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

被引：105

作者：

Zhang, Xuanyu ^{[1
,2
,3
,4
]}

You, Rui ^{[1
,2
]}

Wei, Zeyue ^{[1
,2
]}

Jiang, Xiao ^{[3
,4
]}

Yang, Jiuzhong ^{[7
]}

Pan, Yang ^{[7
]}

Wu, Peiwen ^{[8
]}

Jia, Qingdong ^{[8
]}

Bao, Zhenghong ^{[3
,4
]}

Bai, Lei ^{[3
,4
]}

Jin, Mingzhou ^{[9
]}

Sumpter, Bobby ^{[5
,6
]}

Fung, Victor ^{[5
,6
]}

Huang, Weixin ^{[1
,2
]}

Wu, Zili ^{[3
,4
]}

机构：

[1] Univ Sci & Technol China, Hefei Natl Lab Phys Sci Microscale, Key Lab Surface & Interface Chem & Energy Catalys, CAS Key Lab Mat Energy Convers, Hefei 230026, Peoples R China

[2] Univ Sci & Technol China, Dept Chem Phys, Hefei 230026, Peoples R China

[3] Oak Ridge Natl Lab, Chem Sci Div, POB 2009, Oak Ridge, TN 37831 USA

[4] Oak Ridge Natl Lab, Ctr Nanophase Mat Sci, POB 2009, Oak Ridge, TN 37831 USA

[5] Oak Ridge Natl Lab, Ctr Nanophase Mat Sci & Computat Sci, POB 2009, Oak Ridge, TN 37831 USA

[6] Oak Ridge Natl Lab, Engn Div, POB 2009, Oak Ridge, TN 37831 USA

[7] Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230026, Peoples R China

[8] Jiang Su Univ, Sch Chem & Chem Engn, Zhenjiang 212013, Jiangsu, Peoples R China

[9] Univ Tennessee, Inst Secure & Sustainable Environm, Knoxville, TN 37996 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 21期

基金：

中国国家自然科学基金;

关键词：

hexagonal boron nitride; mass spectrometry; methyl radicals; oxidative dehydrogenation; reaction pathways; RAMAN-SPECTROSCOPY; LIGHT ALKANES; METHANE; ETHANE; OLEFINS; FORMALDEHYDE; SELECTIVITY; ACTIVATION; SIZE; BN;

D O I：

10.1002/anie.202002440

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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 C-2 and C-1 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.

引用

页码：8042 / 8046

页数：5

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