Ligand engineering enhances (photo) electrocatalytic activity and stability of zeolitic imidazolate frameworks via in-situ surface reconstruction

• Published in: Nature communications 2024-10, Vol.15 (1), p.9393-14, Article 9393
• Main Authors: Huang, Zheao, Wang, Zhouzhou, Rabl, Hannah, Naghdi, Shaghayegh, Zhou, Qiancheng, Schwarz, Sabine, Apaydin, Dogukan Hazar, Yu, Ying, Eder, Dominik
• Format: Article
• Language: English
• Subjects: 140/131; 140/133; 140/146; 147/28; 639/301/299/886; 639/301/299/921; 639/638/161/886; 639/638/77/886; Catalysis; Catalytic activity; Chemical synthesis; Cobalt; Electrocatalysis; Electrochemistry; Evolution; Humanities and Social Sciences; Ligands; Metal-organic frameworks; Metals; multidisciplinary; Oxidation; Oxygen evolution reactions; Protective structures; Reconstruction; Science; Science (multidisciplinary); Structural stability; Surface stability; Zeolites
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-53385-0

The current limitations in utilizing metal-organic frameworks for (photo)electrochemical applications stem from their diminished electrochemical stability. In our study, we illustrate a method to bolster the activity and stability of (photo)electrocatalytically active metal-organic frameworks through ligand engineering. We synthesize four distinct mixed-ligand versions of zeolitic imidazolate framework-67, and conduct a comprehensive investigation into the structural evolution and self-reconstruction during electrocatalytic oxygen evolution reactions. In contrast to the conventional single-ligand ZIF, where the framework undergoes a complete transformation into CoOOH via a stepwise oxidation, the ligand-engineered zeolitic imidazolate frameworks manage to preserve the fundamental framework structure by in-situ forming a protective cobalt (oxy)hydroxide layer on the surface. This surface reconstruction facilitates both conductivity and catalytic activity by one order of magnitude and considerably enhances the (photo)electrochemical stability. This work highlights the vital role of ligand engineering for designing advanced and stable metal-organic frameworks for photo- and electrocatalysis. The application of metal-organic frameworks in (photo)electrocatalysis is constrained by their structural stability. Here, the authors report mixed-ligand zeolitic imidazolate frameworks that can in-situ form a protective (oxy)hydroxide layer through surface reconstruction, enhancing both catalytic activity and stability during (photo)electrocatalytic oxygen evolution reactions.