マイクロ波支援酸 - 触媒反応によりシリカナノ粒子の調製
Summary
Silica nanoparticles were prepared using acid-catalysis of a siloxane precursor and microwave-assisted synthetic techniques resulting in the controlled growth of nanomaterials ranging from 30-250 nm in diameter. The growth dynamics can be controlled by varying the initial silicic acid concentration, time of the reaction, and temperature of reaction.
Abstract
Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle diameters ranging from 30-250 nm by varying the reaction conditions. Through the selection of a microwave compatible solvent, silicic acid precursor, catalyst, and microwave irradiation time, these microwave-assisted methods were capable of overcoming the previously reported shortcomings associated with synthesis of silica nanoparticles using microwave reactors. The siloxane precursor was hydrolyzed using the acid catalyst, HCl. Acetone, a low-tan δ solvent, mediates the condensation reactions and has minimal interaction with the electromagnetic field. Condensation reactions begin when the silicic acid precursor couples with the microwave radiation, leading to silica nanoparticle sol formation. The silica nanoparticles were characterized by dynamic light scattering data and scanning electron microscopy, which show the materials' morphology and size to be dependent on the reaction conditions. Microwave-assisted reactions produce silica nanoparticles with roughened textured surfaces that are atypical for silica sols produced by Stöber's methods, which have smooth surfaces.
Introduction
Silica nanoparticles (SiO2 NPs) were first synthesized by Stöber1 and through modifications2-7 have become the preferred method for SiO2 NPs synthesis. Typically, Stöber reactions are catalyzed by alkaline conditions where silica sols are formed. Acid-catalyzed reactions are used less frequently than alkaline-catalyzed reactions due to the greater degree of difficulty of hydrolysis of the siloxane precursor. Unlike alkaline-catalyzed reactions, acid-catalyzed reactions preferentially form silica gels.8
Microwave-assisted chemical reactions are an emerging technique within the scientific community and in literature due to the associated benefits to the techniques9-18. Specifically, microwave-assisted techniques have been shown to be advantageous in the synthesis of nanomaterials where the promotion of spontaneous nucleation events is desired. Microwave conditions are advantageous because microwave reactors deliver controlled power quickly to the reaction10. Until recently19, the synthesis of SiO2 NPs using microwave reactors have been used with limited success mainly as a result of issues with reproducibility20-22.
The details and procedural methods often reported in the literature on the synthesis of nanomaterials often tend to be obscure and sometimes seen as an "art-form." Combining microwave-assisted synthetic techniques and nanomaterial synthesis can compound the subject even further. The purpose of this manuscript is to guide researchers in the synthesis of nanomaterials by microwave-assisted techniques, eliminate obscurity associated with these techniques, and point out common mistakes associated with these techniques.
In a microwave chemical reaction, any molecular species containing a permanent dipole is capable of interacting and perturbing the electromagnetic (EM) field. These species are not limited solely to the reagents and solvents used within the reaction, but can be any substance placed in the EM field i.e. glass vials, salts, ionic liquids.
The ability for a specific substance to effectively convert EM energy into heat is defined as the loss factor of a material or tan δ. Solvents are commonly classified by their loss factor where values for tan δ > 0.5 are considered high, 0.1 > tan δ > 0.5 are considered medium, and tan δ < 0.1 are considered low. These loss factors values relate the ability for a particular solvent to couple or absorb microwave energy and convert that energy into heat. Thermal energy is generated through molecular friction of species attempting to align with the oscillating EM field. If solvents with high tan δ values are used within a reaction, the solvent will dominate the microwave absorption events, masking the precursor or reagents, leading to bulk heating as a result of the solvent strongly coupling with the EM field.
Typically, polar solvents are used in SiO2 NP synthesis to ensure reagent solubility and for donation of labile protons23. Common solvents used in SiO2 NP syntheses are alcohol solvents such as ethanol, methanol or 2-propanol. These solvents all have high tan δ values (0.941, 0.799, and 0.659 for ethanol, 2-propanol and methanol, respectively) making them poor solvent choices for microwave-assisted chemical reactions of SiO2 NPs as they efficiently couple with the EM field. It is our belief that microwave-assisted reactions are most effective when low tan δ solvents are used in combination with polar molecular precursors in synthetic reactions. These circumstances allow for the molecular precursors to couple with the EM field, providing molecular heating, while the solvent interacts minimally. For microwave-assisted reactions in this manuscript, acetone is used as an alternative to the commonly used alcohol solvents associated with SiO2 NPs synthesis. Acetone is considered a low loss factor solvent (tan δ = 0.054), which limits the solvent interactions within the EM field allowing selective microwave absorption with the reactants meditating silica condensation reactions.
In this manuscript, we outline the procedures associated with the microwave-assisted synthesis of SiO2 NPs which are accurate, precise and quick. SiO2 NP growth is achieved by effective coupling of the precursor with the EM field while the solvent has a minimal role in heating. Hydrolysis of the siloxane precursor is achieved by using hydrochloric acid, which leads to slower rates of hydrolysis and limits further condensation reactions. Alkaline-catalyzed reactions have much faster reaction rates and can complicate growth processes when used with microwave-assisted techniques. The resultant SiO2 NPs synthesized by these techniques range in diameters from 30 nm up to diameters greater than 250 nm. SiO2 NP size is controlled by varying the precursor concentration and exposure time to the microwave radiation.
Protocol
Representative Results
Discussion
The microwave-assisted methods described in this manuscript are advantageous over conventional heating methods because SiO2 NPs can be synthesized accurately, precisely, and quickly. The following criteria should be followed to eliminate any potential issues associated with SiO2 NPs formation by these microwave-associated techniques: 1) use of a catalyst such as 1 mM HCl, 2) hydrolysis of the TMOS should be completed before addition of acetone, 3) use of an aprotic solvent such as acetone, 4) use of…
Disclosures
The authors have nothing to disclose.
Acknowledgements
Funding was provided by the Defense Threat Reduction Agency, Physical Science and Technology Division, Protection and Hazard Mitigation technical area. This research was supported in part by an appointment to the Postgraduate Research Participation Program at the Air Force Research Laboratory administered by the Oak Ridge Institute for Science and Education (ORISE) through an interagency agreement between the U.S. Department of Energy and the Air Force Research Laboratory, Materials and Manufacturing Directorate, Airbase Technologies Division (AFRL/RXQ).
Materials
| Name of the reagent | Company | Catalogue number | Comments (optional) |
| Tetramethylorthosilicate | Sigma Aldrich | 218472 | |
| Hydrochloric acid, 37% | Sigma Aldrich | 435570 | |
| Acetone | Fisher | A949SK | |
| Sulfuric acid | EMD Millipore | SX1244 | |
| Hydrogen peroxide, 30% | EMD Millipore | HX0635 | |
| Discover microwave reactor | CEM | ||
| 10 ml Borosilicate reaction vial | CEM | 908035 | |
| 10 ml Snap cap | CEM | 909210 | |
| 3 mm Stir bar | Fisher Scientific | 14-513-65 | |
| Highly polished silicon wafers | Broker | SP064483 | |
| S4800 SEM | Hitachi | ||
| Zetasizer Nano90 | Malvern | ||
| Polystyrene cuvette, (10 mm x 10 mm x 45mm) | Sarstedt | 67.754 | |
| 5415D centrifuge | Eppendorf | ||
| Hummer 6.2 sputter system | Anatech |
References
- Stober, W., Fink, A., Bohn, E. CONTROLLED GROWTH OF MONODISPERSE SILICA SPHERES IN MICRON SIZE RANGE. J. Colloid Interface Sci. 26, 62 (1968).
- Chiang, Y. D., et al. Controlling Particle Size and Structural Properties of Mesoporous Silica Nanoparticles Using the Taguchi Method. J. Phys. Chem. C. 115, 13158-13165 (2011).
- Hartlen, K. D., Athanasopoulos, A. P. T., Kitaev, V. Facile preparation of highly monodisperse small silica spheres (15 to > 200 nm) suitable for colloidal templating and formation of ordered arrays. Langmuir. 24, 1714-1720 (2008).
- Finnie, K. S., Bartlett, J. R., Barbe, C. J. A., Kong, L. G. Formation of silica nanoparticles in microemulsions. Langmuir. 23, 3017-3024 (2007).
- El Hawi, N., et al. Silica Nanoparticles Grown and Stabilized in Organic Nonalcoholic Media. Langmuir. 25, 7540-7546 (2009).
- Qiao, Z. A., Zhang, L., Guo, M. Y., Liu, Y. L., Huo, Q. S. Synthesis of Mesoporous Silica Nanoparticles via Controlled Hydrolysis and Condensation of Silicon Alkoxide. Chem. Mater. 21, 3823-3829 (2009).
- Yu, Q. Y., et al. Hydrothermal Synthesis of Hollow Silica Spheres under Acidic Conditions. Langmuir. 27, 7185-7191 (2011).
- Chen, S. L., Dong, P., Yang, G. H., Yang, J. J. Kinetics of formation of monodisperse colloidal silica particles through the hydrolysis and condensation of tetraethylorthosilicate. Ind. Eng. Chem. Res. 35, 4487-4493 (1996).
- Caddick, S., Fitzmaurice, R. Microwave enhanced synthesis. Tetrahedron. 65, 3325-3355 (2009).
- Baghbanzadeh, M., Carbone, L., Cozzoli, P. D., Kappe, C. O. Microwave-Assisted Synthesis of Colloidal Inorganic Nanocrystals. Angew. Chem. Int. Edit. 50, 11312-11359 (2011).
- Tompsett, G. A., Conner, W. C., Yngvesson, K. S. Microwave synthesis of nanoporous materials. ChemPhysChem. 7, 296-319 (2006).
- Lovingood, D. D., Strouse, G. F. Microwave Induced In-Situ Active Ion Etching of Growing. InP Nanocrystals. Nano Lett. 8, 3394-3397 (2008).
- Washington, A. L., Strouse, G. F. Microwave Synthetic Route for Highly Emissive TOP/TOP-S Passivated CdS Quantum Dots. Chem. Mater. 21, 3586-3592 (2009).
- Washington, A. L., Strouse, G. F. Microwave synthesis of CdSe and CdTe nanocrystals in nonabsorbing alkanes. J. Am. Chem. Soc. 130, 8916-8922 (2008).
- Washington, A. L., Strouse, G. F. Selective Microwave Absorption by Trioctyl Phosphine Selenide: Does It Play a Role in Producing Multiple Sized Quantum Dots in a Single Reaction?. Chem. Mater. 21, 2770-2776 (2009).
- Gerbec, J. A., Magana, D., Washington, A., Strouse, G. F. Microwave-enhanced reaction rates for nanoparticle synthesis. J. Am. Chem. Soc. 127, 15791-15800 (2005).
- Kappe, C. O. Controlled microwave heating in modern organic synthesis. Angew. Chem. Int. Edit. 43, 6250-6284 (2004).
- Nuchter, M., Ondruschka, B., Bonrath, W., Gum, A. Microwave assisted synthesis – a critical technology overview. Green Chem. 6, 128-141 (2004).
- Lovingood, D. D., Owens, J. R., Seeber, M., Kornev, K. G., Luzinov, I. Controlled Microwave-Assisted Growth of Silica Nanoparticles under Acid Catalysis. ACS Appl. Mater. Interfaces. 4, 6875-6883 (2012).
- Davies, G. L., Barry, A., Gun’ko, Y. K. Preparation and size optimisation of silica nanoparticles using statistical analyses. Chem. Phys. Lett. 468, 239-244 (2009).
- Park, S. E., Kim, D. S., Chang, J. S., Kim, W. Y. Synthesis of MCM-41 using microwave heating with ethylene glycol. Catal. Today. 44, 301-308 (1998).
- Mily, E., Gonzalez, A., Iruin, J. J., Irusta, L., Fernandez-Berridi, M. J. Silica nanoparticles obtained by microwave assisted sol-gel process: multivariate analysis of the size and conversion dependence. J. Sol-Gel Sci. Technol. 53, 667-672 (2010).
- Brinker, C. J. HYDROLYSIS AND CONDENSATION OF SILICATES – EFFECTS ON STRUCTURE. J. Non-Cryst. Solids. 100, 31-50 (1988).
- Arriagada, F. J., Osseo-Asare, K. Synthesis of nanosize silica in a nonionic water-in-oil microemulsion: Effects of the water/surfactant molar ratio and ammonia concentration. J. Colloid Interface Sci. 211, 210-220 (1999).
- Burda, C., Chen, X. B., Narayanan, R., El-Sayed, M. A. Chemistry and properties of nanocrystals of different shapes. Chem. Rev. 105, 1025-1102 (2005).
- Iler, R. K. . The Chemistry of Silica – Solubility, Polymerization, Colloid and Surface Properties and Biochemistry. , (1979).
- Artaki, I., Sinha, S., Irwin, A. D., Jonas, J. 29Si NMR study of the initial stage of the sol-gel process under high pressure. J. Non-Cryst. Solids. 72, 391-402 (1985).
- Sorensen, L., Strouse, G. F., Stiegman, A. E. Fabrication of stable low-density silica aerogels, containing luminescent ZnS capped CdSe quantum dots. Adv. Mater. 18, 1965 (2006).
- Lita, A., Washington, A. L., Lvan de Burgt, ., Strouse, G. F., Stiegman, A. E. Stable Efficient Solid-State White-Light-Emitting Phosphor with a High Scotopic/Photopic Ratio Fabricated from Fused CdSe-Silica Nanocomposites. Adv. Mater. 22, 3987-3991 (2010).
- Halas, N. J. Nanoscience under glass: The versatile chemistry of silica nanostructures. ACS Nano. 2, 179-183 (2008).
- Tang, F. Q., Li, L. L., Chen, D. Mesoporous Silica Nanoparticles: Synthesis, Biocompatibility and Drug Delivery. Adv. Mater. 24, 1504-1534 (2012).
- Wang, Y. J., Price, A. D., Caruso, F. Nanoporous colloids: building blocks for a new generation of structured materials. J. Mater. Chem. 19, 6451-6464 (2009).
- Guerrero-Martinez, A., Perez-Juste, J., Liz-Marzan, L. M. Recent Progress on Silica Coating of Nanoparticles and Related Nanomaterials. Adv. Mater. 22, 1182-1195 (2010).
