近日，同济大学费泓涵团队研究了用于近红外驱动CO₂到C₂H₄光转换的高稳定π扩展紫精功能化杂化卤化铅。这一研究成果发表在2025年9月23日出版的、《德国应用化学》杂志上。

杂化卤化铅由于其结构的可调性和优异的光物理性质，在CO₂光还原方面显示出巨大的潜力。然而，它们的固有不稳定性和近红外（NIR）照射下C-C耦合的抑制效率突出了开发一种稳定的、有效利用近红外的单组分光催化剂的重大挑战。

研究组通过配位驱动组装，将π扩展的紫素单元整合到两个杂化卤化铅中，形成本构给受体（D-A）构型。从一维到二维的调制将近红外吸收扩展到965 nm，提供1.28 eV的窄带隙。固有的D-A体系，结合卤化铅优良的载流子迁移率，促进了电子从卤化铅组分向紫光基团的有效迁移，产生稳定的n自由基。所得的单组分光催化剂在700（±15）nm和800（±15）nm处实现了CO₂到C₂H₄的选择性转化，表观量子产率（AQYs）分别为0.81%和0.38%，超过了通常生成C₁产物的典型NIR响应光催化剂。

机制研究表明，积累的载流子促进了邻近N自由基位点上*CO中间体的形成，接近(~4.7 )，促进* CO-CO耦合。研究组提出了一种利用低能量近红外光驱动CO₂转化为高价值C₂烃的有效策略，推进了高性能金属卤化物光催化剂的设计。

附：英文原文

Title: Highly Stable π?Extended Viologen Functionalized Hybrid Lead Halides for Near Infrared-Driven CO2-to-C2H4 Photoconversion

Author: Chen Sun, Jinlin Yin, Honghan Fei

Issue&Volume: 2025-09-23

Abstract: Hybrid lead halides show great potential for CO2 photoreduction owing to their structural tunability and excellent photophysical properties. However, their intrinsic instability and the suppressed efficiency of C–C coupling under near-infrared (NIR) irradiation highlight the significant challenges of developing a stable, single-component photocatalyst with efficient NIR utilization. Herein, we incorporate π-extended viologen units into two hybrid lead halides via coordination-driven assembly, forming intrinsic donor–acceptor (D–A) configurations. Dimensional modulation from 1D to 2D extends the NIR absorption to 965 nm, affording a narrow bandgap of 1.28 eV. The inherent D–A system, combined with excellent carrier mobility of lead halides, promotes efficient electron migration from the lead halide components to the viologen moieties, generating stable N-radical species. The resultant single-component photocatalyst achieves selective CO2-to-C2H4 conversion with high apparent quantum yields (AQYs) of 0.81% at 700(±15) nm and 0.38% at 800(±15) nm, exceeding typical NIR-responsive photocatalysts that typically generate C1 products. Mechanistic investigations reveal that the accumulated carriers enhance *CO intermediate formation on adjacent N radical sites with close proximity (～4.7 ), promoting *CO–CO coupling. This work presents an effective strategy for utilizing low-energy NIR light and drive CO2 conversion to high-value C2 hydrocarbons, advancing the design of high-performance metal halide photocatalysts.

DOI: 10.1002/anie.202514206

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202514206