Dimensionality Reduction of Metal–Organic Frameworks to Monolayers for Enhanced Electrocatalysis
Abstract
Abstract Metal–organic frameworks (MOFs) are potential candidates for electrocatalysis due to their well‐defined, tunable structures, and ability to incorporate diverse active sites. However, their inherent insulating nature restricts electron transfer from electrode to remote active sites, leading to diminished catalytic performance. In this work, we present a novel strategy to overcome this limitation by reducing 3D MOFs (3D_MOFs) into monolayered MOFs (monoMOFs) with a thickness of ∼1.8 nm, maximizing the exposure of catalytic sites to the electrode and enhancing electrocatalytic performance. We designed and synthesized a monoMOF incorporating cobalt(II)–porphyrin sites in the linker (monoMOF‐Co) for CO 2 electroreduction. After being grafted onto graphene oxide, the monoMOF‐Co exhibited a peak faradaic efficiency for CO production (FE CO = 93%), surpassing the performance of a 3D_MOF incorporating the same porphyrin–Co‐based linker (3D_MOF‐Co, FE CO = 51%). Additionally, monoMOF‐Co achieved a turnover frequency of 10 600 h −1 at −0.8 V versus the reversible hydrogen electrode (RHE) and maintained stability over 47 h in a near‐neutral aqueous solution. In situ spectroscopic studies further confirmed the distinct electric field environment in the Stern layer between monoMOF‐Co and 3D_MOF‐Co. Furthermore, similar enhancement effects of monoMOFs over 3D_MOFs were observed in the nitrate and oxygen electroreduction reactions, highlighting the broader applicability of monoMOFs in electrocatalysis.
Article Details
Authors (12)
Zi Yang
Beijing National Laboratory for Molecular Science, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering
An Li
Hao Li
Guotao Lai
Department of Chemistry Southern University of Science and Technology Shenzhen Guangdong 518055 China
Yifan Fu
Yufeng Zhang
Kun Wang
Beijing National Laboratory for Molecular Science, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering
Senhai Zeng
Beijing National Laboratory for Molecular Science, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering
Lin Xie
Mufan Li
Beijing National Laboratory for Molecular Sciences, Center for Integrated Spectroscopy, College of Chemistry and Molecular Engineering
Jun Gu
School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology
Guangxu Lan
Beijing National Laboratory for Molecular Science, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering