Density Functional Theory Study of Hexagonal Boron Nitride Oxidation Mode

doi:10.6023/A24100324

Abstract

Propylene is one of the important raw chemical materials for producing polypropylene, epichlorohydrin and other chemical products. Propylene is traditionally produced by petroleum steam cracking, which is energy demanding and suffers from coking. In contrast, boron-based oxidative dehydrogenation (ODH) of light alkanes offers an alternative strategy with low energy cost and free of coking, and is growing as a promising protocol in the value-added conversion of shale gas and natural gas. Owing to the lack of molecular level of knowledge of the reaction system, there are many issues related to the underlying mechanism remain in debate, and the extensive mechanistic study relies on the choice of catalyst model to be used in computational studies and in interpreting experimental phenomena. In this work, concerning the importance of oxygenated boron species in the ODH of light alkanes, the oxidation modes of hexagonal boron nitride (h-BN) were evaluated by means of density functional theory (DFT) method to provide insights on the speciation of oxidized h-BN under ODH conditions, which is vital to understand ODH reaction catalyzed by boron-containing materials and to determine sensible choices of oxygenated models. Based on previous investigations, in which oxygenated boron species, e.g. >BOH, >BOB<, >BOOB<, were reported to play crucial role in forming active sites, various oxidation models of h-BN were prepared, differing from each other in the type of oxo species (mono-oxo vs peroxo), the position to be oxidized (B or N sites at zigzag or armchair edge), and the quantity of oxygenated groups (the extent of oxidization). The stability of these models were studied from the thermodynamic perspective, and the ¹¹B nuclear magnetic resonance (¹¹B NMR) and harmonic vibrational modes of oxygenated boron species were calculated. The results show that zigzag-edges of h-BN is the main region to accommodate oxygenated boron species under ODH conditions. In order to reproduce the vibrational frequencies of oxygenated boron species measured in experimental studies, we also proposed a scaling factor of 0.9658 fitted based on the calculated harmonic vibrational frequencies of a set of boron-containing molecules. This work provides a strategy for simplification of boron-based catalysis in the study of their structures and properties and their roles in catalytic reactions conducted under oxidative conditions.

Key words: oxidation modes of hexagonal boron nitride, density functional theory, oxidation dehydrogenation of propane, thermodynamic stability, IR analysis, ¹¹B nuclear magnetic resonance

Cite this article

Ying Ma, Weixi Chen, Yuchen Liu, Ziyi Liu, Tao Wu, An-Hui Lu, Dongqi Wang. Density Functional Theory Study of Hexagonal Boron Nitride Oxidation Mode[J]. Acta Chimica Sinica, 2025, 83(1): 52-59.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 7

References 38

[1]	Sattler, J.; Ruiz-Martinez, J.; Santillan-Jimenez, E.; Weckhuysen, B. M. Chem. Rev. 2014, 114, 10613. doi: 10.1021/cr5002436 pmid: 25163050
[2]	Li, C.-Y.; Wang, G.-W. Chem. Soc. Rev. 2021, 50, 4359.
[3]	Cavani, F.; Ballarini, N.; Cericola, A. Catal. Today 2007, 127, 113.
[4]	Vajda, S.; Pellin, M. J.; Greeley, J. P.; Marshall, C. L.; Curtiss, L. A.; Ballentine, G. A.; Elam, J. W.; Catillon-Mucherie, S.; Redfern, P. C.; Mehmood, F.; Zapol, P. Nat. Mater. 2009, 8, 213.
[5]	Sheng, J.; Yan, B.; Lu, W.-D.; Qiu, B.; Gao, X.-Q.; Wang, D.-Q.; Lu, A.-H. Chem. Soc. Rev. 2021, 50, 1438. doi: 10.1039/d0cs01174f pmid: 33300532
[6]	Klisinska, A.; Samson, K.; Gressel, I.; Grzybowska, B. Appl. Catal. A-Gen. 2006, 309, 10.
[7]	Petit, S.; Gode, T.; Thomas, C.; Dzwigaj, S.; Millot, Y.; Brouri, D.; Krafft, J. M.; Rousse, G.; Laberty-Robert, C.; Costentin, G. Phys. Chem. Chem. Phys. 2017, 19, 9630.
[8]	Zhou, H.; Yi, X.-F.; Hui, Y.; Wang, L.; Chen, W.; Qin, Y.-C.; Wang, M.; Ma, J.-B.; Chu, X.-F.; Wang, Y.-Q.; Hong, X.; Chen, Z.-F.; Meng, X.-J.; Wang, H.; Zhu, Q.-Y.; Song, L.-J.; Zheng, A.-M.; Xiao, F.-S. Science 2021, 372, 76.
[9]	Wang, T.-C.; Yin, J.-L.; Guo, X.-J.; Chen, Y.; Lang, W.-Z.; Guo, Y.-J. J. Catal. 2021, 393, 149.
[10]	Grant, J. T.; McDermott, W. P.; Venegas, J. M.; Bur, S. P.; Micka, J.; Phivilay, S. P.; Carrero, C. A.; Hermans, I. ChemCatChem 2017, 9, 3623.
[11]	Li, P.; Zheng, Y.-N.; Liu, Z.-K.; Lu, A.-H. Acta Phys.-Chim. Sin. 2024, 2406012 (in Chinese).
	( 李佩, 郑跃楠, 刘占凯, 陆安慧, 物理化学学报, 2024, 2406012.)
[12]	Li, S.; Wang, Y. Chem. Propellants Polym. Mater. 2020, 18, 1 (in Chinese).
	( 李师, 王毅, 化学推进剂与高分子材料, 2020, 18, 1.)
[13]	Grant, J. T.; Carrero, C. A.; Goeltl, F.; Venegas, J.; Mueller, P.; Burt, S. P.; Specht, S. E.; McDermott, W. P.; Chieregato, A.; Hermans, I. Science 2016, 354, 1570. doi: 10.1126/science.aaf7885 pmid: 27934702
[14]	Shi, L.; Wang, D.-Q.; Song, W.; Sha, D.; Zhang, W.-P.; Lu, A.-H. ChemCatChem 2017, 9, 1788.
[15]	Shi, L.; Wang, D.-Q.; Lu, A.-H. Chinese J. Catal. 2018, 39, 908.
[16]	Zhou, Y.-L.; Lin, J.; Li, L.; Pan, X.-L.; Sun, X.-C.; Wang, X.-D. J. Catal. 2018, 365, 14.
[17]	Lu, W.-D.; Wang, D.-Q.; Zhao, Z.; Song, W.; Li, W.-C.; Lu, A.-H. ACS Catal. 2019, 9, 8263.
[18]	Liu, Y.-C.; Liu, Z.-Y.; Wang, D.-Q.; Lu, A.-H. J. Phys. Chem. C 2022, 126, 21263.
[19]	Liu, Z.-Y.; Lu, W.-D.; Wang, D.-Q.; Lu, A.-H. J. Phys. Chem. C 2021, 125, 24930.
[20]	Liu, Z.-Y.; Xu, D.-T.; Xia, M.-R.; Lu, W.-D.; Lu, A.-H.; Wang, D.-Q. J. Phys. Chem. Lett. 2021, 12, 8770.
[21]	Love, A. M.; Thomas, B.; Specht, S. E.; Hanrahan, M. P.; Venegas, J. M.; Burt, S. P.; Grant, J. T.; Cendejas, M. C.; McDermott, W. P.; Rossini, A. J.; Hermans, I. J. Am. Chem. Soc. 2019, 141, 182.
[22]	Venegas, J. M.; Zhang, Z.-S.; Agbi, T. O.; McDermott, W. P.; Alexandrova, A.; Hermans, I. Angew. Chem. Int. Ed. 2020, 59, 16527.
[23]	Lu, W.-D.; Gao, X.-Q.; Wang, Q.-G.; Li, W.-C.; Zhao, Z.-C.; Wang, D.-Q.; Lu, A.-H. Chinese J. Catal. 2020, 41, 1837.
[24]	Li, P.; Zhang, X.; Wang, J.; Xue, Y.; Yao, Y.; Chai, S.; Zhou, B.; Wang, X.; Zheng, N.; Yao, J. J. Am. Chem. Soc. 2022, 144, 5930.
[25]	Love, A. M.; Cendejas, M. C.; Thomas, B.; McDermott, W. P.; Uchupalanun, P.; Kruszynski, C.; Burt, S. P.; Agbi, T.; Rossini, A. J.; Hermans, I. J. Phys. Chem. C 2019, 123, 27000.
[26]	Huang, R.; Zhang, B.-S.; Wang, J.; Wu, K.-H.; Shi, W.; Zhang, Y.-J.; Liu, Y.-F.; Zheng, A.-M.; Schlogl, R.; Su, D.-S. ChemCatChem 2017, 9, 3293.
[27]	Yan, B.; Li, W.-C.; Lu, A.-H. J. Catal. 2019, 369, 296.
[28]	Liu, Y.-C.; Liu, Z.-Y.; Lu, W.-D.; Wang, D.-Q.; Lu, A.-H. J. Phys. Chem. Lett. 2022, 13, 11729.
[29]	Liu, Z.-K.; Yan, B.; Meng, S.-Y.; Liu, R.; Lu, W.-D.; Sheng, J.; Yi, Y.-H.; Lu, A.-H. Angew. Chem. Int. Ed. 2021, 60, 19691.
[30]	Zhang, X.-Y.; You, R.; Wei, Z.-Y.; Jiang, X.; Yang, J.-Z.; Pan, Y.; Wu, P.-W.; Jia, Q.-D.; Bao, Z.-H.; Bai, L.; Jin, M.-Z.; Sumpter, B.; Fung, V.; Huang, W.-X.; Wu, Z. Angew. Chem. Int. Ed. 2020, 59, 8042.
[31]	Torii, S.; Jimura, K.; Hayashi, S.; Kikuchi, R.; Takagaki, A. J. Catal. 2017, 335, 176.
[32]	Gao, X.; Zhu, L.; Yang, F.; Zhang, L.; Xu, W.; Zhou, X.; Huang, Y.; Song, H.; Lin, L.; Wen, X.; Ma, D.; Yao, S. Nat. Commun. 2023, 14, 1478.
[33]	Song, Y.; Duan, X.; Jiang, Y.-N.; Ma, Y. J. Phys. Chem. Lett. 2024, 15, 6890.
[34]	Lee, C. T.; Yang, W.-T.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/physrevb.37.785 pmid: 9944570
[35]	Becke, A. D. Phys. Rev. A 1988, 38, 3098.
[36]	Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys. 2010, 132, 154104.
[37]	Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J. Chem. Phys. 1980, 72, 650.
[38]	Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr. J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision C01, 2010.

No.	Reaction	Reaction site
Eq. 2a	pristine_h-BN＋1/2O₂→zigzag-BOH	zigzag-BH
Eq. 2b	pristine_h-BN＋1/2O₂→zigzag-NOH	zigzag-NH
Eq. 2c	pristine_h-BN＋1/2O₂→armchair-BOH	armchair-BH
Eq. 2d	pristine_h-BN＋1/2O₂→armchair-NOH	armchair-NH
Eq. 2e	pristine_h-BN＋1/2O₂→armchair-OH	armchair-BH&NH
Eq. 3a	pristine_h-BN＋3/2O₂→zigzag-BOOB＋H₂O	zigzag-BH
Eq. 3b	pristine_h-BN＋3/2O₂→zigzag-NOON＋H₂O	zigzag-NH
Eq. 3c	pristine_h-BN＋3/2O₂→armchair-BOON＋H₂O	armchair-BH&NH
Eq. 4a	pristine_h-BN＋5/4O₂→zigzag-bri-O＋NO＋1/2H₂O	zigzag-NH
Eq. 4b	pristine_h-BN＋3/4O₂→zigzag-bri-O＋1/2N₂＋1/2H₂O	zigzag-NH
Eq. 4c	pristine_h-BN＋H₂O→zigzag-bri-O＋NH₃	zigzag-NH

No.	Reaction	Reaction site
Eq. 2a	pristine_h-BN＋1/2O₂→zigzag-BOH	zigzag-BH
Eq. 2b	pristine_h-BN＋1/2O₂→zigzag-NOH	zigzag-NH
Eq. 2c	pristine_h-BN＋1/2O₂→armchair-BOH	armchair-BH
Eq. 2d	pristine_h-BN＋1/2O₂→armchair-NOH	armchair-NH
Eq. 2e	pristine_h-BN＋1/2O₂→armchair-OH	armchair-BH&NH
Eq. 3a	pristine_h-BN＋3/2O₂→zigzag-BOOB＋H₂O	zigzag-BH
Eq. 3b	pristine_h-BN＋3/2O₂→zigzag-NOON＋H₂O	zigzag-NH
Eq. 3c	pristine_h-BN＋3/2O₂→armchair-BOON＋H₂O	armchair-BH&NH
Eq. 4a	pristine_h-BN＋5/4O₂→zigzag-bri-O＋NO＋1/2H₂O	zigzag-NH
Eq. 4b	pristine_h-BN＋3/4O₂→zigzag-bri-O＋1/2N₂＋1/2H₂O	zigzag-NH
Eq. 4c	pristine_h-BN＋H₂O→zigzag-bri-O＋NH₃	zigzag-NH

Type of B	Chemical shift	Exp.^[15]
bridging-BOOB	26.8~27.2	—
bridging-B-O	22.6~24.8	24.4 —
twin-BOH	23.1~24.4	24.4 —
zigzag-BOH	28.6~28.8 (middle)	—
	25.4~26.6 (corner)	26.0 —
armchair-BOH	25.6~26.2	26.0 —
zigzag-BOOB	27.2~29.4	—
armchair-BOON	27.5~27.6	—

Type of B	Chemical shift	Exp.^[15]
bridging-BOOB	26.8~27.2	—
bridging-B-O	22.6~24.8	24.4 —
twin-BOH	23.1~24.4	24.4 —
zigzag-BOH	28.6~28.8 (middle)	—
	25.4~26.6 (corner)	26.0 —
armchair-BOH	25.6~26.2	26.0 —
zigzag-BOOB	27.2~29.4	—
armchair-BOON	27.5~27.6	—

Calc.			Exp.
Group	ν/cm⁻¹	Mode	Group	ν/cm⁻¹	mode
B-N	1496	β_B-N	B-N	1325^[30]	β_B-N
	819~874	γ_B-N		815^[30]	γ_B-N
B-OH (zigzag)	3484	ν_BO-H	B-OH	3400^[14]	ν_BO-H
B-OH (zigzag)	729	δ_BO-H	B-OH
B-OH (armchair)	3715 994	ν_BO-H δ_BO-H	B(OH)_xO_3-_x	1100~1200^[24]	δ_B-O
B-OH (armchair)	B-OH (twin)	3484	B(OH)_xO_3-_x	ν_BO-H
	1024	δ_BO-H
B-OH (mix)	3484	ν_BO-H
	753	δ_BO-H
O-O	903~1305	δ_O-O	O-O	927, 1033^[24]	δ_O-O
B-O-B	552~702	δ_B-O	B-O-B	561, 665^[24]	δ_B-O

六方氮化硼氧化模式的密度泛函理论研究