Template-Induced Structuring and Tunable Polymorphism of Three-Dimensionally Ordered Mesoporous (3DOm) Metal Oxides
Abstract
Convectively assembled colloidal crystal templates, comprised of size-tunable (ca. 15-50 nm) silica (SiO2) nanoparticles, enable versatile sacrificial templating of three-dimensionally ordered mesoporous (3DOm) metal oxides (MOx) at both mesoscopic and microscopic size-scales. Specifically, we show for titania (TiO2) and zirconia (ZrO2) how this approach not only enables the engineering of the mesopore size, pore volume, and surface area but can also be leveraged to tune crystallite polymorphism of the resulting 3DOm metal oxides. Template-mediated volumetric (i.e., interstitial) effects and interfacial factors are shown to preserve the metastable crystalline polymorphs of each corresponding 3DOm oxide (i.e., anatase TiO2 (A-TiO2) and tetragonal ZrO2 (t-ZrO2)) during high-temperature calcination. Mechanistic investigations suggest that this polymorph stabilization is derived from the combined effects of the templatereplica (MOx/SiO2) interface and simultaneous interstitial confinement that limits the degree of coarsening during high temperature calcination of the template-replica composite. The result is the identification of a facile yet versatile templating strategy for realizing 3DOm oxides with (i) surface areas that are more than an order of magnitude larger than those untemplated control samples, (ii) pore diameters and volumes that can be tuned across a continuum of size-scales, and (iii) selectable polymorphism.
- Authors:
-
- Lehigh Univ., Bethlehem, PA (United States). Dept. of Chemical and Biomolecular Engineering
- Lehigh Univ., Bethlehem, PA (United States). Dept. of Chemical and Biomolecular Engineering
- Department of Chemical and Biomolecular Engineering and ‡Department of Materials Science and Engineering, Lehigh University, Bethlehem, Pennsylvania 18015, United States
- Lehigh Univ., Bethlehem, PA (United States). Dept. of Chemical and Biomolecular Engineering, and Dept. of Materials Science and Engineering
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1469843
- Grant/Contract Number:
- SC0001004
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Langmuir
- Additional Journal Information:
- Journal Volume: 33; Journal Issue: 26; Related Information: CCEI partners with the University of Delaware (lead); Brookhaven National Laboratory; California Institute of Technology; Columbia University; University of Delaware; Lehigh University; University of Massachusetts, Amherst; Massachusetts Institute of Technology; University of Minnesota; Pacific Northwest National Laboratory; University of Pennsylvania; Princeton University; Rutgers University; Journal ID: ISSN 0743-7463
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; catalysis (homogeneous); catalysis (heterogeneous); biofuels (including algae and biomass); bio-inspired, hydrogen and fuel cells; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)
Citation Formats
Gregory, Daniel G., Guo, Qianying, Lu, Li, Kiely, Christopher J., and Snyder, Mark A. Template-Induced Structuring and Tunable Polymorphism of Three-Dimensionally Ordered Mesoporous (3DOm) Metal Oxides. United States: N. p., 2017.
Web. doi:10.1021/acs.langmuir.7b01112.
Gregory, Daniel G., Guo, Qianying, Lu, Li, Kiely, Christopher J., & Snyder, Mark A. Template-Induced Structuring and Tunable Polymorphism of Three-Dimensionally Ordered Mesoporous (3DOm) Metal Oxides. United States. https://doi.org/10.1021/acs.langmuir.7b01112
Gregory, Daniel G., Guo, Qianying, Lu, Li, Kiely, Christopher J., and Snyder, Mark A. Mon .
"Template-Induced Structuring and Tunable Polymorphism of Three-Dimensionally Ordered Mesoporous (3DOm) Metal Oxides". United States. https://doi.org/10.1021/acs.langmuir.7b01112. https://www.osti.gov/servlets/purl/1469843.
@article{osti_1469843,
title = {Template-Induced Structuring and Tunable Polymorphism of Three-Dimensionally Ordered Mesoporous (3DOm) Metal Oxides},
author = {Gregory, Daniel G. and Guo, Qianying and Lu, Li and Kiely, Christopher J. and Snyder, Mark A.},
abstractNote = {Convectively assembled colloidal crystal templates, comprised of size-tunable (ca. 15-50 nm) silica (SiO2) nanoparticles, enable versatile sacrificial templating of three-dimensionally ordered mesoporous (3DOm) metal oxides (MOx) at both mesoscopic and microscopic size-scales. Specifically, we show for titania (TiO2) and zirconia (ZrO2) how this approach not only enables the engineering of the mesopore size, pore volume, and surface area but can also be leveraged to tune crystallite polymorphism of the resulting 3DOm metal oxides. Template-mediated volumetric (i.e., interstitial) effects and interfacial factors are shown to preserve the metastable crystalline polymorphs of each corresponding 3DOm oxide (i.e., anatase TiO2 (A-TiO2) and tetragonal ZrO2 (t-ZrO2)) during high-temperature calcination. Mechanistic investigations suggest that this polymorph stabilization is derived from the combined effects of the templatereplica (MOx/SiO2) interface and simultaneous interstitial confinement that limits the degree of coarsening during high temperature calcination of the template-replica composite. The result is the identification of a facile yet versatile templating strategy for realizing 3DOm oxides with (i) surface areas that are more than an order of magnitude larger than those untemplated control samples, (ii) pore diameters and volumes that can be tuned across a continuum of size-scales, and (iii) selectable polymorphism.},
doi = {10.1021/acs.langmuir.7b01112},
journal = {Langmuir},
number = 26,
volume = 33,
place = {United States},
year = {Mon Jun 12 00:00:00 EDT 2017},
month = {Mon Jun 12 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Synthesis of non-siliceous mesoporous oxides
journal, January 2014
- Gu, Dong; Schüth, Ferdi
- Chem. Soc. Rev., Vol. 43, Issue 1
Catalysis Center for Energy Innovation for Biomass Processing: Research Strategies and Goals
journal, October 2010
- Vlachos, Dionisios G.; Chen, Jingguang G.; Gorte, Raymond J.
- Catalysis Letters, Vol. 140, Issue 3-4
STAFF-INDUSTRY COLLABORATIVE REPORT Vapor-Phase Production of Colloidal Silica
journal, March 1959
- White, Laurence; Duffy, George
- Industrial & Engineering Chemistry, Vol. 51, Issue 3
Recommendations for the characterization of porous solids (Technical Report)
journal, January 1994
- Rouquerol, J.; Avnir, D.; Fairbridge, C. W.
- Pure and Applied Chemistry, Vol. 66, Issue 8, p. 1739-1758
Synthesis of Macroporous Minerals with Highly Ordered Three-Dimensional Arrays of Spheroidal Voids
journal, July 1998
- Holland, Brian T.; Blanford, Christopher F.; Stein, Andreas
- Science, Vol. 281, Issue 5376, p. 538-540
Preparation of large area three-dimensionally ordered macroporous thin films by confined infiltration and crystallisation
journal, May 2008
- McLachlan, M. A.; Barron, C. C. A.; Johnson, N. P.
- Journal of Crystal Growth, Vol. 310, Issue 10
A comparative study of inverted-opal titania photonic crystals made from polymer and silica colloidal crystal templates
journal, December 2004
- Kuai, Su-Lan; Truong, Vo-Van; Haché, Alain
- Journal of Applied Physics, Vol. 96, Issue 11
Deriving hierarchical complexity from simplistic colloidal templates
journal, September 2016
- Snyder, Mark A.
- MRS Bulletin, Vol. 41, Issue 09
Morphological Control in Colloidal Crystal Templating of Inverse Opals, Hierarchical Structures, and Shaped Particles
journal, February 2008
- Stein, Andreas; Li, Fan; Denny, Nicholas R.
- Chemistry of Materials, Vol. 20, Issue 3, p. 649-666
Preparation and characterization of mesoporous SBA-15 supported dye-sensitized TiO2 photocatalyst
journal, January 2005
- Ding, Hanming; Sun, Hong; Shan, Yongkui
- Journal of Photochemistry and Photobiology A: Chemistry, Vol. 169, Issue 1
Hard template synthesis of crystalline mesoporous anatase TiO2 for photocatalytic hydrogen evolution
journal, January 2010
- Zhang, Zhenyu; Zuo, Fan; Feng, Pingyun
- Journal of Materials Chemistry, Vol. 20, Issue 11
Well-Ordered Large-Pore Mesoporous Anatase TiO2 with Remarkably High Thermal Stability and Improved Crystallinity: Preparation, Characterization, and Photocatalytic Performance
journal, April 2011
- Zhou, Wei; Sun, Fanfei; Pan, Kai
- Advanced Functional Materials, Vol. 21, Issue 10
Synthesis of Highly Ordered, Three-Dimensional, Macroporous Structures of Amorphous or Crystalline Inorganic Oxides, Phosphates, and Hybrid Composites
journal, March 1999
- Holland, Brian T.; Blanford, Christopher F.; Do, Thang
- Chemistry of Materials, Vol. 11, Issue 3
Hierarchical nanofabrication of microporous crystals with ordered mesoporosity
journal, October 2008
- Fan, Wei; Snyder, Mark A.; Kumar, Sandeep
- Nature Materials, Vol. 7, Issue 12
Sphere templating methods for periodic porous solids
journal, April 2001
- Stein, Andreas
- Microporous and Mesoporous Materials, Vol. 44-45
Colloidal crystals as templates for porous materials
journal, March 2000
- Velev, Orlin D.; Lenhoff, Abraham M.
- Current Opinion in Colloid & Interface Science, Vol. 5, Issue 1-2
Sol-gel chemistry of transition metal oxides
journal, January 1988
- Livage, J.; Henry, M.; Sanchez, C.
- Progress in Solid State Chemistry, Vol. 18, Issue 4
Container Effect in Nanocasting Synthesis of Mesoporous Metal Oxides
journal, September 2011
- Sun, Xiaohong; Shi, Yifeng; Zhang, Peng
- Journal of the American Chemical Society, Vol. 133, Issue 37
Mesoporous TiO2 single crystals delivering enhanced mobility and optoelectronic device performance
journal, March 2013
- Crossland, Edward J. W.; Noel, Nakita; Sivaram, Varun
- Nature, Vol. 495, Issue 7440
Single-Crystal-like Titania Mesocages
journal, December 2010
- Bian, Zhenfeng; Zhu, Jian; Wen, Jing
- Angewandte Chemie International Edition, Vol. 50, Issue 5
Preparation of Highly Ordered Mesoporous TiO 2 Materials with Crystalline Framework from Different Mesostructured Silica Templates via Nanoreplication
journal, February 2008
- Kim, Sung Soo; Lee, Hyung Ik; Shon, Jeong Kuk
- Chemistry Letters, Vol. 37, Issue 2
Structural evolution in ordered mesoporous TiO 2 anatase electrodes
journal, January 2014
- Yonemoto, Bryan T.; Guo, Qianying; Hutchings, Gregory S.
- Chemical Communications, Vol. 50, Issue 64
Silica Nanoparticle Crystals and Ordered Coatings Using Lys-Sil and a Novel Coating Device
journal, September 2007
- Snyder, Mark A.; Lee, J. Alex; Davis, Tracy M.
- Langmuir, Vol. 23, Issue 20
Nanoparticles in Lysine−Silica Sols
journal, December 2006
- Davis, Tracy M.; Snyder, Mark A.; Krohn, John E.
- Chemistry of Materials, Vol. 18, Issue 25
Periodic Arrangement of Silica Nanospheres Assisted by Amino Acids
journal, October 2006
- Yokoi, Toshiyuki; Sakamoto, Yasuhiro; Terasaki, Osamu
- Journal of the American Chemical Society, Vol. 128, Issue 42
Advances in Colloidal Assembly: The Design of Structure and Hierarchy in Two and Three Dimensions
journal, June 2015
- Vogel, Nicolas; Retsch, Markus; Fustin, Charles-André
- Chemical Reviews, Vol. 115, Issue 13
Template-Free Ordered Mesoporous Silicas by Binary Nanoparticle Assembly
journal, September 2014
- Kung, Shih-Chieh; Chang, Chun-Chih; Fan, Wei
- Langmuir, Vol. 30, Issue 39
Selective Cleavage of Periodic Mesoscale Structures: Two-Dimensional Replication of Binary Colloidal Crystals into Dimpled Gold Nanoplates
journal, May 2012
- Kuroda, Yoshiyuki; Sakamoto, Yasuhiro; Kuroda, Kazuyuki
- Journal of the American Chemical Society, Vol. 134, Issue 20
A structural investigation of titanium dioxide photocatalysts
journal, May 1991
- Bickley, Roger I.; Gonzalez-Carreno, Teresita; Lees, John S.
- Journal of Solid State Chemistry, Vol. 92, Issue 1, p. 178-190
Effects of calcination on the photocatalytic properties of nanosized TiO2 powders prepared by TiCl4 hydrolysis
journal, May 2000
- Zhang, Q.
- Applied Catalysis B: Environmental, Vol. 26, Issue 3
Morphology of a TiO2 Photocatalyst (Degussa, P-25) Consisting of Anatase and Rutile Crystalline Phases
journal, October 2001
- Ohno, Teruhisa; Sarukawa, Koji; Tokieda, Kojiro
- Journal of Catalysis, Vol. 203, Issue 1
Preparation of Controllable Crystalline Titania and Study on the Photocatalytic Properties
journal, April 2005
- Yan, Maocheng; Chen, Feng; Zhang, Jinlong
- The Journal of Physical Chemistry B, Vol. 109, Issue 18
Explaining the High Photocatalytic Activity of a Mixed Phase TiO 2 : A Combined Effect of O 2 and Crystallinity
journal, October 2011
- Cong, Shan; Xu, Yiming
- The Journal of Physical Chemistry C, Vol. 115, Issue 43
Facile synthesis and photocatalytic property of bicrystalline TiO2/rectorite composites
journal, July 2011
- Zhang, Yalei; Deng, Lijuan; Zhang, Gaoke
- Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 384, Issue 1-3
A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films
journal, October 1991
- O'Regan, Brian; Grätzel, Michael
- Nature, Vol. 353, Issue 6346, p. 737-740
Relating n -Pentane Isomerization Activity to the Tungsten Surface Density of WO x /ZrO 2
journal, September 2010
- Soultanidis, Nikolaos; Zhou, Wu; Psarras, Antonis C.
- Journal of the American Chemical Society, Vol. 132, Issue 38
New insights into the nature of the acidic catalytic active sites present in ZrO2-supported tungsten oxide catalysts
journal, May 2008
- Rossmedgaarden, E.; Knowles, W.; Kim, T.
- Journal of Catalysis, Vol. 256, Issue 1
Facile Preparation of Highly Monodisperse Small Silica Spheres (15 to >200 nm) Suitable for Colloidal Templating and Formation of Ordered Arrays
journal, March 2008
- Hartlen, Kurtis D.; Athanasopoulos, Aristidis P. T.; Kitaev, Vladimir
- Langmuir, Vol. 24, Issue 5
Mechanism of Formation of Uniform-Sized Silica Nanospheres Catalyzed by Basic Amino Acids
journal, August 2009
- Yokoi, Toshiyuki; Wakabayashi, Junji; Otsuka, Yuki
- Chemistry of Materials, Vol. 21, Issue 15
Adsorption of Gases in Multimolecular Layers
journal, February 1938
- Brunauer, Stephen; Emmett, P. H.; Teller, Edward
- Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319
The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms
journal, January 1951
- Barrett, Elliott P.; Joyner, Leslie G.; Halenda, Paul P.
- Journal of the American Chemical Society, Vol. 73, Issue 1
Calibration Curve for Quantitative Analysis of the Monoclinic-Tetragonal ZrO 2 System by X-Ray Diffraction
journal, June 1984
- Toraya, Hideo; Yoshimura, Masahiro; Somiya, Shigeyuki
- Journal of the American Ceramic Society, Vol. 67, Issue 6
Quantitative Analysis of Anatase-Rutile Mixtures with an X-Ray Diffractometer
journal, May 1957
- Spurr, R. A.; Myers, Howard.
- Analytical Chemistry, Vol. 29, Issue 5
Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)
journal, October 2015
- Thommes, Matthias; Kaneko, Katsumi; Neimark, Alexander V.
- Pure and Applied Chemistry, Vol. 87, Issue 9-10
Review of the anatase to rutile phase transformation
journal, December 2010
- Hanaor, Dorian A. H.; Sorrell, Charles C.
- Journal of Materials Science, Vol. 46, Issue 4
Energetics of nanocrystalline TiO2
journal, March 2002
- Ranade, M. R.; Navrotsky, A.; Zhang, H. Z.
- Proceedings of the National Academy of Sciences, Vol. 99, Issue Supplement 2
Understanding Polymorphic Phase Transformation Behavior during Growth of Nanocrystalline Aggregates: Insights from TiO 2
journal, April 2000
- Zhang, Hengzhong; Banfield, Jillian F.
- The Journal of Physical Chemistry B, Vol. 104, Issue 15
Interfacial Stabilization of Metastable TiO 2 Films
journal, February 2017
- Gregory, Daniel G.; Lu, Li; Kiely, Christopher J.
- The Journal of Physical Chemistry C, Vol. 121, Issue 8
The Occurrence of Metastable Tetragonal Zirconia as a Crystallite Size Effect
journal, April 1965
- Garvie, Ronald C.
- The Journal of Physical Chemistry, Vol. 69, Issue 4
Stabilization of the tetragonal structure in zirconia microcrystals
journal, January 1978
- Garvie, R. C.
- The Journal of Physical Chemistry, Vol. 82, Issue 2
Preparation and Catalytic Evaluation of Macroporous Crystalline Sulfated Zirconium Dioxide Templated with Colloidal Crystals
journal, May 2003
- Al-Daous, Mohammed A.; Stein, Andreas
- Chemistry of Materials, Vol. 15, Issue 13