• Journal of Korean Society on Water Environment
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• v.21 no.1
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• pp.84-91
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• 2005

$TiO_2-catalyst$ suspensions work efficiently in Photocatalytic oxidation (PCO) for wastewater treatment. Nevertheless, once photocatalysis is completed, separation of the catalyst from solution becomes the main problem. The PCO of Cu(II)-EDTA was studied to determine the reusability of the titanium dioxide catalyst. Aqueous solutions of $10^{-4}M$ Cu(II)-EDTA were treated using illuminated $TiO_2$ particles at pH 6 in a circulating reactor. $TiO_2$ was reused in PCO system for treatment of Cu(II)-EDTA comparing two procedures: reuse of water and $TiO_2$ and reuse of the entire suspension after PCO of Cu(II)-EDTA. The results are as follows; (i) Photocatalytic efficiency worsens with successive runs when catalyst and water are reused without separation and filtration, whereas, when $TiO_2$ is separated from water, the reused $TiO_2$ is not deactivated. (ii) The $TiO_2$ mean recovery (%) with reused $TiO_2$ was 86.4%(1.73g/L). Although the mean initial degradation rate of Cu(II)-EDTA and Cu(II) was lower than that using fresh $TiO_2$, there was no significant change in the rate during the course of the three-trial experiment. It is suggested that Cu(II)-EDTA could be effectively treated using an recycling procedure of PCO and catalyst recovery. (iii) However, without $TiO_2$ separation, the loss of efficiency of the PCO in the use of water and $TiO_2$ due to Cu(II), DOC remained from previous degradation and Cu(II)-EDTA added to the same suspension was observed after 2 trials, and resulted in the inhibition of the Cu(II)-EDTA, Cu(II) and DOC destruction.

• Journal of Environmental Science International
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• v.11 no.1
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• pp.85-91
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• 2002

The effects of initial concentration of dissolved oxygen content, Cu(II) and EDTA in an aqueous Cu(II)-EDTA solution on $TiO_2$ photo-oxidation of EDTA were investigated using $TiO_2$ (Degussa P-25) and UV irradiation at $20{\circ}C$. In the presence of dissolved oxygen and/or Cu(II) the photo-oxidation rates of EDTA were enhanced. The rates linearly increased in the range of initial Cu(II) concentration below 1.79 mM, while abode this concentration those were kept constant. The trend or the EDTA photo-oxidation rates appeared to be akin to the Langmuir-Hinshelwood equation farm and the k values calculated were 0.05 mM/min for the free-EDTA system, and 0.17 mM/min far the Cu(II)-EDTA system. These meant the aqueous EDTA decomposition was enhanced due to weakening of the intra-molecular bond strength of EDTA by complexation with Cu(II) added. It was concluded the decomposition of aqueous EDTA by $TiO_2$ photo-oxidation was maximum in the presence of dissolved oxygen supplied by air purging and of Cu(II) with its concentration for 1:1 Cu(II)-EDTA complexation ratio.

• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.509-519
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• 1987

The tetradentate Schiff base ligand, 3,4-bis(salicylidene diimine) toluene, have been prepared by the reaction of salicylaldehyde with 3,4-diaminotoluene by Duff method. The Schiff base ligand reacts with Ni(II), Co(II), and Cu(II) ions to form new complexes, [Ni(o-BSDT)${\cdot}(H_2O)_2$], [Co(o-BSDT)${\cdot}(H_2O)$], and [Cu(o-BSDT)]. It seems that Ni(II) and Ni(II) complexes are hexacoordinated with the Schiff base ligand and two molecules of water, while the Cu(II) complexes are tetracoordinated with the Schiff base. The mole ratio of tetradentate Schiff base ligand to metals was found to be 1 : 1. The redox chemistry of these complexes was investigated by polarography and cyclic voltammetry with glassy carbon electrode in DMSO with 0.1M TEAP${\cdot}$[Ni(o-BSDT)${\cdot}(H_2O)_2$] hav EC reaction mechanisms which undergo a irreversible electron transfer followed by a fast chemical reaction. [Co(o-BSDT)${\cdot}(H_2O)_2$] undergoes a reduction of Co(II) to Co(I) and a oxidation of Co(II) to Co(III), and [Cu(o-BSDT)] undergoes a reduction of Cu(II) to Cu(I).

• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.719-725
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• 1998

Tridentate Schiff base ligands were prepared by the reactions of salicylaldehyde and 2-hydroxy-1-naphthaldehyde with 2-aminophenol and 2-amino-p-cresol. And then Cu(II) complexes of those ligands were synthesized. The structures and properties of ligands and their complexes were studied by elemental analysis, $^1H$-NMR, IR, UV-visible spectra, and thermogravimetric analysis. The mole ratio of Schiff base to the metal of complexes was found to be 1:1. Cu(II) complexes were contemplated to be four-coordinated square planar configuration containing one water molecule. The redox process of ligands and complexes in DMSO solution containing 0.1 M TBAP as a supporting electrolyte was investigated by cyclic voltammetry and differential pulse voltammetry with glassy carbon electrode. The redox process of the tridentate Schiff base ligands was totally irreversible. The redox process of Cu(II) complexes was quasi-reversible and diffusion-controlled as one electron by one step process Cu(II)/Cu(I). The reduction potentials of the Cu(II) complexes shifted in the positive direction in the order of [Cu(II)(HNIPC)($H_2O$)]>[Cu(II)(HNIP)($H_2O$)]>[Cu(II)(SIP)($H_2O$)]>[Cu(II)(SIPC)($H_2O$)].

• Journal of the Korean Chemical Society
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• v.18 no.3
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• pp.194-201
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• 1974

The tetradentate schiff base ligand, N,N'-bis(salicylaldehyde)-m-phenylenediimine has been prepared from salicylaldehyde and m-phenylenediamine by Duff-reaction. The schiff base ligand has been reacted with Cu(II), Ni(II), Co(II), and Zn(II) to form new complexes; Cu(II)$[C_{20}H_{14}O_2N_2]{\cdot}2H_2O, Ni(II)[C_{20}H_{14}O_2N_2]{\cdot}2H_2O, Co(III)[C_{20}H_{14}O_2N_2]{\cdot}2H_2O and Zn(II)2[C_{20}H_{14}O_2N_2]{\cdot}4H_2O$. It seems to be that the Cu(II), Ni(II) and Co(II) complexes have hexacoordinated configuration with the schiff base and two molecules of water, while Zn(II) complex has tetracoordinated configuration with the schiff base and four molecules of water. The mole ratio of tetradentate schiff base ligand to Cu(II), Ni(II) and Co(II) are 1:1 but to Zn(II) is 1:2. These complexes have been identified by visible spectra, infrared spectra, T.G.A. and elemental analysis.

• Analytical Science and Technology
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• v.9 no.4
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• pp.345-354
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• 1996

Algal(II) Multidentate N, O-Schiff base ligands, such as bis(salicylaldehyde) ethylenediimine(SED), bis(salicylaldehyde) propylenediimine(SPD), bis(salicylaldehyde) diethylenetriimine(SDT), bis (salicylaldehyde) triethylenetetraimine(STT) and bis(salicyl-aldehyde)tetraethylenepentaimine(STP) were prepared. Stepwise proton dissociation constants of the Schiff base were measured potentiometrically in ethanol and a mixture of 70% dioxane and 30% $H_2O$. The stability constants of copper(II)-Schiff base complexes were in the order of Cu(II)-SPD${\leq}$Cu(II)-SED~STT${\leq}$Cu(II)-STP. Oxidation-reduction process of the Cu(II)-Schiff base complexes was involved with one-electron reaction.

• Journal of the Korean Chemical Society
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• v.18 no.3
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• pp.189-193
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• 1974

The tridentate schiff base, salicylidene imino-o-thiolbenzene, has been synthetized from salicylaldehyde and o-amino thiolbenzene by Duff reaction. The schiff base has been reacted with Cu(II), Ni(II), and Zn(II), to form new complexes; Cu(II)$[C_{13}H_9ONS]{\cdot}3H_2O$, Ni(II)$[C_{13}H_9ONS]{\cdot}3H_2O,\;Zn(II)[C_{13}H_9ONS]{\cdot}3H_2O$ It appears that the Cu(II)-complex has tetra-coordinated configuration with the schiff base and one molecule of water, while the Ni(II) and Zn(II)-complexes have hexacoordinated configuration with the schiff base and three molecules of water. The mole ratio of tridentate schiff base ligand to metals was 1:1. These complexes have been identified by infrared spectra, visible spectra, TGA, DTA and elemental analysis.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.8
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• pp.844-851
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• 2005

The purpose of this study was to determine feasibility of application of regenerated or recycled $TiO_2$ on the successive treatment of Cu(II)-EDTA. The recovery of copper, the reuse of $TiO_2$ and the assessment of acute toxicity was studied in the total eight successive photocatalytic reactions. Aqueous solution of $10^{-4}\;M$ Cu(II)-EDTA was treated using an illuminated $TiO_2$ at pH 6 in a circulating reactor. Two different procedures were applied in the reuse of $TiO_2$: i) recycle of $TiO_2$ without acid wash ii) regeneration of $TiO_2$ with acid wash to remove adsorbed copper in a previous experiment. The averaged decomplexation rate constant($k'_{obs}$) of Cu(II)-EDTA in recycle of $TiO_2$ without acid wash was approximately 45% less than that in regeneration of $TiO_2$ with acid wash. Removal of Cu(II) was near complete after 180 minutes in the total eight successive photocatalytic reactions using the regenerated $TiO_2$ after acid wash. In contrast, removal of Cu(II) was minimum at total fifth successive photocatalytic oxidation using the recycled $TiO_2$ without arid wash. The recovered $TiO_2$ was approximately 86% in average in each procedure. The recovered Cu(II) was 67.9% in average. The acute relative toxicity of the treated water rapidly declined at an initial reaction time up to 60 minutes but little declination was observed after 60 minutes due to little degradation of DOC. Relative toxicity of treated water using the recycled $TiO_2$ without acid wash we some what well correlated with the concentration of dissolved Cu(II). From this work, it is suggested that Cu(II)-EDTA can be effectively treated using an integrated cyclic photocatalytic oxidation with recovery of $TiO_2$ and Cu(II).

• Journal of Korean Society of Environmental Engineers
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• v.27 no.2
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• pp.163-169
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• 2005

Photocatalytic oxidation of Cu(II)-EDTA has been studied using solar/$TiO_2$ photocatalysis as an energy source. Photocatalysis efficiency on the treatment of Cu(II)-EDTA was investigated using different types of solar collectors as well as by variation of the angles of solar collector solar light intensities, flow rates, and areas of solar collector. effect of $H_2O_2$ and types of $TiO_2$ catalyst on the treatment of Cu(II)-EDTA was also investigated. Removal of Cu(II) and DOC was favorable with a hemispherical collector than with a flat collector Removal of Cu(II) and DOC increased with increasing angles of solar collector up to $38^{\circ}$. Slurry type $TiO_2$ showed four-times higher removal efficiency than immobilized type $TiO_2$. Removal of both Cu(II) and DOC at a clear sky of solar light intensity ranging from 0.372 to $2.265\;mW/cm^2$ was greater than removal at a cloudy day of solar light intensity ranging from 0.038 to $1.129\;mW/cm^2$. From the result of this research that the removal efficiency of Cu(II) and DOC increased as the solar light intensity increased, it can be inferred that quantum yield in the destruction of Cu(II)-EDTA may directly related with the solar light intensity. Removal of Cu(II) increased as increasing the area of solar collector and was similar at lower flow rates white removal of Cu(II) was interfered at higher flow rates. When immobilized $TiO_2$ was used, removal efficiency of Cu(II) increased in the presence of $H_2O_2$ while negligible effect was found in the use of $TiO_2$ slurry.

• Journal of the Korean Chemical Society
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• v.48 no.2
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• pp.215-219
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• 2004