Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts

Xuanyu Zhang; Rui You; Zeyue Wei; Xiao Jiang; Jiuzhong Yang; Yang Pan; Peiwen Wu; Qingdong Jia; Zhenghong Bao; Lei Bai; Mingzhou Jin; Bobby Sumpter; Victor Fung; Weixin Huang; Zili Wu

doi:10.1002/anie.202002440

Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts

Xuanyu Zhang, Rui You, Zeyue Wei, Xiao Jiang, Jiuzhong Yang, Yang Pan, Peiwen Wu, Qingdong Jia, Zhenghong Bao, Lei Bai, Mingzhou Jin, Bobby Sumpter, Victor Fung, Weixin Huang, Zili Wu

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Abstract

Although hexagonal boron nitride (h-BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas-phase methyl radicals (CH₃^.) in the ODHP reaction over boron-based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV-PIMS), which uncovers the existence of gas-phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C−H activation of propane, while C₂ and C₁ products can be formed via both surface-mediated and gas-phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron-based catalysts.

Original language	English
Pages (from-to)	8042-8046
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	21
DOIs	https://doi.org/10.1002/anie.202002440
State	Published - May 18 2020

Funding

This work was supported by the Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME), an Energy Frontier Research Center funded by U.S. Department of Energy, Office of Science, Basic Energy Sciences. X.Z., R.Y., Z.Y.W., and W.H. were supported by the National Natural Science Foundation of China (21525313, 91745202, 21703227), the Chinese Academy of Sciences, the Changjiang Scholars Program of Ministry of Education of China, and the China Scholarship Council. Part of the work including the synthesis, catalysis test, and DFT calculation was done at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. This work was supported by the Center for Understanding and Control of Acid Gas‐Induced Evolution of Materials for Energy (UNCAGE‐ME), an Energy Frontier Research Center funded by U.S. Department of Energy, Office of Science, Basic Energy Sciences. X.Z., R.Y., Z.Y.W., and W.H. were supported by the National Natural Science Foundation of China (21525313, 91745202, 21703227), the Chinese Academy of Sciences, the Changjiang Scholars Program of Ministry of Education of China, and the China Scholarship Council. Part of the work including the synthesis, catalysis test, and DFT calculation was done at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.

Funders	Funder number
Center for Understanding and Control of Acid
UNCAGE‐ME
U.S. Department of Energy
Office of Science
Basic Energy Sciences
National Natural Science Foundation of China	91745202, 21525313, 21703227
Chinese Academy of Sciences
China Scholarship Council
Changjiang Scholar Program of Chinese Ministry of Education

Keywords

hexagonal boron nitride
mass spectrometry
methyl radicals
oxidative dehydrogenation
reaction pathways

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10.1002/anie.202002440

Cite this

Zhang, X., You, R., Wei, Z., Jiang, X., Yang, J., Pan, Y., Wu, P., Jia, Q., Bao, Z., Bai, L., Jin, M., Sumpter, B., Fung, V., Huang, W., & Wu, Z. (2020). Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts. Angewandte Chemie - International Edition, 59(21), 8042-8046. https://doi.org/10.1002/anie.202002440

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title = "Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts",

abstract = "Although hexagonal boron nitride (h-BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas-phase methyl radicals (CH3.) in the ODHP reaction over boron-based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV-PIMS), which uncovers the existence of gas-phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C−H activation of propane, while C2 and C1 products can be formed via both surface-mediated and gas-phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron-based catalysts.",

keywords = "hexagonal boron nitride, mass spectrometry, methyl radicals, oxidative dehydrogenation, reaction pathways",

author = "Xuanyu Zhang and Rui You and Zeyue Wei and Xiao Jiang and Jiuzhong Yang and Yang Pan and Peiwen Wu and Qingdong Jia and Zhenghong Bao and Lei Bai and Mingzhou Jin and Bobby Sumpter and Victor Fung and Weixin Huang and Zili Wu",

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Zhang, X, You, R, Wei, Z, Jiang, X, Yang, J, Pan, Y, Wu, P, Jia, Q, Bao, Z, Bai, L, Jin, M, Sumpter, B, Fung, V, Huang, W & Wu, Z 2020, 'Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts', Angewandte Chemie - International Edition, vol. 59, no. 21, pp. 8042-8046. https://doi.org/10.1002/anie.202002440

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T1 - Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts

AU - Zhang, Xuanyu

AU - You, Rui

AU - Wei, Zeyue

AU - Jiang, Xiao

AU - Yang, Jiuzhong

AU - Pan, Yang

AU - Wu, Peiwen

AU - Jia, Qingdong

AU - Bao, Zhenghong

AU - Bai, Lei

AU - Jin, Mingzhou

AU - Sumpter, Bobby

AU - Fung, Victor

AU - Huang, Weixin

AU - Wu, Zili

PY - 2020/5/18

Y1 - 2020/5/18

N2 - Although hexagonal boron nitride (h-BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas-phase methyl radicals (CH3.) in the ODHP reaction over boron-based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV-PIMS), which uncovers the existence of gas-phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C−H activation of propane, while C2 and C1 products can be formed via both surface-mediated and gas-phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron-based catalysts.

AB - Although hexagonal boron nitride (h-BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas-phase methyl radicals (CH3.) in the ODHP reaction over boron-based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV-PIMS), which uncovers the existence of gas-phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C−H activation of propane, while C2 and C1 products can be formed via both surface-mediated and gas-phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron-based catalysts.

KW - hexagonal boron nitride

KW - mass spectrometry

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Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts

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