Tailoring 2D metal-organic frameworks for enhanced CO2 reduction efficiency through modulating conjugated ligands

IF 7.2 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology Pub Date : 2024-02-07 DOI:10.1016/j.fuproc.2024.108049

Sajjad Ali , Pir Muhammad Ismail , Muhammad Humayun , Mohamed Bououdina , Liang Qiao

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引用次数: 0

Abstract

The technology of electrocatalytic reduction of CO₂ to produce hydrocarbon fuels not only alleviates energy shortages but also suppresses the greenhouse effect, demonstrating enormous potential applications. In this context, we aim to explore new reliable materials for reducing CO₂ (CO₂RR) through electrocatalysis. Hence, we investigated the performance of Cu₃(C₁₂X)₂, where X signifies organic-ligands (N₁₂H₆, N₉H₃O₃, N₉H₃S₃, N₆O₆, N₆S₆) for the CO₂RR using density functional theory (DFT). The 2D Cu₃(C₁₂X)₂ monolayers show metallic characteristics because of the presence of adequate π electron conjugation network as-well-as a constructive interaction between the metal atom, organic-ligands, and benzene-rings, with the exception of Cu₃(C₁₂N₉H₃O₃)₂, which displayed semiconducting characteristic. The catalytic activity of Cu₃(C₁₂X)₂ can be tuned by adjusting the organic-ligands' ability to facilitate interaction between the CO₂RR intermediates and the metal complex (Cu-X₄). Among all MOFs, Cu₃(C₁₂N₆S₆)₂ have excellent CO₂RR activity towards CO and formic acid. All other Cu₃(C₁₂X)₂ monolayers demonstrated dynamic CO₂RR catalytic activity as well as superior selectivity over hydrogen evolution (HER) suggesting that these materials have the potential to be useful as CO₂RR electrocatalysts. This study introduces the concept of building MOFs with favorable features to meet the specific needs of a number of research domains including catalysis, energy conversion and storage.

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通过调节共轭配体定制二维金属有机框架以提高二氧化碳还原效率

电催化还原二氧化碳以生产碳氢化合物燃料的技术不仅能缓解能源短缺，还能抑制温室效应，具有巨大的应用潜力。在此背景下，我们旨在探索通过电催化还原二氧化碳（CO2RR）的新型可靠材料。因此，我们利用密度泛函理论（DFT）研究了 Cu3(C12X)2（其中 X 表示有机配体（N₁₂H₆、N₉H₃O₃、N₉H₃S₃、N₆O₆、N₆S₆）在 CO2RR 中的性能。由于金属原子、有机配体和苯环之间存在充分的 π 电子共轭网络以及建设性的相互作用，二维 Cu3(C12X)2 单层显示出金属特性，但 Cu3(C12N9H3O3)2 除外，显示出半导体特性。Cu3(C12X)2 的催化活性可通过调整有机配体促进 CO2RR 中间体与金属复合物（Cu-X4）之间相互作用的能力来调节。在所有 MOFs 中，Cu3(C12N6S6)2 对 CO 和甲酸具有出色的 CO2RR 活性。所有其他 Cu3(C12X)2 单层都表现出动态 CO2RR 催化活性以及对氢进化（HER）的卓越选择性，这表明这些材料具有作为 CO2RR 电催化剂的潜力。本研究介绍了构建具有有利特征的 MOFs 的概念，以满足催化、能量转换和存储等多个研究领域的特定需求。

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来源期刊

Fuel Processing Technology 工程技术-工程：化工

CiteScore

13.20

自引率

9.30%

发文量

398

审稿时长

26 days

期刊介绍： Fuel Processing Technology (FPT) deals with the scientific and technological aspects of converting fossil and renewable resources to clean fuels, value-added chemicals, fuel-related advanced carbon materials and by-products. In addition to the traditional non-nuclear fossil fuels, biomass and wastes, papers on the integration of renewables such as solar and wind energy and energy storage into the fuel processing processes, as well as papers on the production and conversion of non-carbon-containing fuels such as hydrogen and ammonia, are also welcome. While chemical conversion is emphasized, papers on advanced physical conversion processes are also considered for publication in FPT. Papers on the fundamental aspects of fuel structure and properties will also be considered.