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构建Co-Fe层状双氢氧化物与Ni-Fe金属有机框架之间的异质结界面作为高效析氧电催化剂:对CoOOH-FeOOH-NiOOH三元体系的机理洞察

Constructing heterojunction interface between Co-Fe layered double hydroxide and Ni-Fe metal-organic framework as efficient oxygen evolution electrocatalyst: Mechanism insights into CoOOH-FeOOH-NiOOH ternary system.

作者信息

Yang Kuo, Ren Wenjie, Li Luowei, Ye Bingjie, Li Wei, Fang Wenhao, Liu Shixi

机构信息

School of Chemical Science and Technology, National Demonstration Center for Experimental Chemistry and Chemical Engineering Education, Yunnan University, 2 North Cuihu Road, 650091 Kunming, China.

School of Chemical Science and Technology, National Demonstration Center for Experimental Chemistry and Chemical Engineering Education, Yunnan University, 2 North Cuihu Road, 650091 Kunming, China.

出版信息

J Colloid Interface Sci. 2025 Nov 15;698:137991. doi: 10.1016/j.jcis.2025.137991. Epub 2025 May 26.

Abstract

The creation of available and cost-effective non-noble-metal electrocatalysts for oxygen evolution was of considerable practical significance. In this study, we introduced a CoFe-layered double hydroxide (LDH) and NiFe metal-organic framework (MOF) electrocatalyst that was supported on nickel foam (NF) for oxygen evolution reaction (OER). The coordination structure between Co/Ni and Fe was modulated by varying the Fe content, which enhances the electron tunneling ability between CoFe-LDH and NiFe-MOF. Additionally, characterization techniques confirmed the synergistic interactions of the active sites Co/Co, Ni/Ni and Fe/Fe in the OER process. Calculations using density-functional theory (DFT) substantiated the swift electron transfer that occurs among the ternary active substances CoOOH, FeOOH, and NiOOH during the generation of OER in strong alkaline environments, which was enhanced by synergistic effects and the efficient adjustment of electronic interactions. CoFe-LDH@NiFe-MOF fully exposes the active centers within its nanosheet structure, featuring a hierarchical porous architecture that promotes rapid charge and mass transfer. The measured overpotential was found to be 225 mV with an current density of 10 mA cm, and Tafel slope was recorded at 28.10 mV dec. The results presented show that the as-prepared electrocatalysts exhibited superior activity in OER compared with commercial RuO catalysts. Furthermore, this self-supported electrocatalyst displays impressive durability, as there was no observed degradation in its activity over a continuous 60h operation period. This research illustrates a straightforward and practical approach to developing effective catalysts for water oxidation, achieving both highly catalytic competence and long-term fixity.

摘要

开发实用且经济高效的非贵金属析氧电催化剂具有重要的现实意义。在本研究中,我们引入了一种负载在泡沫镍(NF)上的钴铁层状双氢氧化物(LDH)和镍铁金属有机框架(MOF)电催化剂用于析氧反应(OER)。通过改变铁含量来调节钴/镍与铁之间的配位结构,这增强了钴铁-LDH和镍铁-MOF之间的电子隧穿能力。此外,表征技术证实了在OER过程中活性位点Co/Co、Ni/Ni和Fe/Fe之间的协同相互作用。使用密度泛函理论(DFT)进行的计算证实,在强碱性环境中OER生成过程中,三元活性物质CoOOH、FeOOH和NiOOH之间会发生快速的电子转移,协同效应和电子相互作用的有效调节增强了这种转移。CoFe-LDH@NiFe-MOF在其纳米片结构中充分暴露了活性中心,具有分级多孔结构,可促进快速的电荷和质量转移。测得的过电位为225 mV,电流密度为10 mA/cm²,塔菲尔斜率为28.10 mV/dec。结果表明,与商业RuO催化剂相比,所制备的电催化剂在OER中表现出优异的活性。此外,这种自支撑电催化剂具有令人印象深刻的耐久性,在连续60小时的运行期间未观察到其活性下降。本研究阐明了一种开发用于水氧化的有效催化剂的直接实用方法,实现了高催化能力和长期稳定性。

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