The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO3 nanocrystals
Abstract
Strontium titanate (SrTiO3) is an extensively investigated perovskite for various applications due to its optical, electrical and chemical properties. To gain an in-depth understanding of the active sites involved in heterogeneous catalysis over the broadly used SrTiO3 (STO), we studied a model reaction, isopropanol conversion, on three differently shape-controlled nanocrystals: cube, truncated cube and dodecahedra. SEM, XRD and XPS confirmed the morphology, phase and composition of STO shapes. Low energy ion scattering (LEIS) revealed the occurrence of surface reconstruction over STO shapes during O2 pretreatment at different temperatures. Based on the catalytic activities, scanning transmission electron microscopy images and density functional theory calculations, the step sites on STO derived from surface reconstruction were proposed to be the active sites for isopropanol conversion. This was further confirmed by steady state isotopic kinetic analysis (SSITKA) which demonstrated similar intrinsic turnover frequencies (TOFs) for the differently reconstructed STO shapes. It is concluded that the crystal facets impose an indirect effect on the catalysis of STO via controlling the degrees of surface reconstruction: the less stable STO (1 1 0) facet (dodecahedra) leads to more step sites after reconstruction and hence higher overall reaction rate than the more stable (1 0 0) facet (cube).more »
- Authors:
-
[1];
[2];
[1];
[1];
[1];
[1]
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of California, Riverside, CA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); West Virginia Univ., Morgantown, WV (United States)
- Univ. of California, Riverside, CA (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1606883
- Alternate Identifier(s):
- OSTI ID: 1601912
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Catalysis
- Additional Journal Information:
- Journal Volume: 384; Journal Issue: C; Journal ID: ISSN 0021-9517
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Surface reconstruction; SrTiO3; Isopropyl alcohol; Nanoshapes; Facet; SSITKA
Citation Formats
Bao, Zhenghong, Fung, Victor, Polo Garzon, Felipe, Hood, Zachary, Cao, Shaohong, Chi, Miaofang, Bai, Lei, Jiang, De-en, and Wu, Zili. The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO3 nanocrystals. United States: N. p., 2020.
Web. doi:10.1016/j.jcat.2020.02.014.
Bao, Zhenghong, Fung, Victor, Polo Garzon, Felipe, Hood, Zachary, Cao, Shaohong, Chi, Miaofang, Bai, Lei, Jiang, De-en, & Wu, Zili. The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO3 nanocrystals. United States. https://doi.org/10.1016/j.jcat.2020.02.014
Bao, Zhenghong, Fung, Victor, Polo Garzon, Felipe, Hood, Zachary, Cao, Shaohong, Chi, Miaofang, Bai, Lei, Jiang, De-en, and Wu, Zili. Thu .
"The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO3 nanocrystals". United States. https://doi.org/10.1016/j.jcat.2020.02.014. https://www.osti.gov/servlets/purl/1606883.
@article{osti_1606883,
title = {The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO3 nanocrystals},
author = {Bao, Zhenghong and Fung, Victor and Polo Garzon, Felipe and Hood, Zachary and Cao, Shaohong and Chi, Miaofang and Bai, Lei and Jiang, De-en and Wu, Zili},
abstractNote = {Strontium titanate (SrTiO3) is an extensively investigated perovskite for various applications due to its optical, electrical and chemical properties. To gain an in-depth understanding of the active sites involved in heterogeneous catalysis over the broadly used SrTiO3 (STO), we studied a model reaction, isopropanol conversion, on three differently shape-controlled nanocrystals: cube, truncated cube and dodecahedra. SEM, XRD and XPS confirmed the morphology, phase and composition of STO shapes. Low energy ion scattering (LEIS) revealed the occurrence of surface reconstruction over STO shapes during O2 pretreatment at different temperatures. Based on the catalytic activities, scanning transmission electron microscopy images and density functional theory calculations, the step sites on STO derived from surface reconstruction were proposed to be the active sites for isopropanol conversion. This was further confirmed by steady state isotopic kinetic analysis (SSITKA) which demonstrated similar intrinsic turnover frequencies (TOFs) for the differently reconstructed STO shapes. It is concluded that the crystal facets impose an indirect effect on the catalysis of STO via controlling the degrees of surface reconstruction: the less stable STO (1 1 0) facet (dodecahedra) leads to more step sites after reconstruction and hence higher overall reaction rate than the more stable (1 0 0) facet (cube). This work highlights the important interplay between the crystal facet and surface reconstruction in controlling the nature and density of active sties and thus catalysis over complex oxides.},
doi = {10.1016/j.jcat.2020.02.014},
journal = {Journal of Catalysis},
number = C,
volume = 384,
place = {United States},
year = {2020},
month = {2}
}
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