Nanocage-Based Tb³⁺-Organic Framework for Efficiently Catalyzing the Cycloaddition Reaction of CO₂ with Epoxides and Knoevenagel Condensation

Abstract

The catalytic performance of metal–organic framework (MOF)-based catalysts can be enhanced by increasing their catalytic sites, which prompts us to explore the multicore cluster-based skeletons by using designed functional ligands. Herein, the exquisite combination of [Tb4(μ2–OH)2(CO2)8] cluster and 2,6-bis­(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)­pyridine (H5BDCP) ligand generated a highly robust nanoporous framework of {[Tb4(BDCP)2(μ2–OH)2]·3DMF·5H2O} n (NUC-58), in which each four {Tb4} clusters are woven together to generate an elliptical nanocage (aperature ca. 12.4 Å). As far as we know, NUC-58 is an excellent nanocage-cluster-based {Tb4}-organic framework with the outstanding confined pore environments of a large specific surface area, high porosity, and plentiful coexisting Lewis acid–base sites of Tb3+, μ2–OH and Npyridine atoms. Performed experiments exhibited that NUC-58 owns a better catalytic performance for the cycloaddition reactions under mild conditions with a high turnover number and turnover frequency. Furthermore, NUC-58, as an eminent heterogeneous catalyst, can enormously boost the Knoevenagel condensation reactions. Thus, this work opens a path for the precise design of polynuclear metal cluster-based MOFs with excellent catalysis, stability, and regenerative behavior.

A multifunctional [CdI4]2−·[H2Bimb]2+complex to probe high performance photocatalytic degradation of methyl violet and fluorescent detection of Cr2O72−and Hg2+ions

“…Non-covalent interactions are useful in crystal engineering, molecular identification, catalysis, drug designing, and selfassembly because they play an important role in cooperative effects in several macromolecular systems. [1][2][3][4] Non-covalent interactions in inorganic-organic hybrids disclose ferroelectricity, magnetism, optical properties, heterogeneous catalysis [5][6][7] and other traits due to the design ability and controllable characteristics of the inorganic and organic constituents. [8][9][10] Physical, chemical, and biological systems can all benefit from these non-covalent interactions.…”

Undulated Ni(II)-Framework with In Situ-Grafted Open-Metal and Basic Sites for High-Performance Electrochemical Water Oxidation and Flexible Composite-Driven Size-Exclusive Autotandem Catalysis

“…Particularly, Ni-based materials have become a promising choice for constructing durable electrocatalysts owing to their earth abundance, high heat and electrical conductivities, low cost, and substantial thermal and chemical stabilities. Most importantly, their high capability to exist in different oxidation states (−1 to +4) leads to great susceptibility to undergo various electronic transitions. − Also, nickel foam (NF)-supported water oxidation catalysts are an emerging class of materials, as NF possesses a three-dimensional (3D) porous structure, large surface area, and high conductivity. − Meanwhile, as a branch of crystalline porous materials, metal–organic frameworks (MOFs) have received momentous attention for a vast range of potential applications − because of their three-dimensional (3D) spanned architectures with assorted topology, regular and adjustable pores, potential for tailorability, and diversity of metal centers as well as functional groups. ,− MOFs have also become best choices for OER electrocatalysis because of their accessible voids and open channels that can accommodate space for electrolytes, facilitate diffusion of the reactants, and assist in transportation of the evolved oxygen gas. ,, Moreover, the homogeneously distributed and pore-directed metal centers in MOFs serve as potential active sites, while organic ligands can aid in swapping of redox features to neighboring metal ions via modifying their coordination mode . However, only a handful of examples persist where MOFs are directly employed as OER electrocatalysts, , which is primarily on account of their insufficient chemical stability and improper orientation of metal sites within the pores.…”

Construction strategies to modulate the photocatalytic efficiency of Cd(ii) MOFs to photodegrade organic dyes

“…Metal–organic frameworks (MOFs) are an assorted class of three-dimensional coordination polymers constructed using metal ions and polyfunctional organic ligands that have received attention due to their remarkable features, such as high surface area and tunable porosity. 1–6 They find applicability in gas storage, catalysis, sensing, and drug delivery. 1–6 Fabrication of MOFs as photocatalysts is a popular area of contemporary research.…”

“…1–6 They find applicability in gas storage, catalysis, sensing, and drug delivery. 1–6 Fabrication of MOFs as photocatalysts is a popular area of contemporary research. 7,8 This is because photocatalysis is a cost-effective and environmentally friendly method that is based on the conversion of solar energy into chemical energy.…”