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用于高效电催化水氧化的有序双金属金属有机框架的组装与价态调制

Assembly and Valence Modulation of Ordered Bimetallic MOFs for Highly Efficient Electrocatalytic Water Oxidation.

作者信息

Wu Yaling, Sun Zhaopeng, Chen Yingying, Liu Dan, Meng Yan, Yan Zheng

机构信息

Anhui Provincial Key Laboratory of Advanced Catalysis and Energy Materials, Anqing Normal University, Anqing 246133, China.

College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, China.

出版信息

Molecules. 2024 Dec 11;29(24):5845. doi: 10.3390/molecules29245845.

Abstract

Metal synergy can enhance the catalytic performance, and a prefabricated solid precursor can guide the ordered embedding, of secondary metal source ions for the rapid synthesis of bimetallic organic frameworks (MM'-MOFs) with a stoichiometric ratio of 1:1. In this paper, containing well-defined binding sites was synthesized by mechanical ball milling, which was used as a template for the induced introduction of Fe ions to successfully assemble the ordered bimetallic (where denotes template-directed synthesis of MOF-74). Its electrocatalytic performance is superior to that of the conventional one-step-synthesized (where denotes one-step synthesis of MOF-74), and the ratio of the two metal sources, Co and Fe, is close to 1:1. Meanwhile, the iron valence states (Fe and Fe) in were further regulated to obtain the electrocatalytic materials and . The electrochemical performance test results confirm that regulated by valence state has a better catalytic performance than in the oxygen evolution reaction (OER) process. This phenomenon is related to the gradual increase in the valence state of Fe ions in , which promotes the continuous improvement in the performance of the MOF before reaching the optimal steady state and makes the OER performance reach the optimum when the Fe/Fe mixed-valence state reaches a certain proportion. This provides a new idea for the directed synthesis and optimization of highly efficient catalysts.

摘要

金属协同作用可以提高催化性能,并且预制的固体前驱体能够引导二次金属源离子有序嵌入,从而快速合成化学计量比为1:1的双金属有机框架材料(MM'-MOFs)。本文通过机械球磨合成了具有明确结合位点的材料,将其用作诱导引入铁离子的模板,成功组装了有序双金属材料(其中表示MOF-74的模板导向合成)。其电催化性能优于传统一步合成的材料(其中表示MOF-74的一步合成),且两种金属源钴和铁的比例接近1:1。同时,进一步调控材料中的铁价态(Fe²⁺和Fe³⁺),得到了电催化材料和。电化学性能测试结果证实,价态调控后的在析氧反应(OER)过程中比具有更好的催化性能。这种现象与材料中Fe离子价态的逐渐升高有关,这促进了MOF在达到最佳稳态之前性能的持续提升,并使得当Fe²⁺/Fe³⁺混合价态达到一定比例时OER性能达到最优。这为高效催化剂的定向合成与优化提供了新思路。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/817b/11728488/ce8315adcdb7/molecules-29-05845-g001.jpg

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