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Title: 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:
 [1];  [2]; ORCiD logo [3];  [4]; ORCiD logo [2]
  1. Lehigh Univ., Bethlehem, PA (United States). Dept. of Chemical and Biomolecular Engineering
  2. Lehigh Univ., Bethlehem, PA (United States). Dept. of Chemical and Biomolecular Engineering
  3. Department of Chemical and Biomolecular Engineering and ‡Department of Materials Science and Engineering, Lehigh University, Bethlehem, Pennsylvania 18015, United States
  4. 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}
}

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