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Interface Components: Nanoparticles, Colloids, Emulsions, Surfactants, Proteins, Polymers
Synthesis of Hollow Doughnut Shape Mesoporous Silica Nanoparticle: a Case of Self-assembly Composite Templates Nhat Tri Vo, Astam Kumar Patra, and Dukjoon Kim Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.7b03536 • Publication Date (Web): 13 Mar 2018 Downloaded from http://pubs.acs.org on March 14, 2018
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Scheme 1. Synthetic protocol and probable formation mechanism of hollow doughnut shape particle which is highly depends on the concentra-tion of ammonium metatungstate. Spherical MSN (MS1, AMT/CTAB=0), hollow sphere MSN (MS2, AMT/CTAB=0.0208), hollow doughnut MSN (MS3, AMT/CTAB=0.0416) and hollow MSN with three large pores (MS4, AMT/CTAB=0.0625). Schematic illustrations of the stepwise evolution of spherical, hollow sphere, hollow doughnut MSN and self-assemble structure of AMT/CTAB/L-arg composite nanoparticles. Self-assemble structure of AMT/CTAB/L-arg composite nanoparticles, MS3 as-synthesized particle showing the silica shell and AMT/CTAB/L-arg composite nanoparticles core and connection between particle by composite nanoparticles, MS3 after template removal. Schematic illustrations images of the stepwise evolution of hollow MSN with three large pores (MS4) and self-assemble structure of AMT/CTAB/Larg composite nanoparticles, self-assemble structure of AMT/CTAB/L-arg composite nanoparticles, MS4 assynthesized particle showing the silica shell and AMT/CTAB/L-arg composite nanoparticles core and connection between particle by composite nanoparticles, MS4 after template removal. 96x55mm (300 x 300 DPI)
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Figure 1. FESEM images of the (a) MS1 (AMT/CTAB=0), (b) MS2 (AMT/CTAB=0.0208), (c) MS3 (AMT/CTAB=0.0416), and (d) MS4 (AMT/CTAB=0.0625) mesoporous silica nanoparticles. The shapes of silica particle are sphere, hollow sphere, hollow doughnut shape and hollow MSN with three large pores, respectively. TEM image of a single particle is shown in the inset of the corresponding SEM image respectively. 62x46mm (300 x 300 DPI)
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Figure 2. N2 adsorption (●) − desorption (○) isotherms of the MS1, MS2, MS3, and MS4 nanoparticles. In inset the corresponding pore size distribution (PSD) curve for these samples obtained by NLDFT model. 66x52mm (300 x 300 DPI)
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Figure 3. SEM images of (a) MS5, (b) MS6, (c) MS7, and (d) MS8 nanoparticles synthesized at room temperature under different catalysts. 62x46mm (300 x 300 DPI)
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Figure 4. SEM images (a) MS9 and (b) MS10 nanoparticles synthesized at different temperature. 31x11mm (300 x 300 DPI)
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Figure 5. a) Bright-field TEM images analysis of the stepwise evolution of hollow doughnut MSN a1) selfassemble structure of AMT/CTAB/L-arg/Silica composite nanoparticles at 1 min for MS3 synthesis, a2) magnified high resolution TEM image of the correspond-ing the area marked ‘a2’ in Fig (a1). The selfassemble structure of AMT/CTAB/L-arg nanoparticle are clearly seen. a3-a4) MS3 as-synthesized particle showing the silica shell and AMT/CTAB/L-arg composite nanoparticles core and connection between particle by composite nanoparticles, a5-a6) MS3 after template removal with different magnification. b) Bright-field TEM images analysis of the of the stepwise evolution of hollow MSN with three large pores (MS4) and selfassemble structure of AMT/CTAB/L-arg composite nanoparticles. b1-b2) self-assemble structure of AMT/CTAB/L-arg composite nanoparticles, b2) magnified high resolution TEM image of the corresponding the area marked ‘b2’ in Fig. (b1). The self-assemble structure of AMT/CTAB/L-arg nanoparticles are clearly seen. b3-b4) MS4 as-synthesized particle showing the silica shell and AMT/CTAB/L-arg composite nanoparticles core and connection between particle by composite nanoparticles, here interestingly with increase the AMT concentration the connection between particle increase than MS3. b5-b6) MS4 after template removal with different magnification. 53x17mm (300 x 300 DPI)
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Figure 6. Zeta potential study of different stage of the reaction 68x54mm (300 x 300 DPI)
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Figure 8. HRTEM images and corresponding elemental mapping images of the hd-MSNs (a) MS3_1 min, (b) MS3_as-synthesized 24 h and (c) MS3_after template removal. Subscript (1) represent the HRTEM images of MS3 particle in different step of the reaction, (2) represent the Silicon mapping, (3) represent the Oxygen mapping, and (4) represent the Tungsten mapping. 51x31mm (300 x 300 DPI)
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Figure 9. XPS analysis of MS3_1 min and MS3_as-syn: (a) survey XPS and High resolution XPS of (b) N 1s (c) C 1s (d) O 1s (e) Si 2p (f) W 4f. 125x187mm (300 x 300 DPI)
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Figure 10. (a) PXRD of as-synthesized MS3 sample and calcined MS3 sample. (b) HRTEM image of calcined MS3 sample and corresponding elemental mapping images represent the (c) Silicon mapping, (d) the Oxygen mapping, and (e)Tungsten mapping. 133x209mm (300 x 300 DPI)
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