Recyclable Cu-MOF-74 Catalyst for Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol

Metal–organic framework (MOF)-based derivatives are attracting increased interest in various research fields. In this study, nano-cellulose MOF-derived carbon-doped CuO/Fe3O4 nanocomposites were successfully synthesized via direct calcination of magnetic Cu-BTC MOF (HKUST-1)/Fe3O4/cellulose microfibril (CMF) composites in air. The morphology, structure, and porous properties of carbon-doped CuO/Fe3O4 nanocomposites were characterized using SEM, TEM, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and vibrating sample magnetometry (VSM). The results show that the as-prepared nanocomposite catalyst is composed of Fe3O4, CuO, and carbon. Compared to the CuO/Fe3O4 catalyst from HKUST-1/Fe3O4 composite and CuO from HKUST-1, this carbon-doped CuO/Fe3O4 nanocomposite catalyst shows better catalytic efficiency in reduction reactions of 4-nitrophenol (4-NP), methylene blue (MB), and methyl orange (MO) in the presence of NaBH4. The enhanced catalytic performance of carbon-doped CuO/Fe3O4 is attributed to effects of carbon preventing the aggregation of CuO/Fe3O4 and providing high surface-to-volume ratio and chemical stability. Moreover, this nanocomposite catalyst is readily recoverable using an external magnet due to its superparamagnetic behavior. The recyclability/reuse of carbon-doped CuO/Fe3O4 was also investigated.

Section: Introductionmentioning

confidence: 99%

Nano-Cellulose/MOF Derived Carbon Doped CuO/Fe3O4 Nanocomposite as High Efficient Catalyst for Organic Pollutant Remedy

Zhang

et al. 2019

Sustainable Synthesis of Zeolitic Imidazolate Frameworks at Room Temperature in Water with Exact Zn/Linker Stoichiometry

Molina,

Rodríguez-Campa,

Flores-Borrell

et al. 2024

Zeolitic imidazolate frameworks (ZIFs) are widely used MOFs because of certain characteristics, but also because they can be prepared at room temperature using water as the unique solvent. However, these a priori sustainable conditions inevitably entail a huge and somehow unusable excess of linker. Here, we present the formation of ZIFs at room temperature in water, starting from mixtures with a linker/metal ratio of two, that is, coinciding with the stoichiometry found in the final MOFs, in the presence of amines. ZIF-8 can be prepared with triethylamine (TEA), giving a yield of Zn of 96.6%. Other bases, like NaOH, tetraethylammonium hydroxide or ammonium hydroxide, do not lead to ZIF-8 under the same conditions. The so-obtained ZIF-8 contains TEA inside its cavities, making it less porous than its conventionally prepared counterparts. Amine can be removed by mild thermal treatments (200–250 °C). Such thermal treatments induce the generation of g-C3N4-like species which could give added value to these materials as potential photocatalysts, increasing their affinity to CO2, as proved in this work. This methodology can be successfully extended to other amines, like N,N-dicyclohexylmethylamine, as well as to other prepared ZIFs, like Co-based ZIF-67, isostructural to ZIF-8.

URJC-1: Stable and Efficient Catalyst for O-Arylation Cross-Coupling

García-Rojas,

Leo,

Tapiador

et al. 2024

The design of metal–organic frameworks (MOFs) allows the definition of properties for their final application in small-scale heterogeneous catalysis. Incorporating various catalytic centers within a single structure can produce a synergistic effect, which is particularly intriguing for cross-coupling reactions. The URJC-1 material exhibits catalytic duality: the metal centers act as Lewis acid centers, while the nitrogen atoms of the organic ligand must behave as basic centers. The impact of reaction temperature, catalyst concentration, and basic agent concentration was evaluated. Several copper-based catalysts, including homogeneous and heterogeneous MOF catalysts with and without the presence of nitrogen atoms in the organic ligand, were assessed for their catalytic effect under optimal conditions. Among the catalysts tested, URJC-1 exhibited the highest catalytic activity, achieving complete conversion of 4-nitrobenzaldehyde with only 3% mol copper concentration in one hour. Furthermore, URJC-1 maintained its crystalline structure even after five reaction cycles, demonstrating remarkable stability in the reaction medium. The study also examined the impact of various substituents of the substrate alcohol on the reaction using URJC-1. The results showed that the reaction had high activity when activating substituents were present and for most cyclic alcohols rather than linear ones.