High-Entropy Lanthanide-Organic Framework as an Efficient Heterogeneous Catalyst for Cycloaddition of CO2 with Epoxides and Knoevenagel Condensation

Siyang Jin; Yu Fu; Kecheng Jie; Huan Dai; YunJie Luo; Liang Ye; Chaohui Zhou; Wei Xu

doi:10.1002/chem.202400756

High-Entropy Lanthanide-Organic Framework as an Efficient Heterogeneous Catalyst for Cycloaddition of CO2 with Epoxides and Knoevenagel Condensation

Chemistry. 2024 May 10:e202400756. doi: 10.1002/chem.202400756. Online ahead of print.

Authors

Siyang Jin¹, Yu Fu¹, Kecheng Jie², Huan Dai³, YunJie Luo³, Liang Ye³, Chaohui Zhou³, Wei Xu⁴

Affiliations

¹ Ningbo University, School of Materials Science and Chemical Engineering, Resource Recycling of Ningbo University - Ningbo Shuangneng Environmental Technology Co., Ltd., CHINA.
² Nanjing University, State Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering,, CHINA.
³ Ningbo University, School of Materials Science and Chemical Engineering, Research Institute of Resource Recycling of Ningbo University - Ningbo Shuangneng Environmental Technology Co., Ltd., CHINA.
⁴ Ningbo University, Chemistry Institute for Synthesis and Green Application, School of Materials Science and Chemical Engineering, 818 Fenghua Road, Jiangbei Distric, 315211, Ningbo, CHINA.

PMID: 38727558
DOI: 10.1002/chem.202400756

Abstract

Multimetallic synergistic effects have the potential to improve CO2 cycloesterification and Knoevenagel reaction processes, outperforming monometallic MOFs. The results demonstrate superior performance in these processes. To investigate this, we created and characterized a selection of single-component Ln(III)-MOFs (Ln = Eu, Tb, Gd, Dy, Ho) and high-entropy lanthanide-organic framework (HE-LnMOF) using solvent-thermal conditions. The experiments revealed that HE-LnMOF exhibited heightened catalytic efficiency in CO2 cycloesterification and Knoevenagel reactions compared to single-component Ln(III) MOFs. Moreover, the HE-LnMOF displayed significant stability, maintaining their structural integrity after five cycles while sustaining elevated conversion and selectivity rates. The feasible mechanisms of catalytic reactions were also discussed. HE-LnMOF possess multiple unsaturated metal centers, acting as Lewis acid sites, with oxygen atoms connecting the metal, and hydroxyl groups on the ligand serving as base sites. This study introduces a novel method for synthesizing HE-LnMOF and presents a fresh application of HE-LnMOF for converting CO2.

Keywords: CO2 fixation; Knoevenagel condensation; Lanthanide-organic framework; dual-functional catalyst; high-entropy.