The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO3 nanocrystals

Bao, Zhenghong; Fung, Victor; Polo Garzon, Felipe; Hood, Zachary; Cao, Shaohong; Chi, Miaofang; Bai, Lei; Jiang, De-en; Wu, Zili

doi:10.1016/j.jcat.2020.02.014

Title: The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO₃ nanocrystals

Journal Article · Thu Feb 27 00:00:00 EST 2020 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2020.02.014· OSTI ID:1606883

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^[1]; Hood, Zachary ^[3];

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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)

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.

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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; AC02-05CH11231

OSTI ID:: 1606883

Alternate ID(s):: OSTI ID: 1601912

Journal Information:: Journal of Catalysis, Vol. 384, Issue C; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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Title: The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO3 nanocrystals

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Title: The interplay between surface facet and reconstruction on isopropanol conversion over SrTiO₃ nanocrystals