<p>As covalent organic frameworks (COFs) are coming of age, the lack of effective approaches to achieve crystalline and centimeter-scale-homogeneous COF films remains a significant bottleneck toward advancing the application of COFs in optoelectronic devices. Here, we present the synthesis of colloidal COF nanoplates, with lateral sizes of ∼200 nm and average heights of 35 nm, and their utilization as photocathodes for solar hydrogen evolution. The resulting COF nanoplate colloid exhibits a unimodal particle-size distribution and an exceptional colloidal stability without showing agglomeration after storage for 10 months and enables smooth, homogeneous, and thickness-tunable COF nanofilms via spin coating. Photoelectrodes comprising COF nanofilms were fabricated for photoelectrochemical (PEC) solar-to-hydrogen conversion. By rationally designing multicomponent photoelectrode architectures including a polymer donor/COF heterojunction and a hole-transport layer, charge recombination in COFs is mitigated, resulting in a significantly increased photocurrent density and an extremely positive onset potential for PEC hydrogen evolution (over +1 V against the reversible hydrogen electrode), among the best of classical semiconductor-based photocathodes. This work thus paves the way toward fabricating solution-processed large-scale COF nanofilms and heterojunction architectures and their use in solar-energy-conversion devices.</p> <p>All primary data files of measurements and processed data of the journal article mentioned under related publications from Lotsch group can be found here.</p> The data is structured according to figures and schemes in the research article and contains the following data types: XRD patterns (*.raw), AFM images (*.ibw), Nitrogen isotherm profiles (*.qps), dynamic light scattering data (*.dts), TEM images (*.dm3), ChemDraw files (*.cdxml), NMR data (*.jdf, *.mnova), python jupyter files (*.ipynb), CorelDraw files (*.cdr), SEM images (*.tif), electrochemistry data (*.paax), origin files (*.opju), COF structure models (*.cif), and FT-IR spectra (*.sp).

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