Yuanyuan Duan1, Mingyue Qiu2, Shaobo Xu1, Dongna Li1, Haonan Wu2, Liping Chang1, Qun Yi3, Lijuan Shi4, Hongbo Zeng5. 1. Training Base of State Key Laboratory of Coal Science and Technology Jointly Constructed by Shanxi Province and Ministry of Science and Technology, Taiyuan University of Technology, Taiyuan 030024, China. 2. School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, China. 3. Training Base of State Key Laboratory of Coal Science and Technology Jointly Constructed by Shanxi Province and Ministry of Science and Technology, Taiyuan University of Technology, Taiyuan 030024, China; School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, China. Electronic address: yq20071001@163.com. 4. School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, China. Electronic address: shilijuanwit@sina.com. 5. Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9, Canada. Electronic address: hongbo.zeng@ualberta.ca.
Abstract
HYPOTHESIS: Two-dimensional hierarchically porous zeolitic imidazolate frameworks (H-ZIFs) show great promising applications in catalysis, gas separation, energy storage and sensing. Herein, a facile ionic-liquid-modulation approach is proposed for constructing H-ZIFs nanosheets with tunable thickness. EXPERIMENTS: Sulfo-functionalized zwitterionic ionic liquids (SFIL) have been designed as monodentate ligands to direct the formation of microporous nanosheets (ZIF-SFIL) in aqueous solution. Anions of SFIL have been tuned to modulate the coordination environment, enabling the control of the structure, thickness and pores of the nanosheets. FINDINGS: SFIL is demonstrated to pre-coordinate with Zn(II) to induce micropores with high specific surface areas (up to 1176 m2·g-1) and accelerate the nucleation of crystals. The BF4- anion serves as a competitive ligand to partially replace SFIL to cause structural defects, thus yielding hierarchically porous ZIF-SFIL nanosheets with high specific surface areas (270-466 m2·g-1) and variable thicknesses (from ca. 58 nm to ca. 455 nm). Benefiting from the versatile designability and multifunctionality of ionic liquids, the strategy in this work offers a facile approach for designing and constructing multifunctional materials with hierarchical pores.
HYPOTHESIS: Two-dimensional hierarchically porous zeolitic imidazolate frameworks (H-ZIFs) show great promising applications in catalysis, gas separation, energy storage and sensing. Herein, a facile ionic-liquid-modulation approach is proposed for constructing H-ZIFs nanosheets with tunable thickness. EXPERIMENTS: Sulfo-functionalized zwitterionic ionic liquids (SFIL) have been designed as monodentate ligands to direct the formation of microporous nanosheets (ZIF-SFIL) in aqueous solution. Anions of SFIL have been tuned to modulate the coordination environment, enabling the control of the structure, thickness and pores of the nanosheets. FINDINGS: SFIL is demonstrated to pre-coordinate with Zn(II) to induce micropores with high specific surface areas (up to 1176 m2·g-1) and accelerate the nucleation of crystals. The BF4- anion serves as a competitive ligand to partially replace SFIL to cause structural defects, thus yielding hierarchically porous ZIF-SFIL nanosheets with high specific surface areas (270-466 m2·g-1) and variable thicknesses (from ca. 58 nm to ca. 455 nm). Benefiting from the versatile designability and multifunctionality of ionic liquids, the strategy in this work offers a facile approach for designing and constructing multifunctional materials with hierarchical pores.
Authors: José Manuel Martínez Gil; Ricardo Vivas Reyes; Marlon José Bastidas Barranco; Liliana Giraldo; Juan Carlos Moreno-Piraján Journal: Molecules Date: 2022-08-24 Impact factor: 4.927