Investigation of the electrocatalytic reaction for the oxidation of alcohols through the formation of a metal organic framework (Mn-MIL-100)/polymer matrix on the surface of an Au electrode

An electrode composite containing a metal organic framework (Mn-MIL-100) was prepared by linkers including gold nanoparticles/polypyrrole and cysteine. The electrocatalytic application of this nanocomposite was evaluated via the oxidation of benzylic and aliphatic alcohols under open air conditions. Various active and inactive alcohol derivatives were successfully converted to the corresponding ketones with excellent yields. This advanced electrocatalyst proved to have remarkable stability over several recovery cycles from the reaction medium without significant change in its activity and selectivity and its regeneration potential. The active surface area of this electrocatalyst is very large due to its structural features, arising from the introduction of a metal organic framework (Mn-MIL-100) on a gold electrode, which provides more accessible surface sites, therefore boosting the electrocatalytic activity. The structure of the synthesized electrocatalyst has been characterized by FESEM, EDX, and AFM techniques. © 2023 The Royal Society of Chemistr

Post-synthetic modification of dual-porous UMCM-1-NH2 with palladacycle complex as an effective heterogeneous catalyst in Suzuki and Heck coupling reactions

Herein, the synthesis of a novel functionalized metal-organic-framework (MOF) UMCM-1-NH2-furfural/Pd Nano composite [UMCM-1-NH2-F2C-Pd Nano composite] is reported using the post-synthetic modification of UMCM-1-NH2. The targeted complex was prepared while chemically attaching the furfural – using Schiff base reaction followed by complexation with Pd ions. Afterward, the synthesized solid was applied as a very effective multifunctional catalyst in Suzuki and Heck coupling reactions. This technique which was facile, clean, and economically justified used only 0.01 g of the catalyst during the reaction. The easy setup, nontoxic solvent, enhanced yield, short reaction times, high turnover frequency, and catalyst durability are among the marked benefits of this synthesis method. Overall, the high catalytic activity of UMCM-1-NH2-F2C-Pd Nano composite may be due to the obtained high surface area and the synergistic features created between Lewis acidic Zn nodes and Pd ions. © 2023 Elsevier B.V

Immobilization of Ag and Pd over a novel amide based covalent organic framework (COF-BASU2) as a heterogeneous reusable catalyst to reduce nitroarenes

Reducing nitroarenes to their amines is among the common and vital reactions with remarkable industrial significance. This study describes an eco-friendly recyclable catalyst for reducing nitroarene. For this purpose, a new strategy was designed to synthesize a new amide-based COF through the reaction between 1,4‑diaminobenzene and trimesic acid (BTC). In this synthesis pathway, BTC is activated with carbonyl diimidazole (CDI), followed by its reaction with 1,4-diaminobenzene. Eventually, the desired COF (i.e., COF-BASU2) is synthesized. Next, it is decorated via silver (Ag) and palladium (Pd) ions to synthesize Ag/COF-BASU2 and Pd/COF-BASU2. The as-synthesized materials are properly characterized through ICP-OES, TG-DTA, FT-IR, EDX, XRD, TEM, and N2 isotherms. The simulation results have suggested a multi layers of two dimensional frameworks of COF-BASU2. Furthermore, Ag and Pb ions have shown to be placed on the surface and between the layers of COF, respectively. Then, we used molecular hydrogen as a reducing agent to investigate the Pd/COF-BASU2′s catalytic activity for nitroaromatic hydrogenation with excellent chemoselectivity and wide scope. In addition, NaBH4 was used as a reductant along with Ag/COF-BASU2 to reduce the nitro group on electronically diversified nitroarenes selectively. The remarkable characteristics of this catalytic system are the great turnover number (TON), considerably high selectivity, good turnover frequency (TOF), high yield, fast and almost complete conversion of nitrobenzene to the desired aniline, and facile and convenient segregation of catalyst and product. According to the obtained results, using Ag/COF-BASU2 offers the highest yields in the shortest reaction time

Pd(II)-immobilized on a novel covalent imine framework (COF-BASU1) as an efficient catalyst for asymmetric Suzuki coupling

This study reports the synthesis of a new imine-based covalent organic framework (COF) stabilizer through the reaction between 1,4-phenylenediamine and 4,4′,4″-(benzene-1,3,5-triyltris(oxy))tribenzaldehyde (COF-BASU1). Next, palladium (Pd) species were decorated on the synthesized COF, and the obtained Pd/COF-BASU1 composite was used as a heterogeneous catalyst in the asymmetric Suzuki-Miyaura coupling (SMC) reaction. The easily prepared imine-linked COF-BASU1 possesses a two-dimensional eclipsed layered-sheet structure, making its incorporation with metal ions feasible. Via a simple post-treatment, a Pd(II)-containing COF, Pd/COF-BASU1, was accordingly synthesized, which showed excellent catalytic activity in catalyzing the asymmetric Suzuki-Miyaura coupling reaction with high stereoselectivity. The eclipsed imine structure provide chiral environment to achieve the asymmetric Suzuki-Miyaura coupling reactionplay. Afterward, the chiral high-performance liquid chromatography (HPLC) was conducted to examine the axially chiral products generated through these reactions. These products were separated via the HPLC method. This technique is based on the function of some columns whose packing groups can segregate chiral products. The fabricated nanocatalyst was structurally authenticated using various analytical techniques such as FT-IR, XRD, FE-SEM, TGA, EDS, ICP-AES, and BET. The outcomes indicated that Pd/COF-BASU1 nanocomposite is a suitable catalyst to synthesis axially chiral biaryl derivatives with high stereoselectivity (up to 85.37% ee)

Facile synthesis of a new covalent organic framework (COF-AYLIN) based on polyamide links and their application in C–N coupling reaction

Among the reactions, C–N coupling is one of the most important and important reactions that have taken a significant part in the industry. This study defines the design/preparation of an eco-friendly recyclable catalyst for C–N coupling reaction. For this target, a new policy was designed to manufacture a new amide-based COF via the reaction amid benzidine and Benzene-1,3,5-tricarboxylic acid (BTC). BTC was activated with carbonyl diimidazole (CDI) and then reacted with benzidine for the synthesis of favorable COF (i.e., COF-AYLIN). Subsequent, the as-prepared COF was decorated via palladium ions to synthesize Pd/COF-AYLIN. The synthesized compounds were identified through the required techniques including N2 isotherms, TEM, EDX FT-IR, XRD, SEM, ICP-OES and TG-DTA. The computer simulation results possess suggested multi sheets of the 2D framework of COF-AYLIN. Consequently, It was found that palladium ions are placed between the layers and on the COF surfaces. This nanocatalyst was used in C–N Cross-Coupling reaction and showed its usage in a diverse range of different functional groups with good efficiency. The reason for introducing this catalyst system is because of its advantages such as considerably high selectivity, almost complete conversion of products, good turnover frequency (TOF), high yield, convenient separation of catalyst and product. The results show that the highest efficiency of the product in the reaction was obtained in the shortest possible time with the use of Pd/COF-AYLIN