• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.13 no.12
• /
• pp.6187-6195
• /
• 2012

Recycling process of iron should be developed for efficient recovery of neodymium(Nd), rare metal, from acid-leaching solution of neodymium magnet. In this study, $FeCl_3$ solution as iron source was used for synthesis of iron nanoparticle with the condition of various factors, etc, reductant, surfactant. $Na_4O_7P_2$ and polyvinylpyrrolidone(PVP) as surfactants, $NaBH_4$ as reductant, and palladium chloride($PdCl_2$) as a nucleation seed were used. Iron powder was analyzed with instruments of XRD, SEM and PSA for measuring shape and size. Iron nanoparticles were made at the ratio of 1 : 5(Fe (III) : $NaBH_4$) after 30 min of reduction time. Size and shape of iron particles synthesized were round-form and 50 nm ~ 100 nm size. Zeta-potential of iron at the 100 mg/L of $Na_4O_7P_2$ was negative value, which is good for dispersion of metal particle. When $Na_4O_7P_2$(100 mg/L), PVP($FeCl_3$ : PVP = 1 : 4, w/w) and Pd($FeCl_3$ : $PdCl_2$ = 1 : 0.001, w/w) were used, iron nanoparticles which are round-shape, well-dispersed, near 100 nm-sized can be made.

• Applied Chemistry for Engineering
• /
• v.29 no.4
• /
• pp.376-381
• /
• 2018

The purpose of this study is to investigate and optimize an effectiveness process for the recovery of Pd from the spent Pd/C catalyst by the process of hydrogenation of maleic anhydride over Pd/C. Pd solution recovered from Pd/C catalyst was used to prepare Pd/C catalysts. Their characteristics were compared to those of Pd/C catalyst prepared by using a reagent grade precursor solution. Pd in the spent catalyst was leached by the modified process with dry and wet methods to obtain the high recovery ratio of Pd. The burn-out of carbon in the spent Pd/C catalyst was carried out in the rage of $600-900^{\circ}C$. Pd content of carbonized catalyst was confirmed by XRF and ICP. Pd was extracted from carbonized spent catalysts with acid solutions of 1,2 and 4 M HCl at a leaching temperature of $90^{\circ}C$ for 2 h. The high recovery ratio of Pd was shown as 92.4% that leached in 4 M HCl. Also Pd/C catalysts were prepared by using the leached solution and the reagent grade of $H_2PdCl_4$ as a precursor solution and the characteristics were analyzed by XRD, CO-chemisorption and FE-TEM. As a result, the dispersion of the catalyst prepared by using the leached solution was 34.6%, which was found to be equal to or more than that of the Pd/C catalyst prepared by the reagent grade precursor solution.

• Korean Chemical Engineering Research
• /
• v.44 no.4
• /
• pp.404-409
• /
• 2006

The catalytic combustion of toluene over Pd-Cu/USY zeolite has been examined by using FT-IR spectroscopy in a closed system under dry and humid conditions. The catalytic combustion of toluene (700 ppmv) in the temperature range of $80-220^{\circ}C$ has been investigated by using a fixed bed reactor. The Pd-Cu/USY catalyst showed the highest catalytic performance with respects to the PdO-CuO/USY and Pd/USY. Comparing to $PdO/Al_2O_3$ catalysts, the slight improvement in conversion was observed over PdO/USY catalysts under humid condition since USY zeolite is hydrophobic substrate and water give an additional oxygen source to zeolite surface like oxygen. The reduced catalysts showed more enhanced catalytic activity due to the reduced activation energy of combustion of toluene than oxidized catalysts such as PdO/USY and PdO-CuO/USY.

• Applied Chemistry for Engineering
• /
• v.18 no.5
• /
• pp.467-474
• /
• 2007

The palladium and gold nanoparticles containing PAN-based active carbon fiber (ACF) with a high specific surface area were prepared. Using the BET, TEM, FE-SEM, and XPS, their specific surface area and pore volume, pore structure, and the change in surface oxygen groups with time were analyzed and $SO_2$ adsorption performances were investigated. Because of the impregnating process, the micropore volume was mostly decreased from 95.5% to 30.5~43.7% compared with the total pore volume. And the change in surface oxygen groups with time was higher for the metal salt than the nanoparticles. Also, $SO_2$ breakthrough time of PAN-ACFs impregnated with Au nanoparticles and metal salts did not change compared with that of the non-impregnated PAN-ACF. But the PAN-ACF impregnated with Pd nanoparticles (100 ppm) showed good $SO_2$ adsorption performance as the breakthrough time of 880 sec. These results indicated that the $SO_2$ adsorption performance depended on the change in surface oxygen groups with time and the moderate impregnation of Pd nanoparticles on the PAN-ACF caused the increase in the $SO_2$ adsorption performance by a catalytic action.

• Applied Chemistry for Engineering
• /
• v.17 no.5
• /
• pp.458-464
• /
• 2006

The Pd-Ni-Ag alloy composite membrane using modified porous stainless steel (PSS) as a substrate was prepared by a electroless plating technique. In this work, we have introduced the intermediate layer between Pd-based alloy and a metal substrate. As an intermediate layer, the mixtures of nickel powder and inorganic sol such as $SiO_{2}$ sol, $Al_{2}O_{3}$ sol, and $TiO_{2}$ sol were used. The intermediate layers were coated onto a PSS substrate according to various membrane preparation conditions and then $N_{2}$ fluxes through the membranes with different intermediate layers were measured. The surface morphology of the intermediate layer in the mixture of nickel powder and inorganic sol was analyzed using scanning electron microscope (SEM). Finally, the Pd-Ni-Ag alloy composite membrane using the support coated with the mixture of nickel powder and silica as an intermediate layer was fabricated and then the gas permeances for $H_{2}$ and $N_{2}$ through the Pd-based membrane were investigated. The selectivity of $H_2/N_2$ was infinite and the $H_{2}$ flux was $1.39{\times}10^{-2}mol/m^2{\cdot}s$ at the temperature of $500^{\circ}C$ and trans-membrane pressure difference of 1 bar.

• Journal of the Korean Chemical Society
• /
• v.55 no.1
• /
• pp.70-80
• /
• 2011

Two new palladium (II) complexes, [Pd (phen)(pip-dtc)]$NO_3$ and [Pd(phen)(mor-dtc)]$NO_3$, (where phen is 1,10-Phenantroline, pip-dtc is piperidinedithiocarbamate anion and mor-dtc is morpholinedithiocarbamate anion) have been synthesized and characterized by elemental analysis, spectroscopic studies (FT-IR, $^1H$ NMR, UV-Vis) and conductance measurement. In these complexes, the dithiocarbamate ligands coordinate with Pd (II) center as bidentate with two sulfur atoms. These two complexes have been tested against chronic myelogenous leukemia cell line, K562. They show $IC_{50}$ values less than cisplatin and thus the mode of binding of the complexes to calf thymus DNA (CT-DNA) were investigated by ultraviolet difference and fluorescence spectroscopy. They can denature DNA, exhibit cooperative binding and intercalate into DNA. Several binding and thermodynamic parameters are also described.

• Journal of the Korean Chemical Society
• /
• v.42 no.4
• /
• pp.369-377
• /
• 1998

The palladium(II) and platinum(II) complexes(where, $([M(L)_2X_2]$, M=Pd(II), Pt(II); L=isoxazole(isox), 3,5-dimethylisoxazole(3,5-diMeisox), 3-methyl, 5-phenylisoxazole(3-Me, 5-Ph-isox), and 4-amino-3,5-dimethylisoxazole (4-ADI); X=Cl, Br) with isoxazole and its derivatives were investigated on antitumor activity by MM2 and EHMO calculation. Because for all the complexes the ${\sigma}MO$ energy level $(E_{{\sigma}(M-X)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of halogen atom is less than ${\sigma}MO$ energy level $(E_{{\sigma}(M-N)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of N atom, without exception. And judging, from the lower $(E_{\'{o}(m-x)})$ value in trans, the bonding strength was found to be weaker in trans isomer than in cis. For the Pd(II) and Pt(II) complexes which have planar ligands, it was shown that for all the complexes dissociation of X-atom in the Pd(II) complexes is easier than that of X-atom in the Pt(II) complexes in both cis- and trans-complexes. Therefore it suggests that the easier dissociation of $X^-$ ion has some relations with antitumor activity, and a linear equation with correlation coefficient of 0.96 was found between ${\Delta}E_{{\sigma}(N-X)}(E_{{\sigma}(M-N)}-E_{{\sigma}(M-X)})$ and inhibitory activity coefficient, logIA.

• Journal of the Korean Chemical Society
• /
• v.39 no.4
• /
• pp.244-251
• /
• 1995

The palladium(II) complexes(where, [Pd(L)2X2], L=isoxazole(isox), 3,5-dimethylisoxazole(3,5-diMeisox), 3-methyl, 5-phenylisoxazole(3-Me, 5-Phisox), and 4-amino, 3,5-dimethylisoxazole(4-ADI); X=Cl, Br] with isoxazole and its derivatives are investigated on antitumor activity by EHMO calculation. It is found that the net charge of the two halogen atoms in trans-isomers are greater than those in cis-ones, indicating that ionic character of Pd-X bond in trans-isomers is greater than that of cis-ones, and so dissociation of Cl- ion is easier than that of Br- ion in aqueous solution in body. Furthermore, it is found that the ${\sigma}MO$ energy of Pd(dx2-y2)-X(px) bond $(E{\sigma}(Pd-X))$ is higher than that of Pd(dx2-y2)-N(px) bond $(E{\sigma}(Pd-N))$ without exception, about all the complexes, and also the $E{\sigma}(Pd-X)$ of trans-isomers is higher than that of cis-isomers. From the above facts, the degree of dissociation in Pd-X bond would be related to antitumor activity. In fact, the linear equation of correlation coefficient 0.96 is fairly established between ${\Delta}E{\sigma}(N-X)(E\sigma(Pd-N)－E{\sigma}(Pd-X))$ and inhibitory activity coefficient, logIA.

• Polymer(Korea)
• /
• v.33 no.6
• /
• pp.615-619
• /
• 2009

Pd-POSS nanoparticles were produced from the reaction of palladium (II) acetate and octa(3-aminopropyl)octasilsesquioxane octahydrochloride (POSS-${NH_3}^+$) in methanol at room temperature. Pd-POSS nanoparticles with a mean diameter of 60-80 nm were the highly ordered spherical aggregates. In contrast, Pd nanoparticles with a size of 4.0 nm were obtained when POSS-${NH_3}^+$ was not introduced. Pd-POSS/PAA nanocomposites of Pd-POSS nanoparticles and poly(acrylic acid) (PAA) were fabricated by utilizing ionic interactions between positively charged Pd-POSS nanoparticles and negatively charged carboxylate groups of PAA. PAA was used as a cross-linker for the preparation of hybrid nanocomposites with the controlled organized structures of Pd-POSS nanoparticles. That is, the self-organization of Pd-POSS nanoparticles was formed into the shape of continuous lines by using PAA as a cross-linker. The composition, structure, surface morphology, and thermal stability of the Pd-POSS/PAA nanocomposites were studied by FE-SEM, AFM, TEM, FT-IR, and TGA.

• Korean Chemical Engineering Research
• /
• v.56 no.1
• /
• pp.119-124
• /
• 2018

The production of methyl N-phenyl carbamate by an oxidative carbonylation method of aniline and methanol is of great interest as an environmentally friendly process that can replace the monomer production process of a polymer produce using conventional phosgene. In this study, heterogeneous catalysts were prepared by using Y-zeolite, $SiO_2$, $Al_2O_3$ as support, and oxidative carbonylation continuous operation from aniline and methanol was attempted using the prepared heterogeneous catalyst. Batch reactor was used to determine the support, and various reaction conditions such as reaction temperature, reaction pressure, and effect of promoter were established using palladium catalyst. A reaction kinetics study was conducted under optimum reaction conditions. The basic data for carbamate process development were obtained by performing continuous operation for a long time under established reaction condition.