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Facile Synthesis of 2D Metal-Organic Framework as an Efficient Heterogeneous Catalyst for the Epoxidation of Olefin With H2O2

Journal 2025 · IF 3.7 · 发表于 2025 年 11 月 24 日
作者: Yan Cai,Wei Yang,Ali Morsali,Chunyan Zhang,Zhengguo Zhang,Guoying Zhang
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摘要

The 2D ultrathin MOF nanosheets, which effectively integrate metals and functional ligands, possess the advantageous features of molecular catalysts and exhibit remarkable catalytic activity in multiphase catalysis. Herein, we employed the sacrificial template method to achieve in situ attachment of metalloporphyrin onto a ZnO substrate, resulting in the formation of surfactant-free 2D dispersed structures of Zn-TCPP(Mn)/ZnO. The multilayered stacked B-Zn-TCPP(Mn) (3D) blocks were prepared by growing Zn 2+ mixed with metalloporphyrin as a comparison. The novel composite catalyst Zn-TCPP(Mn)/ZnO was employed for the efficient epoxidation of various alkenes using H 2 O 2 as an oxidant at ambient temperatures. Notably, alkenes conversion within 20 min achieves a high yield and impressive 1980 h − 1 turnover frequency. The composite catalyst can still maintain its structural integrity after undergoing five consecutive cycles, and the total yield of oxidized styrene is slightly reduced. This was confirmed by a series of characterization analyses and other assessments. Additionally, comparative experiments revealed that the B-Zn-TCPP(Mn) blocks underwent partial exfoliation into 2D nanosheets following the catalytic reaction, thereby enhancing the catalytic conversion efficiency in subsequent epoxidation reactions. This finding provides compelling evidence for the heightened catalytic activity of 2D materials. Graphical Using the sacrificial template method, metal porphyrin was attached in situ to the ZnO surface to prepare surfactant-free, highly dispersed Zn-TCPP(Mn)/ZnO, which had a positive effect on the stability and activity of the catalyst. Notably, styrene underwent complete conversion within 20 min, with an impressive epoxide selectivity reaching 97%, and exhibits a remarkable conversion frequency of 1980 h − 1 . More significantly, the composite catalyst Zn-TCPP(Mn)/ZnO exhibits a structurally stable framework and maintains a substantial level of catalytic activity even after undergoing five consecutive cycles. Meanwhile, other substrates exhibited varying degrees of selectivity, ranging from moderate to commendable.