Synergistically enhanced capture of perfluorooctanoic acid using a novel dual metal-organic framework adsorbent--颗粒学报PARTICUOLOGY

Lin, H., Xia, Z., Xue, K., Zhou, X., Yao, Y., Ma, N., & Dai, W. (2025). Synergistically enhanced capture of perfluorooctanoic acid using a novel dual metal-organic framework adsorbent. Particuology, 97, 130-142. https://doi.org/10.1016/j.partic.2024.12.009

Synergistically enhanced capture of perfluorooctanoic acid using a novel dual metal-organic framework adsorbent

Heng Lin^a, Zhouheng Xia^a, Kunpeng Xue^{a b}, Xiaojing Zhou^a, Yifan Yao^a, Na Ma^c, Wei Dai^a *

a Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, Jinhua, 321004, China
b One Two Chromatography Technology (Hangzhou) Co., Ltd, Jinhua, 321000, China
c College of Geography and Environmental Sciences, Zhejiang Normal University, Jinhua, 321004, China

10.1016/j.partic.2024.12.009

Volume 97, February 2025, Pages 130-142

Received 25 October 2024, Revised 16 December 2024, Accepted 19 December 2024, Available online 13 January 2025, Version of Record 13 January 2025.

E-mail: daiwei@zjnu.edu.cn

Highlights

• A novel MIL-101(Cr)@ZIF-8 was first prepared and developed.

• MIL-101(Cr)@ZIF-8 exhibits excellent adsorption performances toward perfluorooctanoic acid.

• Synergistic effects of pores and bimetallic features enhance the adsorption performance.

Abstract

Metal-Organic Framework (MOF) have gained widespread attention as potential adsorbents for the removal of perfluorooctanoic acid (PFOA). However, single-component MOF often exhibit limitations in adsorption capacity, functionality, and pore structure. Hereby, we innovatively designed and synthesized a dual-metal core-shell MOF composite adsorbent, MIL-101(Cr)@ZIF-8 (a chromium-zinc bimetallic MOF, CZDM), which exhibits an excellent adsorption removal performance of PFOA from aqueous solutions. The results showed that the CZDM composite material has a high specific surface area (2091 m²/g), with pore structures exhibiting typical micropores (∼1.16 nm) and mesopores (∼3.4 nm), which are crucial for the efficient adsorption of PFOA. SEM and TEM images revealed that CZDM has a uniform core-shell morphology, with MIL-101(Cr) as the core and ZIF-8 as the shell, maintaining a stable and intact structure. EDX analysis further confirmed the successful incorporation of Cr and Zn elements. Batch experiments evaluated the effects of temperature, solution pH, and PFOA concentration on adsorption efficiency. The results demonstrated that the CZDM-3 adsorbent exhibited rapid adsorption kinetics and good PFOA removal efficiency across a wide pH range. The superior adsorption performance of CZDM is attributed to the synergistic effect of the dual-metal active sites, optimized pore structure, electrostatic interactions, and coordination bonds. The maximum adsorption capacity for PFOA reached 625.5 mg/g, with equilibrium achieved within 60 min, outperforming some related reported adsorbents. The experimental data of the adsorption process fit well with both Langmuir adsorption isotherms and pseudo-second-order kinetics models, indicating that the adsorption process is spontaneous, endothermic, and accompanied by an increase in entropy. Notably, even after five cycles, the CZDM material maintained high removal efficiency toward PFOA. This study advances a new synthesizing strategy of the MOF@MOF, and the CZDM exhibits a potential application in PFOA elimination from water.

Graphical abstract

Keywords

MIL-101(Cr); ZIF-8; MIL-101(Cr)@ZIF-8; Perfluorooctanoic acid; Adsorption

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