中南大学物理学院刘敏团队近日取得一项新成果。经过不懈努力，他们的最新研究揭示了原子协同Lewis和Br促进全氟化合物分解的C-F键活化嵌套酸位。2025年2月19日出版的《美国化学会杂志》发表了这项成果。

在此，该研究团队通过构建协同的Lewis和Br在原子分散的Zn-O-Al位点上嵌套酸对，以促进C-F键的激活，从而分解典型的PFCs， CF₄。密度泛函理论（DFT）计算表明三配位Al （Al_III）和Zn-OH分别具有Lewis和Br在Zn-O-Al上嵌套酸位，协同促进CF₄的吸附和分解。x射线吸收光谱（XAS）、吡啶红外光谱（Py-IR）和氨程序升温解吸（NH₃-TPD）证实了在原子分散的Zn-O-Al位点上存在Al_III和Zn-OH。CF₄-TPD和原位红外光谱证实，Zn-O-Al位点有利于CF₄吸附和C-F键活化。结果表明，Zn-O-Al位点具有Lewis和Br嵌套酸对在560°C的低温下实现了100%的CF₄分解，并在超过250h的时间内表现出出色的稳定性。

研究人员表示，催化水解是降解全氟化合物（PFCs）的一种可持续的方法，但由于裂解强C-F键所需的高反应温度而受到挑战。

附：英文原文

Title: Promoting C–F Bond Activation for Perfluorinated Compounds Decomposition via Atomically Synergistic Lewis and Brnsted Acid Sites

Author: Wenjie Luo, Kang Liu, Tao Luo, Junwei Fu, Hang Zhang, Chao Ma, Ting-Shan Chan, Cheng-Wei Kao, Zhang Lin, Liyuan Chai, Michelle L. Coote, Min Liu

Issue&Volume: February 19, 2025

Abstract: Catalytic hydrolysis is a sustainable method for the degradation of perfluorinated compounds (PFCs) but is challenged by the high reaction temperatures required to cleave strong C–F bonds. Herein, we developed an innovative C–F activation strategy by constructing synergistic Lewis and Brnsted acid pairs over atomically dispersed Zn–O–Al sites to promote C–F bond activation for decomposition of typical PFCs, CF4. Density functional theory (DFT) calculations demonstrate tricoordinated Al (AlIII) sites and Zn–OH functional, respectively, as Lewis and Brnsted acid sites over Zn–O–Al, synergistically enhancing the adsorption and decomposition of CF4. X-ray absorption spectroscopy (XAS), pyridine infrared spectroscopy (Py-IR), and ammonia temperature-programmed desorption (NH3-TPD) verified the presence of both AlIII and Zn–OH on the atomically dispersed Zn–O–Al sites. CF4-TPD and in situ infrared spectroscopy confirmed that the Zn–O–Al sites facilitate CF4 adsorption and C–F bond activation. As a result, the Zn–O–Al sites with synergistic Lewis and Brnsted acid pairs achieved 100% CF4 decomposition at a low temperature of 560 °C and demonstrated outstanding stability for more than 250 h.

DOI: 10.1021/jacs.4c15280

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c15280