Monolayered Metal–Organic Framework Unlocks Integration of Shaped Nanoparticles for Synergistic Photocatalysis
Kun Wang, Yufeng Zhang, Zizhuo Gong, An Li, Yiyang Ma, Jun‐Hao Wang, Hu Zhang, Ruizhi Huang, Zi Yang, Zixuan Yu, Senhai Zeng, Jiangnan Li, Sihai Yang⧫, Ya‐Wen Zhang, Guangxu Lan
Abstract
Metal–organic frameworks (MOFs) with ordered structures and high surface areas are promising supports for metal nanoparticles (MNPs) in synergistic catalysis. However, their limited pore sizes restrict integration to small spherical MNPs, excluding shaped MNPs that are critical for exposing specific lattice surfaces and achieving a superior catalytic performance. In this work, we address this limitation by reducing MOFs to monolayers, enabling the integration of shaped MNPs onto their surfaces to significantly enhance the catalytic efficiency. The monolayered MOF (monoMOF), Hf 12 -Ir, with a thickness of ∼1.8 nm, was synthesized using photosensitizing DBB-Ir-F linkers. Freshly synthesized cubic Cu nanoparticles (Cu-NPs, ∼35 nm) were functionalized with thioctic acid (TA) via Cu–S coordination and integrated onto the surface of Hf 12 -Ir through carboxylate-Hf 12 coordination, forming the Cu/Hf 12 -Ir composite. Upon light irradiation, Cu/Hf 12 -Ir achieved exceptional CO 2 -to-CO conversion with a turnover frequency of 82.9 mmol g Cu –1 h –1 and a CO selectivity of 98.3%. This catalytic performance was over an order of magnitude higher than that of the homogeneous system (Cu-NPs and H 2 DBB-Ir-F) and the small spherical MNPs-based composite (S-Cu/Hf 12 -Ir). Mechanistic studies revealed a synergistic effect between the Cu-NPs and Hf 12 -Ir, where their proximity enhanced electron transfer from the photoexcited DBB-Ir-F centers to the Cu-NPs. This work demonstrates a straightforward strategy for constructing MNP-monoMOF composites and highlights the critical charge transfer pathway between the photosensitizing monoMOF and catalytic MNPs.