Engineering O-O Species in Boron Nitrous Nanotubes Increases Olefins for Propane Oxidative Dehydrogenation

Panpan Li; Xuejing Zhang; Jingnan Wang; Yanming Xue; Yongbin Yao; Shanshan Chai; Bo Zhou; Xi Wang; Nanfeng Zheng; Jiannian Yao

doi:10.1021/jacs.1c13563

Engineering O-O Species in Boron Nitrous Nanotubes Increases Olefins for Propane Oxidative Dehydrogenation

J Am Chem Soc. 2022 Apr 6;144(13):5930-5936. doi: 10.1021/jacs.1c13563. Epub 2022 Mar 22.

Authors

Panpan Li¹, Xuejing Zhang², Jingnan Wang³, Yanming Xue⁴, Yongbin Yao¹, Shanshan Chai¹, Bo Zhou⁵, Xi Wang¹, Nanfeng Zheng⁶, Jiannian Yao^{2

7}

Affiliations

¹ Department of Physics, School of Science, Beijing Jiaotong University, Beijing 100044, P. R. China.
² School of Chemical Engineering and Technology, Molecular Plus and Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin 300072, P. R. China.
³ School of Chemical Engineering and Technology, Tianjin University, Molecular Plus and Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, P. R. China.
⁴ School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300401, P. R. China.
⁵ Chemistry and Chemical Engineering Guangdong Laboratory, Shantou 515031, P. R. China.
⁶ State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
⁷ Key Laboratory of Photochemistry Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.

PMID: 35316601
DOI: 10.1021/jacs.1c13563

Abstract

Boron nitride (BN) has been widely studied as an efficient catalyst for oxidative propane dehydrogenation (OPDH). Oxygen-containing boron species (e.g., BO·, B(OH)_xO_3-x) are generally considered as the active centers in BN for OPDH. Here, we show an effective progressive substitution strategy toward the development of boron-oxygen-nitrogen nanotubes (BONNTs) enriched with O-O species as a highly active, selective, and stable catalyst for OPDH. At 525 °C, an olefin yield of 48.6% is achieved over BONNTs with a propane conversion of 64.4%, 2.8 times that of boron nitrogen nanotubes (BNNTs). Even after reaction for 150 h (475 °C), BONNTs exhibit good olefin yield. Both the B(OH)_xO_3-x and O-O species that coexist in the BONNT catalyst are demonstrated as active centers, which differs from the B(OH)_xO_3-x one in BNNTs. Based on catalytic results, propane and oxygen alternate treatment experiments, and theoretical calculations, the O-O center is more favorable for producing both propylene (C₃₌) and ethylene (C₂₌), which experiences a dehydration pathway and two possible reaction paths with a lower energy barrier to yield olefins, while B(OH)_xO_3-x is mainly responsible for producing few C₃₌.