Selective Metal-Free CO₂ Photoreduction in Water Using Porous Nanostructures with Internal Molecular Free Volume

The conversion of CO₂ to a sole carbonaceous product using photocatalysis is a sustainable solution for alleviating the increasing levels of CO₂ emissions and reducing our dependence on nonrenewable resources such as fossil fuels. However, developing a photoactive, metal-free catalyst that is highly selective and efficient in the CO₂ reduction reaction (CO₂RR) without the need for sacrificial agents, cocatalysts, and photosensitizers is challenging. Furthermore, due to the poor solubility of CO₂ in water and the kinetically and thermodynamically favored hydrogen evolution reaction (HER), designing a highly selective photocatalyst is challenging. Here, we propose a molecular engineering approach to design a photoactive polymer with high CO₂ permeability and low water diffusivity, promoting the mass transfer of CO₂ while suppressing HER. We have incorporated a contorted triptycene scaffold with "internal molecular free volume (IMFV)" to enhance gas permeability to the active site by creating molecular channels through the inefficient packing of polymer chains. Additionally, we introduced a pyrene moiety to promote visible-light harvesting capability and charge separation. By leveraging these qualities, the polymer exhibited a high CO generation rate of 77.8 μmol g^-1 h^-1, with a high selectivity of ∼98% and good recyclability. The importance of IMFV was highlighted by replacing the contorted triptycene unit with a planar scaffold, which led to a selectivity reversal favoring HER over CO₂RR in water. In situ electron paramagnetic resonance (EPR), time-resolved photoluminescence spectroscopy (TRPL), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) techniques, further supported by theoretical calculations, were employed to enlighten the mechanistic insight for metal-free CO₂ reduction to exclusively CO in water.