Ion-doping-regulated Electron-phonon Coupling Behavior in Two-dimensional Covalent Organic Frameworks and Its Influence on Thermal Transport Mechanisms

Zi-han Tan; Sheng-yang Zhou; Zhong-ming Li

doi:10.11777/j.issn1000-3304.2026.26179

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Ion-doping-regulated Electron-phonon Coupling Behavior in Two-dimensional Covalent Organic Frameworks and Its Influence on Thermal Transport Mechanisms

更新时间：2026-10-14

- Ion-doping-regulated Electron-phonon Coupling Behavior in Two-dimensional Covalent Organic Frameworks and Its Influence on Thermal Transport Mechanisms
- Acta Polymerica Sinica Pages: 1-11(2026)
- 作者机构：
  
  四川大学材料科学与工程学院高分子科学与工程学院先进高分子材料全国重点实验室成都 610065
- 作者简介：
  
  Sheng-yang Zhou, E-mail: shengyang.zhou@scu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26179
  CLC：
- CSTR：32057.14.GFZXB.2026.7691
- Received：26 May 2026，
  
  Accepted：17 July 2026，
  
  Online First：14 October 2026，
- 稿件说明：
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谭子涵, 周生洋, 李忠明. 离子掺杂调控二维共价有机框架的声电耦合行为及其对热传导的影响机制. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26179.

Tan, Z. H.; Zhou, S. Y.; Li, Z. M. Ion-doping-regulated electron-phonon coupling behavior in two-dimensional covalent organic frameworks and its influence on thermal transport mechanisms. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26179.
谭子涵, 周生洋, 李忠明. 离子掺杂调控二维共价有机框架的声电耦合行为及其对热传导的影响机制. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26179. DOI： CSTR： 32057.14.GFZXB.2026.7691.

Tan, Z. H.; Zhou, S. Y.; Li, Z. M. Ion-doping-regulated electron-phonon coupling behavior in two-dimensional covalent organic frameworks and its influence on thermal transport mechanisms. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26179. DOI： CSTR： 32057.14.GFZXB.2026.7691.

摘要

二维共价有机框架材料(2D-COFs)因其高度有序的晶体孔道结构与可编程的分子设计特性，在气体分离、分子吸附及光催化等功能材料领域展现出广阔的应用前景. 然而，相较于其电子与离子输运行为，关于2D-COFs热传导机制的研究仍相对有限. 作为典型的有机半导体聚合物材料，2D-COFs的热输运过程在很大程度上受到声电耦合行为的调控. 本研究以含联吡啶基团的2D-COFs为模型体系，系统

考察了2种具有不同d轨道电子构型的金属离子掺杂对声电耦合行为及热传导性能的影响规律. 研究结果表明，掺杂金属离子可通过其不同的d轨道电子排布与有机配体

轨道之间产生不同程度的轨道杂化与电子离域，同时作为局域配位锚点有效限制骨架局部声子振动自由度并抑制声电耦合，从而降低晶格振动散射并提升材料的热传导效率. 本研究不仅揭示了2D-COFs中电子结构调控热输运行为的内在机制，也为基于分子结构与电子态协同设计优化2D-COFs热传导性能提供了新的研究思路与策略.

Abstract

Two-dimensional covalent organic frameworks (2D-COFs)

featuring highly ordered crystalline porous architectures and tailorable molecular structures

have attracted considerable attention in gas separation

molecular adsorption

photocatalysis

and energy conversion. Despite extensive studies on their electronic and ionic transport properties

the thermal transport behavior of 2D-COFs remains insufficiently understood. As a class of organic semiconducting porous polymers

the thermal conductivity of 2D-COFs is strongly correlated with their electronic structures and phonon transport characteristics

in which electron-phonon coupling plays a crucial role in governing lattice thermal transport. In this work

bipyridine-containing 2D-COFs were employed as model systems to systematically investigate the influence of metal-ion doping with distinct d-orbital electronic configurations on el

ectron-phonon coupling behavior and thermal transport properties. The results demonstrated that the introduced metal ions could effectively modulate the local electronic states and electron delocalization through orbital hybridization between the metal d orbitals and the

-conjugated framework of the COFs. Meanwhile

the coordinated metal centers acted as localized anchoring sites that restrict local vibrational degrees of freedom of the framework

thereby suppressing electron-phonon coupling strength and reducing phonon scattering arising from low-frequency lattice vibrations. Consequently

enhanced lattice thermal transport and increased thermal conductivity were achieved. Furthermore

the differences in d-orbital electronic configurations were found to induce distinct orbital coupling strengths and charge delocalization behaviors

which critically determined the electron-phonon coupling characteristics and phonon transport efficiency. This study elucidates the intrinsic relationship between electronic structure modulation and phonon transport in ion-doped 2D-COFs

providing new insights into thermal transport mechanisms in crystalline organic porous materials. The findings further establish an effective strategy for optimizing the thermal transport performance of 2D-COFs through synergistic regulation of molecular structure and electronic states.

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references

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