Identifying Boron Active Sites for the Oxidative Dehydrogenation of Propane

Huan Yan; Selim Alayoglu; Weiqiang Wu; Yongbo Zhang; Eric Weitz; Peter Curran Stair; Justin M. Notestein

doi:10.1021/acscatal.1c02168

Identifying Boron Active Sites for the Oxidative Dehydrogenation of Propane

Huan Yan, Selim Alayoglu, Weiqiang Wu, Yongbo Zhang, Eric Weitz, Peter Curran Stair^*, Justin M. Notestein

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

29 Scopus citations

Abstract

Oxidative dehydrogenation of propane (ODHP) to propylene could have a significant impact on the production of this critical chemical intermediate, if appropriate catalysts can be discovered. Recently, heterogeneous catalysts based on boron (oxides and nitrides) have been demonstrated to be promising for ODHP, but their active sites have not been conclusively identified. Here, we report that the deposition of differently sized boronic acids into the micropores of silica supports results in different distributions of surface borate species after calcination. These materials, in turn, display a wide range of rates in ODHP but similar selectivity, suggesting that they differ only in the numbers of active sites. Features identified by in situ Raman, IR, and magic-angle-spinning 11B solid-state NMR spectroscopies are compared to catalyst activity. This correlation identifies the S2 borate species, a hydroxylated nonring boron, as the likely active site and provides a target for directed syntheses of future catalysts.

Original language	English (US)
Pages (from-to)	9370-9376
Number of pages	7
Journal	ACS Catalysis
Volume	11
Issue number	15
DOIs	https://doi.org/10.1021/acscatal.1c02168
State	Published - Aug 6 2021

Funding

This paper is based upon the work supported primarily by the National Science Foundation under Cooperative Agreement no. EEC-1647722. This work made use of the IMSERC NMR facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), Int. Institute of Nanotechnology, and Northwestern University. This work made use of Raman spectroscopy in the REACT facility of the Center for Catalysis and Surface Science (CCSS), which has received support from the Department of Energy (DE-FG02-03ER15457). We acknowledge Professor Marek Pruski (Iowa State University and Ames Laboratory) and Dr. Yuyang Wu (IMSERC) for the discussion of solid-state NMR. All data and images are available in the body of the paper or as the supporting online material.

Keywords

NMR
ODHP
precursor
propylene
selective oxidation
silica

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1021/acscatal.1c02168

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abstract = "Oxidative dehydrogenation of propane (ODHP) to propylene could have a significant impact on the production of this critical chemical intermediate, if appropriate catalysts can be discovered. Recently, heterogeneous catalysts based on boron (oxides and nitrides) have been demonstrated to be promising for ODHP, but their active sites have not been conclusively identified. Here, we report that the deposition of differently sized boronic acids into the micropores of silica supports results in different distributions of surface borate species after calcination. These materials, in turn, display a wide range of rates in ODHP but similar selectivity, suggesting that they differ only in the numbers of active sites. Features identified by in situ Raman, IR, and magic-angle-spinning 11B solid-state NMR spectroscopies are compared to catalyst activity. This correlation identifies the S2 borate species, a hydroxylated nonring boron, as the likely active site and provides a target for directed syntheses of future catalysts.",

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AU - Alayoglu, Selim

AU - Wu, Weiqiang

AU - Zhang, Yongbo

AU - Weitz, Eric

AU - Stair, Peter Curran

AU - Notestein, Justin M.

PY - 2021/8/6

Y1 - 2021/8/6

N2 - Oxidative dehydrogenation of propane (ODHP) to propylene could have a significant impact on the production of this critical chemical intermediate, if appropriate catalysts can be discovered. Recently, heterogeneous catalysts based on boron (oxides and nitrides) have been demonstrated to be promising for ODHP, but their active sites have not been conclusively identified. Here, we report that the deposition of differently sized boronic acids into the micropores of silica supports results in different distributions of surface borate species after calcination. These materials, in turn, display a wide range of rates in ODHP but similar selectivity, suggesting that they differ only in the numbers of active sites. Features identified by in situ Raman, IR, and magic-angle-spinning 11B solid-state NMR spectroscopies are compared to catalyst activity. This correlation identifies the S2 borate species, a hydroxylated nonring boron, as the likely active site and provides a target for directed syntheses of future catalysts.

AB - Oxidative dehydrogenation of propane (ODHP) to propylene could have a significant impact on the production of this critical chemical intermediate, if appropriate catalysts can be discovered. Recently, heterogeneous catalysts based on boron (oxides and nitrides) have been demonstrated to be promising for ODHP, but their active sites have not been conclusively identified. Here, we report that the deposition of differently sized boronic acids into the micropores of silica supports results in different distributions of surface borate species after calcination. These materials, in turn, display a wide range of rates in ODHP but similar selectivity, suggesting that they differ only in the numbers of active sites. Features identified by in situ Raman, IR, and magic-angle-spinning 11B solid-state NMR spectroscopies are compared to catalyst activity. This correlation identifies the S2 borate species, a hydroxylated nonring boron, as the likely active site and provides a target for directed syntheses of future catalysts.

KW - NMR

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KW - precursor

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KW - selective oxidation

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Identifying Boron Active Sites for the Oxidative Dehydrogenation of Propane

Abstract

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