Isomers of organic structure directing agent influence the Al distribution of AEI zeolite and catalytic performance in methane oxidation

doi:10.1016/S1872-2067(25)64702-4

Abstract

Abstract:

Small pore zeolites have been reported to show salient performance in methane oxidation reactions. Among them, the synthesis of AEI zeolite is highly dependent on organic structure-directing agents (OSDA). The isomer OSDAs have been informed to influence the crystallization rate and spatial Al distribution on the crystalline particle of AEI zeolite. Still, its impact on the framework Al distribution of the AEI zeolite is not well known, which significantly impacts the subsequent loading of metal cations and thus active sites available for catalytic reactions. We herein report the impact of the isomer OSDA for synthesizing AEI-type aluminosilicate zeolite on the Al distribution. The discrepancy of Al distribution in as-synthesized AEI zeolites directed by trans and cis-rich OSDAs was identified by ²⁷Al MQMAS/MAS NMR and density functional theory (DFT). The cis-OSDA gave a higher intensity of bands at 60-63 ppm as the shoulder of tetracoordinated Al. The trans-rich OSDA guided to a slightly higher Al content and a slightly higher proportion of Al pairs than the cis-one. The DFT calculation indicated that trans- and cis-OSDAs preferentially led to the Al atoms at the T3 and T1 sites, respectively. The exchanged Cu/AEI zeolites with varied Cu content were applied in the direct and continuous oxidation of methane reaction and exhibited different activities. Given the results, we report here the methane activation properties of the Cu/AEI zeolites and how the isomer identity of the OSDA impacts the activity of Cu/AEI in methane oxidation to methanol. This work highlighted that isomer OSDA influenced the Al distribution as well as crystallization kinetics and gave an insight into the design of the OSDA for zeolite synthesis.

Key words: AEI zeolite, Isomer organic structure-directing, agents, Al distribution, Methane to methanol

Peipei Xiao, Yong Wang, Xiaomin Tang, Anmin Zheng, Trees De Baerdemaeker, Andrei-Nicolae Parvulescu, Dirk De Vos, Xiangju Meng, Feng-Shou Xiao, Hermann Gies, Toshiyuki Yokoi. Isomers of organic structure directing agent influence the Al distribution of AEI zeolite and catalytic performance in methane oxidation[J]. Chinese Journal of Catalysis, 2025, 73: 252-260.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64702-4

https://www.cjcatal.com/EN/Y2025/V73/I6/252

Figures/Tables 9

Fig. 1. (a) XRD patterns of AEI zeolites synthesized by trans and cis isomers of OSDAs. SEM images of AEI(trans) (b) and AEI(cis) (c). (d) N2 adsorption-desorption isothermals of AEI zeolites synthesized by isomers of OSDAs. Compared TG (e) and DTA (f) curves of AEI zeolites synthesized by isomers of OSDAs.

Fig. 2. 27Al MQMAS NMR spectra for as-synthesized AEI(trans) (a) and AEI(cis) zeolite (b). (c) 27Al MAS NMR spectra of as-synthesized AEI(trans) and AEI(cis) zeolites. (d) The location of three T sites in AEI zeolite. Al location in AEI zeolite directed by trans (e) and cis OSDA (f).

Fig. 3. NH3-TPD curves for xCu/AEI(trans) (a) and yCu/AEI(cis) (b).

Table 1 Chemical composition and acid amount of AEI zeolite measured by NH3-TPD.

Sample	Si/Al ^a	Cu/Al ^a	Cu content (wt%)	Acid amount by NH₃-TPD (mmol/g)
Sample	Si/Al ^a	Cu/Al ^a	Cu content (wt%)	LT ^b	MT ^c	HT ^d	Total
H-AEI(trans)	8.7	—	—	0.50	0.41	0.52	1.43
1Cu/AEI(trans)	9.6	0.07	0.65	0.34	0.48	0.53	1.35
5Cu/AEI(trans)	9.6	0.09	0.88	0.29	0.62	0.47	1.38
50Cu/AEI(trans)	9.7	0.20	1.85	0.28	0.73	0.46	1.46
H-AEI(cis)	9.6	—	—	0.50	0.43	0.50	1.43
1Cu/AEI(cis)	10.1	0.07	0.59	0.33	0.46	0.48	1.27
5Cu/AEI(cis)	10.1	0.09	0.83	0.33	0.61	0.45	1.39
50Cu/AEI(cis)	10.2	0.20	1.80	0.37	0.69	0.39	1.46

Fig. 4. Compare UV-vis spectra (a), NO adsorption (PNO = 80 Pa) FTIR spectra at -120 °C after activation at 500 °C for 1 h (b), and CO adsorption (PNO = 1000 Pa) FTIR spectra at -120 °C after activation at 500 °C for 1 h (c) of 5Cu/AEI (trans) and 5Cu/AEI(cis).

Fig. 5. Reaction performance of 1Cu/AEI(trans) (a), 5Cu/AEI(trans) (b), and 50Cu/AEI(trans) (c) zeolite at 300-450 °C. (d) Compare the CH4 conversion of xCu/AEI(trans) zeolite at 300-450 °C. Reaction conditions: 100 mg catalyst, CH4/N2O/H2O/Ar = 10/10/2/3 mL/min, WHSV=15000 mL/(g·h).

Fig. 6. Compare the product distribution of xCu/AEI(trans) (a) and yCu/AEI(cis) (b) zeolite at 300 °C. Compare the methanol formation rate (c) and CH4 conversion (d) of xCu/AEI(trans) and yCu/AEI(cis) zeolite at 300 °C. Reaction conditions:100 mg catalyst, CH4/N2O/H2O/Ar = 10/10/2/3 mL/min, WHSV = 15000 mL/(g·h).

Fig. 7. Compare the stability of 1Cu/AEI(trans) (a) and 1Cu/AEI(cis) (b) zeolite at 350 °C. Reaction conditions: 100 mg catalyst, CH4/N2O/H2O/Ar = 10/10/2/3 mL/min, WHSV=15000 mL/(g·h). (c) Compare the CO adsorption FTIR spectra of 1Cu/AEI(trans) and 1Cu/AEI (cis) at -120 °C after activation at 500 °C for 1 h.

Fig. 8. Compare the stability of 5Cu/AEI(trans) (a) and 5Cu/AEI(cis) (b) zeolite at 350 °C. Reaction conditions: 100 mg catalyst, CH4/N2O/H2O/Ar = 10/10/2/3 mL/min, WHSV=15000 mL/(g·h).

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