C-H bond activation of propane on Ga2O22+ in Ga/H-ZSM-5 and its mechanistic implications

doi:10.1016/S1872-2067(24)60065-3

Abstract

Abstract:

Propane dehydrogenation (PDH) on Ga/H-ZSM-5 catalysts is a promising reaction for propylene production, while the detail mechanism remains debatable. Ga₂O₂²⁺ stabilized by framework Al pairs have been identified as the most active species in Ga/H-ZSM-5 for PDH in our recent work. Here we demonstrate a strong correlation between the PDH activity and a fraction of Ga₂O₂²⁺ species corresponding to the infrared GaH band of higher wavenumber (GaH_HW) in reduced Ga/H-ZSM-5, instead of the overall Ga₂O₂²⁺ species, by employing five H-ZSM-5 supports sourced differently with comparable Si/Al ratio. This disparity in Ga₂O₂²⁺ species stems from their differing capacity in completing the catalytic cycle. Spectroscopic results suggest that PDH proceeds via a two-step mechanism: (1) C-H bond activation of propane on H-Ga₂O₂²⁺ species (rate determining step); (2) β-hydride elimination of adsorbed propyl group, which only occurs on active Ga₂O₂²⁺ species corresponding to GaH_HW.

Key words: Propane dehydrogenation, Ga₂O₂²⁺, Activation of C-H bond, Ga species

Zhaoqi Zhao, Yunzhu Zhong, Xiaoxia Chang, Bingjun Xu. C-H bond activation of propane on Ga₂O₂²⁺ in Ga/H-ZSM-5 and its mechanistic implications[J]. Chinese Journal of Catalysis, 2024, 64: 32-43.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60065-3

https://www.cjcatal.com/EN/Y2024/V64/I9/32

Figures/Tables 12

Table 1 The physicochemical characterization of five zeolite samples.

Sample	Si/Al ratio ^a	BAS density^b (μmol g^-1)	Micropore volume^c (mL g^-1)	Al pairs density^d(%)	Ga/Al ratio ^e	BAS_res^f (μmol g^-1)
A	10.2	1522	0.13	37.9	0.25	1269
B	11.2	1424	0.11	22.6	0.25	1382
C	9.0	1675	0.14	33.9	0.27	988
D	9.6	1212	0.12	24.8	0.24	825
E	11.4	1235	0.13	16.8	0.24	870

Fig. 1. (a) The Ga2O22+/BAS ratio as a function of the Ga/Al ratio on Sample A. (b) STY of C3H6 normalized to the Ga2O22+ density determined with pulse titration as a function of the Ga/Al ratio.

Fig. 2. (a) In-situ FTIR spectra of GaH formed in a pure H2 atmosphere in different Ga/H-ZSM-5 samples. The background spectrum was collected in the spectral cell with a dehydrated sample pellet at 500 °C under vacuum. Spectra presented have been background corrected. (b) Normalized GaH area determined in infrared spectra and PDH rates between different types of zeolites. Reaction conditions: 500 °C; C3H8 partial pressure, 5.07 kPa with balancing N2. The propane conversions are below 3.5% in the rate measurements.

Fig. 3. (a) In-situ FTIR spectra of GaH in Sample A when treated with C3H8 (5.07 kPa, N2 as the carrier gas). Background spectrum was collected in the transmission cell on a dehydrated sample pellet at 500 °C under vacuum. (b) Normalized GaHHW area determined in infrared spectra and PDH rates on the five zeolite samples investigated.

Fig. 4. (a) Peak fitting on the overlapping GaH peaks of sample A before and after oxidation. The spectra presented have been background corrected. (b) STY of propylene normalized to the amount of framework Al atoms vs. time-on-stream. Reaction conditions: 500 °C; C3H8 partial pressure, 5.07 kPa with balancing N2. Propane conversions are below 2.0% in the rate measurements.

Scheme 1. Schematic hypothesis of the transformation of Ga species under redox treatment on Ga/H-ZSM-5.

Fig. 5. In-situ FTIR spectra of the GaH species on Sample A under varied H2 partial pressure with peak fitting analysis: 5% (a); 10% (b); 100% (c) (N2 as the balance gas). Black dots represent the experimental data, thick black trace represents the overall fitting, and red lines represent the deconvoluted peaks. The raw spectra presented have been background corrected. (d) Normalized GaHLW and GaHHW peak areas under different H2 partial pressures.

Fig. 6. (a) In-situ FTIR spectra of GaH in Ga/H-ZSM-5 (sample A) during H2 treatment for 2, 6, 10, 14, 20, 40 min. (b) In-situ FTIR spectra of GaH during evacuation after H2 reduction and evacuating H2 for 2, 4, 6, 10, 18, 42 min. Background spectra were collected in the spectral cell with a dehydrated sample pellet at 500 °C under vacuum.

Scheme 2. Proposed PDH mechanism on D2-pretreated Ga2O22+ corresponding to GaHHW and GaHLW respectively.

Fig. 7. (a) In-situ FTIR spectra of GaH in the reduced Sample A (Ga/Al = 0.24) (i) being treated with D2 for ~20 min; (ii) after C3H8 treatment under PDH conditions. Background spectra were collected in the spectral cell with a dehydrated sample pellet under vacuum at 500 °C. (b) In-situ FTIR spectra of GaD in Sample A (Ga/Al = 0.24) (i) after H2-D2 exchange under D2 atmosphere; (ii) after C3H8 treatment followed by evacuation. Background spectra were collected in the spectral cell with a reduced sample pellet at 500 °C under H2 atmosphere. The spectra in (ii) and (iii) have been background corrected.

Scheme 3. Schematic of proposed mechanism for the PDH on Ga2O22+ species.

Fig. 8. (a) In-situ FTIR spectra collected on H2 treated Ga/H-MFI (black), Ga/H-BEA (blue), and Ga/H-MOR (green) at 500 °C. Background spectra were collected at the same conditions but without the H2 treatment. The spectra presented have been background corrected. (b) Space-time-yield (STY) of C3H6, CH4 and C2H4 normalized to the mass of the catalysts and corresponding selectivity to C3H6 on Ga/H-MFI, Ga/H-BEA and Ga/H-MOR. Reaction conditions: 500 °C; C3H8 partial pressure, 5.07 kPa with balancing N2. The propane conversions are below 3.5% in the rate measurements.

References

[1]	X. Li, C. Pei, J. Gong, Chem, 2021, 7, 1755-1801.
[2]	W. Yan, Q. Sun, J. Yu, Matter, 2021, 4, 2642-2644.
[3]	Y. He, Y. Song, D. A. Cullen, S. Laursen, J. Am. Chem. Soc., 2018, 140, 14010-14014.
[4]	N. M. Schweitzer, B. Hu, U. Das, H. Kim, J. Greeley, L. A. Curtiss, P. C. Stair, J. T. Miller, A. S. Hock, ACS Catal., 2014, 4, 1091-1098.
[5]	J. H. Yun, R. F. Lobo, J. Catal., 2014, 312, 263-270.
[6]	J. J. H. B. Sattler, J. Ruiz-Martinez, E. Santillan-Jimenez, B. M. Weckhuysen, Chem. Rev., 2014, 114, 10613-10653.
[7]	S. Chen, X. Chang, G. Sun, T. Zhang, Y. Xu, Y. Wang, C. Pei, Chem. Soc. Rev, 2021, 50, 3315-3354.
[8]	H. Kitagawa, Y. Sendoda, Y. Ono, J. Catal., 1986, 101, 12-18.
[9]	E. Iglesia, J. E. Baumgartner, G. L. Price, J. Catal., 1992, 134, 549-571.
[10]	S. Song, Y. Sun, K. Yang, Y. Fo, X. Ji, H. Su, Z. Li, C. Xu, G. Huang, J. Liu, W. Song, ACS Catal., 2023, 13, 6044-6067.
[11]	M. Raad, A. Astafan, S. Hamieh, J. Toufaily, T. Hamieh, J. D. Comparot, C. Canaff, T. J. Daou, J. Patarin, L. Pinard, J. Catal., 2018, 365, 376-390.
[12]	Y. Yuan, Z. Zhao, R. F. Lobo, B. Xu, Adv. Sci., 2023, 10, 2207756.
[13]	S. Shen, X. Liu, Y. Guo, Y. Wang, Acta Phys.-Chim. Sin., 2023, 39, 2209043.
[14]	G. D. Meitzner, E. Iglesia, J. E. Baumgartner, E. S. Huang, J. Catal., 1993, 140, 209-225.
[15]	V. B. Kazansky, I. R. Subbotina, R. A. van Santen, E. J. M. Hensen, J. Catal., 2004, 227, 263-269.
[16]	V. B. Kazansky, I. R. Subbotina, R. A. van Santen, E. J. M. Hensen, J. Catal., 2005, 233, 351-358.
[17]	M. W. Schreiber, C. P. Plaisance, M. Baumgärtl, K. Reuter, A. Jentys, R. Bermejo-Deval, J. A. Lercher, J. Am. Chem. Soc., 2018, 140, 4849-4859.
[18]	N. M. Phadke, E. Mansoor, M. Bondil, M. Head-Gordon, A. T. Bell, J. Am. Chem. Soc., 2019, 141, 1614-1627.
[19]	N. Rane, A. Overweg, V. Kazansky, R. Vansanten, E. Hensen, J. Catal., 2006, 239, 478-485.
[20]	N. M. Phadke, J. van der Mynsbrugge, E. Mansoor, A. B. Getsoian, M. Head-Gordon, A. T. Bell, ACS Catal., 2018, 8, 6106-6126.
[21]	Y. Yuan, R. F. Lobo, B. Xu, ACS Catal., 2022, 12, 1775-1783.
[22]	Y. Yuan, C. Brady, L. Annamalai, R. F. Lobo, B. Xu, J. Catal., 2021, 393, 60-69.
[23]	Y. Yuan, C. Brady, R. F. Lobo, B. Xu, ACS Catal., 2021, 11, 10647-10659.
[24]	E. J. M. Hensen, E. A. Pidko, N. Rane,R. A. van Santen, Angew. Chem. Int. Ed., 2007, 46, 7273-7276.
[25]	E. Pidko, E. Hensen, G. Zhidomirov, R. Vansanten, J. Catal., 2008, 255, 139-143.
[26]	E. Iglesia, J. E. Baumgartner, Catal. Lett., 1993, 21, 55-70.
[27]	E. Iglesia, J. E. Baumgartner, G. D. Meitzner, Stud. Surf. Sci. Catal., 1993, 75, 2353-2357.
[28]	E. Mansoor, M. Head-Gordon, A. T. Bell, ACS Catal., 2018, 8, 6146-6162.
[29]	N. S. Gould, B. Xu, ACS Catal., 2018, 8, 8699-8708.
[30]	J. A. Biscardi, E. Iglesia, Catal. Today, 1996, 31, 207-231.
[31]	J. A. Biscardi, E. Iglesia, J. Phys. Chem. B, 1998, 102, 9284-9289.

C-H bond activation of propane on Ga₂O₂²⁺ in Ga/H-ZSM-5 and its mechanistic implications

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