Near‐Infrared Light Catalysis of Carbon Dioxide Reduction by Conjugated Porous Aromatic Frameworks

Current CO₂ photocatalytic systems mainly work in ultraviolet (UV) and visible (Vis) light regions, and the inability to utilize the abundant near-infrared (NIR) radiation or the low utilization rate is still a bottleneck for practical applications. We address this challenge through the strategic synthesis of metal-free conjugated porous aromatic frameworks (PAFs), PAF-332-DCM, to enhance the NIR absorption capabilities, achieving a CO production rate of ~74.7 µmol g^-1 h^-1 in gas-solid phase CO₂ reduction, surpassing typical NIR-responsive catalysts. Meanwhile, PAF-332-DCM can obtain a CO production rate of 344.1 µmol g^-1 h^-1 in full-spectrum irradiated CO₂ reduction. Infrared thermography reveals that the non-radiative attenuation of PAF-332-DCM leads to high photothermal temperature under NIR irradiation, which accounts for its reduction performance. Mechanistic studies combining fs-TA spectroscopy and in situ infrared characterization elucidate the photocatalytic pathway and intermediate formation. This result indicates that PAF-332-DCM can be a promising metal-free catalyst for practical solar-driven CO₂ conversion.