摘要
金属主链高分子是一类完全以金属原子作为主链的新材料,在光电、传感、电化学储能等领域都具有重要的应用前景.但是,如何获得具有较高分子量的金属主链高分子,仍然是一个挑战.本文通过密度泛函理论计算方法,对镍金属主链高分子进行了结构优化和稳定性分析,发现随着聚合物分子量的增加,镍金属主链高分子的单点能逐渐降低,说明高分子量的金属主链高分子具有稳定的分子构型.但是,随着分子量的进一步提高,计算量显著增加,密度泛函理论计算方法收敛困难.为此,本文进一步通过Hartree-Fock计算方法对该系列镍金属主链高分子进行了分子构型优化,得到了与密度泛函理论计算结果相似的规律,并且发现当分子量超过1×10^(4)时,金属主链高分子仍然具有较高的结构稳定性.此外,这种电子离域在整个金属主链上的独特金属-金属的相互作用有利于实现电荷的高效传输;以金属原子为重复单元的分子结构,有望实现金属和高分子材料性能的有效结合,可以获得较高的热失重温度和熵弹性.
Metal-backboned polymers(MBPs)are a new class of materials with metal atoms for backbones,which offer excellent electronic properties for promising applications in a variety of fields such as optoelectronics,sensing,and energy storage.However,it remains challenges to synthesize MBPs with high molecular weights for practical applications.Here,the structures of nickel-backboned polymers(NiBPs)with increasing molecular weights were optimized by density functional theory(DFT)method,based on which their stabilities were further studied.It was found that the energies of NiBPs gradually decreased with the increasing molecular weight,indicating that NiBPs with higher molecular weights showed stable molecular configurations.However,with the further increase of molecular weights,it was difficult for NiBPs to converge by DFT method.To this end,these structures were further studied by Hartree-Fock method.Similar results had been concluded as DFT calculation did,and it also proved that an NiBP with molecular weight exceeding ×10^(4) was also stable.In addition,the unique metal-metal interaction of the electron delocalization on the whole metal backbone is conducive to the efficient transmission of charge.As polymers with repeating metal atom units,MBPs are expected to have combined properties of metal and polymer materials,and may demonstrate high thermal weight loss temperatures and entropy elasticities.This work provides a theoretical basis for the synthesis of MBP materials.
作者
张义锋
曾凯雯
杨依蓓
唐伟强
彭慧胜
Yi-feng Zhang;Kai-wen Zeng;Yi-bei Yang;Wei-qiang Tang;Hui-sheng Peng(State Key Laboratory of Molecular Engineering of Polymers,Department of Macromolecular Science,Laboratory of Advanced Materials,Fudan University,Shanghai 200438;State Key Laboratory of Chemical Engineering,School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237)
出处
《高分子学报》
SCIE
CAS
CSCD
北大核心
2023年第4期413-417,共5页
Acta Polymerica Sinica
基金
国家重点研发计划(基金号2022YFA1200023)
上海市科学技术委员会重大基础研究项目(基金号21511104900,20JC1414902)
国家自然科学基金青年科学基金(基金号22105045)资助项目。
关键词
金属主链
镍原子
高分子
理论计算
Metal-backboned
Nickel
Polymer
Molecular simulation
