Tröger's base derived 3D-porous aromatic frameworks with efficient exciton dissociation and well-defined reactive site for near-unity selectivity of CO2 photo-conversion

The overall photocatalytic conversion of CO 2 and H 2 O to fuel and O 2 is challenging. In this study, a series of three-dimensional Tröger's base-derived porous aromatic frameworks (3D- X -TB-PAFs ( X = TEPE, TEPM, SPF)) featuring designated reaction sites and unique charge transfer properties were developed. The incorporation of V-shaped Tröger's base (TB) units and aromatic alkynes imparts the polymers with permanent porosity, additional photon scattering cross-sections, and enhanced CO 2 adsorption/activation capabilities. Density functional theory calculations and optoelectronic measurements revealed the formation of intramolecular built-in polarization and electron-trap sites induced by TB, which modulated charge separation and customized reaction sites in collaboration with 3D networks. In addition, product allocation during the photoreduction of CO 2 was regulated by the photooxidation of H 2 O. Among the as-prepared 3D-PAFs, the most efficient electron transport channel was demonstrated by the TEPE-TB-PAF with fully conjugated TEPE-T. In the absence of cocatalysts and sacrificial agents, TEPE-TB-PAF exhibits a competitive CO formation rate (194.50 μmol g −1 h −1 ) with near-unity selectivity (99.74%). Significantly, the low energy barrier for CO desorption and the high energy barrier for *CHO formation contribute to the high efficiency of TEPE-TB-PAF, as demonstrated by computational exploration and in situ diffuse reflectance infrared Fourier transform spectra. This work offers efficient building blocks for the synthesis of multifunctional organic photocatalysts and groundbreaking insights into the simultaneous enhancement of photocatalytic reactivity and selectivity.