多孔配位笼的电荷操纵调节电化学合成的效率和选择性

IF 16.9 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Zhifang Su, Kang-Kai Liu, Yu-Qi Xu, Bing Yan, Shuangyin Wang, Zong-Jie Guan, Yuqin Zou, Yu Fang
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引用次数: 0

摘要

电催化合成高价值化学品因其对环境无害的反应途径而受到越来越多的关注。其中,硝酸(NO3-)电催化还原为氨(NH3) (NO3RR)和5-羟甲基糠醛(HMFOR)氧化反应是两个重要的基础反应;然而,它们的效率和选择性构成了持续的挑战。在这项研究中,我们引入了一种电荷操纵方法来设计高效的电催化剂,用于NO3RR和HMFOR的同时耦合。我们合成了一系列多孔配位笼(PCCs),它们具有相同的拓扑结构和Co/Ni金属中心,但包含不同的带电分子,赋予它们不同的表面净电荷。电催化评价表明PCC-Co在NO3RR中表现出电压依赖的活性。相反,PCC-Ni在HMFOR中表现出精确可调的产物选择性,这取决于笼的电荷状态。原位分析和密度泛函理论(DFT)计算强调了催化剂电荷对反应中间体的差异吸附和关键反应步骤中最低自由能变化(ΔG)的深刻影响,从而导致活性和选择性的改变。这些发现为NO3RR/HMFOR催化剂的“结构-性能关系”提供了宝贵的见解,突出了PCCs作为先进电催化剂的有前途的竞争者。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Charge Manipulation of Porous Coordination Cages Tunes the Efficiency and Selectivity in Electrochemical Synthesis

Charge Manipulation of Porous Coordination Cages Tunes the Efficiency and Selectivity in Electrochemical Synthesis

Electrocatalytic synthesis of high-value chemicals has been attracting growing interest owing to its environmentally benign reaction pathways. Among these processes, the electrocatalytic reduction of nitrate (NO3) to ammonia (NH3), known as NO3RR, and the oxidation of 5-hydroxymethylfurfural (HMFOR) stand out as two cornerstone reactions; yet, their efficiency and selectivity pose ongoing challenges. In this study, we introduce a charge manipulation approach for the design of highly efficient electrocatalysts tailored for the simultaneous coupling of NO3RR and HMFOR. We have synthesized a range of porous coordination cages (PCCs) that share the same topology and Co/Ni metal centers but incorporate different charged moieties, imparting them with distinct surface net charges. Electrocatalytic evaluations revealed that PCC-Co demonstrated a voltage-dependent activity in NO3RR. Conversely, PCC-Ni exhibited a precisely adjustable product selectivity in HMFOR, contingent upon the cage‘s charge state. In situ analysis and Density functional theory (DFT) calculations underscored the profound impact of catalyst charge on the differential adsorption of reaction intermediates and the lowest free energy change (ΔG) during the pivotal reaction step, resulting in alterations to both activity and selectivity. These discoveries provide invaluable insights into the “structure-performance relationship” of NO3RR/HMFOR catalysts, highlighting PCCs as promising contenders for advanced electrocatalysts.

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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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