Impregnation of Metal ions on ZIF-67 Towards the Production of Mixed-Metals Spinels for OER Electrocatalysis

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry Pub Date : 2025-04-02 DOI:10.1016/j.jssc.2025.125352

Annaíres de Almeida Lourenço , Rafael A. Raimundo , Ricardo Francisco Alves , Rodolfo B. da Silva , Daniel Araújo Macedo , Fausthon Fred da Silva

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Abstract

Electrochemical water splitting is a key method for sustainable hydrogen (H₂) production, but its efficiency is hindered by the slow kinetics and high overpotential of the oxygen evolution reaction (OER). This study investigates the synthesis and OER electrocatalytic performance of MCo₂O₄ (M = Co, Fe, Ni, Mn, or Zn) nanoparticles derived from ZIF-67, named here Co₃O₄, Co₃O₄(Fe), Co₃O₄(Ni), Co₃O₄(Mn), and Co₃O₄(Zn). Here, a systematic detailed study was also conducted to investigate the influence of metal cation impregnation on ZIF-67 and its impact on the OER electrocatalytic activity of these transition metal cobaltites nanoparticles. The materials were obtained via direct calcination of the previously modified ZIF-67, and the impregnation process was also investigated. Structural (XRD), physicochemical (Raman spectroscopy, FT-IR and UV-VIS), and magnetic characterizations confirm the formation of pure crystalline phases for Co₃O₄, NiCo₂O₄, MnCo₂O₄, and ZnCo₂O₄, while the Fe-modified sample resulted in a nanocomposite (FeCo₂O₄/Co₃O₄). Morphological analysis revealed highly agglomerated sphere-like nanoparticles, with sizes between 12.1 nm (Co₃O₄(Fe)) and 20.8 nm (Co₃O₄(Mn)). OER performance in 1.0 M KOH showed overpotential values of 330 mV, 318 mV, 321 mV, 316 mV, and 310 mV for Co₃O₄, Co₃O₄(Fe), Co₃O₄(Ni), Co₃O₄(Mn), and Co₃O₄(Zn), respectively, at 10 mA cm^-2. Tafel slopes ranged from 64.13 mV dec^-1 (Co₃O₄(Fe)) to 97.42 mV dec^-1 (Co₃O₄(Ni)), indicating a surface adsorption-controlled kinetics. Co₃O₄(Zn) exhibited the highest electrochemical surface area (123.50 cm²) and double-layer capacitance (4.94 mF), correlating with superior electrocatalytic performance. Stability tests confirmed chemical durability for up to 15 hours. These results demonstrate the potential of ZIF-67-derived transition metal cobaltites as effective OER electrocatalysts, with Co₃O₄(Zn) showing the most promising activity.

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金属离子在ZIF-67上浸渍制备OER电催化用混合金属尖晶石

电化学水分解是一种可持续制氢的关键方法，但其效率受到析氧反应（OER）动力学缓慢和高过电位的制约。本研究研究了由ZIF-67衍生的MCo2O4 （M = Co, Fe, Ni， Mn或Zn）纳米粒子的合成和OER电催化性能，这里命名为Co3O4， Co3O4(Fe), Co3O4(Ni), Co3O4（Mn）和Co3O4（Zn）。本文还系统详细地研究了金属阳离子浸渍对ZIF-67的影响及其对过渡金属钴酸盐纳米颗粒OER电催化活性的影响。对改性后的ZIF-67进行了直接煅烧制备，并对其浸渍工艺进行了研究。结构（XRD）、物理化学（拉曼光谱、FT-IR和UV-VIS）和磁性表征证实了Co3O4、NiCo2O4、MnCo2O4和ZnCo2O4形成了纯晶相，而fe修饰后的样品形成了纳米复合材料（FeCo2O4/Co3O4）。形貌分析显示，纳米颗粒高度团聚，粒径在12.1 nm （Co3O4(Fe)）至20.8 nm （Co3O4(Mn)）之间。在1.0 M KOH中，Co3O4、Co3O4（Fe）、Co3O4（Ni）、Co3O4（Mn）和Co3O4（Zn）在10 mA cm-2下的过电位分别为330 mV、318 mV、321 mV、316 mV和310 mV。Tafel斜率范围从64.13 mV dec-1 （Co3O4(Fe)）到97.42 mV dec-1 (Co3O4(Ni))，表明表面吸附控制动力学。Co3O4（Zn）表现出最高的电化学表面积（123.50 cm2）和双层电容（4.94 mF），具有优异的电催化性能。稳定性测试证实了长达15小时的化学耐久性。这些结果证明了zif -67衍生的过渡金属钴酸盐作为有效的OER电催化剂的潜力，其中Co3O4（Zn）表现出最有希望的活性。

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来源期刊

Journal of Solid State Chemistry 化学-无机化学与核化学

CiteScore

6.00

自引率

9.10%

发文量

848

审稿时长

25 days

期刊介绍： Covering major developments in the field of solid state chemistry and related areas such as ceramics and amorphous materials, the Journal of Solid State Chemistry features studies of chemical, structural, thermodynamic, electronic, magnetic, and optical properties and processes in solids.