Nanoscale covalent organic frameworks for enhanced photocatalytic hydrogen production.

Nanosizing confers unique functions in materials such as graphene and quantum dots. Here, we present two nanoscale-covalent organic frameworks (nano-COFs) that exhibit exceptionally high activity for photocatalytic hydrogen production that results from their size and morphology. Compared to bulk analogues, the downsizing of COFs crystals using surfactants provides greatly improved water dispersibility and light-harvesting properties. One of these nano-COFs shows a hydrogen evolution rate of 392.0 mmol g-1 h-1 (33.3 µmol h-1), which is one of the highest mass-normalized rates reported for a COF or any other organic photocatalysts. A reverse concentration-dependent photocatalytic phenomenon is observed, whereby a higher photocatalytic activity is found at a lower catalyst concentration. These materials also show a molecule-like excitonic nature, as studied by photoluminescence and transient absorption spectroscopy, which is again a function of their nanoscale dimensions. This charts a new path to highly efficient organic photocatalysts for solar fuel production.

Minimizing buried interfacial defects for efficient inverted perovskite solar cells.

Controlling the perovskite morphology and defects at the buried perovskite-substrate interface is challenging for inverted perovskite solar cells. In this work, we report an amphiphilic molecular hole transporter, (2-(4-(bis(4-methoxyphenyl)amino)phenyl)-1-cyanovinyl)phosphonic acid, that features a multifunctional cyanovinyl phosphonic acid group and forms a superwetting underlayer for perovskite deposition, which enables high-quality perovskite films with minimized defects at the buried interface. The resulting perovskite film has a photoluminescence quantum yield of 17% and a Shockley-Read-Hall lifetime of nearly 7 microseconds and achieved a certified power conversion efficiency (PCE) of 25.4% with an open-circuit voltage of 1.21 volts and a fill factor of 84.7%. In addition, 1-square centimeter cells and 10-square centimeter minimodules show PCEs of 23.4 and 22.0%, respectively. Encapsulated modules exhibited high stability under both operational and damp heat test conditions.

Reconstructed covalent organic frameworks.

Covalent organic frameworks (COFs) are distinguished from other organic polymers by their crystallinity1-3, but it remains challenging to obtain robust, highly crystalline COFs because the framework-forming reactions are poorly reversible4,5. More reversible chemistry can improve crystallinity6-9, but this typically yields COFs with poor physicochemical stability and limited application scope5. Here we report a general and scalable protocol to prepare robust, highly crystalline imine COFs, based on an unexpected framework reconstruction. In contrast to standard approaches in which monomers are initially randomly aligned, our method involves the pre-organization of monomers using a reversible and removable covalent tether, followed by confined polymerization. This reconstruction route produces reconstructed COFs with greatly enhanced crystallinity and much higher porosity by means of a simple vacuum-free synthetic procedure. The increased crystallinity in the reconstructed COFs improves charge carrier transport, leading to sacrificial photocatalytic hydrogen evolution rates of up to 27.98 mmol h-1 g-1. This nanoconfinement-assisted reconstruction strategy is a step towards programming function in organic materials through atomistic structural control.

Engineering Nanoparticulate Organic Photocatalysts via a Scalable Flash Nanoprecipitation Process for Efficient Hydrogen Production.

Directly converting sunlight into hydrogen fuels using particulate photocatalysts represents a sustainable route for clean energy supply. Organic semiconductors have emerged as attractive candidates but always suffer from optical and exciton recombination losses with large exciton "dead zone" inside the bulk material, severely limiting the catalytic performance. Herein, we demonstrate a facile strategy that combines a scalable flash nanoprecipitation (FNP) method with hydrophilic soluble polymers (PC-PEG5 and PS-PEG5) to prepare highly efficient nanosized photocatalysts without using surfactants. Significantly, a 70-fold enhancement of hydrogen evolution rate (HER) is achieved for nanosized PC-PEG5, and the FNP-processed PS-PEG5 shows a peak HER rate of up to 37.2 mmol h-1 g-1 under full-spectrum sunlight irradiation, which is among the highest results for polymer photocatalysts. A scaling-up production of nanocatalyst is demonstrated with the continuously operational FNP.