沸石咪唑酯框架衍生碳基电催化剂的制备及其性能研究

发展新型能源技术如可逆金属-空气电池，为能源危机提供了可行的解决方案。氧还原反应（Oxygen reduction reaction, ORR）和析氧反应（Oxygen evolution reaction, OER）是这类体系的核心，决定能量转换效率。有着多级孔结构和丰富活性位点的金属有机框架（Metal-organic framework，MOF）衍生碳材料是理想的ORR/OER电催化剂，但热处理过程中的烧结现象不利于活性位点暴露，此外电子结构优化是提高催化剂性能的重要途径。本文利用金属-有机酸自组装技术实现MOF衍生碳材料的几何、电子结构双重调控，制备高效双功能氧电极反应催化剂。研究内容包括：

在二维叶状沸石咪唑酯框架（Leaf-like zeolitic imidazolate framework，ZIF-L）表面构建金属-植酸（Phytic acid cross-linked metal ion, M-PA）涂层，制备ZIF-L@M-PA复合结构，提升材料在热处理时的结构稳定性，并通过原位磷化策略调控衍生碳材料电子结构。所获得的Co₂P@NPC呈现优异ORR/OER活性（E_1/2 = 0.852 V vs. RHE，η₁₀ = 336 mV），在锌-空气电池应用中表现出色。Co₂P@NPC形貌特征与前驱体保持一致，良好的多级孔结构保障反应过程中的物质传输，原位磷化策略优化了材料的电子结构，从而实现Co₂P@NPC高效双功能活性。

将甲硫氨酸（Methionine，Me）螯合在ZIF-L表面，构建ZIF-L-Me复合结构以制备硫掺杂碳基底（S-C），借助金属-载体相互作用锚定Co纳米颗粒。所获得的Co@NSC具有出色ORR/OER活性（E_1/2 = 0.866 V vs. RHE，η₁₀ = 340 mV），实现锌-空气电池250 h超长循环。S-C对Co的锚定作用有效抑制金属烧结倾向，改善活性位点暴露情况，并借助杂原子掺杂策略调控催化剂的电子结构，赋予Co@NSC高效双功能活性。

Developing renewable energy technologies, such as metal-air battery, offers a viable solution for energy crisis. As the core of these systems, oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) determine energy conversion efficiency. Metal-organic framework (MOF)-derived materials with multilevel pore structure and plenty of active sites are ideal electrocatalysts for ORR and OER. However, the obtained electrocatalysts normally suffer from noncontrollable sintering during the pyrolysis process, which is unfavorable for the exposure of active sites. In addition, the optimization of electronic structures is also a pivotal approach to improving the performance of catalysts. In this paper, we achieved dual-regulation on geometric and electronic structures of MOF-derived materials by using metal-organic acid self-assembly method, to prepare highly efficiency bifunctional electrocatalysts for oxygen electrode reaction.

Herein, the phytic acid cross-linked metal ion (M-PA) film was constructed on the surface of leaf-like zeolitic imidazolate framework (ZIF-L), to improve the structural stability of the material with in-situ phosphating during the pyrolysis process. The obtained Co₂P@NPC showed excellent activity both in the ORR/OER test (E_1/2 = 0.852 V vs. RHE, η₁₀ = 336 mV), showing great performance in zinc-air battery. Co₂P@NPC completely maintained the morphological characteristics of the precursor with optimized multilevel pore structure, guaranteeing the mass transfer during reaction. The in-situ phosphating strategy optimized the electronic structure of the material, thus realizing the efficient bifunctional activity of Co₂P@NPC

In addition，ZIF-L-Me composite structure was designed by chelating methionine (Me) on the surface of ZIF-L, to construct sulfur-doped carbon (S-C), and Co nanoparticles were anchored on S-C due to metal-support interaction. The obtained Co@NSC exhibits high bifunctional activity towards ORR (E_1/2 = 0.866 V vs. RHE) and OER (η₁₀ = 340 mV), realizing the ultra-long cycle of zinc-air battery for 250 h. Interaction between Co and the S-C matrix largely suppressed NPs sintering, improving active site exposure. Meanwhile, the optimization of electronic structures was achieved by using heteroatom doping strategy, thus enabling efficient bifunctional activity of Co@NSC.

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