid and their photocatalytic activity on different wavelengths. Mater Res Bull 83:360–368CrossRef
36.
Zurück zum Zitat Chen CY, Li HX, Davis ME (1993) Studies on mesoporous materials: I. Synthesis and characterization of MCM-41. Microporous Mater 2:17–26CrossRef Chen CY, Li HX, Davis ME (1993) Studies on mesoporous materials: I. Synthesis and characterization of MCM-41. Microporous Mater 2:17–26CrossRef
37.
Zurück zum Zitat Zhao XS, Lu GQ, Millar GJ (1996) Synthesis and characterization of highly ordered MCM-41 in an alkali-free system and its catalytic activity. Catal Lett 38:33–37CrossRef Zhao XS, Lu GQ, Millar GJ (1996) Synthesis and characterization of highly ordered MCM-41 in an alkali-free system and its catalytic activity. Catal Lett 38:33–37CrossRef
38.
Zurück zum Zitat Li T, Senesi AJ, Lee B (2016) Small angle X-ray scattering for nanoparticle research. Chem Rev 116:11128–11180CrossRef Li T, Senesi AJ, Lee B (2016) Small angle X-ray scattering for nanoparticle research. Chem Rev 116:11128–11180CrossRef
39.
Zurück zum Zitat Pizzio LR, Cáceres CV, Blanco MN (1999) Equilibrium adsorption of 11-tungstophosphate anion on different supports. Appl Surf Sci 151:91–101CrossRef Pizzio LR, Cáceres CV, Blanco MN (1999) Equilibrium adsorption of 11-tungstophosphate anion on different supports. Appl Surf Sci 151:91–101CrossRef
Metadaten
Titel
Synthesis and characterization of tungstophosphoric acid-modified mesoporous silica nanoparticles with tuneable diameter and pore size distribution
verfasst von
Alexis A. Sosa
Marina N. Gorsd
Mirta N. Blanco
Luis R. Pizzio
Publikationsdatum
25.05.2017
Verlag
Springer US
Erschienen in
Journal of Sol-Gel Science and Technology / Ausgabe 2/2017
Print ISSN: 0928-0707
Elektronische ISSN: 1573-4846
DOI
https://doi.org/10.1007/s10971-017-4428-6

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