Unleashing the photocatalytic potential of a noble-metal-free heteroleptic copper complex-based nanomaterial for an enhanced aza-Henry reaction.

In this work, we fabricated a versatile and noble metal free copper-based heterogeneous photocatalyst, representing a green shift away from precious group metals such as Ir, Ru, Pt, which have been widely utilized as photocatalysts. The successfully synthesized and characterized copper photocatalyst was employed to establish a cross dehydrogenative coupling via C-H activation between tertiary amines and carbon nucleophiles. The highly efficient copper-based photocatalyst was characterized by numerous physico-chemical techniques, which confirmed its successful formation as well as its high activity. Inductively coupled plasma (ICP-OES) analysis revealed that the composite Cu@Xantphos@ASMNPs had a very high loading of 0.423 mmol g-1 of copper. The magnetic Cu@Xantphos@ASMNPs were utilized as a potential heterogeneous photocatalyst for the very facile and regioselective conversion of aryl tetrahydroqinoline to the respective nitroalkyl aryl tetrahydroisoquinoline in high yield using air as an oxidant and methanol as a green solvent with irradiation with visible light under mild reaction conditions. Additionally, the catalyst shows exceptional chemical stability and reusability without any agglomeration even after several cycles of use, which is one of the key features of this material, rendering it a potential candidate from economic and environmental perspectives.

A simple and straightforward strategy for expedient access to benzoxazoles using chemically engineered 2D magnetic graphene oxide nanosheets as an eco-compatible catalyst.

Two-dimensional (2D) graphene oxide nanosheets serve as an excellent support material for immobilizing metal complexes to deal with the drawbacks of homogeneous catalysis. In this work, we report a magnetically retrievable graphene oxide (MGO) based copper nanocatalytic system that has been efficiently exploited for obtaining a series of pharmaceutically and biologically active benzoxazole scaffolds. The nanocatalyst was designed by covalent immobilization of dehydroacetic acid (DHA) onto a magnetic amino-silanized graphene oxide nanosupport which was accompanied by its metallation with copper acetate. The structure of the synthesized MGO hybrid material (Cu@DHA@APTES@MGO) was characterized by numerous physico-chemical techniques such as transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), vibrating sample magnetometry (VSM), elemental mapping, atomic absorption spectroscopy (AAS), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) surface area analysis and energy-dispersive X-ray fluorescence spectroscopy (ED-XRF). The fabricated architectures exhibited high efficiency for cyclization of 2-aminophenols and ß-diketones with wide substrate scope, excellent functional group tolerance, a higher conversion percentage (>98%) and a high turnover number (TON). The exceptional catalytic activity could be attributed to the 2D architecture of graphene oxide which provides space for trapping of reactants between 2D graphitic overlayers and metal surfaces and the reaction proceeds to afford benzoxazole products with moderate to excellent conversion percentages. Notably, this nanocomposite could be recovered easily through an external magnetic force and reused for multiple runs without any appreciable loss in its catalytic efficacy.

Hierarchical 3D Flower-like Metal Oxides Micro/Nanostructures: Fabrication, Surface Modification, Their Crucial Role in Environmental Decontamination, Mechanistic Insights, and Future Perspectives.

Hierarchical micro/nanostructures are constructed by micro-scaled objects with nanoarchitectures belonging to an interesting class of crystalline materials that has significant applications in diverse fields. Featured with a large surface-to-volume ratio, facile mass transportation, high stability against aggregation, structurally enhanced adsorption, and catalytical performances, three dimenisional (3D) hierarchical metal oxides have been considered as versatile functional materials for waste-water treatment. Due to the ineffectiveness of traditional water purification protocols for reclamation of water, lately, the use of hierarchical metal oxides has emerged as an appealing platform for the remediation of water pollution owing to their fascinating and tailorable physiochemical properties. The present review highlights various approaches to the tunable synthesis of hierarchical structures along with their surface modification strategies to enhance their efficiencies for the removal of different noxious substances. Besides, their applications for the eradication of organic and inorganic contaminants have been discussed comprehensively with their plausible mechanistic pathways. Finally, overlooked aspects in this field as well as the major roadblocks to the implementation of these metal oxide architectures for large-scale treatment of wastewater are provided here. Moreover, the potential ways to tackle these issues are also presented which may be useful for the transformation of current water treatment technologies.

Preparation and characterization of the h-BN/Fe3O4/APTES-AMF/CuII nanocomposite as a new and efficient catalyst for the one-pot three-component synthesis of 2-amino-4-aryl(or heteroaryl)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitriles.

The intriguing features of surface-engineered hexagonal two-dimensional boron nitride (h-BN) nanostructures have captivated the immense interest of researchers working in the arena of materials science. Inspired by striking attributes exhibited by h-BN nanosheets as the support material, we devoted our efforts towards synthesizing a novel magnetically retrievable h-BN/Fe3O4/APTES-AMF/CuII catalytic system, which was then comprehensively characterized using various techniques including SEM, TEM, EDX, SEM-based elemental mapping, ED-XRF, AAS, XRD, FT-IR, VSM, XPS, TGA, and BET. Further, the catalytic potential of h-BN/Fe3O4/APTES-AMF/CuII nanocomposites was investigated in the one-pot multicomponent coupling reaction to gain access to a library of biologically active 2-amino-4-aryl(or heteroaryl)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitriles under ambient conditions. In addition, the use of green solvent, facile magnetic recoverability, and reusability of up to six successive runs made this protocol environmentally benign and economical. This work throws light on the development of covalently functionalized 2D-BN nanostructure-based copper catalysts and establishes its significance in furnishing industrially demanding products that would pave the way towards sustainable chemistry.

Enhanced catalysis through structurally modified hybrid 2-D boron nitride nanosheets comprising of complexed 2-hydroxy-4-methoxybenzophenone motif.

Tuning the structural architecture of the pristine two dimensional hexagonal boron nitride (h-BN) nanosheets through rational surface engineering have proven advantageous in the fabrication of competent catalytic materials. Inspired by the performance of h-BN based nanomaterials in expediting key organic transformations, we channelized our research efforts towards engineering the inherent surface properties of the exclusively stacked h-BN nanosheets through the incorporation of a novel competent copper complex of a bidentate chelating ligand 2-hydroxy-4-methoxybenzophenone (BP). Delightfully, this hybrid nanomaterial worked exceptionally well in boosting the [3 + 2] cycloaddition reaction of azide and nitriles, providing a facile access to a diverse variety of highly bioactive tetrazole motifs. A deep insight into the morphology of the covalently crafted h-BN signified the structural integrity of the exfoliated h-BN@OH nanosheets that exhibited lamellar like structures possessing smooth edges and flat surface. This interesting morphology could also be envisioned to augment the catalysis by allowing the desired surface area for the reactants and thus tailoring their activity. The work paves the way towards rational design of h-BN based nanomaterials and adjusting their catalytic potential by the use of suitable complexes for promoting sustainable catalysis, especially in view of the fact that till date only a very few h-BN nanosheets based catalysts have been devised.

Fabrication, functionalization and advanced applications of magnetic hollow materials in confined catalysis and environmental remediation.

Magnetic hollow-structured functional hybrid materials with unique architectures and preeminent properties have always been an area of extensive research. They represent a subtle collaboration of hollow architecture, mesoporous nanostructure and magnetic character. Owing to the merits of a large void space, low density, high specific surface area, well-defined active sites and facile magnetic recovery, these materials present promising application projections in numerous fields, such as drug delivery, adsorption, storage, catalysis and many others. In this review, recent progress in the design, synthesis, functionalization and applications of magnetic hollow-meso/nanostructured materials are discussed. The first part of the review has been dedicated to the preparation and functionalization of the materials. The synthetic protocols have been broadly classified into template-assisted and template-free methods and major trends in their synthesis have been elaborated in detail. Furthermore, the benefits and drawbacks of each method are compared. The later part summarizes the application aspects of confined catalysis in organic transformations and environmental remediation such as degradation of organic pollutants, dyes and antibiotics and adsorption of heavy metal ions. Finally, an outlook of future directions in this research field is highlighted.

A magnetically retrievable copper ionic liquid nanocatalyst for cyclooxidative synthesis of 2-phenylquinazolin-4(3H)-ones.

In the present work, we report the design and fabrication of a copper-containing ionic liquid supported magnetic nanocatalyst via a convenient and straightforward synthetic approach for the formation of 2-phenylquinazolin-4(3H)-ones using o-aminobenzamide and benzaldehydes as the reaction partners. The successful formation and properties of the as-prepared catalyst have been thoroughly investigated using diverse physico-chemical techniques including FT-IR, XRD, FE-SEM, TEM, ICP, VSM, BET and TGA. Using this nanocatalytic system, a variety of 2-phenylquinazolin-4(3H)-ones are synthesized in excellent yields with operational ease and short reaction times in an environmentally preferable solvent under open air and without using any external oxidizing agent. Besides, the catalyst possessed facile magnetic recoverability and remarkable reusability for six consecutive runs without any appreciable decrease in the catalytic efficiency.