Amino‐Induced 2D Cu‐Based Metal–Organic Framework as an Efficient Heterogeneous Catalyst for Aerobic Oxidation of Olefins

Abstract

With the assistance of hydrogen bonds of the o‐amino group, we have successfully tuned a coordination structure from a metal–organic polyhedron (MOP) to a two‐dimensional (2D) metal–organic framework (MOF). The amino group forms hydrogen bonds with the two vicinal carboxylic groups, and induces the ligand to coordinate with copper ions to form the 2D structure. The obtained 2D Cu‐based MOF (Cu‐AIA) has been applied as an efficient heterogeneous catalyst in the aerobic epoxidation of olefins by using air as oxygen source. Without the aggregation problem of active sites in MOPs, Cu‐AIA possesses much higher reactivity than MOP‐1. Furthermore, the amino group of the framework has been used as a modifiable site through post‐synthetic metalation (PSMet) to prepare a 2D MOF‐supported Pd single‐site heterogeneous catalyst, which shows excellent catalytic performance for the Suzuki reaction. It indicates that Cu‐AIA can also work as a good 2D MOF carrier for the derivation of other heterogeneous catalysts.

Emerging Two-Dimensional-Based Nanostructured Catalysts: Applications in Sustainable Organic Transformations

“…Compared to other traditional porous materials (e.g., mesoporous silica and zeolite), MOFs present a number of advantages, such as rich surface chemistry, structural versatility, and tunable pore size. , Moreover, compared with that of 3D MOFs, the accessibility of exposed active sites on the surface of 2D MOFs is superior, which facilitates the interaction between the substrate molecules and active sites and favors the transfer pathway of solvents, substrates, and reactants. Tang et al successfully constructed a 2D MOF by tuning a coordination structure to form a metal–organic polyhedron . The obtained Cu-based 2D MOF was utilized to support Pd-NPs by a postsynthetic metalation method.…”

Ultrathin 2D Eu3+@Zn-MOF Nanosheets: A Functional Nanoplatform for Highly Selective, Sensitive, and Visualized Detection of Organochlorine Pesticides in a Water Environment

“…Thus, 2D MOF nanosheets combine the advantages of MOFs and 2D nanomaterials simultaneously. At present, 2D MOF nanosheets have been widely used in various fields, including sensing, − catalysis/electrocatalysis, , supercapacitors, , gas separation, biomimetic enzymes, etc. Particularly, 2D MOF nanosheets are noticeably attractive platform candidates for signal transduction via a photoinduced electron-transfer pathway or photoluminescence resonance energy transfer. , Usually, ultrathin 2D MOF nanosheets are synthesized through two routes: the top-down delamination and the bottom-up synthesis .…”

Azo‐Functionalized Zirconium‐Based Metal−Organic Polyhedron as an Efficient Catalyst for CO2 Fixation with Epoxides

“…[39,40] Among these, technically recoverable heterogeneous catalysts such as MOFs have attracted much attention due to their characteristics of high surface area, uniform pore structure and tunable functionalities. [42][43][44][45][46][47][48][49][50] However, relatively low catalytic activity and harsh reaction conditions (elevated temperature and high pressure) are frequently encountered, which urges researchers to develop novel types of catalysts possessing high activity under milder reaction conditions.…”