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3D Printing of Ordered Mesoporous Silica Complex Structures

Efrat Shukrun Farrell, Yaelle Schilt, May Yam Moshkovitz, Yael Levi-Kalisman, Uri Raviv,*
and Shlomo Magdassi*
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ABSTRACT: Ordered mesoporous silica materials gain high

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interest because of their potential applications in catalysis, selective

adsorption, separation, and controlled drug release. Due to their
morphological characteristics, mainly the tunable, ordered nano-
metric pores, they can be utilized as supporting hosts for confined
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chemical reactions. Applications of these materials, however, are

limited by structural design. Here, we present a new approach for
the 3D printing of complex geometry silica objects with an ordered
mesoporous structure by stereolithography. The process uses
photocurable liquid compositions that contain a structure-directing
agent, silica precursors, and elastomer-forming monomers that,
after printing and calcination, form porous silica monoliths. The
objects have extremely high surface area, 1900 m2/g, and very low
density and are thermally and chemically stable. This work enables the formation of ordered porous objects having complex
geometries that can be utilized in applications in both the industry and academia, overcoming the structural limitations associated
with traditional processing methods.
KEYWORDS: ordered mesoporous silica, 3D printing, DPL, porous materials, sol−gel

O rdered mesoporous silica are used in widespread

technological applications requiring both functionality
and high porosity such as catalysis,1 selective adsorption,2
oxides with thick walls that mechanically stabilize the
monolith.10
3D printing technology is a powerful additive manufacturing
separation,3 and controlled drug release,4 due to their tunable (AM) approach for fast, accurate, and customized fabrication
pore diameter (2−50 nm), uniform cylindrical structure,5 high of objects with complex geometries, in the macro-,11−15
chemical and thermal stability, and high surface area.6 meso-,16,17 and microscales.18−23 To the best of our knowl-
Applications of these materials, however, are limited by the edge, there are no reports yet on the formation of ordered
structural design of currently available methods. mesoporous structures by printing precursor solutions, which
One possible strategy to synthesize ordered mesoporous result in ordered monolithic complex structures at high
silica (OMS) is by blending silica-forming precursors with a resolution. The 3D printing reports in this field were
liquid crystal template. 7,8 The template is based on conducted by applying a direct ink writing (DIW) process,
concentrated surfactants that self-assemble into mesophase which is based on the extrusion of a viscous liquid and typically
micelles. The condensation polymerization of silica precursors has low resolution and structural complexity. The printed
by a sol−gel process is confined by the template, forming a compositions were based on either mesoporous particles
ceramic-like framework with an ordered orientation of dispersed in a liquid or a sol−gel composition. The first
channels (e.g., hexagonal, cubic, etc.). After condensation, an utilized the incorporation of mesoporous silica particles within
aging process takes place, making the formed silica framework a matrix, for biomedical applications, such as bone
stronger, though accompanied by shrinking of the obtained regeneration24,25 and drug delivery.26,27 The second approach
monolith.9 After the aging process, the organic templates can
used a sol−gel-based ink, composed of glycolated silanes and
be calcined, resulting in OMS monolith. Triblock copolymers
such as poly(ethylene oxide)−poly(propylene oxide)−poly-
(ethylene oxide) (PEO−PPO−PEO) surfactants are good Received: June 7, 2020
templating agents because of their microstructural ordering Revised: August 2, 2020
properties, amphiphilic character, commercial availability, and Published: August 4, 2020
biodegradability. Specifically, Pluronic F-127 is a unique
surfactant because it has a high molecular weight and long
hydrophilic chains, allowing the synthesis of mesoporous

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.nanolett.0c02364

6598 Nano Lett. 2020, 20, 6598−6605
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Figure 1. Fabrication process of ordered mesoporous silica monoliths. Schematic presentation of (a) the templating agent molecule, Pluronic F-
127; (b) hexagonal liquid crystalline arrangement of the rod micelles; (c) hydrolysis and condensation of the TEOS precursor around the
templating agent, resulting in the silica skeleton; (d) printing of the ink in a DLP printer; (e) printed hybrid object; and (f) mesostructure of the
calcined monoliths. Resulting objects: (g−i) printed OMS monoliths with high geometrical complexity (scale bars, 1 cm).

structure-directing agents, to fabricate hierarchical porous silica The presented process for the fabrication of complex objects
objects.28 However, these objects do not have a very high with porous structures is based on the formation of new ink
surface area, only 100−700 m2/g, and their structural compositions, 3D printing, aging, and calcination, as schemati-
complexity and resolution are limited. It is therefore highly cally shown in Figure 1. The ink solutions are composed of a
desired to develop new AM pathways for the fabrication of templating agent, silica precursor, and polymerizable mono-
high-resolution, complex 3D objects, with ordered porous mers. The templating agent, F-127, leads to the formation of a
microstructures that enable very high surface area, while hexagonal liquid crystalline structure, composed of rodlike
utilizing the beneficial features of silica such as high thermal micelles (Figure 1a,b). When the silica precursor, tetraethyl
and mechanical stabilities. orthosilicate (TEOS), is added, a sol−gel process begins to
Here, we utilize digital light processing (DLP) printing, form a silica skeleton around the rodlike micelles, by hydrolysis
which is a stereolithography 3D printing technology which and condensation reactions (Figure 1c). For enabling the
photopolymerization process by the DLP printing, the above
applies a patterned UV light to cure sequential 2D layers of
solution is mixed with a UV-curable monomer composition
UV-polymerizable ink to create OMS 3D objects. This
that was previously reported by us, which leads to highly elastic
technology is characterized by micrometer-resolution abilities,
polymer upon UV exposure.31 The UV-curable composition is
fast processing speed, and the capability of generating highly a mixture of epoxy aliphatic acrylate monofunctional
complex 3D objects from macro- to microscale without monomer, aliphatic urethane diacrylate cross-linker, and a
support materials.29,30 The printed objects have unprecedented photoinitiator (PI). During the UV irradiation, the PI initiates
complexity while maintaining a highly ordered mesoporous a localized photopolymerization of the organic monomers,
structure of silica (OMS) monolith, with very low density and corresponding to the desired computer-aided design (CAD)
extremely high surface area due to the nanometric hierarchical model (Figure 2a), to form an elastomeric polymeric organic
structure. This state-of-the-art printing process bypasses the network that confines the ordered silica−surfactant network
structural limitations associated with OMS monolith fabrica- (Figure 2b). The role of the stretchable organic network is
tion, a significant step toward new and improved reactors and crucial for preventing the deformation of the ordered
thermal insulators. microstructure, occurring later during the sol−gel aging
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Figure 2. Hexagonal morphology of the printed objects. The CAD model (a), a printed object with hybrid ink (b), an object aged at 22 °C for 1
week (c), and calcined printed monolith (d). (e, f) STEM micrographs showing the pores viewed along the (1, 0) direction. (h, i) STEM
micrographs showing the arrangement of the rods viewed along the (1, 1) direction. (g, j) Corresponding overlay mapping of Si (blue) and O
(green) based on EDS scans.

process, which causes a shrinkage of the silica network (12 ± 5 showed a type IV isotherm according to the IUPAC
vol %) (Figure 2c). The last stage of the OMS fabrication classification of SBA-15 mesoporous structures. The BET
process is calcination at high temperature. During the surface area of the OMS objects was calculated to be 1900 ±
calcination process performed at 700 °C, the organic polymer 80 m2/g, which is about twice the highest value reported so far
and the liquid crystal template decompose, and isotopic for monoliths prepared from solutions32 in using Pluronic F-
shrinkage is observed (61.8 ± 0.8 vol %) (Figure 2d). The 127 as a template, and comparable to the highest surface area
resulting objects (Figure 1f−i) are mesoporous monoliths for OMS powders obtained by any other surfactant.33 The
having a high geometrical complexity and a very low density of pore size distribution was analyzed by Barrett−Joyner−
0.26 ± 0.02 g/mL. Halenda (BJH) desorption plots, showing an average size of
The calcined 3D-printed porous objects were visualized by 5.6 ± 0.3 nm (Figure 3b), in agreement with the observations
SEM (Figure S1) and STEM. Figure 2e,f,h−i shows the in the STEM images (Figure 2f). The low density of the
hexagonal morphology, with an average pore size of 5.7 ± 0.3 objects, 0.26 ± 0.02 g/mL, is a result of both the mesopores
nm and an average silica wall thickness of 6.3 ± 0.3 nm. An within the ordered structure and the macropores occurring
energy-dispersive X-ray spectroscopy (EDS) analysis con- during the fabrication process. The contribution of the
firmed that the final monolith contained only Si and O atoms macrosize pores (seen in Figure S1) to the object volume
(Figure 2g,j), in agreement with thermal gravimetric analysis was calculated as follows: from the BJH desorption results, the
(TGA) showing no weight loss after heating the calcined total volume of the nanometric pores is 2.7 ± 0.2 cm3/g. The
monoliths to 950 °C, as expected (Figure S2). volume of the objects used for density measurements was 3.8
To further study the mesoporous printed structures, N2 ± 0.3 cm3/g, and the volume of the silica is 0.37 cm3/g.
adsorption−desorption measurements and small-angle X-ray Therefore, the volume of the macropores is 0.7 ± 0.4 cm3/g,
scattering (SAXS) measurements were performed. The surface which means that approximately 78% of the volume of the
area was calculated from the BET curves (Figure 3a) which objects results from the presence of the nanopores. SAXS
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Figure 3. Characterization of the mesoporous structure of calcined 3D-printed monolith. (a) BET isotherm. (b) Pore volume distribution. The
pore volume means the total volume of the pores at a specific diameter, in cm3/(g nm) as evaluated from the BJH desorption measurements. (c)
SAXS intensity as a function of the magnitude of the scattering vector, q, showing a hexagonal phase with a lattice size of 12.06 nm (peak indexes
are indicated in the figure). The inset shows an STEM image (scale bar, 10 nm).

measurements show the typical three peaks of SBA-15 which lattices’ symmetry could not be determined. However, they are
were indexed into a 2D hexagonal phase, with a lattice size of likely to be hexagonal phases, as observed at 40 and 22 °C and
12.06 nm (Figure 3c). The (1, 1) peak was not observed revealed from the TEM images of the sample (Figure S4).
because it was localized at a minimum of the form factor of a Figure 4d presents the nearest neighbor distance between the
long cylinder. pores, as a function of the aging temperature, assuming that the
We attribute the high surface area of this material to the high organization of the hollow cylinders is hexagonal.
order of the pores and high pore density. To evaluate the best The liquid crystal template is a key factor in determining the
ink composition for the fabrication of OMS, objects with order of the final monolith. Figure 5a presents the cryo-TEM
various ratios of liquid-crystal solution to elastomer were image of the template before the silica precursor addition,
prepared and measured by SAXS. Figure 4a shows scattering visualizing large arrays of long wormlike mesophase micelles.
curves from the ordered mesoporous structure with 50%, 45%, Image analysis of the micelles shows a wall to wall thickness of
and 60% elastomer. Figure 4b shows line-shape analysis of the 8.2 ± 0.4 nm. Scattering curves at low (Figure 5b) and high
first correlation peak, extracting the hexagonal lattice (Figure 5c) q values from the micellar solution, measured in
parameter as well as the average domain size (the length our wide-angle X-ray scattering (WAXS) setup,35 reveal and
over which positional correlations are maintained) of the confirm the hexagonal phase of elongated F-127 micelles, with
ordered structure.34 The largest ordered domain size was a lattice size of 7.98 nm in agreement with the image analysis
obtained with 50% elastomer. Two hexagonal phases coexisted data. The main peaks visible at the wide-angle signal are
when the ratio was 40% or 70%. These samples had a small characteristic of the PEO monoclinic crystalline phase36,37 with
bump at very low q, arising from a loose arrangement with a lattice parameters of a = 0.804 nm, b = 1.30 nm, c = 1.95 nm,
correlation distance of about 30 nm. The low-order pore and β = 125.4°. After the addition of TEOS, the center-to-
arrangement can be seen from the TEM images presented in center lattice spacing is 14.3 ± 0.5 nm, and the arrangement of
Figure S3. the pores is hexagonal (Figure S5).
The aging process of the sol−gel also affected the order of In summary, we described a 3D printing process to fabricate
the pores due to the change of the micelles’ arrangements at SBA-15 silica composed of highly ordered, nanometric pores.
various temperatures. To investigate the optimal aging The 3D printing of these inorganic monoliths enables the
conditions, printed hybrid objects with inks consisting of construction of complex shaped objects, which have chemical
50% of elastomer were aged at several temperatures between resistance,38 are stable at elevated temperatures, and have very
−18 and 60 °C, prior to calcination. The absence of high low density with an extremely high surface area. This opens the
harmonic correlation peaks in the SAXS data at 60, 4, and −18 way for many applications such as catalysis, adsorption,
°C (Figure 4c) shows that the level of order was lower separation, and thermal insulators in which the performance
compared with the samples which were aged at 40 and 22 °C, of materials with high surface area can be improved by shaping
suggesting that there is a narrow range of temperature that them into specific structures, such as catalytic plug-flow
supports higher order. Aging at 4 °C showed two adjacent reactors.39 An additional field in which the presented approach
peaks, corresponding to two arrangements of pores. As only can be utilized is bioprinting, for example, in the fabrication of
the first harmonics of both arrangements were detected, the bioceramic scaffolds for bone regeneration.40,41 Although we
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Figure 4. (a) SAXS curves from the monoliths with different elastomer percentages. (b) Hexagonal lattice size and domain size (the length along
which positional correlations are maintained) based on line-shape analysis of the data in part a, as a function of the elastomer percentages. In the
case of the coexistence of two ordered structures, the parameters of the secondary structures are represented by red symbols. (c) SAXS curves from
the printed monoliths, aged at various temperatures. (d) Center-to-center hexagonal lattice spacing and domain size based on the data in part c, as a
function of aging temperature. In the case of the coexistence of two ordered structures, the parameters of the secondary structures are represented
by red symbols.

Figure 5. Cryo-TEM image (a) and small- (b) and wide-angle (c) X-ray scattering curves of solutions of Pluronic F-127 in water and ethanol
(14:33:8 wt %).

report here on mesoporous silica, the same approach can be (tripled distilled water) and 1 wt %, 2 M HCl solution (Sigma-
applied for a variety of other ceramic materials. We expect that Aldrich) were added, and the solution was stirred for another 1
the same type of compositions can be utilized in two-photon min at 35 °C. Then, the solution was cooled down to room
printing, to yield micron-size objects with submicron features. temperature (RT) under stirring for 15 min, and 45 wt % of
Experimental Section. Ink Preparation. The sol−gel TEOS (tetraethoxysilane, 98%, Alfa Aesar) was added slowly
solution was prepared as follows: 14 wt % Pluronic F-127 into the solution. For the preparation of the UV-curable
(Sigma-Aldrich) was slowly added to 33 wt % warm (35 °C) stretchable ink, aliphatic urethane diacrylate (Ebecryl 8413,
ethanol (ethanol absolute, ACROS Organics) under stirring. Allnex), epoxy aliphatic acrylate (Ebecryl 113, Allnex), and
After the full dissolution of the Pluronic F-127, 7 wt % TDW TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide, IGM)
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with a weight ratio of 48.5:48.5:6, respectively, were mixed for were examined at −177 °C using an FEI Tecnai 12 G2 TWIN
1 h at 50 °C until a homogeneous solution was obtained. TEM instrument operated at 120 kV and equipped with a
Before printing, the sol−gel solution and the stretchable ink Gatan 626 cold stage. TIA (Tecnai Imaging & Analysis)
were mixed for 5 min at different wt % ratios (usually 50:50). software was used to record the images in low-dose mode by a
Sample Fabrication. A predesigned CAD model was 3D- 4K × 4K FEI Eagle CCD (charge-coupled device) camera.
printed using a DLP 3D printer (Freeform PICO 2, Asiga). The specific surface area and pore size distribution were
This printer operates by a UV-LED light source (385 nm), measured with the use of a N2 adsorption−desorption
with a light intensity of 30 mW/cm2. The printer bath was apparatus (Micromeritics ASAP 2020), at −196 °C. All
filled with the ink, and the exposure was set to be 6 s for a layer samples were degassed under vacuum at 120 °C for 10 h
thickness of 200 μm. After 3D printing, the structures were before analysis. The surface area was calculated using the BET
kept in an open vessel at temperatures from −18 to 60 °C for 1 equation, over acquired adsorption data in the P/P0 range
week. Then, the aged samples were calcined at 700 °C (heating 00.2−1. The pore distribution was analyzed using the BJH
profile, 1 °C/min to 480 °C for 4 h, then 1 °C/min to 700 °C method, over the acquired desorption data points.
for 2 h).
Characterization. Shrinkage and the density were measured
by a caliber for printed cube models with a size of 5 × 5 × 5
■
*
ASSOCIATED CONTENT
sı Supporting Information
mm3, after printing, aging, and calcination. The Supporting Information is available free of charge at
TGA measurements of the objects were performed with a https://pubs.acs.org/doi/10.1021/acs.nanolett.0c02364.
TGA/DSC1 stare system Mettler−Toledo in the range 25− SEM images, TEM images of objects with varies
950 °C at a heating rate of 1 °C/min under air. elastomer percentages, TEM images of objects aged at
Small-/wide-angle X-ray scattering (SAXS/WAXS) measure- different aging temperatures, cryo-TEM of the liquid
ments were performed using the Kα photons with an energy of crystal template with the silica precursor, and TGA of
8 keV (λ = 1.54 Å) and X-ray beam size defined by two the objects (PDF)
scatterless slits whose opening were set to be 1 × 1 mm2 and
600 × 600 μm2. Azimuthal integration of the 2D scattering
pattern was performed using FIT2D.42 Before each measure-
ment, silver behenate was used as a standard to determine the
■ AUTHOR INFORMATION
Corresponding Authors
sample-to-detector distance (about 1850 mm for the SAXS Uri Raviv − Institute of Chemistry and Center for Nanoscience
setup and 450 mm for the WAXS setup).43 Before measure- and Nanotechnology, The Hebrew University of Jerusalem,
ments, samples were prepared as powders and introduced into 91904 Jerusalem, Israel; orcid.org/0000-0001-5992-9437
a thin quartz capillary (1.5 mm in diameter and a wall Shlomo Magdassi − Institute of Chemistry and Center for
thickness of 0.01 mm) to minimize beam absorption by the Nanoscience and Nanotechnology, The Hebrew University of
sample holder. The scattering signal of an empty capillary was Jerusalem, 91904 Jerusalem, Israel; orcid.org/0000-0002-
measured and used as a background measurement. The 6794-0553
background-subtracted data were analyzed using our home- Authors
developed cutting edge data analysis software X+44 and D+.45 Efrat Shukrun Farrell − Institute of Chemistry and Center for
Whereas D+ computes exactly, without approximation, the Nanoscience and Nanotechnology, The Hebrew University of
scattering of the ordered structure, according to the parameters Jerusalem, 91904 Jerusalem, Israel
introduced in the model (radius of the pores, D spacing, and Yaelle Schilt − Institute of Chemistry and Center for
domain size), X+ uses the Warren’s approximation34 in order Nanoscience and Nanotechnology, The Hebrew University of
to calculate the average domain size of the organized hollow Jerusalem, 91904 Jerusalem, Israel
cylinders. May Yam Moshkovitz − Institute of Chemistry and Center for
Direct imaging of the samples was performed by electron Nanoscience and Nanotechnology, The Hebrew University of
microscopy. The slicing of the printed object for the STEM Jerusalem, 91904 Jerusalem, Israel
imaging was performed by a focused ion beam (FIB) Yael Levi-Kalisman − Institute of Chemistry and Center for
instrument (Helios 460F1, FEI), after selective coating of the Nanoscience and Nanotechnology, The Hebrew University of
surface-of-interest with a layer of platinum to prevent Jerusalem, 91904 Jerusalem, Israel; orcid.org/0000-0002-
damaging of the sample. STEM imaging was performed 2764-2738
using a Themis-Z instrument equipped with a superX EDX
probe (Thermo Fisher Scientific). TEM images were obtained Complete contact information is available at:
with the use of a high-resolution transmission scanning https://pubs.acs.org/10.1021/acs.nanolett.0c02364
electron microscope (Tecnai F20 G2), and SEM images
were obtained with the use of an extra-high-resolution Author Contributions
scanning electron microscope (XHR Magellan 400L). The The manuscript was written through the contributions of all
imaging of the micelle solution in their native, aqueous authors. All authors have approved the final version of the
environment was performed using cryogenic transmission manuscript.
electron microscopy (cryo-TEM). In this method, a drop (2.5 Notes
μL) of the solution was deposited on a glow-discharged TEM The authors declare no competing financial interest.
grid (300 mesh Cu Lacey substrate, Ted Pella, Ltd.). A
Vitrobot Mark IV (FEI) instrument was used to blot the excess
liquid in a controlled environment (temperature and humidity)
■ ACKNOWLEDGMENTS
This research was supported by the Israel Ministry of Science,
and to vitrify the specimens by a rapid plunging into liquid The Israel Ministry of Defense and Technology and the
ethane precooled with liquid nitrogen. The vitrified samples National Research Foundation, Prime Minister’s Office,
6603 https://dx.doi.org/10.1021/acs.nanolett.0c02364
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Singapore under its Campus of Research Excellence and (22) Lefevere, J.; Protasova, L.; Mullens, S.; Meynen, V. 3D-Printing
Technological Enterprise (CREATE) program. of Hierarchical Porous ZSM-5: The Importance of the Binder System.

■
Mater. Des. 2017, 134, 331−341.
(23) Thakkar, H.; Eastman, S.; Hajari, A.; Rownaghi, A. A.; Knox, J.
REFERENCES C.; Rezaei, F. 3D-Printed Zeolite Monoliths for CO2 Removal from
(1) Sujandi; Han, S. C.; Han, D. S.; Jin, M. J.; Park, S. E. Catalytic Enclosed Environments. ACS Appl. Mater. Interfaces 2016, 8 (41),
Oxidation of Cycloolefins over Co(Cyclam)-Functionalized SBA-15 27753−27761.
Material with H2O2. J. Catal. 2006, 243 (2), 410−419. (24) Li, C.; Jiang, C.; Deng, Y.; Li, T.; Li, N.; Peng, M.; Wang, J.
(2) Asgari, M. S.; Zonouzi, A.; Rahimi, R.; Rabbani, M. Application RhBMP-2 Loaded 3D-Printed Mesoporous Silica/Calcium Phosphate
of Porphyrin Modified Sba-15 in Adsorption of Lead Ions from Cement Porous Scaffolds with Enhanced Vascularization and
Aqueous Media. Orient. J. Chem. 2015, 31 (3), 1537−1544. Osteogenesis Properties. Sci. Rep. 2017, 7, 41331.
(3) Lee, J. W.; Cho, D. L.; Shim, W. G.; Moon, H. Application of (25) Zhang, J.; Zhao, S.; Zhu, Y.; Huang, Y.; Zhu, M.; Tao, C.;
Mesoporous MCM-48 and SBA-15 Materials for the Separation of Zhang, C. Three-Dimensional Printing of Strontium-Containing
Biochemicals Dissolved in Aqueous Solution. Korean J. Chem. Eng. Mesoporous Bioactive Glass Scaffolds for Bone Regeneration. Acta
2004, 21 (1), 246−251. Biomater. 2014, 10 (5), 2269−2281.
(4) Fathi Vavsari, V.; Mohammadi Ziarani, G.; Badiei, A. The Role (26) Zhu, M.; Li, K.; Zhu, Y.; Zhang, J.; Ye, X. 3D-Printed
of SBA-15 in Drug Delivery. RSC Adv. 2015, 5, 91686−91707. Hierarchical Scaffold for Localized Isoniazid/Rifampin Drug Delivery
(5) Chaudhary, V.; Sharma, S. An Overview of Ordered Mesoporous and Osteoarticular Tuberculosis Therapy. Acta Biomater. 2015, 16
Material SBA-15: Synthesis, Functionalization and Application in (1), 145−155.
Oxidation Reactions. J. Porous Mater. 2017, 24 (3), 741−749. (27) Pei, P.; Tian, Z.; Zhu, Y. 3D Printed Mesoporous Bioactive
(6) Salimian, S.; Zadhoush, A.; Mohammadi, A. A Review on New Glass/Metal-Organic Framework Scaffolds with Antitubercular Drug
Mesostructured Composite Materials: Part I. Synthesis of Polymer- Delivery. Microporous Mesoporous Mater. 2018, 272, 24−30.
Mesoporous Silica Nanocomposite. J. Reinf. Plast. Compos. 2018, 37 (28) Putz, F.; Scherer, S.; Ober, M.; Morak, R.; Paris, O.; Hüsing, N.
(7), 441−459. 3D Printing of Hierarchical Porous Silica and α-Quartz. Adv. Mater.
(7) Hoffmann, F.; Cornelius, M.; Morell, J.; Fröba, M. Silica-Based Technol. 2018, 3 (7), 1800060.
Mesoporous Organic-Inorganic Hybrid Materials. Angew. Chem., Int. (29) Zheng, X.; Deotte, J.; Alonso, M. P.; Farquar, G. R.;
Weisgraber, T. H.; Gemberling, S.; Lee, H.; Fang, N.; Spadaccini,
Ed. 2006, 45, 3216−3251.
C. M. Design and Optimization of a Light-Emitting Diode Projection
(8) Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.;
Micro-Stereolithography Three-Dimensional Manufacturing System.
Beckt, J. S. Ordered Mesoporous Molecular Sieves Synthesized by a
Rev. Sci. Instrum. 2012, 83 (12), 125001.
Liquid-Crystal Template Mechanism. Nature 1992, 359, 710.
(30) Pawar, A. A.; Saada, G.; Cooperstein, I.; Larush, L.; Jackman, J.
(9) Buckley, A. M.; Greenblatt, M. J. Chem. Educ. 1994, 71, 599.
A.; Tabaei, S. R.; Cho, N. J.; Magdassi, S. High-Performance 3D
(10) Feng, P.; Bu, X.; Pine, D. J. Control of Pore Sizes in
Printing of Hydrogels by Water-Dispersible Photoinitiator Nano-
Mesoporous Silica Templated by Liquid Crystals in Block
particles. Sci. Adv. 2016, 2 (4), e1501381.
Copolymer-Cosurfactant-Water Systems. Langmuir 2000, 16, 5304.
(31) Patel, D. K.; Sakhaei, A. H.; Layani, M.; Zhang, B.; Ge, Q.;
(11) Kotz, F.; Arnold, K.; Bauer, W.; Schild, D.; Keller, N.;
Magdassi, S. Highly Stretchable and UV Curable Elastomers for
Sachsenheimer, K.; Nargang, T. M.; Richter, C.; Helmer, D.; Rapp, B.
Digital Light Processing Based 3D Printing. Adv. Mater. 2017, 29
E. Three-Dimensional Printing of Transparent Fused Silica Glass. (15), 1606000.
Nature 2017, 544 (7650), 337−339. (32) Feng, P.; Bu, X.; Stucky, G. D.; Pine, D. J. Monolithic
(12) Sydney Gladman, A.; Matsumoto, E. A.; Nuzzo, R. G.; Mesoporous Silica Templated by Microemulsion Liquid Crystals. J.
Mahadevan, L.; Lewis, J. A. Biomimetic 4D Printing. Nat. Mater. Am. Chem. Soc. 2000, 122 (5), 994−995.
2016, 15 (4), 413−418. (33) Bera, B.; Das, N. Synthesis of High Surface Area Mesoporous
(13) Eckel, Z. C.; Zhou, C.; Martin, J. H.; Jacobsen, A. J.; Carter, W. Silica SBA-15 for Hydrogen Storage Application. Int. J. Appl. Ceram.
B.; Schaedler, T. A. Additive Manufacturing of Polymer-Derived Technol. 2019, 16 (1), 294−303.
Ceramics. Science (Washington, DC, U. S.) 2016, 351 (6268), 58−62. (34) Warren, B. E. X-Ray Diffraction in Random Layer Lattices.
(14) Cooperstein, I.; Shukrun, E.; Press, O.; Kamyshny, A.; Phys. Rev. 1941, 59 (9), 693−698.
Magdassi, S. Additive Manufacturing of Transparent Silica Glass (35) Nadler, M.; Steiner, A.; Dvir, T.; Szekely, O.; Szekely, P.;
from Solutions. ACS Appl. Mater. Interfaces 2018, 10 (22), 18879− Ginsburg, A.; Asor, R.; Resh, R.; Tamburu, C.; Peres, M.; Raviv, U.
18885. Following the Structural Changes during Zinc-Induced Crystallization
(15) Shukrun, E.; Cooperstein, I.; Magdassi, S. 3D-Printed Organic- of Charged Membranes Using Time-Resolved Solution X-Ray
Ceramic Complex Hybrid Structures with High Silica Content. Adv. Scattering. Soft Matter 2011, 7, 1512−1523.
Sci. 2018, 5 (8), 1800061. (36) Shatalova, O. V.; Krivandin, A. V.; Aksenova, N. A.; Solov’eva,
(16) Smay, J. E.; Cesarano, J.; Lewis, J. A. Colloidal Inks for Directed A. B. Structure of Pluronic F-127 and Its Tetraphenylporphyrin
Assembly of 3-D Periodic Structures. Langmuir 2002, 18, 5429. Complexes: X-Ray Diffraction Study. Polym. Sci., Ser. A 2008, 50 (4),
(17) Tubío, C. R.; Guitián, F.; Gil, A. Fabrication of ZnO Periodic 417−421.
Structures by 3D Printing. J. Eur. Ceram. Soc. 2016, 36 (14), 3409− (37) Takahashi, Y.; Tadokoro, H. Structural Studies of Polyethers,
3415. (-(CH 2)m-O-) n. X. Crystal Structure of Poly(Ethylene Oxide).
(18) Xia, X.; Afshar, A.; Yang, H.; Portela, C. M.; Kochmann, D. M.; Macromolecules 1973, 6 (5), 672−675.
Di Leo, C. V.; Greer, J. R. Electrochemically Reconfigurable (38) Glasspoole, B. W.; Webb, J. D.; Crudden, C. M. Catalysis with
Architected Materials. Nature 2019, 573 (7773), 205−213. Chemically Modified Mesoporous Silicas: Stability of the Meso-
(19) Saha, S. K.; Wang, D.; Nguyen, V. H.; Chang, Y.; Oakdale, J. S.; structure under Suzuki-Miyaura Reaction Conditions. J. Catal. 2009,
Chen, S. C. Scalable Submicrometer Additive Manufacturing. Science 265 (2), 148−154.
(Washington, DC, U. S.) 2019, 366 (6461), 105−109. (39) Lu, Z.; Cao, J.; Song, Z.; Li, D.; Lu, B. Research Progress of
(20) Vyatskikh, A.; Delalande, S.; Kudo, A.; Zhang, X.; Portela, C. Ceramic Matrix Composite Parts Based on Additive Manufacturing
M.; Greer, J. R. Additive Manufacturing of 3D Nano-Architected Technology. Virtual and Physical Prototyping 2019, 14, 333−348.
Metals. Nat. Commun. 2018, 9 (1), 1−8. (40) Shie, M.-Y.; Fang, H.-Y.; Lin, Y.-H.; Kai-Xing Lee, A.; Yu, J.;
(21) Halevi, O.; Tan, J. M. R.; Lee, P. S.; Magdassi, S. Hydrolytically Chen, Y.-W. Application of Piezoelectric Cells Printing on Three-
Stable MOF in 3D-Printed Structures. Adv. Sustain. Syst. 2018, 2 (2), Dimensional Porous Bioceramic Scaffold for Bone Regeneration. Int.
1700150. J. Bioprinting 2019, 5 (2), 22.

6604 https://dx.doi.org/10.1021/acs.nanolett.0c02364
Nano Lett. 2020, 20, 6598−6605
Nano Letters pubs.acs.org/NanoLett Letter

(41) An, J.; Chua, C. K.; Mironov, V. A Perspective on 4D

Bioprinting. Int. J. Bioprinting 2016, 2 (1), 3−5.
(42) Hammersley, A. P.; Svensson, S. O.; Hanfland, M.; Fitch, A. N.;
Hausermann, D. Hammersley - High Pressure Research - 1996 - Two-
Dimensional Detector Software from Real Detector to Idealised
Image or Two-Theta Scan.Pdf. High Pressure Res. 1996, 14, 235.
(43) Huang, T. C.; Toraya, H.; Blanton, T. N.; Wu, Y. X-Ray
Powder Diffraction Analysis of Silver Behenate, a Possible Low-Angle
Diffraction Standard. J. Appl. Crystallogr. 1993, 26 (2), 180−184.
(44) Ben-Nun, T.; Ginsburg, A.; Székely, P.; Raviv, U. X+: A
Comprehensive Computationally Accelerated Structure Analysis Tool
for Solution X-Ray Scattering from Supramolecular Self-Assemblies. J.
Appl. Crystallogr. 2010, 43 (6), 1522−1531.
(45) Ginsburg, A.; Ben-Nun, T.; Asor, R.; Shemesh, A.; Fink, L.;
Tekoah, R.; Levartovsky, Y.; Khaykelson, D.; Dharan, R.; Fellig, A.;
Raviv, U. D+: Software for High-Resolution Hierarchical Modeling of
Solution X-Ray Scattering from Complex Structures. J. Appl.
Crystallogr. 2019, 52 (1), 219−242.

6605 https://dx.doi.org/10.1021/acs.nanolett.0c02364
Nano Lett. 2020, 20, 6598−6605