Engineering spin-dependent catalysts: chiral covalent organic frameworks with tunable electroactivity for electrochemical oxygen evolution

IF 16.3 1区综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES

National Science Review Pub Date : 2024-09-17 DOI:10.1093/nsr/nwae332

Ziping Li, Yueyuan Xiao, Chao Jiang, Bang Hou, Yan Liu, Yong Cui

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引用次数: 0

Abstract

The chiral-induced spin selectivity (CISS) effect offers promising prospects for spintronics, yet designing chiral materials enabling efficient spin-polarized electron transport remains challenging. Here, we report the utility of covalent organic frameworks (COFs) in manipulating electron spin for spin-dependent catalysis via CISS. This facilitates us to design and synthesize three three-dimensional chiral COFs (CCOFs) with tunable electroactivity and spin-electron conductivity through imine condensations of enantiopure 1,1'-binaphthol-derived tetraaldehyde and tetraamines derived from 1,4-benzenediamine, pyrene, or tetrathiafulvalene skeletons. The CISS effect of CCOFs is verified by magnetic conductive atomic force microscopy. Compared with their achiral analogs, these CCOFs serve as efficient spin filters, reducing the overpotential of oxygen evolution and improving the Tafel slope. Particularly, the diarylamine-based CCOF showed a low overpotential of 430 mV (vs RHE) at 10 mA cm−2 with long-term stability comparable to the commercial RuO2. This enhanced spin-dependent OER activity stems from its excellent redox-activity, good electron conductivity and effective suppressed formation of H2O2 byproducts.

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工程自旋催化剂：具有可调电活性的手性共价有机框架，用于电化学氧进化

手性诱导自旋选择性（CISS）效应为自旋电子学提供了广阔的前景，然而设计出能够实现高效自旋极化电子传输的手性材料仍然充满挑战。在此，我们报告了共价有机框架（COFs）在通过 CISS 操纵电子自旋进行自旋催化方面的效用。通过对映纯 1,1'-联萘酚衍生的四醛和 1,4-苯二胺、芘或四硫富戊烯骨架衍生的四胺的亚胺缩合，我们设计并合成了三种具有可调电活性和自旋电子传导性的三维手性 COF（CCOF）。磁导原子力显微镜验证了 CCOFs 的 CISS 效应。与非手性类似物相比，这些 CCOFs 可作为高效的自旋过滤器，降低氧进化的过电位，改善塔菲尔斜率。特别是，基于二芳基胺的 CCOF 在 10 mA cm-2 的条件下显示出 430 mV 的低过电位（相对于 RHE），其长期稳定性与商用 RuO2 相当。这种增强的自旋依赖性 OER 活性源于其出色的氧化还原活性、良好的电子传导性和有效抑制 H2O2 副产物的形成。

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

National Science Review MULTIDISCIPLINARY SCIENCES-

CiteScore

24.10

自引率

1.90%

发文量

249

审稿时长

13 weeks

期刊介绍： National Science Review (NSR; ISSN abbreviation: Natl. Sci. Rev.) is an English-language peer-reviewed multidisciplinary open-access scientific journal published by Oxford University Press under the auspices of the Chinese Academy of Sciences.According to Journal Citation Reports, its 2021 impact factor was 23.178. National Science Review publishes both review articles and perspectives as well as original research in the form of brief communications and research articles.