In this work, we introduce a novel and general strategy for the environmentally friendly fabrication of mesoporous metal-organic framework (mMOF) thin films via the electrochemically assisted self-assembly (EASA) technique. Implementation of this procedure as a one-step, additive-free, and versatile protocol leads to the in situ simultaneous synthesis and deposition of mesoporous architectures of MOFs at room temperature under green conditions without the need for any base, pretreatment, or chemical modification of the underlying surface. Our procedure provides a controllable method for the synthesis of mMOF thin films (modified electrodes) consisting of hollow three-dimensional hexagonally packed crystals with two-dimensional honeycomb-like mesopores in the walls of the cavities, which grow perpendicularly onto any of the conducting surface. The resulting modified electrodes show enhanced electron transfer properties and better mass transfer performance along with the appropriate signal suitable for electrochemical sensing applications. This work can be a breakthrough and provide a new perspective for the modification and functionalization of the surface with any type of mMOF by the electrochemically driven cooperative (soft-templating) mechanism.

Kinetic studies and optimization are of interest as essential steps in the field of catalysis. We performed a complementary study of the electrocatalytic performances of (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) and N‐hydroxyphthalimide (NHPI) towards alcohol oxidation by using voltammetry as a versatile and informative technique. Both organocatalysts exhibited a good and well‐defined electrocatalytic activity in aqueous solution. Investigations of the efficacy of the reaction conditions revealed that the catalytic performance is greatly affected by the pH of the solution—and that there is a fundamental difference in reactivity between these apparently similar systems. TEMPO is an efficient catalyst in mild basic carbonate buffer, whereas NHPI acts efficiently in diluted acetic acid solution. Moreover, the effects of the alcohol type and the substituents were evaluated for a complete series of alcohols, and new kinetic data were obtained by means of voltammetric analyses and digital simulations of the cyclic voltammograms. Preparative electrocatalytic conversions of some alcohols were also examined under optimum conditions, and the results were encouraging.

A metal–organic framework (MOF) with sulfonic acid tags as a novel mesoporous catalyst was synthesized. The precursor of Zr-UiO-66-PDC was synthesized both via chemical and electrochemical methods. Then, zirconium-based mesoporous metal–organic framework [Zr-UiO-66-PDC-SO3H]Cl was prepared by reaction of Zr-UiO-66-PDC and SO3HCl. The structure of [Zr-UiO-66-PDC-SO3H]Cl was confirmed by FT-IR, PXRD, FE-SEM, TEM, BET, EDX, and Mapping analysis. This mesoporous [Zr-UiO-66-PDC-SO3H]Cl was successfully applied for the synthesis of dicyanomethylene pyridine derivatives via condensation of various aldehyde, 2-aminoprop-1-ene-1,1,3-tricarbonitrile and malononitrile. At the electrochemical section, a green electrochemical method has successfully employed for rapid synthesis of the zirconium-based mesoporous metal–organic framework UiO-66-PDC at room temperature and atmospheric pressure. The synthesized UiO-66-PDC has a uniform cauliflower-like structure with a 13.5 nm mean pore diameter and 1081.6 m2 g−1 surface area. The described catalyst [Zr-UiO-66-PDC-SO3H]Cl was also employed for the convergent paired electrochemical synthesis of dihydropyridine derivatives as an environmentally friendly technique under constant current at 1.0 mA cm−2 in an undivided cell. The proposed method proceeds with moderate to good yields for the model via a cooperative vinylogous anomeric based oxidation.

In this paper, the MIL-53(Al)-NH2 metal–organic frameworks (MOFs) was prepared based on the anodic electrosynthesis under green conditions. The anodic electrosynthesis as an environmentally friendly procedure was performed in the aqueous solution, room temperature, atmospheric pressure, and in the short reaction time (30 min). Also, the employed procedure was accomplished without the need for the ex-situ salt and base/probase additives as cation source and ligand activating agent at the constant current mode (10.0 mA cm−2). The electrosynthesized MOFs was functionalized with phosphorus acid tags as a novel mesoporous catalyst. This mesoporous catalyst was successfully employed for synthesis of new series (N-methyl-pyrrol)-pyrazolo[3,4-b]pyridines by one-pot condensation reaction of 3-methyl-1-phenyl-1H-pyrazol-5-amine, 3-(1-methyl-1H-pyrrol-2-yl)-3-oxopropanenitrile and various aromatic aldehydes (mono, bis and tripodal). This catalyst proceeded the organic synthetic reaction via a cooperative vinylogous anomeric based oxidation mechanism with a marginal decreasing its catalytic activity after recycling and reusability.

The development of a highly efficient and waste-free system for the selective oxidation of alcohols without using expensive transition metal catalysts using a novel electrogenerated TEMPO-functionalized MCM-41 modified electrode is described.