Three-Dimensional Fully Conjugated Covalent Organic Frameworks for Efficient Photocatalytic Water Splitting.

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.