Boosting CO2-mediated aromatic cycle via mesoporous design in propane aromatization catalysis

doi:10.1016/S1872-2067(26)64950-9

Abstract

Abstract:

Understanding how structure regulates reaction pathways is critical for the rational design of propane (C₃H₈)-coupled CO₂ aromatization (PCA) catalysts. Here, alkaline treatments precisely tuned zeolite pore size (3.8 → 8.9 Å) and Al distribution, boosting benzene, toluene, and xylene selectivity from 18% (Ga-T-ZSM-5) to 57% (Ga/M-ZSM-5). Mechanistic studies, including ¹³CO₂ isotope tracing, mass spectrometry, pulse reactions, and in-situ Fourier transformed infrared confirmed that this reaction follows a dual-cycle hydrocarbon pool mechanism. Critically, CO₂ was inserted into the hydrocarbon pool, generating oxygenated intermediates that underwent dehydration and cyclization to form aromatic intermediate species, thereby accelerating the aromatic cycle. The intensified aromatic cycle generated bulky polycyclic aromatics that may obstruct micropores under diffusion-limited conditions. Introducing mesopores alleviated such accumulation by facilitating rapid molecular transport of these high-carbon species. The synergy between the CO₂-mediated hydrocarbon pool pathway and mesopore-enhanced diffusion of aromatic intermediates significantly boosted aromatic selectivity. This interplay provides fundamental insights for future catalyst design.

Key words: Alkaline treatments, Mesoporous structure, Aromatic cycle, CO₂ synergy, Mass transfe

Luyuan Yang, Yitao Yang, Min Yang, Yucai Qin, Xiaoxin Zhang, Saeed Soltanali, Jian Liu, Weiyu Song. Boosting CO₂-mediated aromatic cycle via mesoporous design in propane aromatization catalysis[J]. Chinese Journal of Catalysis, 2026, 84: 226-235.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64950-9

https://www.cjcatal.com/EN/Y2026/V84/I5/226

Figures/Tables 6

Fig. 1. XRD patterns (a), pore size distribution curves (b), and nitrogen adsorption-desorption isotherms (c) of M-ZSM-5, N-ZSM-5, T-ZSM-5, ZSM-5, and Ga/ZSM-5. (d) -OH FTIR spectra of samples. P = 1 atm, pCO2:pC3H8:pN2 = 1:1:18, total flow rate: 30 mL/min, T = 150 °C.

Fig. 2. The SEM and TEM spectra of Ga/T-ZSM-5 (a1-a4), Ga/ZSM-5 (b1-b4), Ga/N-ZSM-5 (c1-c4), and Ga/M-ZSM-5 (d1-d4).

Fig. 3. Acid content measured by NH3-TPD (a), Py-IR (b), and the difference between the two measurement methods (c) in zeolite samples. (d) UV-vis-DRS spectra of Co(II) ions for 27Al MAS NMR spectra of ZSM-5, T-ZSM-5, N-ZSM-5, and M-ZSM-5. (e) Schematic diagram of Al-pairs and Single Al adsorbed the product benzene and the intermediate cyclopentanone.

Fig. 4. (a-d) Product distribution (bars) and C3H8 and CO2 conversion under 550 °C, p = 1 atm, C3H8: CO2: N2 = 1:1:1, WHSV= 5.24 h-1 (black and red points, respectively). CO2-TPD (e) and C3H8-TPD (f) profiles of samples.

Fig. 5. (a-d) Mass detection of benzene in the early reaction stage when a propane pulse is injected at 400 °C. (e) Mass detection of benzene when a C3H8/CO2 pulse is injected at 400 °C. (f) In-situ FTIR of Ga/ ZSM-5 under increasing temperature (100-400 °C), p = 1 atm, C3H8: CO2: N2 = 1:1:18, WHSV = 31.72 h-1. (g) In-situ MS of Ga/M-ZSM-5 under 550 °C, 1 atm, C3H8: CO2: N2 = 1:1:1, WHSV = 50.6 h-1. 13C isotope tracing MS spectra of pentanoic acid (h) and cyclopentenone (i) of 13CO2 and 12CO2 during the coupling reaction, 0.05 g Ga/M-ZSM-5, T = 400 °C, p = 1 atm, C3H8: 12CO2(13CO2): N2 = 1.5:1.5:10, WHSV = 22.07 h-1. (j) Schematic diagram of the double cycle involving CO2 in PCA.

Fig. 6. UV-vis spectra (a) and ZLC desorption curve (b) of benzene on the sample at 230 °C. (c) Benzene content with the change in partial pressure of CO2 in C3H8 coupling CO2 aromatization, 0.05 g catalyst, T = 550 °C, P = 0.1 MPa, pC3H8:pCO2 = 5:x:10-x, (x = 5, 6, 8, 10), N2 as an equilibrium gas, total flow rate: 15 mL/min.

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Boosting CO₂-mediated aromatic cycle via mesoporous design in propane aromatization catalysis

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