Insight into the Selectivity of Isopropanol Conversion at Strontium Titanate (100) Surfaces: A Combination Kinetic and Spectroscopic Study
Abstract
This work aims to better understand the role of interfacial molecular structure that governs selectivity and activity in heterogeneous catalytic reactions. To address this, a comprehensive study of isopropanol conversion over an archetypal perovskite material, strontium titanate (SrTiO3 or STO), was performed with an array of techniques sensitive to orthogonal aspects of the ensuing chemistry. Cubic-shape STO nanoparticles with only the (100) facet exposed were synthesized and used to study the ensemble kinetic conversion of isopropanol over the surfaces, which showed a remarkable selectivity to form acetone, with minor propylene products appearing at elevated temperatures. These results in combination with inelastic neutron scattering measurements provide not only new insight into the selectivity and overall activity of the catalysts but also low frequency vibrational signatures of the adsorbed and reacted species. To compliment these measurements, pristine thin films of STO (100) were synthesized and used in combination with vibrational sum frequency generation spectroscopy to extract the absolute molecular orientation of the adsorbed molecules at the interface. It was found that the isopropanol assumes an orientation where the -CH group points towards the STO surface; this pre-reaction geometry offers an obvious pathway to produce acetone by abstracting the alpha-proton and, thus, providesmore »
- Authors:
-
[1];
[1];
[3];
[4];
[4];
[1];
[1];
[1]
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
- The Ohio State Univ., Columbus, OH (United States). Dept. of Chemistry and Biochemistry
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division, Neutron Sciences Directorate
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
- 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:
- 1429202
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 12; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; isopropyl alcohol; neutron spectroscopy; perovskite; SFG; strontium titanate
Citation Formats
Tan, Shuai, Grey, Matthew B., Kidder, Michelle, Cheng, Yongqiang, Daemen, Luke L., Lee, Dongkyu, Lee, Ho Nyung, Ma, Ying-zhong, Doughty, Benjamin L., and Lutterman, Daniel A. Insight into the Selectivity of Isopropanol Conversion at Strontium Titanate (100) Surfaces: A Combination Kinetic and Spectroscopic Study. United States: N. p., 2017.
Web. doi:10.1021/acscatal.7b02417.
Tan, Shuai, Grey, Matthew B., Kidder, Michelle, Cheng, Yongqiang, Daemen, Luke L., Lee, Dongkyu, Lee, Ho Nyung, Ma, Ying-zhong, Doughty, Benjamin L., & Lutterman, Daniel A. Insight into the Selectivity of Isopropanol Conversion at Strontium Titanate (100) Surfaces: A Combination Kinetic and Spectroscopic Study. United States. https://doi.org/10.1021/acscatal.7b02417
Tan, Shuai, Grey, Matthew B., Kidder, Michelle, Cheng, Yongqiang, Daemen, Luke L., Lee, Dongkyu, Lee, Ho Nyung, Ma, Ying-zhong, Doughty, Benjamin L., and Lutterman, Daniel A. Fri .
"Insight into the Selectivity of Isopropanol Conversion at Strontium Titanate (100) Surfaces: A Combination Kinetic and Spectroscopic Study". United States. https://doi.org/10.1021/acscatal.7b02417. https://www.osti.gov/servlets/purl/1429202.
@article{osti_1429202,
title = {Insight into the Selectivity of Isopropanol Conversion at Strontium Titanate (100) Surfaces: A Combination Kinetic and Spectroscopic Study},
author = {Tan, Shuai and Grey, Matthew B. and Kidder, Michelle and Cheng, Yongqiang and Daemen, Luke L. and Lee, Dongkyu and Lee, Ho Nyung and Ma, Ying-zhong and Doughty, Benjamin L. and Lutterman, Daniel A.},
abstractNote = {This work aims to better understand the role of interfacial molecular structure that governs selectivity and activity in heterogeneous catalytic reactions. To address this, a comprehensive study of isopropanol conversion over an archetypal perovskite material, strontium titanate (SrTiO3 or STO), was performed with an array of techniques sensitive to orthogonal aspects of the ensuing chemistry. Cubic-shape STO nanoparticles with only the (100) facet exposed were synthesized and used to study the ensemble kinetic conversion of isopropanol over the surfaces, which showed a remarkable selectivity to form acetone, with minor propylene products appearing at elevated temperatures. These results in combination with inelastic neutron scattering measurements provide not only new insight into the selectivity and overall activity of the catalysts but also low frequency vibrational signatures of the adsorbed and reacted species. To compliment these measurements, pristine thin films of STO (100) were synthesized and used in combination with vibrational sum frequency generation spectroscopy to extract the absolute molecular orientation of the adsorbed molecules at the interface. It was found that the isopropanol assumes an orientation where the -CH group points towards the STO surface; this pre-reaction geometry offers an obvious pathway to produce acetone by abstracting the alpha-proton and, thus, provides a mechanistic explanation of selectivity at STO (100) surfaces. This new insight opens up pathways to explore and modify surfaces to tune the activity/selectivity though a molecular level understanding of the reactions at the surface.},
doi = {10.1021/acscatal.7b02417},
journal = {ACS Catalysis},
number = 12,
volume = 7,
place = {United States},
year = {2017},
month = {10}
}
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