Metal Node Engineering by Decorating Ferrocene Complexes To Enhance the CO₂ Photoreduction Performance of Metal...

Metal organic frameworks (MOFs) with tunable structures and high surface areas offer a versatile platform for photocatalyst design. Herein, we report a node engineering strategy by incorporating ferrocenecarboxylic acid (Fca) and ferroceneacetic acid (Fcaa) in situ into MOF-545 via stable Zr-O coordination bonds, aiming to enhance its CO₂ photoreduction performance. The structural and chemical properties of the resulting MOF-545-Fca and MOF-545-Fcaa were systematically characterized using powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and other techniques, confirming the successful incorporation of ferrocene without disrupting MOF's crystalline structure. The introduction of ferrocene constructs a potential dual-channel electron transfer pathway, extending the light-harvesting range, accelerating interfacial electron transport, and suppressing photogenerated electron-hole recombination. The synthesized MOF-545-Fcaa exhibits the highest CO production rate of 940.2 μmol·g^-1·h^-1, which is 1.88 times and 16.1 times higher than that of MOF-545 (500.7 μmol·g^-1·h^-1) and pristine MOF-545 without Fe center (58.4 μmol·g^-1·h^-1), respectively. In-situ attenuated total reflection infrared (ATR-IR) spectroscopy reveals the reaction pathway. This work demonstrates the effectiveness of ferrocene-based node engineering in optimizing MOF photocatalysts, providing valuable insights into the rational design of high-performance materials for CO₂ photoreduction and sustainable energy conversion.