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通过费林法由红碳介导形成分散在氧化碳骨架上的氧化铜簇及其在酸性条件下用于硝酸盐电还原的应用。

Red Carbon Mediated Formation of CuO Clusters Dispersed on the Oxocarbon Framework by Fehling's Route and their Use for the Nitrate Electroreduction in Acidic Conditions.

作者信息

Ba Jingwen, Dong Hongliang, Odziomek Mateusz, Lai Feili, Wang Rui, Han Yandong, Shu Jinfu, Antonietti Markus, Liu Tianxi, Yang Wensheng, Tian Zhihong

机构信息

Engineering Research Center for Nanomaterials, Henan University, Kaifeng, 475004, P. R. China.

Center for High Pressure Science and Technology Advanced Research, Shanghai, 201203, P. R. China.

出版信息

Adv Mater. 2024 Jun;36(25):e2400396. doi: 10.1002/adma.202400396. Epub 2024 Apr 2.

Abstract

The oligomers of carbon suboxide, known as red carbon, exhibit a highly conjugated structure and semiconducting properties. Upon mild heat treatment, it transforms into a carbonaceous framework rich in oxygen surface terminations, called oxocarbon. In this study, the abundant oxygen functionalities are harnessed as anchors to create oxocarbon-supported nanohybrid electrocatalysts. Starting with single atomic Cu (II) strongly coordinated to oxygen atoms on red carbon, the Fehling reaction leads to the formation of CuO clusters. Simultaneously, a covalent oxocarbon framework emerges via cross-linking, providing robust support for CuO clusters. Notably, the oxocarbon support effectively stabilizes CuO clusters of very small size, ensuring their high durability in acidic conditions and the presence of ammonia. The synthesized material exhibits a superior electrocatalytic activity for nitrate reduction under acidic electrolyte conditions, with a high yield rate of ammonium (NH ) at 3.31 mmol h mg and a Faradaic efficiency of 92.5% at a potential of -0.4 V (vs RHE).

摘要

被称为红碳的低氧化碳聚合物具有高度共轭结构和半导体特性。经过温和的热处理后,它会转变为富含氧表面端基的碳质骨架,即氧化碳。在本研究中,大量的氧官能团被用作锚定物,以制备氧化碳负载的纳米杂化电催化剂。从与红碳上的氧原子强烈配位的单原子铜(II)开始,费林反应导致氧化铜簇的形成。同时,通过交联形成了共价氧化碳骨架,为氧化铜簇提供了强大的支撑。值得注意的是,氧化碳载体有效地稳定了非常小尺寸的氧化铜簇,确保了它们在酸性条件和氨存在下的高耐久性。合成材料在酸性电解质条件下对硝酸盐还原表现出优异的电催化活性,在-0.4 V(相对于可逆氢电极)的电位下,铵(NH₄⁺)的高产率为3.31 mmol h⁻¹ mg⁻¹,法拉第效率为92.5%。

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