Cucurbituril‐Manipulated Supramolecular Electrodes for Highly Active and Stable (Photo)electrocatalytic Oxidation Reactions

• Published in: Advanced functional materials 2024-12
• Main Authors: Jiang, Shuai, Zhang, Kefan, Yin, Xianjun, Peng, Hui‐Qing, Zhang, Wenjun, Liu, Bin
• Format: Article
• Language: English
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.202419705

The robust immobilization and activity regulation of molecular catalysts on solid electrodes have remained persistent challenges in catalysis. Herein, cucurbituril (CB[7]) acts is first demonstrated as a bifunctional medium to firmly immobilize molecular catalyst CoTMPyP onto various metal oxide electrodes, including TiO 2 , BiVO 4 , α‐Fe 2 O 3 , and WO 3 , through host‐guest and electrostatic interactions. This approach not only secures stable attachment of the catalyst but also optimizes its electronic structure and catalytic activity. The CB[7]‐mediated supramolecular electrodes exhibit exceptional performance in electrocatalytic oxygen evolution reaction (OER), ethanol oxidation reaction, hydrazine oxidation reaction, and photoelectrocatalytic water oxidation. For instance, TiO 2 ‐CB[7]‐CoTMPyP electrode achieves a turnover frequency (TOF) of 5.30 s −1 at an overpotential of 600 mV for OER, and BiVO 4 ‐CB[7]‐CoTMPyP photoanode delivers a water oxidation photocurrent density of 6.00 mA cm −2 at 1.23 V versus RHE under simulated solar irradiation. Mechanistic studies reveal CB[7] plays a critical role beyond merely serving as a linker: it enhances charge accumulation around the cobalt sites, promotes reactants adsorption at these sites, reduces reaction energy barrier, and accelerates charge transfer rate, thereby significantly boosting catalytic activity. This work provides a groundbreaking pathway for the design and fabrication of cost‐effective, high‐performance molecular‐based electrodes for (photo)electrocatalytic reactions.