Near-infrared-driven photocatalytic CO2 reduction to C2 hydrocarbons by bis(terpyridine)-metal functionalized lead halide frameworks

Abstract Hybrid lead halides have demonstrated significant promise for CO₂ photoreduction due to their excellent photophysical properties. However, developing a single-component hybrid lead halide that combines high intrinsic stability with near-infrared (NIR) absorption (accounting for over 50% of solar enrgy) remains a significant challenge. Herein, to address both issues, we design a series of nine ultra-stable lead halide frameworks functionalized by bis(terpyridine)-metal (M(tpy) 2 , M = Fe 2+ /Co 2+ /Ni 2+ ) complexes, which exhibit strong light absorption extending into the NIR region up to 1150 nm. Unlike their symmetric chloride and bromide analogues, the charge-polarized Pb 2 I 4 (DMF) sites in lead iodide-M(tpy) 2 frameworks serve as highly efficient C–C coupling centers for C 2 production in NIR-driven CO 2 photoreduction, achieving remarkable C 2 production rates of up to 14.3 µ mol g − 1 h − 1 with electron selectivities as high as 86%. These performances substantially surpass all previously reported single-component NIR-responsive photocatalysts, highlighting the potential of coordination-driven assembly of ultra-stable lead halide frameworks for NIR-driven artificial photosynthesis.