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

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

doi:10.1002/anie.202002440

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

Journal Article · Wed Apr 15 00:00:00 UTC 2020 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202002440 · OSTI ID:1813272

Zhang, Xuanyu ^[1]; You, Rui ^[2]; Wei, Zeyue ^[2];

^[1]; Yang, Jiuzhong ^[2];

^[2]; Wu, Peiwen ^[3]; Jia, Qingdong ^[3];

^[1]; Bai, Lei ^[1];

^[4];

^[1];

^[2];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Science and Technology of China, Hefei (China)
Jiangsu University (China)
Univ. of Tennessee, Knoxville, TN (United States)

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

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

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1813272

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 21 Vol. 59; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Verbrennungschemie der Biokraftstoffe: von Ethanol bis Biodiesel Kohse-Höinghaus, Katharina; Oßwald, Patrick; Cool, Terrill A. Angewandte Chemie, Vol. 122, Issue 21 https://doi.org/10.1002/ange.200905335	journal	May 2010
Experimental Confirmation of the Low-Temperature Oxidation Scheme of Alkanes Battin-Leclerc, Frédérique; Herbinet, Olivier; Glaude, Pierre-Alexandre Angewandte Chemie, Vol. 122, Issue 18 https://doi.org/10.1002/ange.200906850	journal	April 2010
Zentren der Methanaktivierung auf Oberflächen von Lithium-dotiertem MgO Kwapien, Karolina; Paier, Joachim; Sauer, Joachim Angewandte Chemie, Vol. 126, Issue 33 https://doi.org/10.1002/ange.201310632	journal	April 2014
Controlled Gas Exfoliation of Boron Nitride into Few-Layered Nanosheets Zhu, Wenshuai; Gao, Xiang; Li, Qian Angewandte Chemie, Vol. 128, Issue 36 https://doi.org/10.1002/ange.201605515	journal	July 2016
Carbon-Doped BN Nanosheets for the Oxidative Dehydrogenation of Ethylbenzene Guo, Fangsong; Yang, Pengju; Pan, Zhiming Angewandte Chemie, Vol. 129, Issue 28 https://doi.org/10.1002/ange.201703789	journal	June 2017
B‐MWW Zeolite: The Case Against Single‐Site Catalysis Altvater, Natalie R.; Dorn, Rick W.; Cendejas, Melissa C. Angewandte Chemie, Vol. 132, Issue 16 https://doi.org/10.1002/ange.201914696	journal	April 2020
Biofuel Combustion Chemistry: From Ethanol to Biodiesel Kohse-Höinghaus, Katharina; Oßwald, Patrick; Cool, Terrill A. Angewandte Chemie International Edition, Vol. 49, Issue 21 https://doi.org/10.1002/anie.200905335	journal	May 2010
Experimental Confirmation of the Low-Temperature Oxidation Scheme of Alkanes Battin-Leclerc, Frédérique; Herbinet, Olivier; Glaude, Pierre-Alexandre Angewandte Chemie International Edition, Vol. 49, Issue 18 https://doi.org/10.1002/anie.200906850	journal	April 2010
Sites for Methane Activation on Lithium-Doped Magnesium Oxide Surfaces Kwapien, Karolina; Paier, Joachim; Sauer, Joachim Angewandte Chemie International Edition, Vol. 53, Issue 33 https://doi.org/10.1002/anie.201310632	journal	April 2014
Controlled Gas Exfoliation of Boron Nitride into Few-Layered Nanosheets Zhu, Wenshuai; Gao, Xiang; Li, Qian Angewandte Chemie International Edition, Vol. 55, Issue 36 https://doi.org/10.1002/anie.201605515	journal	July 2016
Carbon-Doped BN Nanosheets for the Oxidative Dehydrogenation of Ethylbenzene Guo, Fangsong; Yang, Pengju; Pan, Zhiming Angewandte Chemie International Edition, Vol. 56, Issue 28 https://doi.org/10.1002/anie.201703789	journal	June 2017
B‐MWW Zeolite: The Case Against Single‐Site Catalysis Altvater, Natalie R.; Dorn, Rick W.; Cendejas, Melissa C. Angewandte Chemie International Edition, Vol. 59, Issue 16 https://doi.org/10.1002/anie.201914696	journal	April 2020
Edge-hydroxylated Boron Nitride for Oxidative Dehydrogenation of Propane to Propylene Shi, Lei; Wang, Dongqi; Song, Wei ChemCatChem, Vol. 9, Issue 10 https://doi.org/10.1002/cctc.201700004	journal	April 2017
Direct Insight into Ethane Oxidative Dehydrogenation over Boron Nitrides Huang, Rui; Zhang, Bingsen; Wang, Jia ChemCatChem, Vol. 9, Issue 17 https://doi.org/10.1002/cctc.201700725	journal	July 2017
Boron and Boron-Containing Catalysts for the Oxidative Dehydrogenation of Propane Grant, Joseph T.; McDermott, William P.; Venegas, Juan M. ChemCatChem, Vol. 9, Issue 19 https://doi.org/10.1002/cctc.201701140	journal	September 2017
Photoionization Mass Spectrometry for Online Detection of Reactive and Unstable Gas‐Phase Intermediates in Heterogeneous Catalytic Reactions You, Rui; Huang, Weixin ChemCatChem, Vol. 12, Issue 3 https://doi.org/10.1002/cctc.201901639	journal	December 2019
Selective oxidative dehydrogenation of ethane to ethylene over a hydroxylated boron nitride catalyst Shi, Lei; Yan, Bing; Shao, Dan Chinese Journal of Catalysis, Vol. 38, Issue 2 https://doi.org/10.1016/S1872-2067(17)62786-4	journal	February 2017
A viewpoint on catalytic origin of boron nitride in oxidative dehydrogenation of light alkanes Shi, Lei; Wang, Dongqi; Lu, An-Hui Chinese Journal of Catalysis, Vol. 39, Issue 5 https://doi.org/10.1016/S1872-2067(18)63060-8	journal	May 2018
Oxidative dehydrogenation of ethane and propane: How far from commercial implementation? Cavani, F.; Ballarini, N.; Cericola, A. Catalysis Today, Vol. 127, Issue 1-4, p. 113-131 https://doi.org/10.1016/j.cattod.2007.05.009	journal	September 2007
Propane ammoxidation over Mo–V–Te–Nb–O M1 phase: Density functional theory study of propane oxidative dehydrogenation steps Yu, Junjun; Xu, Ye; Guliants, Vadim V. Catalysis Today, Vol. 238 https://doi.org/10.1016/j.cattod.2014.02.053	journal	December 2014
Global energy & emissions reduction potential of chemical process improvements Rightor, Edward G.; Tway, Cathy L. Catalysis Today, Vol. 258 https://doi.org/10.1016/j.cattod.2015.02.023	journal	December 2015
NbO x /CeO 2 -rods catalysts for oxidative dehydrogenation of propane: Nb–CeO 2 interaction and reaction mechanism You, Rui; Zhang, Xuanyu; Luo, Liangfeng Journal of Catalysis, Vol. 348 https://doi.org/10.1016/j.jcat.2016.12.012	journal	April 2017
Enhanced performance of boron nitride catalysts with induction period for the oxidative dehydrogenation of ethane to ethylene Zhou, Yanliang; Lin, Jian; Li, Lin Journal of Catalysis, Vol. 365 https://doi.org/10.1016/j.jcat.2018.05.023	journal	September 2018
Metal-free silicon boride catalyst for oxidative dehydrogenation of light alkanes to olefins with high selectivity and stability Yan, Bing; Li, Wen-Cui; Lu, An-Hui Journal of Catalysis, Vol. 369 https://doi.org/10.1016/j.jcat.2018.11.014	journal	January 2019
Serendipity in Catalysis Research: Boron-Based Materials for Alkane Oxidative Dehydrogenation Venegas, Juan M.; McDermott, William P.; Hermans, Ive Accounts of Chemical Research, Vol. 51, Issue 10 https://doi.org/10.1021/acs.accounts.8b00330	journal	September 2018
Support Effect of the Fe/BN Catalyst on Fischer–Tropsch Performances: Role of the Surface B–O Defect Wu, Jianghong; Wang, Liancheng; Yang, Xi Industrial & Engineering Chemistry Research, Vol. 57, Issue 8 https://doi.org/10.1021/acs.iecr.7b04864	journal	February 2018
Boron-Containing Catalysts for the Oxidative Dehydrogenation of Ethane/Propane Mixtures Loiland, Jason A.; Zhao, Zhun; Patel, Ashwin Industrial & Engineering Chemistry Research, Vol. 58, Issue 6 https://doi.org/10.1021/acs.iecr.8b04906	journal	January 2019
The Influence of Reactor Parameters on the Boron Nitride-Catalyzed Oxidative Dehydrogenation of Propane Venegas, Juan M.; Hermans, Ive Organic Process Research & Development, Vol. 22, Issue 12 https://doi.org/10.1021/acs.oprd.8b00301	journal	November 2018
Single-Site VO _x Moieties Generated on Silica by Surface Organometallic Chemistry: A Way To Enhance the Catalytic Activity in the Oxidative Dehydrogenation of Propane Barman, Samir; Maity, Niladri; Bhatte, Kushal ACS Catalysis, Vol. 6, Issue 9 https://doi.org/10.1021/acscatal.6b01263	journal	August 2016
Gas-Phase Reaction Network of Li/MgO-Catalyzed Oxidative Coupling of Methane and Oxidative Dehydrogenation of Ethane Luo, Liangfeng; You, Rui; Liu, Yiming ACS Catalysis, Vol. 9, Issue 3 https://doi.org/10.1021/acscatal.8b04728	journal	February 2019
Supported Boron Oxide Catalysts for Selective and Low-Temperature Oxidative Dehydrogenation of Propane Lu, Wen-Duo; Wang, Dongqi; Zhao, Zhenchao ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b02284	journal	July 2019
Selective C–H Bond Activation via NO _x -Mediated Generation of Strong H-Abstractors Annamalai, Leelavathi; Liu, Yilang; Deshlahra, Prashant ACS Catalysis, Vol. 9, Issue 11 https://doi.org/10.1021/acscatal.9b03862	journal	September 2019
Oxidative Dehydrogenation of Propane over a High Surface Area Boron Nitride Catalyst: Exceptional Selectivity for Olefins at High Conversion Chaturbedy, Piyush; Ahamed, Momin; Eswaramoorthy, Muthusamy ACS Omega, Vol. 3, Issue 1 https://doi.org/10.1021/acsomega.7b01489	journal	January 2018
Recent Applications of Synchrotron VUV Photoionization Mass Spectrometry: Insight into Combustion Chemistry Li, Yuyang; Qi, Fei Accounts of Chemical Research, Vol. 43, Issue 1 https://doi.org/10.1021/ar900130b	journal	January 2010
Catalytic Dehydrogenation of Light Alkanes on Metals and Metal Oxides Sattler, Jesper J. H. B.; Ruiz-Martinez, Javier; Santillan-Jimenez, Eduardo Chemical Reviews, Vol. 114, Issue 20 https://doi.org/10.1021/cr5002436	journal	August 2014
Oxidative Dehydrogenation of Cyclohexane on Cobalt Oxide (Co ₃ O ₄ ) Nanoparticles: The Effect of Particle Size on Activity and Selectivity Tyo, Eric C.; Yin, Chunrong; Di Vece, Marcel ACS Catalysis, Vol. 2, Issue 11 https://doi.org/10.1021/cs300479a	journal	September 2012
Critical Literature Review of the Kinetics for the Oxidative Dehydrogenation of Propane over Well-Defined Supported Vanadium Oxide Catalysts Carrero, C. A.; Schloegl, R.; Wachs, I. E. ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs5003417	journal	September 2014
NO _x -Mediated Homogeneous Pathways for the Synthesis of Formaldehyde from CH ₄ −O ₂ Mixtures Zalc, Jeffrey M.; Green, William H.; Iglesia, Enrique Industrial & Engineering Chemistry Research, Vol. 45, Issue 8 https://doi.org/10.1021/ie050885t	journal	April 2006
Size-Dependent Catalytic Activity of Supported Vanadium Oxide Species: Oxidative Dehydrogenation of Propane Rozanska, Xavier; Fortrie, Remy; Sauer, Joachim Journal of the American Chemical Society, Vol. 136, Issue 21 https://doi.org/10.1021/ja503130z	journal	May 2014
Probing the Transformation of Boron Nitride Catalysts under Oxidative Dehydrogenation Conditions Love, Alyssa M.; Thomas, Brijith; Specht, Sarah E. Journal of the American Chemical Society, Vol. 141, Issue 1 https://doi.org/10.1021/jacs.8b08165	journal	November 2018
Raman Spectroscopy and Time-Resolved Photoluminescence of BN and B _x C _y N _z Nanotubes Wu, J.; Han, Wei-Qiang; Walukiewicz, W. Nano Letters, Vol. 4, Issue 4 https://doi.org/10.1021/nl049862e	journal	April 2004
Raman Spectroscopy of Single-Wall Boron Nitride Nanotubes Arenal, R.; Ferrari, A. C.; Reich, S. Nano Letters, Vol. 6, Issue 8 https://doi.org/10.1021/nl0602544	journal	August 2006
Cobalt carbide nanoprisms for direct production of lower olefins from syngas Zhong, Liangshu; Yu, Fei; An, Yunlei Nature, Vol. 538, Issue 7623 https://doi.org/10.1038/nature19786	journal	October 2016
Methyl Radicals in Oxidative Coupling of Methane Directly Confirmed by Synchrotron VUV Photoionization Mass Spectroscopy Luo, Liangfeng; Tang, Xiaofeng; Wang, Wendong Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep01625	journal	April 2013
Progress in selective oxidative dehydrogenation of light alkanes to olefins promoted by boron nitride catalysts Shi, Lei; Wang, Yang; Yan, Bing Chemical Communications, Vol. 54, Issue 78 https://doi.org/10.1039/C8CC04604B	journal	January 2018
Effects of ball-milling treatment on physicochemical properties and solid base activity of hexagonal boron nitrides Namba, Shoichiro; Takagaki, Atsushi; Jimura, Keiko Catalysis Science & Technology, Vol. 9, Issue 2 https://doi.org/10.1039/C8CY00940F	journal	January 2019
Activation of methane by oxygen and nitrogen oxides Tabata, K.; Teng, Y.; Takemoto, T. Catalysis Reviews, Vol. 44, Issue 1 https://doi.org/10.1081/CR-120001458	journal	August 2002
Propane oxidative dehydrogenation over highly selective hexagonal boron nitride catalysts: The role of oxidative coupling of methyl Tian, Jinshu; Tan, Jiangqiao; Xu, Mingliang Science Advances, Vol. 5, Issue 3 https://doi.org/10.1126/sciadv.aav8063	journal	March 2019
Selective conversion of syngas to light olefins Jiao, F.; Li, J.; Pan, X. Science, Vol. 351, Issue 6277 https://doi.org/10.1126/science.aaf1835	journal	March 2016
Selective oxidative dehydrogenation of propane to propene using boron nitride catalysts Grant, J. T.; Carrero, C. A.; Goeltl, F. Science, Vol. 354, Issue 6319 https://doi.org/10.1126/science.aaf7885	journal	December 2016

Similar Records

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

Journal Article · Wed Apr 15 00:00:00 UTC 2020 · Angewandte Chemie · OSTI ID:1615042

Zhang, Xuanyu; You, Rui; Wei, Zeyue; +12 more

Tracking Active Phase Behavior on Boron Nitride during the Oxidative Dehydrogenation of Propane Using Operando X-ray Raman Spectroscopy

Journal Article · Mon Nov 06 00:00:00 UTC 2023 · Journal of the American Chemical Society · OSTI ID:2337933

Cendejas, Melissa C.; Paredes Mellone, Oscar A.; Kurumbail, Unni; +9 more

Dynamically Formed Active Sites on Liquid Boron Oxide for Selective Oxidative Dehydrogenation of Propane

Journal Article · Mon Jun 05 00:00:00 UTC 2023 · ACS Catalysis · OSTI ID:1988427

Tian, Jinshu; Collinge, Gregory; Yuk, Simuck F.; +5 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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

Citation Formats

References (50)

Similar Records

Related Subjects