Conductive polymer polyacetylene under voltage captures carbon dioxide

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids Pub Date : 2025-05-12 DOI:10.1016/j.molliq.2025.127765

Nadezhda A. Andreeva , Vitaly V. Chaban

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Abstract

Conductive polymer polyacetylene (PA) was computationally shown to support its direct carboxylation by the CO₂ molecule when used as a cathode. The carbon atoms of the negatively charged PA partially acquire the capability of nitrogen atoms in amines and nitrogen-containing heterocycles to undergo carboxamidation in the presence of CO₂. A higher electron density of the PA cathode results in a more thermochemically favorable carboxamidation and lowers an activation barrier. Whereas both enthalpic and entropic contributions to chemisorption are moderately unfavorable, the shapes of the reaction energy profiles suggest the kinetic stability of the chemisorption product at moderate cathode charges. The cathode charging levels up to –0.04e per atom of polymer were investigated to ensure the thermodynamic stability of PA. Note that CO₂ desorption does not require additional costs, occurring spontaneously after the external energy supply is removed. The reactivity-related data regarding a conductive carbon-based polymer has practical implications for CO₂ scavenging.

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导电聚合物聚乙炔在电压下捕获二氧化碳

计算表明，当用作阴极时，导电聚合物聚乙炔（PA）支持其被CO2分子直接羧化。带负电的PA的碳原子部分获得胺和含氮杂环中氮原子在CO2存在下进行羧酰胺化的能力。PA阴极的高电子密度导致更有利的热化学羧胺化和降低激活势垒。尽管焓和熵对化学吸附的贡献都是适度不利的，但反应能量谱的形状表明，在中等阴极电荷下，化学吸附产物的动力学稳定性。为了保证聚合物的热力学稳定性，研究了每原子-0.04e的阴极充电水平。请注意，二氧化碳解吸不需要额外的费用，在外部能源供应被移除后自然发生。关于导电碳基聚合物的反应性相关数据对CO2清除具有实际意义。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Molecular Liquids 化学-物理：原子、分子和化学物理

CiteScore

10.30

自引率

16.70%

发文量

2597

审稿时长

78 days

期刊介绍： The journal includes papers in the following areas: – Simple organic liquids and mixtures – Ionic liquids – Surfactant solutions (including micelles and vesicles) and liquid interfaces – Colloidal solutions and nanoparticles – Thermotropic and lyotropic liquid crystals – Ferrofluids – Water, aqueous solutions and other hydrogen-bonded liquids – Lubricants, polymer solutions and melts – Molten metals and salts – Phase transitions and critical phenomena in liquids and confined fluids – Self assembly in complex liquids.– Biomolecules in solution The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include: – Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.) – Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.) – Light scattering (Rayleigh, Brillouin, PCS, etc.) – Dielectric relaxation – X-ray and neutron scattering and diffraction. Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.