Metal ion assistant transformation strategy to synthesize catechol-based metal–organic frameworks from Ti3C2Tx precursors

• Published in: Science bulletin (Beijing) Vol. 68; no. 19; pp. 2180 - 2189
• Main Authors: Wang, Weikang, Bai, Yan, Yang, Pin, Yuan, Shuai, Li, Feiyang, Zhao, Weiwei, Jin, Beibei, Zhang, Xuan, Liu, Shujuan, Yuan, Daqiang, Zhao, Qiang
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-10-2023
• Subjects: Electron transfer; Insoluble metal precursors; Metal ion assistant transformation strategy; Metal–organic frameworks; MXene; Electron transfer; Insoluble metal precursors; Metal–organic frameworks; MXene; Metal ion assistant transformation strategy
• ISSN: 2095-9273
• DOI: 10.1016/j.scib.2023.07.038

This work first exploits the feasibility of metal ion assistant transformation strategy to synthesize 3D catechol-based MOFs using 2D MXene as metal precursors, which exhibit obvious originality and universality in the field of transform synthesis. The unique synergetic transformation mechanism involves the electron transfer from Ti3C2Tx to electrostatically adsorbed Cu2+ ion for redox reaction, subsequent Ti–C bond rupture for Ti4+ ion release, and the continuous chelation coordination between Ti4+/Cu2+ and HHTP. It motivates further works to utilize the electron transfer to provide a bridge for the conversion of MXene to MOFs and serve as a key step for the release of transition metal ions.
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Chemical transformation strategy is capable of fabricating nanomaterials with well-defined structures and fascinating performance via controllable crystallization kinetics in the phase transformation. V2CTx MXene has been used as precursors to fabricate vanadium porphyrin metal–organic frameworks (V-PMOFs) via the coordination of deprotonated carboxylic acid ligands. However, the rational and in-depth exploration of synthesis mechanism with the aim of enriching the variety of MXene (i.e., Ti3C2Tx) and organic ligands (i.e., catechol-based) to design new MOFs is rarely reported. Herein, we have first developed a metal ion assistant transformation strategy to synthesize three-dimensional catechol-based TiCu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) MOFs with a non-interpenetrating SrSi2 (srs) framework using two-dimensional Ti3C2Tx as precursors. The unique synergetic transformation mechanism involves the electron transfer from Ti3C2Tx to electrostatically adsorbed Cu2+ ion for redox reaction, the subsequent Ti–C bond rupture for Ti4+ ion release, and the continuous chelation coordination between Ti4+/Cu2+ and HHTP. Ti3C2Tx precursors and auxiliary metal ion could be rationally substituted by V2CTx and Mn+ (e.g., Ni2+, Co2+, Mn2+, and Zn2+), respectively. This strategy lays the foundation for the design and synthesis of innovative and multifarious MOFs derived from MXene or other unconventional metal precursors.