RESUMEN
Covalent organic frameworks (COFs) are promising photocatalysts for water splitting, but their efficiency lags behind that of inorganic counterparts partly due to the limited charge transport and optical absorption properties. To overcome this limitation, we proposed to employ three-dimensional (3D) fully conjugated (FC) COFs with a topological assembly of cyclooctatetraene derivatives for photocatalytic water splitting. On the basis of first-principles calculations, we demonstrated that these 3D FC-COFs are semiconductors with exceptional charge transport and optical absorption properties. The carrier mobilities are comparable to those of inorganic semiconductors and superior to the record mobility observed in two-dimensional COFs. Additionally, the 3D FC-COFs exhibit broad visible light absorption with direct band gaps and high optical absorption coefficients. Among them, two 3D FC-COFs are identified for overall water splitting, while three others can facilitate the hydrogen evolution half-reaction. This study pioneers the design of 3D FC-COF photocatalysts, potentially advancing their applications in photocatalysis and optoelectronics.
RESUMEN
Two-dimensional (2D) covalent organic frameworks (COFs) with versatile structural and optoelectronic properties that can be tuned with building blocks and topological structures have received widespread attention for photocatalytic water splitting in recent years. However, few of these have been reported for overall water splitting under visible light. Here, we present a data-driven search of 2D COFs capable of visible-light-driven overall water splitting by combining high-throughput first-principles computations and experimental validations. Seven 2D COFs were identified to be capable of overall water splitting from the CoRE COF database, and their photocatalytic activities were further verified and optimized by our preliminary experiments. The production rates of H2 and O2 reached 80 and 32 µmol g-1â¯h-1, respectively, without using sacrificial agents. This work represents an attempt to explore 2D COFs for visible-light-driven overall water splitting with a data-driven approach that could accelerate the discovery and design of COFs toward photocatalytic overall water splitting.