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CN 37-1316/TU

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Research progress on thermoelectric metalorganic frameworks and covalent organic frameworks materials

XU Biao, ZHANG Wanjia, ZHOU Zihang, LU Xiaoqing, LI Jiao, PAN Guilong, LOU Yue

School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China


Abstract

Significance This review summarizes the latest research progress on functional materials in the field of energy conversion, specifically focusing on metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and their composites. It discusses optimization strategies for the thermoelectric figure of merit (Z), a key parameter that determines the thermoelectric performance of materials, and summarizes the research achievements of MOFs and COFs in thermoelectric applications. The review also explores methods to optimize the thermoelectric properties of MOFs and COFs.

Progress Optimizing the Z value requires balancing three key parameters: the Seebeck coefficient, electrical conductivity, and thermal conductivity. Increasing the Seebeck coefficient generally enhances the Z value, but it can reduce electrical conductivity. Conversely, increasing electrical conductivity may decrease the Seebeck coefficient or increase thermal conductivity. By controlling the types of metal ions and ligand functional groups, and introducing guest molecules with redox activity or inherent conductivity, the Seebeck coefficient and electrical conductivity of MOFs can be optimized. Meanwhile, increasing scattering centers can reduce thermal conductivity. For COFs, improving conductivity can be achieved by adjusting covalent bonds and connecting molecules to create different electronic properties, or through chemical doping to form charge-transfer composites.

Conclusions and Prospects Despite the potential of MOFs and COFs materials, their thermoelectric performance still faces significant challenges due to their relatively low conductivity. The future development of MOFs, COFs, and their composites remains difficult. MOFs possess unique periodicity and porous structures, which help achieve ultra-low thermal conductivity. However, factors such as the size and valence of metal ions, pore size and distribution, structural rigidity, and the impact of guest molecules on thermal conductivity require systematic study. Therefore, calculations and analyses of the electron and phonon transport mechanisms in MOFs are needed to provide a basis for the rational selection of metal ions and organic linkers. Due to the challenges in synthesis and their inherently low conductivity, the thermoelectric properties of COFs have not yet been fully explored. Most studies focus either on the electrical or thermal conductivity of COFs, and much of the research still lack practical applications. Future studies should combine theoretical research with experimental design, using precise molecular design to prepare COFs with high periodicity, fewer defects, and better alignment. This would improve mass transport and charge transfer, continuously enhancing the thermoelectric performance of COFs. The ultimate goal of developing flexible thermoelectric devices based on MOFs and COFs is to enable their widespread applications in thermoelectric field.

Keywords: thermoelectric performance; metal-organic framework materials; covalent organic framework materials; material design


Get Citation:ZHANG Wanjia, ZHOU Zihang, et al. Research progress on thermoelectric metalorganic frameworks and covalent organic frameworks materials[J]. China Powder Science and Technology, 2025, 31(1): 62−74.

Received:2024-07-07.Revised: 2024-10-10,Online:2024-10-18.

Funding Project: 国家自然科学基金项目,编号:22375093。

First Author:徐骉(1987—), 男, 教授, 博士, 博士生导师, 国家第十五批“海外高层次人才计划”, 研究方向为纳米热电材料的液相 合成。E-mail:xubiao@njust. edu. cn。

Corresponding Author: 娄悦(1992—), 女, 副教授, 博士, 硕士生导师, 江苏省双创博士, 研究方向为纳米热电材料的合成。E-mail:louyue@njust.edu.cn。

CLC No:TB383; O642.3; TB44              Type Code:A

Serial No:1008-5548(2025)01-0062-13