Leveraging Co Spin State in Metal–Organic Frameworks for Efficient Water Oxidation

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-09-29 DOI:10.1021/acscatal.5c03901

Yi Zhang, Habib Ullah, Linfeng Li, Hsiao-Chien Chen, Xia Zhang, Qiangli Lv, Xuefei Xu, Shaowei Zhang, Chao Hu, Zhishan Li, Muhammad Humayun, Mohamed Bououdina, Hussein A. Younus, Deli Wang, Chundong Wang

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引用次数: 0

Abstract

The design and development of highly efficient, stable, and low-cost electrocatalysts for the oxygen evolution reaction (OER) is crucial for green hydrogen production. Metal–organic frameworks (MOFs), with the merits of structural diversity and tunable organic ligand nature, have significant potential. Herein, a Co-based MOF (CoMnFcMOF) electrocatalyst was fabricated under hydrothermal conditions using Mn as a dopant and a ferrocene-based dicarboxylate linker. The as-prepared CoMnFcMOF enables a current density of 100 mA·cm^–2 with an overpotential of 238 mV under an alkaline condition. The well-addressed OER activity is attributed to the spin state modulation of Co induced by Mn incorporation, as verified experimentally and from density functional theory calculations. The total effective magnetic moment (μ_eff) considerably decreases from 3.992 μ_B/f.u. in CoFcMOF to 1.974 μ_B/f.u. in CoMnFcMOF, indicating a spin transition from a high spin (HS) to an intermediate spin (IS) state. This spin modulation facilitates the adsorption of the O* intermediates, thereby accelerating the reaction kinetics. This work establishes a design paradigm for high-performance transition metal-based catalysts through spin state engineering.

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利用金属-有机框架中的Co自旋态进行高效水氧化

设计和开发高效、稳定、低成本的析氧反应电催化剂是实现绿色制氢的关键。金属-有机框架具有结构多样性和有机配体可调性等优点，具有广阔的应用前景。本文以锰为掺杂剂，二茂铁为二羧酸盐连接剂，在水热条件下制备了co基MOF （CoMnFcMOF）电催化剂。制备的CoMnFcMOF在碱性条件下电流密度为100 mA·cm-2，过电位为238 mV。经实验和密度泛函理论计算证实，良好的OER活性归因于Mn掺入引起的Co自旋态调制。总有效磁矩（μeff）从3.992 μB/f.u显著减小。为1.974 μB/f.u。在CoMnFcMOF中，表明自旋从高自旋（HS）状态过渡到中自旋（IS）状态。这种自旋调制促进了O*中间体的吸附，从而加快了反应动力学。本研究通过自旋态工程建立了高性能过渡金属基催化剂的设计范式。

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

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.