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The photocatalytic degradation has been considered to be an efficient process for the degradation of organic pollutants, which are present in the effluents released by industries. The photocatalytic bleaching of cationic dye methylene blue was carried out spectrometrically on irradiation of UV light using Cu(II), Ni(II), and Co(II) complexes of (2E...
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... In particular, nickel is a vital element to contribute to the removal of dyes [19,20]. Additionally, thiosemicarbazones are also beneficial for the dyes removal by forming hydrogen bonds and π-π stacking interactions [21]. Thus, the combination of [P 2 Mo 5 O 23 ] 6− , nickel ion and 2-acetylpyrazine-thiosemicarbazone at a molecular 2 will contribute to the dye removal by synergic effect. ...
The magnetic adsorbent, Fe3O4@[Ni(HL)2]2H2[P2Mo5O23]·2H2O (Fe3O4@1), is synthesized by employing the nanoparticles Fe3O4 and polyoxometalate hybrid 1. Zero-field-cooled (ZFC) and field-cooled (FC) curves show that the blocking temperature of Fe3O4@1 was at 120 K. Studies of Fe3O4@1 removing cationic and anionic dyes from water have been explored. The characterization of Fe3O4@1, effects of critical factors such as dosage, the concentration of methylene blue (MB), pH, adsorption kinetics, isotherm, the removal selectivity of substrate and the reusability of Fe3O4@1 were assessed. The magnetic adsorbent displayed an outstanding removal activity for the cationic dye at a broad range of pH. The adsorption kinetics and isotherm models revealed that the adsorption process of Fe3O4@1 was mainly governed via chemisorption. The maximum capacity of Fe3O4@1 adsorbing substance was 41.91 mg g−1. Furthermore, Fe3O4@1 showed its high stability by remaining for seven runs of the adsorption-desorption process with an effective MB removal rate, and could also be developed as a valuable adsorbent for dyes elimination from aqueous system.
... 48 These results indicate that the Cu(II) complexes have a faster degradation rate for the RhB than the Ni(II) complex, which can be attributed to the nature of the metal cation used, that Cu(II) is a more active metal cation than Ni(II). 49 Meanwhile, Cu(II) and Ni(II) have different electronic congurations and geometries, which may also inuence the photocatalytic activity. 50,51 In addition, based on the good catalytic performance of complexes 1-2, the catalytic performance of 1-2 for methylene blue (MB) and methyl orange (MO) was measured. ...
... The reaction mechanism for dyes photodegradation has been discussed based on semiconductor theory. 26,48,49,52 When the complex is irradiated by a xenon lamp, the electrons in the valence band are easily excited into the conduction band, which increases the amount of holes (h + ) in the valence band. Then electrons may combine with O 2 on the surface of the complex to form oxygen radical, which will further produce hydroxyl free ($OH). ...
Four new complexes, namely, Cu2(O-cpia)(btb)0.5·(OH) (1), Cu3(O-cpia)2(bpy)2 (2), [Ni2(O-cpia)(phen)·(OH)·H2O]·2H2O (3) and [Ni3(O-cpia)2(bpy)3·2H2O]·2H2O (4) (O-cpia = 5-(2-carboxyphenoxy)isophthalic acid, btb = 1,4-bis(1,2,4-triazol-1-yl)butane, bpy = 4,4'-bipyridine) were successfully isolated under hydrothermal conditions. The four complexes exhibit different architectures constructed from different homometallic clusters varying from mononuclear, binuclear to tetranuclear metal(ii) polyhedra as Second Building Blocks (SBUs). 1 features a 3D framework constructed from the tetranuclear clusters [Cu4(μ3-OH)2] as SBUs, linked with Cu(1)O4N and Cu(2)O5 polyhedra by O-cpia/btb mixed linkers. 2 also exhibits a 3D structure based on trinuclear clusters [Cu3(COO)4] SBUs, bridged with Cu(1)O3N2 and Cu(2)O4 polyhedra via O-cpia/bpy mixed ligands. 3 shows a 2D network consisting of tetranuclear clusters [Ni4(μ3-OH)2] SBUs, which are bridged with Ni(1)O4N2 and Ni(2)O6 through O-cpia ligands. It is worth noting that 4, with a 3D structure, is generated from the binuclear clusters [Ni2(COO)4] (Ni(1)O4N) and mononuclear metal Ni(2) cores (Ni(2)O4N2) as SBUs, and bridged by O-cpia/bpy mixed ligands. Meanwhile, the degradation of dyes (RhB) by the complexes under visible light irradiation was studied. 1-4 are semiconducting in nature, with E g of 1.30 eV (1), 1.78 eV (2), 2.85 eV (3) and 2.14 eV (4). Cu(ii) complexes 1 and 2 are highly efficient photocatalysts for the degradation of RhB under visible light irradiation.
... In particular, Strandberg-type phosphomolybdate [P 2 Mo 5 O 23 ] 6− has been extensively studied. Thiosemicarbazones are of special application in efficient dye removal due to their amine and pyridyl, which are beneficial for the formation of hydrogen bonds and π-π stacking interactions [15]. Transition metal ions have been used for the removal of dyes due to coordination with most of organic dyes containing -C=C-, -N=N-and heterocyclic compounds [16]. ...
In this work, two magnetic adsorbents Fe3O4@1 and Fe3O4@2 were prepared by combining Fe3O4 nanoparticles and polyoxometalate hybrids [Ni(HL)2]2H2[P2Mo5O23]·4H2O (1), [H2L]5H[P2Mo5O23]·12H2O (2) (HL = 2-acetylpyridine-thiosemicarbazone). The temperature-dependent zero-field-cooled (ZFC) and field-cooled (FC) measurements indicated the blocking temperature at 160 K and 180 K, respectively. The Brunauer–Emmett–Teller (BET) surface area of Fe3O4@1 and Fe3O4@2 is 8.106 m2/g and 1.787 m2/g, respectively. Cationic dye methylene blue (MB) and anionic dye methyl orange (MO) were investigated for selective dye adsorption on Fe3O4@1 and Fe3O4@2. The two adsorbents were beneficial for selective adsorption of cationic dyes. The adsorption efficiency of MB was 94.8% for Fe3O4@1, 97.67% for Fe3O4@2. Furthermore, the two adsorbents almost maintained the same adsorption efficiency after seven runs. The maximum MB adsorption capacity of Fe3O4@1 and Fe3O4@2 is 72.07 and 73.25 mg/g, respectively. The fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) spectra of the adsorbents collected after adsorption of MB are very similar to the initial as-synthesized Fe3O4@polyoxometalates indicating the high stability of the two adsorbents. The adsorption kinetics indicated that the MB removal followed the pseudo-second-order model. These results showed that the two adsorbents had a potential application in treating wastewater.
... In some cases, thiosemicarbazones act as a C, N, S donor, forming cyclometallated complexes 11,12 . The metal complexes of thiosemicarbazones are not only the bioinorganic relevance but also the chemistry of transition metal complexes of the thiosemicarbazones is receiving significant current attention as potent Analytical agents 13-15 , Photocatalysts 16,17 , intermediates for the synthesis of pharmaceutical, dyes, photographic films, plastic and in textile industry. ...
This paper describes the synthesis of nickel (II) complexes of (2E)-4N-substituted-2-[4-(propan-2-yl)benzylidene]hydrazinecarbothioamide Schiff bases derived from 4N substituted thiosemicarbazides and cuminal. The prepared ligands and complexes were characterized using various physicochemical techniques viz. elemental analysis, molar conductance, magnetic susceptibility measurements, IR, electronic absorption spectral studies and cyclic voltammetry. The spectral data indicates that the complexes are square planar geometry in solid state while in coordinating solvents like DMSO solvent exhibits octahedral geometry suggesting coordination of solvent molecules presumably in axial position. The absorption titration studies revealed that each of these complexes is an avid binder to calf thymus-DNA. The apparent binding constants are in the order of 107–108 M-1. The nucleolytic cleavage activities of the ligands and their complexes were assayed on pUC18 plasmid DNA using gel electrophoresis in the presence and absence of H2O2. The ligands showed increased nuclease activity when administered as copper complexes. All these nickel (II) complexes behave as efficient chemical nucleases with hydrogen peroxide activation. These studies revealed that the complexes exhibit both oxidative and hydrolytic chemistry in DNA cleavage.
This work illustrates the preparation of an effective photocatalyst, CuO/TiO2 nano metal mixed oxide (NMMO). The desired synthesis was carried out by calcination assisted reaction of Cu[DBAPD]/TiO2 at 650°C. Additionally, the prepared nano metal mixed oxide material has also been confirmed by numerous characterization techniques such as XRD, FTIR, HRTEM, FESEM with EDS, XPS, BET, ESR and Photoluminescence which revealed the occurence of strong interfacial interactions between CuO and TiO2. The optical properties of the prepared NMMO have also been measured by UV-Vis. spectroscopy. The prepared NMMO exhibited excellent photo-response for the total degradation of amaranth (99.21%) as well as brilliant blue (99.68%) after just 40 minutes during intense solar irradiation. It has been found that the photocatalytic degradation mechanism over the surface of CuO and TiO2 can be well explained by considering the charge flow from TiO2 to CuO. Such type of structure offered higher redox capability as well as improved separation of photogenerated charge carriers, thus providing phenomenal photocatalytic performance. In addition to this, the degradation process has been investigated utilizng mass spectrometry and UV-Vis. spectral analysis. Moreover, the CuO/TiO2-NMMO photocatalytic material offered good stability and reusability and can therefore act as a strong contender to be use in environmental remediation.
In this study, two copper(II) complexes, [Cu(C6H8N3S2)2]Cl2 (1) and [Cu(C7H10N3S2)2]Cl2·H2O (2), were synthesized from 2-(thiophen-2-ylmethylene)hydrazine-1-carbothioamide (L1H) and 2-(1-(thiophen-2-yl)ethylidene)hydrazine-1-carbothioamide (L2H) respectively and characterized using various spectroscopic techniques and elemental analyses. The as-prepared complexes were used as single-source precursors for the synthesis of oleylamine-capped (OLA@CuxSy), hexadecylamine-capped (HDA@CuxSy), and dodecylamine-capped (DDA@CuxSy) copper sulphide nanoparticles (NPs) via the thermolysis method at 190 °C and 230 °C and then characterized using powder X-ray diffraction (p-XRD), UV-visible spectroscopy, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The p-XRD diffraction patterns confirmed the formation of crystalline rhombohedral digenite Cu9S5 with the space group R-3m. The TEM images showed the formation of nanoparticles of various shapes including hexagonal, rectangular, cubic, truncated-triangular, and irregularly shaped Cu9S5 nanomaterials. The SEM results showed aggregates and clusters as well as the presence of pores on the surfaces of nanoparticles synthesized at 190 °C. The UV-visible spectroscopy revealed a general blue shift observed in the absorption band edge of the copper sulphide NPs, as compared to bulk CuxSy, with energy band gaps ranging from 2.52 to 3.00 eV. Energy-dispersive X-ray spectroscopy (EDX) confirmed the elemental composition of the Cu9S5 nanoparticles. The nanoparticles obtained at 190 °C and 230 °C were used as catalysts for the photocatalytic degradation of methylene blue (MB) under UV irradiation. Degradation rates varying from 47.1% to 80.0% were obtained after 90 min of exposure time using only 10 mg of the catalyst, indicating that Cu9S5 nanoparticles have potential in the degradation of organic pollutants (dyes).
A thiazole-based chalcone ligand and its bidentate Co(II), Ni(II), Cu(II), and Zn(II) complexes of general formula [M (DMTP)2], (DMTP = (E)-3-(3,4-dimethoxyphenyl)-1-(thiazol-2-yl)prop-2-en-1-one) have been synthesized. The compounds were characterized by elemental analyses, molar conductance, fourier-transform infrared (FTIR) spectra, ¹H NMR, ¹³C NMR, mass, UV–Vis., magnetic susceptibility, and thermal and powder X-ray diffraction (XRD) techniques. Based on spectral data, tetrahedral geometry is assigned for Co(II), Ni(II), and Zn(II) complexes. Square planar geometry was observed for Cu(II) complex. Molecular geometries of the compounds were fully optimized with density functional theory (DFT) computations. Additionally, the Lewis base character of DMTP, flexibility toward metal ions, structural stabilization on coordination, frontier molecular orbitals (FMO), quantum chemical parameters, and theoretical vibrational frequencies were evaluated. The antibacterial and antifungal (in vitro and in silico) activities of the complexes were studied and compared with those of DMTP. Finally, the metal(II) complexes of DMTP were successfully used to enhance the removal of methylene blue (MB) dye from an aqueous solution.
Three tetrahedral coordination compounds formed from Ni(II), Cu(II), and Zn(II) transition-metal ions with ON-donor, (2-aminophenol) ligand (L), were synthesized and characterized by Fourier-transform infrared (FTIR) spectroscopy, ultraviolet–visible (UV–Vis) absorption spectroscopy, elemental analysis, and magnetic susceptibility measurements. The magnetic properties revealed that the NiL2 and CuL2 complexes were paramagnetic while the ZnL2 complex was diamagnetic. Also, photodegradation of methylene blue as model organic pollutant by the synthesized complexes was studied based on an oxidation process under visible-light irradiation. The results showed that the photocatalytic activity of the Cu complex was greater compared with the Ni and Zn complexes, with degradation efficiency of 100, 85, and 60 %, respectively, after 30 min of irradiation in this condition. Thus, the Cu (bis-chelate) complex is more efficient, produces higher yield, is easily produced, and represents a more stable heterogeneous photocatalyst for degradation of organic dyes such as methylene blue.
