Photocatalytic hydrogen production from water offers an abundant, clean fuel source, but it is challenging to produce photocatalysts that use the solar spectrum effectively. Many hydrogen-evolving photocatalysts are active in the ultraviolet range, but ultraviolet light accounts for only 3% of the energy available in the solar spectrum at ground level. Solid-state crystalline photocatalysts have light absorption profiles that are a discrete function of their crystalline phase and that are not always tunable. Here, we prepare a series of amorphous, microporous organic polymers with exquisite synthetic control over the optical gap in the range 1.94–2.95 eV. Specific monomer compositions give polymers that are robust and effective photocatalysts for the evolution of hydrogen from water in the presence of a sacrificial electron donor, without the apparent need for an added metal cocatalyst. Remarkably, unlike other organic systems, the best performing polymer is only photoactive under visible rather than ultraviolet irradiation.
Anthropogenic carbon dioxide emissions are thought to be one cause of global warming. Current methods for CO2 capture result in large energy penalties. Solid adsorbents are a potential method to capture CO2, but the sorbent-sorbate affinity is critical in determining the energetic viability of such processes. In this study, the adsorption of CO2 in a range of microporous organic polymers was tested. These materials adsorb up to 2.20 mmol/g CO2 at 298 K and 1 bar, and thus performance is compared with related porous solids in the literature. The relationship between CO2 uptake and apparent surface area and pore size is described, and this showed that heats of adsorption were important in the low pressure regime. The chemical tuning of gas-sorbent affinity provides a blueprint for the development of improved materials in this area.
We report here the carbon dioxide sorption properties for a series of conjugated microporous polymer (CMP) networks. These CMP materials incorporate a range of chemical functionalities including carboxylic acids, amines, hydroxyl groups, and methyl groups. The carboxylic acid functionalised network, rather than its amine analogue, shows the highest isosteric heat of sorption for CO2. This supports recent computational predictions for metal–organic frameworks and suggests that acid-functionalised frameworks could outperform more widely studied amine sorbents in CO2 capture and separation application.