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<p>The electrosynthesis of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) has been widely considered as an environmentally friendly and sustainable alternative to the conventional anthraquinone protocol. Covalent organic frameworks (COFs) have emerged as promising metal-free catalysts for oxygen reduction reaction (ORR) processes. The designable molecular structures of COFs render adjustable catalytic selectivity towards two-electron (2e<sup>−</sup>) ORR pathway for the electrosynthesis of H<sub>2</sub>O<sub>2</sub>. Here, we synthesized a viologen-linked cationic COF, namely PTBD, via Zincke reaction using a conventional solvothermal strategy. To investigate the correlation between the structure and the catalytic performance, imine-linked neutral COFs of PTBP and PBBP with varying heteroatom nitrogen contents are prepared via Schiff-base condensation reaction. Notably, the PTBD COF, which is constructed by di-cationic viologen linkages and triazine blocks, delivers an exceptional H<sub>2</sub>O<sub>2</sub> selectivity of ~92%, considerably surpassing the imine-bridged neutral PTBP (~30%) and PBBP (~78%) COFs. Theoretical calculations are performed to uncover how the thermodynamic tendency of PTBD COF towards 2e<sup>−</sup> ORR route is related to its proper activation of O<sub>2</sub>. This work highlights the role of linkage and heteroatom contents in COFs regarding the catalytic selectivity, paving a way for designing metal-free catalysts for the selective electrosynthesis of H<sub>2</sub>O<sub>2</sub>.</p>

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Designing cationic covalent organic frameworks with redox-active linkages for high-performance electrocatalytic H2O2 synthesis

  • 期刊论文

  • 发表日期：

    2025年9月24日

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  • Jia Liu,
  • Xiaowei Wu,
  • Yuchen Xiao,
  • Shanyue Wei,
  • Yachong Wang,
  • Chaoyue Zheng,
  • Yi-Ming Xie,
  • Can-Zhong Lu

摘要

The electrosynthesis of hydrogen peroxide (H2O2) has been widely considered as an environmentally friendly and sustainable alternative to the conventional anthraquinone protocol. Covalent organic frameworks (COFs) have emerged as promising metal-free catalysts for oxygen reduction reaction (ORR) processes. The designable molecular structures of COFs render adjustable catalytic selectivity towards two-electron (2e−) ORR pathway for the electrosynthesis of H2O2. Here, we synthesized a viologen-linked cationic COF, namely PTBD, via Zincke reaction using a conventional solvothermal strategy. To investigate the correlation between the structure and the catalytic performance, imine-linked neutral COFs of PTBP and PBBP with varying heteroatom nitrogen contents are prepared via Schiff-base condensation reaction. Notably, the PTBD COF, which is constructed by di-cationic viologen linkages and triazine blocks, delivers an exceptional H2O2 selectivity of ~92%, considerably surpassing the imine-bridged neutral PTBP (~30%) and PBBP (~78%) COFs. Theoretical calculations are performed to uncover how the thermodynamic tendency of PTBD COF towards 2e− ORR route is related to its proper activation of O2. This work highlights the role of linkage and heteroatom contents in COFs regarding the catalytic selectivity, paving a way for designing metal-free catalysts for the selective electrosynthesis of H2O2.