• Bulletin of the Korean Chemical Society
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• v.9 no.5
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• pp.298-303
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• 1988

Kinetic studies on cupric ion ($Cu^{2+}$) oxidation of 1-benzyl- and 1-aryl-1,4-dihydronicotinamides (XNAH) in aqueous solution were performed. In the presence of dioxygen ($O_2$), the reaction followed first order kinetics with respect to both XNAH and $Cu^{2+}$. The oxidation reaction was found to be independent and parallel to the acid-catalyzed hydration reaction of XNAH. The catalytic role of $Cu^{2+}$ for the oxidation of XNAH in the presence of $O_2$ was attributed to $Cu^{2+}/Cu^+$ redox cycle by the reactions with XNAH and $O_2$. The second order rate constants of the Cu2+ oxidation reaction kCu, and acid-catalyzed hydration reaction $k_H$ were strongly dependent on the nature of the substituents in 1-aryl moiety. The slopes of log $k_{Cu}$ vs log $K_H$ and log $k_{Cu}$ vs ${\sigma}_p$ of the substituents plots were 1.64 and -2.2, respectively. This revealed the greater sensitivity of the oxidation reaction rate to the electron density on the ring nitrogen than the hydration reaction rate. A concerted two-electron transfer route involving XNAH-$Cu^{2+}$ complex was proposed for mechanism of the oxidation reaction.

• Korean Journal of Materials Research
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• v.31 no.10
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• pp.552-561
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• 2021

For the purpose of manufacturing a high efficiency TiO₂ photocatalyst, B-doped TiO₂ photocatalysts are synthesized using a plasma electrolytic oxidation method in 0.5 M H₂SO₄ electrolyte with different concentrations of H₃BO₃ as additive. For the B doped TiO₂ layer fabricated from sulfuric electrolyte having a higher concentration of H₃BO₃ additive, the main XRD peaks of (101) and (200) anatase phase shift gradually toward the lower angle direction, indicating volume expansion of the TiO₂ anatase lattice by incorporation of boron, when compared with TiO₂ layers formed in sulfuric acid with lower concentration of additive. Moreover, XPS results indicate that the center of the binding energy peak of B1s increases from 191.45 eV to 191.98 eV, which suggests that most of boron atoms are doped interstitially in the TiO₂ layer rather than substitutionally. The B doped TiO₂ catalyst fabricated in sulfuric electrolyte with 1.0 M H₃BO₃ exhibits enhanced photocurrent response, and high efficiency and rate constant for dye degradation, which is ascribed to the synergistic effect of the new impurity energy band induced by introducing boron to the interstitial site and the improvement of charge transfer reaction.

• Analytical Science and Technology
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• v.14 no.1
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• pp.15-20
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• 2001

Photocatalytic $TiO_2$ films were prepared by anodic oxidation at 180 V and their structural difference caused by oxidation conditions was studies. The microstructure of $TiO_2$ films in $H_2SO_4$ and $H_2SO_4/H_2O_2$ solution was mixed type of rutile and anatase. However, the $TiO_2$ layer formed in $H_2SO_4/H_3PO_4$ and $H_2SO_4/H_3PO_4/H_2O_2$ mixture was mostly anatase type. All $TiO_2$ films prepared by anodic oxidation exhibited photocatalytic properties. The photocatalytic degradation of aniline blue was first order reaction with similar rate constants at all oxidative conditions examined in this work.

• Bulletin of the Korean Chemical Society
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• v.24 no.12
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• pp.1835-1837
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• 2003

• Journal of Soil and Groundwater Environment
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• v.12 no.5
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• pp.105-114
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• 2007

The most advanced oxidation processes (AOPs) are based on reactivity of strong and non-selective oxidants such as hydroxyl radical (${\cdot}OH$). Decomposition of typical DNAPL chlorinated compounds (TCE, PCE) using various advanced oxidation processes ($UV/Fe^{3+}$-chelating agent/$H_2O_2$ process, $UV/H_2O_2$ process) was approached to develop appropriate methods treating chlorinated compound (TCE, PCE) for further field application. $UV/H_2O_2$ oxidation system was most efficient for degrading TCE and PCE at neutral pH and the system could remove 99.92% of TCE after 150 min reaction time at pH 6($[H_2O_2]$ = 147 mM, UVdose = 17.4 kwh/L) and degrade 99.99% of PCE within 120 min ($[H_2O_2]$ = 29.4 mM, UVdose = 52.2 kwh/L). Whereas, $UV/Fe^{3+}$-chelating agent/$H_2O_2$ system removed TCE and PCE ca. > 90% (UVdose = 34.8 kwh/L, $[Fe^{3+}]$ = 0.1 mM, [Oxalate] = 0.6 mM, $[H_2O_2]$ = 147 mM) and 98% after 6hrs (UVdose = 17.4 kwh/L, $[Fe^{3+}]$ = 0.1 mM, [Oxalate] = 0.6 mM, $[H_2O_2]$ = 29.4 mM), respectively. We improved the reproduction system with addition of UV light to modified Fenton reaction by increasing reduction rate of $Fe^{3+}$ to $Fe^{2+}$. We expect that the system save the treatment time and improve the removal efficiencies. Moreover, we expect the activity of low molecular organic compounds such as acetate or oxalate be effective for maintaining pH condition as neutral. This oxidation system could be an economical, environmental friendly, and practical treatment process since the organic compounds and iron minerals exist in nature soil conditions.

• Environmental Engineering Research
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• v.11 no.2
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• pp.84-90
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• 2006

UV-catalytic oxidation technique was applied for the treatment of bio-refractory character of the leachate, which is generally present in the form of adsorbable organic halogens (AOX). Destruction of AOX was likely to be governed by pH adjustment, quantitative measurement of oxidants, and the selection of oxidation model type. Peroxide induced degradation ($UV/H_2O_2$) facilitated the chemical oxidation of organic halides in acidic medium, however, the system showed least AOX removal efficiency than the other two systems. Increased dosage of hydrogen peroxide (from 0.5 time to 1.0 time concentration) even did not contribute to a significant increase in the removal rate of AOX. In ozone induced degradation system ($UV/O_3$), alkaline medium (pH 10) favored the removal of AOX and the removal rate was found 11% higher than the rate at pH 3. Since efficiency of the $UV/O_3$ increases with the increase of pH, therefore, more OH-radicals were available for the destruction of organic halides. UV-light with the combination of both ozone and hydrogen peroxide ($UV/H_2O_2$ 0.5 time/$O_3$ 25 mg/min) showed the highest removal rate of AOX and the removal efficiency was found 26% higher than the removal efficiency of $UV/O_3$. The system $UV/H2O_2/O_3$ got the economic preference over the other two systems since lower dose of hydrogen peroxide and relatively shorter reaction time were found enough to get the highest AOX removal rate.

• Journal of the Korean Chemical Society
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• v.34 no.6
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• pp.534-538
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• 1990

Chromium(Ⅵ) compound, [$C_9H_7$NH]$_2Cr_2O_7$ has been prepared by the reaction of isoquinoline with chromium trioxide under the presence of water. [$C_9H_7$NH]$_2Cr_2O_7$ is nonhydroscopic and dissolved in water very well. Structure of [$C_9H_7$NH]$_2Cr_2O_7$ is identified by FTIR spectra and elemental analysis data. The ability of [$C_9H_7$NH]$_2Cr_2O_7$ for the oxidation of alcohols were examined in methylene chloride. [$C_9H_7$NH]$_2Cr_2O_7$ was found as efficient oxidizing agent for the conversion of allyl, primary and secondary alcohols to the corresponding aldehydes or ketones.

• Transactions of the Korean Society of Automotive Engineers
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• v.20 no.5
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• pp.71-80
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• 2012

To improve the $NO_X$ conversion over a SCR (selective catalytic reduction) catalyst, the DOC (diesel oxidation catalyst) is usually placed upstream of the SCR catalyst to enhance the fast SCR reaction ($4NH_3+2NO+2NO_2{\rightarrow}4N_2+6H_2O$) using equimolar amounts of NO and $NO_2$. Here, a ratio of $NO_2/NO_X$ above 50% should be avoided, because the reaction with $NO_2$ only ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$) is slower than the standard SCR reaction ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$). In order to accurately predict the performance characteristics of SCR catalysts, it is therefore desired to develop a more simple and reliable mathematical and kinetic models on the oxidation kinetics of nitric oxide over a DOC. In the present work, the prediction accuracy and limit of three different chemical reaction kinetics models are presented to describe the chemicophysical characteristics and conversion performance of DOCs. Steady-state experiments with DOCs mounted on a light-duty four-cylinder 2.0-L turbocharged diesel engine then are performed, using an engine-dynamometer system to calibrate the kinetic parameters such as activation energies and preexponential factors of heterogeneous reactions. The reaction kinetics for NO oxidation over Pt-based catalysts is determined in conjunction with a transient one-dimensional (1D) heterogeneous plug flow reactor (PFR) model with diesel exhaust gas temperatures in the range of 115~$525^{\circ}C$ and space velocities in the range of $(0.4{\sim}6.5){\times}10^5\;h^{-1}$.

• Clean Technology
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• v.17 no.1
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• pp.41-47
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• 2011

[ $MnO_2$ ]catalysts were prepared by precipitation method using potassium manganate and manganese acetate. The effect of calcination temperatures of $MnO_2$ catalysts for CO oxidation has been studied and their physicochemical properties were studied by X-ray diffraction (XRD), $N_2$ sorption, temperature programmed reduction of $H_2$ ($H_2-TPR$), and temperature programmed desorption of CO (CO-TPD) techniques. $MnO_2$ calcined at $300^{\circ}C$ catalyst has a large surface area $181m^2/g$ having a narrow pore size distribution at 9 nm. The results of XRD and $H_2-TPR$ showed that the catalysts calcined at different temperatures showed mixed oxidation states of Mn such as $Mn^{4+}$ and $Mn^{3+}$. CO-TPD showed that the quantity of $CO_2$ desorbed was decreased with increasing the calcination temperatures. The catalytic activity over the catalyst calcined at $300^{\circ}C$ exhibited the highest conversion reaching to 100% at $200^{\circ}C$. $H_2O$ vapor showed an inhibiting effect on the efficiency of the catalyst because of co-adsorption with CO on the active sites of manganese oxide catalysts and the initial catalytic activity of CO oxidation could be regenerated by removing $H_2O$ vapor in the reactants.

• Applied Chemistry for Engineering
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• v.18 no.4
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• pp.314-319
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• 2007

The destruction of synthetic acetic acid wastewater was carried out using UV, $O_3$, $H_2O_2$, $Fe^{2+}$ oxidants in various combinations by the advanced oxidation processes. $UV/H_2O_2$, $UV/H_2O_2/Fe^{2+}$, $O_3$, $O_3/H_2O_2$, $UV/O_3/H_2O_2$, $UV/O_3/H_2O_2/Fe^{2+}$ processes were tested. $UV/H_2O_2/Fe^{2+}$, $O_3/H_2O_2$, $UV/O_3/H_2O_2$, $UV/O_3/H_2O_2/Fe^{2+}$ processes shows the most effective destruction efficiency at low pH (3.5) condition of wastewater, but $UV/H_2O_2$ and $O_3$ processes were observed less than 20%. Destruction efficiency was gradually increased with the reaction time in the $O_3/H_2O_2$ and $UV/O_3/H_2O_2$ processes, in case of the $UV/H_2O_2/Fe^{2+}$ and $UV/O_3/H_2O_2/Fe^{2+}$ processes shows rapid increasing of destruction efficiency within 90 min, then slightly decreasing with time. The destruction efficiencies of $UV/H_2O_2/Fe^{2+}$, $O_3/H_2O_2$, $UV/O_3/H_2O_2$ and $UV/O_3/H_2O_2/Fe^{2+}$ processes were observed 55, 66, 66 and 64%, respectively.