Periodic Mesoporous Organosilica Nanorice
© to the authors 2008
Received: 14 October 2008
Accepted: 11 November 2008
Published: 22 November 2008
A periodic mesoporous organosilica (PMO) with nanorice morphology was successfully synthesized by a template assisted sol–gel method using a chain-type precursor. The PMO is composed of D and T sites in the ratio 1:2. The obtained mesoporous nanorice has a surface area of 753 m2 g−1, one-dimensional channels, and a narrow pore size distribution centered at 4.3 nm. The nanorice particles have a length of ca. 600 nm and width of ca. 200 nm.
KeywordsNanorice Mesoporous materials Periodic mesoporous organosilica
Periodic mesoporous organosilicas (PMOs) have emerged as a diverse class of materials with numerous potential applications [1–3]. PMOs are attractive because they have a much higher and uniformly distributed loading of organic groups compared to organosilicas with post-grafted organic groups and organosilicas with terminal organic groups that have to be prepared by co-condensation methods [1–3]. Very little is known about the synthesis of PMO nanoparticles of controlled size and shape [4–7], and to our best knowledge there are no reports about uniform submicron PMO nanoparticles. Size and shape of mesoporous particles have a considerable impact on their potential uses. For example, periodic mesoporous silica nanoparticles of designed shapes have emerged as promising candidates for drug-delivery applications . Generally, it is difficult to achieve periodic mesoporous particles of uniform anisotropic shape and size, and special techniques are needed to produce them rationally and reproducibly [9–11]. Nanorices have been so far reported for dense nanoparticles, namely, iron oxide , organic polymers , silver , gold , and cobalt .
The nanorice was reproducibly obtained in a standard block copolymer template assisted sol–gel route  at room temperature without the need of any special reaction conditions.
Materials and Methods
Triblock copolymers EO20PO70EO20Pluronic P123 (BASF, USA), octaethoxy-1,3,5-trisilapentane (EtO)3Si–CH2–Si(OEt)2–CH2–Si(OEt)3(Gelest) and NaCl (EM Science) were used as-received without further purification.
Synthesis of PMO Nanorice
To a mixture of 6 g NaCl, 1.3 g of Pluronic 123, 32.4 mL (33.6 g) of 2 molar HCl and 11.2 mL H2O, 1.44 g of1 was added drop wise under vigorous stirring. The mixture was continuously stirred for another 24 h under the formation of a suspension of a white solid. The solid particles were centrifuged off and re-suspended in a mixture of 100 mL acetone and 10 mL 2 molar HCl. This mixture was stirred for another 48 h to extract the template. The extracted particles were centrifuged again and dried at 80 °C for 1 h to yield 443 mg of final product.
Characterization of the Materials
The TEM images were taken on a JEOL JEM-2000 electron microscope operated at 200 kV. Samples for the TEM analysis were prepared by dispersing the particles in acetone and dropping a small volume of it onto a holey carbon film on a copper grid. SEM images of the specimen were taken on a Hitachi S-4300 SEM. SAXS patterns were obtained using a Rigaku Rotaflex diffractometer with a Cu Kαradiation source (λ = 0.15405 nm). The N2adsorption isotherm was measured at 77 K using an ASAP 2010 (Micromeritics Instrument Corp.). The free space He was determined prior to measuring the N2isotherm on a sample that was activated at 150 °C under dynamic vacuum to a vacuum of <10−5 Torr. After measuring the free space with He, the sample was again outgassed at 150 °C prior to measuring the N2isotherm. The BET surface area was calculated over the pressure range of 0.04–0.1 P/P0. The13C and29Si NMR spectra were obtained at 59.616 MHz (silicon-29) or 75.468 MHz (carbon-13) on a General Electric NMR Instruments model GN-300 equipped with a Doty Scientific 7 mm MAS probe. One pulse spectra were measured with a 1.0 μs pulse length (corresponding to a 20 degree tip angle) and a relaxation delay of 5.0 s (silicon) or 10 s (carbon) for 16,000 to 29,000 acquisitions while spinning at typically 5.0 kHz. Additional spectra (not shown) were acquired to assure quantitative NMR signal intensities. Proton decoupling during the 40 ms acquisition time was performed with a continuous 70 kHz radiofrequency field at 300.107 MHz. The time domain signal was conditioned with a Gaussian line-broadening function equivalent to 50 Hz prior to Fourier transformation.
Results and Discussion
In summary, we have synthesized a PMO with well-defined nanorice morphology. The particles are rather uniform and have a length of 600 nm and a width of 200 nm. A novel chain-type precusor with a DT2structural motif was used in the self-assembly process. The nanorice particles could be obtained in a surfactant templated self-assembly process without the need of a novel methodology or any other special aids.
We gratefully acknowledge the financial support from Lehigh University. We further thank Dr. Charles G. Coe and Michael F. Kimak for the N2gas sorption experiments. Dr. James E. Roberts is gratefully acknowledged for MAS NMR measurements. We further thank Dr. Chris Kiely and Dr. Dave Ackland for generously supporting our TEM investigations. Dr. G. Slade Cargill is gratefully acknowledged for supporting our X-ray diffraction experiments.
- Asefa T, MacLachlan MJ, Coombs N, Ozin GA: Nature. 1999, 402: 867. COI number [1:CAS:528:DC%2BD3cXitFSgtg%3D%3D]; Bibcode number [1999Natur.402..867A]Google Scholar
- Inagaki S, Guan S, Fukushima Y, Ohsuna T, Terasaki O: J. Am. Chem. Soc.. 1999, 121: 9611. COI number [1:CAS:528:DyaK1MXmt1yqsrw%3D] 10.1021/ja9916658View ArticleGoogle Scholar
- Melde BJ, Holland BT, Blanford CF, Stein A: Chem. Mater.. 1999, 11: 3302. COI number [1:CAS:528:DyaK1MXmsVensbc%3D] 10.1021/cm9903935View ArticleGoogle Scholar
- Guan S, Inagaki S, Ohsuna T, Terasaki O: J. Am. Chem. Soc.. 2000, 122: 5660. COI number [1:CAS:528:DC%2BD3cXjsFKjs7o%3D] 10.1021/ja000839eView ArticleGoogle Scholar
- Cho E-B, Kim D, Jaroniec M: Langmuir. 2007, 23: 11844. COI number [1:CAS:528:DC%2BD2sXhtFalurjF] 10.1021/la701948gView ArticleGoogle Scholar
- Cho E-B, Kim D, Jaroniec M: J. Phys. Chem. C. 2008, 112: 4897. COI number [1:CAS:528:DC%2BD1cXjtVShs7g%3D] 10.1021/jp710772wView ArticleGoogle Scholar
- Rebbin V, Schmidt R, Froeba M: Angew. Chem. Int. Ed.. 2006, 45: 5210. COI number [1:CAS:528:DC%2BD28Xot12mt7s%3D] 10.1002/anie.200504568View ArticleGoogle Scholar
- Slowing II, Vivero-Escoto JL, Wu C-W, Lin VSY: Adv. Drug Deliv. Rev.. 2008, 60: 1278. COI number [1:CAS:528:DC%2BD1cXosVOnsrg%3D] 10.1016/j.addr.2008.03.012View ArticleGoogle Scholar
- Che S, Liu Z, Ohsuna T, Sakamoto K, Terasaki O, Tatsumi T: Nature. 2004, 429: 281. COI number [1:CAS:528:DC%2BD2cXktVOqtbg%3D]; Bibcode number [2004Natur.429..281C] 10.1038/nature02529View ArticleGoogle Scholar
- Trewyn BG, Slowing II, Giri S, Chen H-T, Lin VSY: Acc. Chem. Res.. 2007, 40: 846. COI number [1:CAS:528:DC%2BD2sXotFSms7s%3D] 10.1021/ar600032uView ArticleGoogle Scholar
- H. Chen, J. He, Chem. Commun. (Camb.) 4422 (2008). doi: 10.1039/b807787h
- Rebolledo AF, Bomati-Miguel O, Marco JF, Tartaj P: Adv. Mater.. 2008, 20: 1760. COI number [1:CAS:528:DC%2BD1cXmslWjsrc%3D] 10.1002/adma.200701782View ArticleGoogle Scholar
- Srivastava D, Lee I: Adv. Mater.. 2006, 18: 2471. COI number [1:CAS:528:DC%2BD28XhtVOhsb7K] 10.1002/adma.200601123View ArticleGoogle Scholar
- Wiley BJ, Chen Y, McLellan J, Xiong Y, Li Z-Y, Ginger D, Xia Y: Nano. Lett.. 2007, 7: 1032. COI number [1:CAS:528:DC%2BD2sXisFSjtLY%3D] 10.1021/nl070214fView ArticleGoogle Scholar
- Wang H, Brandl Daniel W, Le F, Nordlander P, Halas Naomi J: Nano. Lett.. 2006, 6: 827. COI number [1:CAS:528:DC%2BD28Xit1Wmtrc%3D] 10.1021/nl060209wView ArticleGoogle Scholar
- Cha SI, Mo CB, Kim KT, Hong SH: J. Mater. Res.. 2005, 20: 2148. COI number [1:CAS:528:DC%2BD2MXosVehtb4%3D]; Bibcode number [2005JMatR..20.2148C] 10.1557/JMR.2005.0267View ArticleGoogle Scholar
- Guo W, Park J-Y, Oh M-O, Jeong H-W, Cho W-J, Kim I, Ha C-S: Chem. Mater.. 2003, 15: 2295. COI number [1:CAS:528:DC%2BD3sXjvVahsbk%3D] 10.1021/cm0258023View ArticleGoogle Scholar