• Bulletin of the Korean Chemical Society
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• v.18 no.7
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• pp.749-754
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• 1997

Rate constants have been measured spectrophotometrically for the reactions of alkali metal ethoxides (EtOM) with S-p-nitrophenyl 2-thiofuroate (1b) and 2-thiophenethiocarboxylate (2b) in absolute ethanol at 25.0±0.1 ℃. 1b is observed to be more reactive than 2b toward all the EtOM studied. The reactivity of EtOM is in the order EtOK > EtONa > EtO- > EtOLi for both substrates, indicating that K+ and Na+ behave as a catalyst while Li+ acts as an inhibitor in the present system. Equilibrium association constants of alkali metal ions with the transition state (KaTS) have been calculated from the known equilibrium association constants of alkali metal ion with ethoxide ion (Ka) and the rate constants for the reactions of EtOM with 1b and 2b. The catalytic effect (KaTS/Ka) is larger for the reaction of 1b than 2b, and decreases with decreasing the size of the alkali metal ions. Formation of 5-membered chelation at the transition state appears to be responsible for the catalytic effect.

• Bulletin of the Korean Chemical Society
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• v.15 no.8
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• pp.654-658
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• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of p-and m-nitrophenyl 2-furoates (4 and 5, respectively) with alkali metal ethoxides ($EtO^-M^+$) in absolute ethanol at 25$^{\circ}$C. The reactivity of $EtO^-M^+$ toward 4 is in the order $EtO^-K^+$ > $EtO^-Na^+$> $EtO^-Li^+$ > $EtO^-K^+$+ 18-crown-6 ether. This is further confirmed by an ion pairing treatment method. The present result indicates that (1) ion paired $EtO^-M^+$ is more reactive than dissociated $EtO^-$ ; (2) the alkali metal ions ($K^+,\;Na^+,\;Li^+$) behave as a catalyst; (3) the catalytic effect increases with increasing the size of the metal ion. A similar result has been obtained for the reaction of 5, however, the catalytic effects shown by the metal ions are more significant in the reaction of 5 than in that of 4.

• Analytical Science and Technology
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• v.18 no.2
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• pp.120-129
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• 2005

Volatile organic compounds (VOCs) have been recognized as major contributor to air pollution. The catalytic oxidationis is one of the most important processes for VOCs destruction due to the possibility getting high efficiency at low temperature. In this study, monometallic Pt, Ir and bimetallic Pt-Ir were supported to $TiO_2$. In order to distribute metals uniformly, $H_2O-H_2$ treatment method was used. Xylene, toluene and MEK were used as reactants. The monometallic or bimetallic catalysts were prepared by the excess wetness impregnation method and characterized by XRD, XPS, and TEM analysis. Pt catalyst showed higher conversion than Ir catalyst and Pt-Ir bimetallic catalyst showed the highest conversion. The catalysts prepared by $H_2O-H_2$ treatment had better VOC's conversion than that of nothing treatment. In the VOCs oxidation, Pt-Ir bimetallic catalysts had multipoint active sites, so it improved the range of Pt metal state. Therefore, bimetallic catalysts showed higher conversion of VOCs than monometallic ones. $H_2O-H_2$ treatment effected an uniform distribution of Pt particles. In VOCs oxidation was found to follow first order reaetion kinetics. The activation energy of $H_2O-H_2$ treatment catalysts was lower than that of untreated ones. In this study, the a small amount of Ir was used with Pt to promote the oxidation conversion of VOCs.

• Journal of Korean Society of Environmental Engineers
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• v.22 no.12
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• pp.2255-2261
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• 2000

To eliminate $NO_x$ in diesel emission. selective catalyst reduction (SCR) was used in real diesel engine. Among the SCR methods, metal oxide and perovskite catalysts were introduced in this paper. The removal efficiencies with various major, promoter catalysts on ${\gamma}-Al_2O_3$ at different reaction temperature were investigated, and $LaCuMnO_x$ catalyst which has high removal efficiency at the temperature of real diesel exhaust gas was selected. $NO_x$ reduction was carried out over these catalysts in the flow-through type reactor using by-pass ($SV=3,300h^{-1}$). Under the given condition to this study, perovskite catalysts showed considerably high removal efficiency and $LaCuMnO_x$ was the best one among these catalysts in the temperature range of $150{\sim}450^{\circ}C$.

• Journal of the Korea Organic Resources Recycling Association
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• v.29 no.4
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• pp.47-54
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• 2021

In this study, the performance of a honeycomb-type hydrogen oxidation catalyst to remove hydrogen in a hydrogen economy society to secure leaking hydrogen. The Pd/TiO₂ catalyst was prepared based on a liquid phase reduction method that is not exposed to a heat source, and it was showed through H₂-chemisorption analysis that it existed as very small active particles of 2~4 nm. In addition, it was found that the metal dispersion decreased and the active particle size increased as the reduction reaction temperature increased. It was meant that the active metal particle size and the hydrogen oxidation performance were in a proportional correlation, so that it was consistent with the hydrogen oxidation performance reduction result. The prepared catalyst was coated on a support in the form of a honeycomb so that it could be applied to the hydrogen industrial process. When 20 wt% or more of the AS-40 binder was coated, oxidation performance of 90% or more was observed under low-concentration hydrogen conditions. It was showed through SEM analysis that long-term catalytic activity can be expected by enhancing the adhesion strength of the catalyst and preventing catalyst desorption. It is a basic research that can secure safety in a hydrogen society such as gasification, organic resource, and it can be utilized as a system that can respond to unexpected safety accidents in the future.

• Clean Technology
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• v.16 no.4
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• pp.284-291
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• 2010

Nitrous oxide ($N_2O$) is a greenhouse material which is hard to remove. Even with a catalytic process it requires a reaction temperature, at least, higher than 670 K. This study has been performed to see the effects of Ce addition to the mixed oxide catalyst which shows the highest activity in decomposing $N_2O$ completely at temperature as low as 473 K when CO is used as a reducing agent. Mixed metal oxide(MMO) catalyst was made through co-precipitation process with small amount of Ce added to the base components of Co, Al and Rh or Pd. Consequently, the surface area of the catalyst decreased with the contents of Ce, and the catalytic activity of direct decomposition of $N_2O$ also decreased. However, in the presence of CO, the activity was found high enough to compensate the portion of activity decrease by Ce addition, so that it can be ascertained that the catalytic activity and stability can be maintained in the CO involved $N_2O$ reduction system when Ce is added for the physical stability of the catalyst.

• Applied Chemistry for Engineering
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• v.27 no.3
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• pp.313-318
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• 2016

In this study, an amorphous silica was functionalized with aminosilane, N-[(3-trimethoxysilyl)propyl]ethylenediamine (2NS) and the late transition metal catalysts including ($(DME)NiBr_2$ and $PdCl_2$(COD)) were subsequently immobilized on the functionalized amorphous silica for norbornene polymerization. Effects of the polymerization temperature, polymerization time, Al/Ni molar ratio, and type of co-catalyst on norbornene polymerization were investigated. Unsupported late transition metal catalysts did not show any activities for norbornene polymerization. However, the $SiO_2$/2NS/Ni catayst with MAO system, with increasing polymerization temperature, increased the polymerization activity and decreased the molecular weight of the polynorbornene (PNB). Furthermore, the catalyst when increasing polymerization temperature caused the decrease in both the polymerization activity and molecular weight of PNB. This confirmed that the stability of $SiO_2$/2NS/Ni at a high temperature was greater than that of $SiO_2$/2NS/Pd. Also the longer polymerization time resulted in the higher conversion of norbornene for both catalysts. When the Al : Ni molar ratio was 1000 : 1, the highest activity (15.3 kg-PNB/($({\mu}mol-Ni^*hr$)) but lowest molecular weight ($M_n$ = 124,000 g/mol) of PNB were achieved. Also $SiO_2$/2NS/Ni catalyst with borate/TEAL resulted in diminishing the polymerization activity and molecular weight of PNB with increasing the polymerization temperature.

• Applied Chemistry for Engineering
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• v.29 no.1
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• pp.22-27
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• 2018

In this study, the effect of physical properties of $Pt/TiO_2$ on $NH_3$-selective catalytic oxidation (SCO) reaction at $200{\sim}350^{\circ}C$ was investigated. CO-chemisoption and BET analysis were carried out to verify physical properties of $Pt/TiO_2$. By characterizing physical properties of $Pt/TiO_2$ with respect to the Pt loading, the metal dispersion degree decreased as a function of the Pt loading amount. Also, the catalyst having a higher metal dispersion showed an excellent conversion efficiency of $NH_3$ to $N_2$. Since the specific surface area of the support affects the metal dispersion, $Pt/TiO_2$ catalysts were prepared using $TiO_2$ with different physical properties. As a result, it was confirmed that the catalyst having a wide specific surface area exhibited a excellent conversion of $NH_3$ to $N_2$.

• Applied Chemistry for Engineering
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• v.30 no.6
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• pp.757-761
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• 2019

The catalytic yields of POM to hydrogen over M(1)-Ni(5)/AlCeO₃ (M = La, Ce, Y) were investigated using a fixed bed flow reactor under atmosphere. The crystal phase behavior of reduced La(1)-Ni(5)/AlCeO₃ catalysts before and after the reaction were studied via XRD analysis. FESEM and EDS analyses were further performed to show the uniformed distribution of La, Ni, and Ce metal particles on the catalyst surface. XPS results showed O^2-, O₂^2- species and metal ions such as Ce³⁺, Ce⁴⁺, La³⁺ and Ni²⁺ etc. were on the catalyst surface. When 1 wt% of La was added to Ni(5)/AlCeO₃ catalyst, Ni2p_3/2 and Ce3d_5/2 increased 52.7 and 6.3%, respectively. The yield of hydrogen on the La(1)-Ni(5)/AlCeO₃ catalyst was 89.1%, which was much better than that of M(1)-Ni(5)/AlCeO₃ (M = Ce, Y). As Ce⁴⁺ ions of CeO₂ produced by the reaction of AlCeO₃ with oxygen were substitute to La³⁺, it made oxygen vacancies in the lattice and further improved the hydrogen yield by increasing the dispersion of Ni atoms with strong metal-support interaction (SMSI) effect.

• Journal of the Korean GEO-environmental Society
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• v.17 no.10
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• pp.5-11
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• 2016

In this study, the factors affecting commercialization of $Pt/TiO_2$ catalyst, which can oxidize HCHO at room temperature, was investigated. In order to determine the optimum noble metal loading, the catalytic activity was evaluated by varying the Pt loadings; the best catalytic activity was achieved for 1 wt% of Pt. In addition, the catalyst prepared under the reduction condition showed an excellent HCHO oxidation conversion at room temperature. Based on these results, it was confirmed that the activity could be changed by oxidation state of active metal, and in case of Pt, metallic Pt ($Pt^0$) species was more active on HCHO oxidation at room temperature. As a result of evaluating an effect of space velocity to determine the optimum operating condition, it was found that in the lower space velocity, conversion rate of HCHO was increased due to increase of catalyst bed. Catalytic activity was greater in the presence of moisture than in its absence. Through above results, the key factors for commercialization of oxidation catalyst, which was operated at room temperature even without any additional energy source was confirmed.