Zhu Genwang, Zhao Shuaijie, Yu Yueling, Fan Xinfei, Liu Kaiyuan, Quan Xie, Liu Yanming
Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), School of Environmental Science and Technology, Dalian University of Technology, Dalian, 116024, China.
College of Environmental Science and Engineering, Dalian Maritime University, Dalian, 116024, China.
Angew Chem Int Ed Engl. 2025 May 7:e202503626. doi: 10.1002/anie.202503626.
Electrocatalytic oxygen reduction is a sustainable method for on-site HO synthesis. The HO in acidic media has wide downstream applications, but acidic HO electrosynthesis suffers from poor efficiency due to high proton concentration and unfavourable *OOH (key intermediate) generation. Herein, acidic HO electrosynthesis was enhanced by regulating local proton availability and *OOH generation via fluorine-doped on inner and outer walls of carbon nanotubes (F-CNTs). It was efficient and stable for HO electrosynthesis with Faradaic efficiency of 95.6% and HO yield of 606.6 mg cm h at 1.0 A cm and 0.05 M HSO, outperforming the state-of-the-art electrocatalysts. The F-doping regulated the electronic structure of CNTs with elevated p-band center, and F-doping on its inner and outer walls also enhanced nanoconfinement effect and superhydrophobicity, respectively. As a result, a local alkaline microenvironment was created on F-CNTs surface during acidic HO electrosynthesis. The energy barrier for *OOH generation was significantly reduced and oxygen mass transfer was boosted. Their synergistic effects promoted acidic HO electrosynthesis. This work provides new insights into the mechanism for regulating HO electrosynthesis.
电催化氧还原是一种现场合成过氧化氢的可持续方法。酸性介质中的过氧化氢具有广泛的下游应用，但由于高质子浓度和不利的OOH（关键中间体）生成，酸性过氧化氢电合成效率较低。在此，通过在碳纳米管（F-CNTs）的内壁和外壁上进行氟掺杂来调节局部质子可用性和OOH生成，从而增强酸性过氧化氢电合成。在1.0 A cm和0.05 M HSO条件下，该方法对于过氧化氢电合成高效且稳定，法拉第效率为95.6%，过氧化氢产率为606.6 mg cm h，优于目前最先进的电催化剂。氟掺杂通过提高p带中心来调节碳纳米管的电子结构，并且在其内壁和外壁上的氟掺杂分别增强了纳米限域效应和超疏水性。结果，在酸性过氧化氢电合成过程中，F-CNTs表面形成了局部碱性微环境。*OOH生成的能垒显著降低，氧传质得到促进。它们的协同效应促进了酸性过氧化氢电合成。这项工作为调节过氧化氢电合成的机制提供了新的见解。
