The Effect of Pore Functionality in Multicomponent Covalent Organic Frameworks on Stable Long-Term Photocatalytic H2 Production

In nature, organic molecules play a vital role in light harvesting and photosynthesis. However, regarding artificial water splitting, the research focus is primarily on inorganic semiconductors. Although organic photocatalysts have high structural variability, they tend to exhibit lower quantum efficiencies for water splitting than their inorganic counterparts. Multicomponent reactions (MCRs) offer an attractive route to introduce different functional units into covalent organic frameworks (COFs) and enable semiconducting properties and high chemical stability, creating promising materials for long-term photocatalytic applications, such as H-2 production. Herein we present several highly crystalline donor-acceptor based, 4-substituted quinoline-linked MCR-COFs prepared via the three-component Povarov reaction. The pore functionality was varied by applying different vinyl derivatives (e.g. styrene, 2-vinyl pyridine, 4-vinylpyridine, 4-vinyl imidazole, 2,3,4,5,6-pentafluorostyrene), which has a strong influence on the obtained photocatalytic activity. Especially an imidazole-functionalized COF displayed high photocatalytic performance due to its high surface area, crystallinity, and wettability. These properties enable it to maintain its photocatalytic activity even in a membrane support. Furthermore, such MCR-COFs display dramatically enhanced (photo)chemical stability even after long-term solar light irradiation and exhibit a high and steady H-2 evolution for at least 15 days.