Vinylene-Linked Covalent Organic Frameworks as Superior Photocatalysts for Hydrogen Evolution over Imine-Linked Counterparts

The scheme of photocatalysis of water, a way of hydrogen generation as a clean, high-efficiency fuel source for aircraft and long-range transport systems has received considerable interest. The development of the covalent organic framework (COF) - derived materials for hydrogen evolution reaction (HER) has since become a research highlight. Compared to traditional methods, photocatalytic hydrogen evolution systems based on COFs can provide ways of generating hydrogen gas without depending upon noble metal catalysts, thereby enhancing the sustainability and prospects of this technology for future aerospace energy applications.In this work, two covalent organic frameworks (COFs) with distinct linkages—a vinylene-linked COF A (via Knoevenagel condensation) and an imine-linked COF B (via Schiff-base reaction)—were designed and synthesized to compare their performance in the photocatalystic hydrogen evolution reaction (HER). Structural and electrochemical characterizations confirmed that, despite lower crystallinity and specific surface area due to pore blockage, COF A exhibited a suitable band structure for photocatalysis and achieved an HER rate of 56 μmol h^–1 g^–1 under simulated sunlight. In contrast, COF B was ineffective. This study experimentally validates the superior photocatalytic potential of vinylene-linked COFs over imine-linked counterparts for HER, highlighting their potential as non-noble-metal catalysts for aerospace and transport-oriented fuel generation.