Enhancing Visible Light CO 2 Reduction via π-Electron Delocalization in Barbituric Acid-Modified Poly(triazine imide) Crystals

作者：Feng Liu, Zongyuan Xie, Bo Su, Binbin Guo, Xiahui Lin, Wandong Xing, Xue Feng Lu, Zhiming Pan, Guigang Zhang, Sibo Wang · 发表于：ACS Catalysis · 年份：2025 · DOI：10.1021/acscatal.5c03730 · 被引用次数：60 · 研究领域：Advanced Photocatalysis Techniques、Covalent Organic Framework Applications、Luminescence and Fluorescent Materials

Poly(triazine imide) (PTI) holds significant promise for photocatalytic CO 2 reduction by addressing the limitations of conventional carbon nitrides. However, its practical application remains constrained by a narrow visible-light absorption. Herein, we report a barbituric acid (BA)-mediated copolymerization strategy to engineer π-electron delocalization within the triazine framework for broadening light-harvesting spectrum and optimizing charge carrier transport. Under visible light irradiation (λ ≥ 400 nm), the optimized PTI-BA 1.0 photocatalyst achieves a CO evolution rate of 10 μmol h –1 (333 μmol g –1 h –1 ) with 95% selectivity, representing a 5-fold enhancement over pristine PTI. Remarkably, the apparent quantum efficiency reaches 13.6% at 365 nm, underscoring its superior CO 2 photoconversion capability. Mechanistic investigations via in situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory calculations elucidate the energetically favorable pathways for CO 2 activation, reduction and CO desorption. This work not only provides a rational design strategy for modulating the optoelectronic properties of crystalline carbon nitride but also advances the development of high-performance photocatalysts for sustainable CO 2 conversion.