Sonochemically Synthesized Spin-Canted CuFe2O4 Nanoparticles for Heterogeneous Green Catalytic Click Chemistry.
ABSTRACT: Heterogeneous green catalysis by using magnetically separable nanometal-oxide catalysts has become a subject of prime focus recently. PXRD (powder X-ray diffraction), FESEM (field emission scanning electron microscopy), and HRTEM (high-resolution tunneling electron microscopy) with IR and Raman spectroscopy are applied to analyze the structural and microstructural properties of nanosized (?15.3 nm) CuFe2O4 synthesized by both sonochemical and mechanochemical processes. The sonochemical process provides a better uniformity of sizes of the nanoparticles (NPs). Rietveld refinement with the PXRD pattern reveals the inverse spinel-like architecture of CuFe2O4 NPs. The Raman spectra also indicate the phase purity of the synthesized material. The static magnetic measurements are performed at different magnetic fields and temperature ranges from 300 to 5 K, which confirms the existence of the ferrimagnetic phase mixed with some finer superparamagnetic (SPM) nanophases within the sample. Unsaturated magnetization is observed even at an applied 5 T magnetic field for the presence of spin-canting nature in the partially inverted copper ferrite phases at the surfaces of the nanoparticles. Now, these coupled magnetic CuFe2O4 NPs are used as a heterogeneous catalyst for three-component Huisgen 1,3-dipolar cycloaddition click reaction in aqueous media. By this catalyst system, we were able to couple alkyl halide, epoxide, or boronic acid with alkynes efficiently to furnish 1,4-disubstituted 1,2,3-triazoles in excellent yields within very short reaction time. The test for heterogeneity, reusability, and reproducibility of the catalyst has also been performed successfully without prominent decrease in yield up to the fifth cycle.
Project description:A facile, efficient and environmentally-friendly protocol for the synthesis of xanthenes by graphene oxide based nanocomposite (GO-CuFe2O4) has been developed by one-pot condensation route. The nanocomposite was designed by decorating copper ferrite nanoparticles on graphene oxide (GO) surface via a solution combustion route without the use of template. The as-synthesized GO-CuFe2O4 composite was comprehensively characterized by XRD, FTIR, Raman, SEM, EDX, HRTEM with EDS mapping, XPS, N2 adsorption-desorption and ICP-OES techniques. This nanocomposite was then used in an operationally simple, cost effective, efficient and environmentally benign synthesis of 14H-dibenzo xanthene under solvent free condition. The present approach offers several advantages such as short reaction times, high yields, easy purification, a cleaner reaction, ease of recovery and reusability of the catalyst by a magnetic field. Based upon various controlled reaction results, a possible mechanism for xanthene synthesis over GO-CuFe2O4 catalyst was proposed. The superior catalytic activity of the GO-CuFe2O4 nanocomposite can be attributed to the synergistic interaction between GO and CuFe2O4 nanoparticles, high surface area and presence of small sized CuFe2O4 NPs. This versatile GO-CuFe2O4 nanocomposite synthesized via combustion method holds great promise for applications in wide range of industrially important catalytic reactions.
Project description:This study report on the synthesis of spinel CuFe2O4 nanostructures by surfactant-assisted method. The catalysts were characterized by X-ray diffraction (XRD), laser Raman, transition electron microscope (TEM), scanning electron microscope (SEM), energy dispersive X-ray (EDX), hydrogen temperature programmed reduction (H2-TPR), and Brunauer-Teller-Emmett-Teller (BET) surface area techniques. CuFe2O4 was active for pinene oxidation using tertiary butyl hydroperoxide (TBHP) to pinene oxide, verbenol, and verbenone aroma oxygenates. Under optimized reaction conditions, the spinel CuFe2O4 catalyst could afford 80% pinene conversion at a combined verbenol/verbenone selectivity of 76% within the reaction time of 20 h. The changes in catalyst synthesis solvent composition ratios induced significantly varying redox, phases, and textural structure features, which resulted in various catalytic enhancement effect. Characterization results showed the spinel CuFe2O4 catalyst possessing less than 5 wt% impurity phases, Cu(OH)2, and CuO to afford the best catalytic performance. The CuFe2O4 catalyst was recyclable to up to five reaction cycles without loss of its activity. The recyclability of the bimetal CuFe2O4 oxide catalyst was simply rendered by use of an external magnet to separate it from the liquid solution.
Project description:In this study, zinc sulfide nanoparticles were loaded on reduced graphene oxide (ZnS NPs/rGO) using simple sonochemical method. The nanocomposite was characterized using different morphological and electrochemical techniques such as TEM, SEM, PXRD, EDX, Raman spectroscopy, FTIR, N<sub>2</sub>-adsorption-desorption, CV, and EIS. The ZnS NPs/rGO modified glassy carbon electrode (GCE) was used to simultaneously estimate hydroxychloroquine (HCQ) and daclatasvir (DAC) in a binary mixture for the first time. The modified nanocomposite exhibited good catalytic activity towards HCQ and DAC detection. In addition, it showed higher sensitivity, good selectivity and stability; and high reproducibility towards HCQ and DAC analysis. The activity of the modified electrode was noticeably improved due to synergism between ZnS NPs and rGO. Under optimum conditions of DPV measurements, the anodic peak currents (Ipa) were obviously increased with the increase of HCQ and DAC amounts with linear ranges of 5.0-65.0 and 7.0-65.0 nM with LODs of 0.456 and 0.498 nM for HCQ and DAC, respectively. The ZnS NPs/ rGO modified GCE was used to quantify HCQ and DAC in biological fluids with recoveries of 98.7-102.7% and 96.9-104.5% and RSDs of 1.89-3.57% and 1.91-3.70%, respectively.
Project description:In this work, magnetic CuFe2O4/Ag nanoparticles activated by porous covalent organic frameworks (COF) was fabricated to evaluate the heterogenous reduction of 4-nitrophenol (4-NP). The core-shell CuFe2O4/Ag@COF was successfully prepared by polydopamine reduction of silver ions on CuFe2O4 nanoparticles, followed by COF layer condensation. By integrating the intrinsic characteristics of the magnetic CuFe2O4/Ag core and COF layer, the obtained nanocomposite exhibited features of high specific surface area (464.21 m2 g-1), ordered mesoporous structure, strong environment stability, as well as fast magnetic response. Accordingly, the CuFe2O4/Ag@COF catalyst showed good affinity towards 4-NP via ?-? stacking interactions and possessed enhanced catalytic activity compared with CuFe2O4/Ag and CuFe2O4@COF. The pseudo-first-order rate constant of CuFe2O4/Ag@COF (0.77 min-1) is 3 and 5 times higher than CuFe2O4/Ag and CuFe2O4@COF, respectively. The characteristics of bi-catalytic CuFe2O4/Ag and the porous COF shell of CuFe2O4/Ag@COF made a contribution to improve the activity of 4-NP reduction. The present work demonstrated a facile strategy to fabricate COF-activated nano-catalysts with enhanced performance in the fields of nitrophenolic wastewater treatment.
Project description:In this study, mesoporous halloysite nanotubes (HNTs) were modified by CuFe2O4 nanoparticles for the first time. The morphology, porosity and chemistry of the CuFe2O4@HNTs nanocomposite were fully characterized by Fourier transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (FE-SEM) image, transmission electron microscope (TEM) images, energy-dispersive X-ray (EDX), X-ray diffraction (XRD) pattern, Brunauer-Emmett-Teller (BET) adsorption-desorption isotherm, thermogravimetric (TG) and vibrating sample magnetometer (VSM) curve analyses. The results confirmed that CuFe2O4 with tetragonal structure, uniform distribution, and less agglomeration was located at HNTs. CuFe2O4@HNTs nanocomposite special features were high thermal stability, crystalline structure, and respectable magnetic property. SEM and TEM results showed the nanotube structure and confirmed the stability of basic tube in the synthetic process. Also, inner diameters of tubes were increased in calcination temperature at 500 °C. A good magnetic property of CuFe2O4@HNTs led to use it as a heterogeneous catalyst in the synthesis of pyrazolopyridine derivatives. High efficiency, green media, mild reaction conditions and easily recovery of the nanocatalyst are some advantages of this protocol.
Project description:The combination of magnetic nanoparticles with a porous silica is a composite that has attracted significant attention for potential multifunctional theranostic applications. In this study, 30 wt % CuFe2O4 was impregnated into a matrix of monodispersed spherical hydrophilic silica (HYPS) nanoparticles through a simple dry impregnation technique. The chemotherapy drug cisplatin was loaded through electrostatic equilibrium adsorption over 24 h in normal saline solution. The presence of cubic spinel CuFe2O4 on HYPS was confirmed through powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR) and diffuse reflectance UV-vis spectroscopy (DR UV-vis) analysis. The HYPS particles showed a surface area of 170 m2/g, pore size of 8.3 nm and pore volume of 0.35 cm3/g. The cisplatin/CuFe2O4/HYPS nanoformulation showed the accumulation of copper ferrite nanoparticles on the surface and in the pores of HYPS with a surface area of 45 m2/g, pore size of 16 nm and pore volume of 0.18 cm3/g. Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) mapping analysis showed the presence of homogeneous silica particles with nanoclusters of copper ferrite distributed on the HYPS support. Vibrating sample magnetometry (VSM) analysis of CuFe2O4/HYPS showed paramagnetic behavior with a saturated magnetization value of 7.65 emu/g. DRS UV-vis analysis revealed the functionalization of cisplatin in tetrahedral and octahedral coordination in the CuFe2O4/HYPS composite. Compared to other supports such as mesocellular foam and silicalite, the release of cisplatin using the dialysis membrane technique was found to be superior when CuFe2O4/HYPS was applied as the support. An in vitro experiment was conducted to determine the potential of CuFe2O4/HYPS as an anticancer agent against the human breast cancer cell line MCF-7. The results show that the nanoparticle formulation can effectively target cancerous cells and could be an effective tumor imaging guide and drug delivery system.
Project description:In the present investigation, the silver present in photographic waste is reclaimed catalytically using magnetically separable TiO2@CuFe2O4 nanocomposites (NCs), and further, the recovered silver nanoparticles [Ag(0) NPs] are tested against the representative bacteria for the antibacterial activity. Initially, a series of the different composites between TiO2 nanoparticles and CuFe2O4 nanoparticles are synthesized by a sol-gel "ex situ" method to enhance the catalytic activity of bare nanomaterials toward the visible region of the electromagnetic spectrum. X-ray diffraction reveals the presence of characteristic patterns for the tetragonal structure in the bare materials or TiO2@CuFe2O4 NCs; however, the dominance in the phase as well as intensity of the respective XRD reflections in the NCs is observed according to the content of TiO2 or CuFe2O4 in the NCs. Field-emission electron microscopic images show the uniform spherical particles for the representative TiO2@CuFe2O4 NCs, which is also confirmed through the HRTEM images. The magnetically separable behavior of the representative TiO2@CuFe2O4 NCs is confirmed through the VSM measurements, which also shows the superparamagnetic properties due to the S-shaped nature of the hysteresis loop. Thereafter, a photoconversion reaction of Ag(I) ions to Ag(0) NPs as a model reaction is carried out using the different TiO2@CuFe2O4 NCs under visible light irradiation, and hence, the higher catalytic recovery of Ag(0) NPs is observed for a composite containing 10 wt % TiO2 and 90 wt % CuFe2O4 than that of other NCs or the bare one alone. The optimized protocol of the model reaction is adopted for reclaiming Ag(0) NPs from photographic waste. The progress of the catalytic reclamation reaction is monitored using UV-visible, and then sizes of the recovered Ag(0) NPs are confirmed through the HRTEM images. Thereafter, the recovered Ag(0) NPs are tested for complete photoinactivation of Escherichia coli bacteria within 120 min.
Project description:A versatile method is reported for the manufacturing of antimicrobial (AM) surgery equipment utilising fused deposition modelling (FDM), three-dimensional (3D) printing and sonochemistry thin-film deposition technology. A surgical retractor was replicated from a commercial polylactic acid (PLA) thermoplastic filament, while a thin layer of silver (Ag) nanoparticles (NPs) was developed via a simple and scalable sonochemical deposition method. The PLA retractor covered with Ag NPs (PLA@Ag) exhibited vigorous AM properties examined by a reduction in Staphylococcus aureus (S. aureus), Pseudomonas aeruginosa (P. aeruginosa) and Escherichia coli (E. coli) bacteria viability (%) experiments at 30, 60 and 120 min duration of contact (p < 0.05). Scanning electron microscopy (SEM) showed the surface morphology of bare PLA and PLA@Ag retractor, revealing a homogeneous and full surface coverage of Ag NPs. X-Ray diffraction (XRD) analysis indicated the crystallinity of Ag nanocoating. Ultraviolent-visible (UV-vis) spectroscopy and transmission electron microscopy (TEM) highlighted the AgNP plasmonic optical responses and average particle size of 31.08 ± 6.68 nm. TEM images of the PLA@Ag crossection demonstrated the thickness of the deposited Ag nanolayer, as well as an observed tendency of AgNPs to penetrate though the outer surface of PLA. The combination of 3D printing and sonochemistry technology could open new avenues in the manufacturing of low-cost and on-demand antimicrobial surgery equipment.
Project description:A series of the magnetic CuFe2O4-loaded corncob biochar (CuFe2O4@CCBC) materials was obtained by combining the two-step impregnation of the corncob biochar with the pyrolysis of oxalate. CuFe2O4@CCBC and the pristine corncob biochar (CCBC) were characterized using XRD, SEM, VSM, BET, as well as pHZPC measurements. The results revealed that CuFe2O4 had a face-centered cubic crystalline phase and was homogeneously coated on the surface of CCBC. The as-prepared CuFe2O4@CCBC(5%) demonstrated a specific surface area of 74.98 m2·g-1, saturation magnetization of 5.75 emu·g-1 and pHZPC of 7.0. The adsorption dynamics and thermodynamic behavior of Pb(II) on CuFe2O4@CCBC and CCBC were investigated. The findings indicated that the pseudo-second kinetic and Langmuir equations suitably fitted the Pb(II) adsorption by CuFe2O4@CCBC or CCBC. At 30 °C and pH = 5.0, CuFe2O4@CCBC(5%) displayed an excellent performance in terms of the process rate and adsorption capacity towards Pb(II), for which the theoretical rate constant (k2) and maximum adsorption capacity (qm) were 7.68 × 10-3 g·mg-1··min-1 and 132.10 mg·g-1 separately, which were obviously higher than those of CCBC (4.38 × 10-3 g·mg-1·min-1 and 15.66 mg·g-1). The thermodynamic analyses exhibited that the adsorption reaction of the materials was endothermic and entropy-driven. The XPS and FTIR results revealed that the removal mechanism could be mainly attributed to the replacement of Pb2+ for H+ in Fe/Cu-OH and -COOH to form the inner surface complexes. Overall, the magnetic CuFe2O4-loaded biochar presents a high potential for use as an eco-friendly adsorbent to eliminate the heavy metals from the wastewater streams.
Project description:Because of its electrically conducting properties combined with excellent thermal stability and transparency throughout the visible spectrum, tin oxide (SnO2) is extremely attractive as a transparent conducting material for applications in low-emission window coatings and solar cells, as well as in lithium-ion batteries and gas sensors. It is also an important catalyst and catalyst support for oxidation reactions. Here, we describe a novel nonaqueous sol-gel synthesis approach to produce tin oxide nanoparticles (NPs) with a low NP size dispersion. The success of this method lies in the nonhydrolytic pathway that involves the reaction between tin chloride and an oxygen donor, 1-hexanol, without the need for a surfactant or subsequent thermal treatment. This one-pot procedure is carried out at relatively low temperatures in the 160-260 °C range, compatible with coating processes on flexible plastic supports. The NP size distribution, shape, and dislocation density were studied by powder X-ray powder diffraction analyzed using the method of whole powder pattern modeling, as well as high-resolution transmission electron microscopy. The SnO2 NPs were determined to have particle sizes between 3.4 and 7.7 nm. The reaction products were characterized using liquid-state 13C and 1H nuclear magnetic resonance (NMR) that confirmed the formation of dihexyl ether and 1-chlorohexane. The NPs were studied by a combination of 13C, 1H, and 119Sn solid-state NMR as well as Fourier transform infrared (FTIR) and Raman spectroscopy. The 13C SSNMR, FTIR, and Raman data showed the presence of organic species derived from the 1-hexanol reactant remaining within the samples. The optical absorption, studied using UV-visible spectroscopy, indicated that the band gap (E g) shifted systematically to lower energy with decreasing NP sizes. This unusual result could be due to mechanical strains present within the smallest NPs perhaps associated with the organic ligands decorating the NP surface. As the size increased, we observed a correlation with an increased density of screw dislocations present within the NPs that could indicate relaxation of the stress. We suggest that this could provide a useful method for band gap control within SnO2 NPs in the absence of chemical dopants.