CuTM‐BTC via Linker Fluorination: A Promising Photocatalyst for Hydrogen Evolution Reaction

ABSTRACT The photocatalysts play a key role in hydrogen evolution photocatalysis. In this work, we systematically investigated the hydrogen evolution performance of the copper‐based metal‐organic framework CuTM‐BTC functionalized via linker fluorination by means of density functional theory calculations, wherein the systems are named as CuTM‐F for simplification. Herein, CuSc‐F, CuTi‐F, CuY‐F, and CuRe‐F are identified as promising candidates to boost hydrogen evolution photocatalysis. The corresponding overpotentials η HER are 0.39, 0.03, 0.65, and 0.56 V, respectively. Furthermore, the energy gaps between HOMO and LUMO are 2.94, 2.35, 3.10, and 2.93 eV, indicating the good ability of light absorption. Consistently, the absorption peaks are located at 423, 621, 428, and 506 nm for CuSc‐F, CuTi‐F, CuY‐F, and CuRe‐F according to the absorption spectra, respectively. Herein, the linker fluorination enhances the efficiency of visible light harvest as compared with the counterparts without linker fluorination. Therefore, our research sheds light on the positive influence of the linker functionalization on the photocatalysis improvement.