An Ester‐Functionalized Bidentate Titanium‐based Metal–Organic Framework with Visible‐Light Enhanced Activity for CO2 Photoreduction

Abstract

AbstractThe limited visible light response is a critical drawback that hampers the photocatalytic efficacy of Ti‐MOFs. However, study concerning the enhancement of the visible‐light response of Ti‐MOFs is still in its nascent stage. In this study, we employ the ‘dual‐ligand decrystallization strategy’ to manipulate the electronic environment of Ti4+, leading to the synthesis of three ester‐functionalized bidentate Ti‐MOFs with enhanced visible light response. Our findings reveal that this approach not only reduces the bandgap of Ti‐MOFs but also enhances their photocatalytic activity for carbon dioxide reduction. Specifically, compared to the bandgap of Ti‐BPDC at 2.98 eV, the bandgap of Ti‐BPDC‐CA 1 : 2 has been reduced to 2.14 eV. Moreover, Ti‐BPDC‐CA 1 : 2 exhibits extraordinary photocatalytic activity with the formic acid (HCOOH) production rate of 617 μmol g−1 h−1 with over 99.5 % selectivity, which is 3.47 times higher than that of Ti‐BPDC. Besides providing a cost‐effective strategy for enhancing the visible light response of Ti‐MOFs, our study also serves as an illustrative example for establishing the correlation between electronic structure and optical properties.