Insight into the Selectivity of Isopropanol Conversion at Strontium Titanate (100) Surfaces: A Combination Kinetic and Spectroscopic Study

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.

doi:10.1021/acscatal.7b02417

Title: Insight into the Selectivity of Isopropanol Conversion at Strontium Titanate (100) Surfaces: A Combination Kinetic and Spectroscopic Study

Journal Article · Fri Oct 13 00:00:00 EDT 2017 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.7b02417· OSTI ID:1429202

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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

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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1429202

Journal Information:: ACS Catalysis, Vol. 7, Issue 12; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 17 works

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Title: Insight into the Selectivity of Isopropanol Conversion at Strontium Titanate (100) Surfaces: A Combination Kinetic and Spectroscopic Study

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