Controllable Regulation of CO2 Adsorption Behavior via Precise Charge Donation Modulation for Highly Selective CO2 Electroreduction to Formic Acid

IF 13 2区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Small Pub Date : 2024-10-24 DOI:10.1002/smll.202408351

Rou-Yu Li, Wenyu Yuan, Shuo Wang, Peng Zhang, Heng Wu, Yi-Min Su, En-Lei Wen, Xiaolin Zhu, Quan-Guo Zhai

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Abstract

The synthesis of value-added products via CO₂ electroreduction (CO₂ER) is of great significance, but the development of efficient and versatile strategies for the controllable selectivity tuning is extremely challenging. Herein, the tuning of CO₂ER selectivity through the modulation of CO₂ adsorption behavior is proposed. Using the constructed zeolitic MOF (SNNU-339), CO₂ adsorption behavior is controllably changed from *CO₂ to CO₂* via the precise ligand-to-metal charge donation (LTMCD) regulation. It is confirmed that the high electronegativity of the coordinate ligand directly restricts the LTMCD, reduces the charge density on the metal sites, lowers the Gibbs free energy for CO₂* adsorption, and leads to the transformation of CO₂ adsorption mode from *CO₂ to CO₂*. Owing to the modulated CO₂ adsorption behavior and regulated kinetics, SNNU-339 exhibits superior HCOOH selectivity (≈330% promotion, 85.6% Faradaic efficiency) and high CO₂ER activity. The wide applicability of the proposed approach sheds light on the efficient CO₂ER. This study provides a competitive strategy for rational catalyst design and underscores the significance of adsorption behavior tuning in electrocatalysis.

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通过精确电荷捐赠调制对二氧化碳吸附行为进行可控调节，实现高选择性二氧化碳电还原成甲酸

通过二氧化碳电还原（CO2ER）合成高附加值产品意义重大，但开发高效、多用途的可控选择性调节策略却极具挑战性。本文提出了通过调节 CO2 吸附行为来调节 CO2ER 选择性的方法。利用构建的沸石 MOF（SNNU-339），通过精确的配体-金属电荷捐赠（LTMCD）调节，可控地将 CO2 吸附行为从 *CO2 转变为 CO2*。研究证实，配位配体的高电负性直接限制了 LTMCD，降低了金属位点上的电荷密度，降低了 CO2* 吸附的吉布斯自由能，导致 CO2 吸附模式从 *CO2 转变为 CO2*。由于调制的 CO2 吸附行为和调节的动力学，SNNU-339 表现出卓越的 HCOOH 选择性（促进率≈330%，法拉第效率 85.6%）和高 CO2ER 活性。所提出方法的广泛适用性为高效 CO2ER 提供了启示。这项研究为催化剂的合理设计提供了一种有竞争力的策略，并强调了吸附行为调整在电催化中的重要意义。

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来源期刊

Small 工程技术-材料科学：综合

CiteScore

17.70

自引率

3.80%

发文量

1830

审稿时长

2.1 months

期刊介绍： Small serves as an exceptional platform for both experimental and theoretical studies in fundamental and applied interdisciplinary research at the nano- and microscale. The journal offers a compelling mix of peer-reviewed Research Articles, Reviews, Perspectives, and Comments. With a remarkable 2022 Journal Impact Factor of 13.3 (Journal Citation Reports from Clarivate Analytics, 2023), Small remains among the top multidisciplinary journals, covering a wide range of topics at the interface of materials science, chemistry, physics, engineering, medicine, and biology. Small's readership includes biochemists, biologists, biomedical scientists, chemists, engineers, information technologists, materials scientists, physicists, and theoreticians alike.