Design and Development of Sustainable Cu2 (II)- and Mn2 (III)-Embedded Bifunctional Electrocatalysts: Enhanced Hydrogen and Oxygen Generation.

Nowadays, environmentally friendly, low-cost-effective, and sustainable electrocatalysts used widely for hydrogen and oxygen evolution reactions have come into the limelight as a new research topic for scientists. This study highlights the preparation of two unique and symmetrical dinuclear Cu (II) and Mn (III) bifunctional catalysts by a facile simple slow evaporation and diffusion route. [C32H24Cu2F4N4O4] (1) and [C32H24Mn2F4N4O4] (2) both have monoclinic (C2/c (15)) crystal systems, with oxidation states +2 and +3, respectively. Prominent SPR peaks at 372 and 412 nm indicate an M-L charge transfer transition in both complexes. The synthesized electrocatalysts display exceptional catalytic activity for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Complex 1 exhibits enhanced hydrogen generation in 0.5 M H2SO4 with a small overpotential of 216 mV at -10 mA cm-2 along with a significantly lower Tafel value of 97 mV/dec compared to Complex 2. Moreover, Complex 1 is highly active for the OER in 1 M KOH with a small Tafel slope of 103 mV/dec and a low overpotential of 340 mV to acquire 10 mA cm-2 current density, compared to Complex 2. Complex 1 and Complex 2 remain stable up to 20 h in acidic electrolyte and up to 36 h and 20 h in the basic electrolyte, respectively.

Biosynthesis of JC-La2CoO4 magnetic nanoparticles explored in catalytic and SMMs properties.

We have reported the synthesis of JC-La2CoO4 magnetic nanoparticles from Jatropha Curcas L. leaf extract in aqueous medium and potential application study in catalytic & Single Molecule Magnets (SMMs). Several techniques were used to investigate the structural, morphological, and elemental composition, particle size, optical properties, catalytic and magnetic properties by XRD, FTIR, SEM, EDAX, XPS, UV-visible and squid magnetic measurement. It was found that the crystallite sizes and grain sizes of JC-La2CoO4 NPs were 11.3 ± 1 and 24.1 ± 1 nm respectively and surface morphology of the nanoparticles looks spherical shape with good surface area. The band gap of JC-La2CoO4 was found to be 4.95 eV indicates good semiconductor in nature. XPS studies shows that La and Co present in + 3 and + 2 oxidation state respectively and suggest the composition formula is La2CoO4 with satisfied all the valency of metal ions. The photocatalytic efficiency of La2CoO4 shows good result against methylene blue (MB) compared to other dyes like MO, NO, RhB in presence of sunlight with rate constant 56.73 × 10-3 min-1 and completely degraded within 115 mints. The importance of JC-La2CoO4 has magnetic properties with antiferromagnetic coupling and SMMs properties with nature.

Synthesis of CeO2/ZrO2/ZnO nano alloy oxide and investigation of photocatalysis of naphthol orange under sunlight.

Novel metal-like cerium- and zirconium-doped ZnO photocatalysts were prepared herein with various proportions of molar ratios via a cost-effective co-precipitation method. The effects of novel metal doping on the photocatalytic activity of ZnO were studied. Various techniques were used to investigate the structural, morphological, and elemental composition, particle size, optical properties, and catalytic activity of the synthesized photocatalysts. It was found that the crystallite size and particle size of the nano alloy oxides were 15.12 ± 1 and 5 ± 1 nm, respectively, and the surface morphology of the nanoparticles indicated a satisfactory surface area. Among all synthesized nanocomposites, CexZrxZnxO5 (x = 1) [CZ1Z2-A] exhibited satisfactory photo-oxidation activity against naphthol orange (NO) under sunlight with a rate constant of 57.5 × 10-3 min-1. The effects of pH, inorganic salts, dye concentrations, and catalytic dosage on NO degradation were studied. A probable mechanistic pathway for the degradation of NO in the presence of CZ1Z2-A was proposed, and studies of sacrificial agents indicated that superoxide radical anion (O2˙-) was the main accountable active species in NO degradation. In addition, CZ1Z2-A exhibited excellent recyclability potential, and XRD studies revealed that there was no change in the crystal structure before or after degradation, which indicated its high stability. The intriguing finding was that Ce- and Zr-doped ZnO did not exhibit satisfactory catalytic performance in the photo-oxidation of NO. However, the composite formula of CexZrxZnxO5 (x = 1) with a 1 : 1 : 1 ratio of metal ions offered excellent catalytic activity.

Catalytic Use toward the Redox Reaction of Toxic Industrial Wastes in Innocuous Aqueous Medium and Antibacterial Activity of Novel Cu x Ag x Zn1-2x O Nanocomposites.

In this work, we report the redox properties in organic catalytic transformation and antibacterial activity of novel Cu x Ag x Zn1-2x O nanocomposites. Cu- and Ag-doped ZnO [Cu x Ag x Zn1-2x O (x = 0.1)] (CAZ), Cu-doped ZnO [Cu x Zn1-x O (x = 0.1)] (CZ), and Ag-doped ZnO [Ag x Zn1-x O (x = 0.1)] (AZ) were prepared via a chemical co-precipitation method. The synthesized nanocomposites were characterized using different spectroscopic techniques. The catalytic activity of CAZ, CZ, and AZ was examined for the reduction of 4-nitrophenol (4-NP) and 4-nitroaniline (4-NA) in the presence of NaBH4 in an aqueous medium. The photocatalytic oxidation efficiency of these catalysts was also observed against naphthol orange (NO) under ultraviolet light. It was found that the catalytic reduction and oxidation efficiency of CAZ is higher than that of CZ and AZ in 4-NP/4-NA and NO in a water solvent, respectively. The antibacterial property of CAZ was also studied against Gram-positive and Gram-negative bacteria by agar well diffusion and the minimum inhibitory concentration methods. It was found that CAZ shows better antimicrobial activity compared to its parental Cu(NO3)2·3H2O, AgNO3, and ZnO. Therefore, the incorporation of Cu and Ag into ZnO increases its catalytic and antimicrobial activity remarkably. Fourier-transform infrared and X-ray diffraction (XRD) studies of CAZ indicate the incorporation of Cu and Ag into the lattice of ZnO. The phase structure of CAZ was wurtzite hexagonal, and the average crystallite size was 93 ± 1 nm measured from XRD. The average grain size and particle size of CAZ were found to be 200 and 100 ± 5 nm originating from SEM and transmission electron microscopy studies, respectively. The optical energy band gap of CAZ is 3.15 eV, which supports the excellent photocatalyst under UV light. CAZ also exhibits good agreement for photoluminescence properties with a high intensity peak at 571 nm, indicating surface oxygen vacancies and defects which might be responsible for higher photocatalytic activity compared to others. The nanocomposite shows excellent reusability without any significant loss of activity.

Single Molecule Magnets of Co2 and Co2La MOFs Synthesized by New Schiff Base Ligand N,N'-bis(o-Vanillinidene) Ethylenediamine (o-VEDH2).

Schiff base ligand N,N'-bis(o-vanillinidene) ethylenediamine (o-VEDH2) has been employed to synthesize new [CoIICoIV(o-VED)(OAc)2(µ2-OAc)(OMe)]•MeOH (1) and [ Co 2 IV (o-VED)2(en)2(NCCH3)(OCH3)][La(NO3)6]( NO 3 - )•2MeOH•MeCN•H2O (2) metal-organic frameworks (MOFs) that have interesting single molecule magnets (SMMs) property. The synthesized complexes are characterized by single crystal X-ray diffraction, fourier transform infrared spectroscopy (FTIR), UV-visible spectroscopy, and squid magnetic measurement. Single crystal X-ray data show that both complexes crystallize in the monoclinic crystal system with P21/c(14) and P21/n(14) space groups and generate unique MOF-like structures. Overall, both the metal centers of 1 form octahedral geometry with a butterfly core structure. Variable temperature (T) and field (H) solid-state direct-current (dc) and alternative current (ac) magnetic susceptibility measurements were performed on both the complexes over 1.8 to 300 K, which exhibited a ground state spins (S) of 4 and 5 of complexes 1 and 2, respectively. The AC out-phase and in-phase properties of complexes show SMMs. Other properties such as optical, sensing, and DNA-binding interactions were also investigated by the complexes. Complexes 1 and 2 have energy band gaps of 3.7 and 3.03 eV indicating semiconductor properties. Simultaneously, complex 1 was found to sense H2O2 with a rate constant (k) = 1.59 × 10-4 s-1, whereas complex 2 was found to bind with calf-thymus-DNA by intercalation mode with binding constant (K b ) of 1.22 × 105 M-1.

Green synthesis of copper nanoparticles from an extract of Jatropha curcas leaves: characterization, optical properties, CT-DNA binding and photocatalytic activity.

The green synthesis of copper nanoparticles (CuNPs) using a leaf extract from Jatropha curcas (JC) has been documented in our present research work. The existence of flavonoids, tannins, glycosides, and alkaloids was confirmed by the phytochemical analysis of the plant extract and these chemicals can be used as reducing, stabilizing and capping agents. After six months, the JC-CuNPs were found to be stable without any evidence of agglomeration. The JC-CuNPs were characterised by XRD, FT-IR, SEM, TEM and UV-vis spectrophotometry. The average particle and crystal sizes of the JC-CuNPs were found to be 10 ± 1 and 12 ± 1 nm, respectively. The SPR peaks were found at 266 and 337 nm, measured using electronic spectroscopy, and the calculated optical band gap was found to be 3.6 eV at 337 nm, indicating the semiconductor behaviour of the JC-CuNPs. JC-CuNPs have potential photocatalytic activity against methylene blue (MB) compared with other dyes in the presence of sunlight and the rate constant (k) value is 2.30 × 10-4 s-1. The JC-CuNPs also have a binding property with CT-DNA through an intercalation mode and the binding constant (K b) is 1.024 × 102 M-1.

New Dual-Functional and Reusable Bimetallic Y2ZnO4 Nanocatalyst for Organic Transformation under Microwave/Green Conditions.

A novel bimetallic and reusable Y2ZnO4 nanocatalyst was synthesized by a simple coprecipitation method. The prepared nanocatalyst exhibited dual catalytic activity and was characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), energy-dispersive X-ray spectroscopy (EDX), and scanning electron microscopy (SEM). The average crystallite and grain sizes were found to be 17 ± 1 and 10 ± 2 nm, respectively. On the one hand, the catalytic activity of the nanocatalyst was studied for the Knoevenagel condensation reaction of aromatic aldehydes with active methylene compounds, such as ethyl cyanoacetate and malononitrile, under microwave irradiation and solvent-free conditions. On the other hand, the nanoparticles also showed faster photocatalytic activity against methyl orange (MO) compared to other dyes. The nanocatalyst was easily recoverable by a simple filtration method and was recycled without any significant loss of catalytic activity. The advantages of this nanocatalyst were a simple workup procedure, high reaction yields, solvent-free conditions, reusability, and a short reaction time under green reaction conditions.

Synthesis of Two Mononuclear Schiff Base Metal (M = Fe, Cu) Complexes: MOF Structure, Dye Degradation, H2O2 Sensing, and DNA Binding Property.

O-Vanillin and ethylenediamine were used for the synthesis of N,N'-bis(O-vanillinidene)ethylenediamine (O-VEDH2) Schiff base ligand, which was characterized by UV-visible and 1H NMR spectroscopy. The Schiff base ligand O-VEDH2 has been employed to synthesize novel [C18H22FeN2O6]NO3 (1) and C18H16CuN2O5 (2) complexes by the simple slow evaporation method. The single crystals were characterized by X-ray crystallography, as well as Fourier-transform infrared and UV-visible spectroscopy techniques. Complexes 1 and 2 crystallize in monoclinic and orthorhombic space groups with P121/n1 (14) and Pnma (62) point groups, respectively, and both show metal-organic frameworks like structures. Complexes 1 and 2 have optical band gaps of 4.1 and 2.9 eV, respectively, indicating their semiconducting properties. The dye degradation activity and H2O2 sensing of the complexes 1 and 2 were determined in different conditions. The photocatalytic test was performed in the presence of sunlight, methylene blue (MB), and complexes 1 and 2. An interesting result was obtained that complex 2 has degradation ability against MB and the rate constant (K) is 5.46 × 10-5 s-1, whereas complex 1 has H2O2 sensing properties. Both complexes are bound to Calf-thymus DNA by intercalation binding mode, and binding constants (K b) of complexes 1 and 2 are 3.77 × 103 and 1.49 × 104 M-1, respectively.