Atomically distributed Al-F3 nanoparticles towards precisely modulating pore size of carbon membranes for gas separation

Xiuling Chen; Zhiguang Zhang; Shan Xu; Bin Zhang; Yong Qin; Canghai Ma; Gaohong He; Nanwen Li

doi:10.1038/s41467-024-54275-1

Atomically distributed Al-F₃ nanoparticles towards precisely modulating pore size of carbon membranes for gas separation

Nat Commun. 2025 Jan 2;16(1):133. doi: 10.1038/s41467-024-54275-1.

Authors

Xiuling Chen^{1

2}, Zhiguang Zhang¹, Shan Xu¹, Bin Zhang³, Yong Qin¹, Canghai Ma⁴, Gaohong He⁵, Nanwen Li⁶

Affiliations

¹ State Key Laboratory of Coal Conversion, Institute of Coal Chemistry Chinese Academy of Sciences, Taiyuan, China.
² Hubei Key Laboratory of Radiation Chemistry and Functional Materials, Hubei University of Science and Technology, Xianning, China.
³ State Key Laboratory of Coal Conversion, Institute of Coal Chemistry Chinese Academy of Sciences, Taiyuan, China. [email protected].
⁴ State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian, China. [email protected].
⁵ State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian, China. [email protected].
⁶ State Key Laboratory of Coal Conversion, Institute of Coal Chemistry Chinese Academy of Sciences, Taiyuan, China. [email protected].

Abstract

To confront the energy consumption, high performance membrane materials are urgently needed. Carbon molecular sieve (CMS) membranes exhibit superior capability in separating gas mixtures efficiently. However, it remains a grand challenge to precisely tune the pore size and distribution of CMS membranes to further improve their molecular sieving properties. Herein, we report an approach of finely modulating CMS pore structure by using the reactive Al(CH₃)₃ to in situ defluorinate the polymer precursor to form Al-F_x(CH₃)_3-x in the polymer matrix, which is further converted to atomic-level Al₂O₃ and Al-F₃ in the polymer matrix. These nanoparticles play the key role in regulating the pore size of CMS membranes by suppressing the formation of unfavorable large pores during pyrolysis, thus enhancing the gas selectivity considerably. The resultant CMS membranes demonstrate a H₂/CH₄ and CO₂/CH₄ selectivity of 192.6, and 58.4, respectively, 128% and 93% higher than the untreated samples, residing far above the latest upper bounds.