NiO 촉매에 의한 CO 산화반응에 관한 연구

최재시,김규홍,Jae Shi Choi,Keu Hong Kim 대한화학회 1969 대한화학회지 Vol.13 No.4

The catalytic reaction between carbon monoxide and oxygen was investigated with the various nickel oxide catalysts at different partial pressures of carbon monoxide and oxygen and at reaction temperatures in the region of 120$^{circ}$to 250$^{circ}C$. The reaction has the highest rate with the nickel oxide catalyst which is sintered at low temperature. A reaction mechanism to explain the data is derived. From the Arrhenius equation, the activation energies in the region of experimental temperatures are found to be from 5.49 to 9.15 kcal/mole. The concentration of excess oxygen in the nickel oxide seems to vary according to the sintering temperatures and periods and is the controlling factor in determining the type of kinetics followed by the catalytic reaction.

A Study on the Nonstoichiometry of the Iron Oxide System

최재시,여철현,최승락,Choi, Jae-Shi,Yo, Chul-Hyun,Choi, Sung-Nack Korean Chemical Society 1973 대한화학회지 Vol.17 No.5

$0^{\circ}C\sim1200^{\circ}C$ 온도범위와 $10^{-4}\sim10^2mmHg$ 산소압력하에 산화철계의 무게감소를 석영마이크로 천평을 사용하여 측정하므로써 산화철계의 비화학양론에 대한연구를 실시하였다. 이를 측정하기 위한 종래의 방법으로 시료를 급냉시킨 후 분석을 하는 방법을 피하고 직접측정하여 $FeO_{1+Y}$의 Y값을 구하였다. log Y 대 $log Po_2$(혹은 $log Y=_nlog Po_2$)의 Plot은 직선관계가 성립된다. 이의 기울기에서 n값을 구한결과 $1000^{\circ}C$에서는 $n=\frac{1}{10}$을 얻을 수 있고 이로부터 산화반응기구와 비화학양론적 반응기구의 차이를 설명하였다. 화학양론적 FeO(Fe:O = 1:1)를 형성하는 기준조건을 $1200^{\circ}C$와 $10^{-3}mmHg$ 산소압력으로 하였으며 표준조건에서의 이산화철계의 조성은 $FeO_{1.11185}$로 표시된다. 일반적으로 낮은온도와 높은산소압력하에서 더 많은 산소가 산화물계에 용해되어 화학양론적 FeO로부터 편기가 크다. 산화철계의 전기전도도를 Y값과 비교해보면 전기전도의 전이점이 산화철계의 완전한 상전이를 동반하지 않음을 알 수 있었다. The nonstoichiometry of the iron oxide system has been studied by analyzing the weight loss of a sample, measured by using a quartz microbalance, in a temperature range from $0^{\circ}C$ to $1200^{\circ}C$ under oxygen pressures from $10^{2}mmHg$ to $10^{-4}mmHg$. The Y values of the formula, $FeO_{1+\gamma}$, that have been obtained by this means for various conditions of temperature and pressure in this range are considered to be more accurate than values obtained by methods requiring thste quenching of the sample before measurements are made. The plots of log Y vs $log PO_2$ (or $log Y =_n log PO_2$) show linearity and n calculated from the slope of the plot is about 1/10 at $1000^{\circ}C$, indicating a difference between the nonstoichiometric and oxidation mechanisms. The condition for the formation of stoichiometric FeO was determined to be $1200^{\circ}C$ under $10^{-3}mmHg$ of $O_2$ and the composition of the oxide under standard conditions was $FeO_{1.11185}$. As in general more oxygen dissolves into the oxide system at lower temperatures and higher oxygen pressures, the deviation from stoichiometric FeO is greater under those conditions. A comparison of the change in conductivity of the sample indicates that full phase transition does not take place with conductivity transition.

NiO의 Semiconductivity에 關한 硏究

최재시,여철현,Choi, Jae-Shi,Yo, Chul-Hyun 대한화학회 1968 대한화학회지 Vol.12 No.2

The conductivity of polycrystalline NiO is measured in the temperature range of $200^{\circ}C\;to\;800^{\circ}C$ under oxygen pressures from $1.52{\times}10^2\;mmHg\;to\;10^{-4}$ mmHg. The plots of the log ${\sigma}$ vs 1/T at constant oxygen pressure are found to be linear and the activation energies obtained from the slopes of these plots show that the energies are greater under high oxygen pressure than under low pressure. The transition points are found from the curves. The dependence of the conductivity on the $O_2$ pressure, in the above temperature range, is to be regular but it does not obey the theoretical expression, i.e. ${\sigma}=K_{ox}P^{1/6}.$ The activation energies are calculated from the curves at the various condition.

NiO-$Y_2O_3$계의 전기전도성

최재시,김규홍,정원양,Jae Shi Choi,Keu Hong Kim,Won Yang Chung 대한화학회 1986 대한화학회지 Vol.30 No.1

Electrical conductivities of NiO-$Y_2O_3$ systems containing 0.8, 1.6, and 3.2 mol% NiO have been measured in the temperature range of 400 to 1100$^{\circ}$C at $PO_2$'s of 1 ${\times}10^{-5}$ to 2 ${\times}10^{-1}$ atm. Plots of $log\sigma$ vs 1/T at constant $PO_2$'s are found to be linear with an inflection at temperature around 650$^{\circ}$C. The slopes are steeper in the high temperature region above 650$^{\circ}$C than in the low temperature region below 650$^{\circ}$C. The average activation energies are 41.8kcal/mol in the high temperature region and 12.5kcal/mol in the low temperature region. $PO_2$'s dependence value, 1/n, is 1/5.1~1/5.4 in the high temperature region and 1/5.9~1/6.2 in the low temperature region. The NiO-$Y_2O_3$ systems are found to be an electronic p-type semiconductor. The predominant defects in the systems are believed to be triply ionized yttrium vacancy in the high temperature region and doubly ionized oxygen interstitial in the low temperature region. Ionic contribution to the total conductivity is found from ${\sigma}^{\propto}PO_2$ in the temperatures below 650$^{\circ}$C. 0.8, 1.6 및 3.2 mol%의 산화니켈을 혼입한 산화니켈-산화이트륨계의 전기전도도를 1 ${\times} 10^{-5}$ ~ 2 ${\times}10^{-1}$ atm의 산소압력과 400 ~ 1100$^{\circ}$C의 온도영역에서 산소압력 및 온도의 함수로서 측정하였다. 전기전도도의 온도의존성은 약 650$^{\circ}$C부근에서 두 영역으로 나뉘었으며, 650$^{\circ}$C이하 영역보다 650$^{\circ}$C이상 영역에서의 온도의존성이 더 큰 것으로 밝혀졌다. 평균 활성화에너지는 650$^{\circ}$C이상 영역에서 41.8kcal/mol, 650$^{\circ}$C이하 영역에서 12.5kcal/mol이다. 산소압력의존성, 1/n값은 650$^{\circ}$C이상 영역에서는 1/5.1~1/5.4이며, 650$^{\circ}$C이하에서는 1/5.9~1/6.2이다. NiO-$Y_2O_3$계는 결함구조가 고온영역에서 3가로 이온화한 이트륨공위이며, 저온영역에서는 2가로 이온화한 틈새형 산소 인전자성 p-형 반도체임이 밝혀졌다. 그러나, 저온영역에서는 이온성 전기전도에 의한 기여가 어느 정도 존재하는 것으로 밝혀졌다.

Specpure Nikel의 Oxidation

최재시,신수희,이규용,Choi, Jae-Shi,Sin, Soo-Hee,Lee, Kyu-Yong 대한화학회 1966 대한화학회지 Vol.10 No.4

순수한 nickel의 酸化에 대하여 大氣中에서와 各種 酸素壓力下 $500^{\circ}{\sim}800^{\circ}C$에서 石英製 微量天秤을 使用하여 그 速度를 測定하였다. Nickel의 速度常數는 Parabolick rate Law에 의하여 계산하였다. 活性化 에너지는 Arrhenius式에 의하여 구하였으며 ${\Delta}E^*=35.4{\pm}$1.5 Kcal/mole을 얻었다. Nickel酸化에서 酸化速度常數는 酸素壓力의 1/4.93乘에 比例함을 확인하였고 Nickel의 酸化機構는 Oxide Film에 용해되어 과잉으로 存在하는 酸素에 의해서 形成된 陽이온 Vacancy (空位)에 依存한다는 結論에 도달하였다. The measurement of Oxidation of nickel has been investigated using vacuum quartz microbalance in the temperature range of $500^{\circ}{\sim}800^{\circ}C$ at various oxygen pressure. The rate constants of nickel-oxidation were evaluated according to the parabolic rate law. From the Arrhenius equation, the activation energy in the range of experimental temperatures were found that $E_{act}$= 35.4 Kcal/mole. It was also found that the parabolic rate constants varied approximately as the one fifth power of the oxygen pressure for nickel-oxidation. The mechanism for the oxidation of this metal were seemed to be via cation vacancy produced by excess of oxygen dissolved in the oxide film.

A Study of the Semiconductivity of Polycrystalline Cuprous Oxide

최재시,여철현,Choi, Jae-Shi,Yo, Chul-Hyun Korean Chemical Society 1972 대한화학회지 Vol.16 No.2

The semiconductivity of polycrystalline $Cu_2O$ has been studied between $220^{\circ}C$ and $680^{\circ}C under partial pressures of oxygen from $4.06{\times}10^{-3}\;to\;10^{-5 }\;mmHg$. The plots of log conductivity vs 1/T at constant oxygen pressure were found to be linear, and the activation energies obtained from the slopes of these plots above the first transition point showed that the energies were greater under high oxygen pressure than under low pressure. The transition points between the stable range and the unstable range of $Cu_2O$ were found from the curves. The dependence of the semiconductivity on the $O_2$ pressure, in the above temperature range, is shown hysteresis.

Kinetics of the Oxidation of Carbon Monoxide on NiO at Low Temperature

최재시,김규홍,Choi, Jae-Shi,Kim, Keu-Hong Korean Chemical Society 1974 대한화학회지 Vol.18 No.2

반응온도 $40^{\circ}C∼95^{\circ}C$에서 일산화탄소를 여러가지 온도에서 처리한 산화니켈을 촉매로 하여 산화시켰다. 일산화탄소의 산화 속도는 낮은 온도에서 진공속에서 처리한 산화니켈상에서 제일 빠르다. 이때 반응속도는 일차 반응에 따르며 활성화 에너지는 이 반응온도 범위에서 4kcal정도이다. 공기중에서 $NiCO_3$를 분해하여 얻은 산화니켈촉매는 반응 온도가 $95^{\circ}C$이상에서도 활성이 없다. 그러나 이산화 니켈을 진공에서 처리했을 경우 이 반응온도 범위에서 활성이 있다. 이때 산화니켈의 비화학 양론적인 과량의 산소가 일산화탄소의 산화속도를 지배하는 것 같다. The catalytic reaction between carbon monoxide and oxygen was investigated in the presence of catalysts which were specially treated by applying an annealing method at different monoxide and oxygen and at reaction temperatures in the region of partial pressures of carbon $40^{\circ}C$ to $95^{\circ}C$. The oxidation rate is highest on NiO annealed at low temperature in vacuum. The data has been correlated with the first order kinetics, and the activation energies from the Arrhenius equation are found to be 4Kcal/mole in the region of the experimental temperatures. The excess oxygen in NiO obtained from the decomposition of $NiCO_3$does not cause activation at $95^{\circ}C$. But NiO catalysts annealed again in vacuum display activation even at $40^{\circ}C$. The quantity of the excess oxygen in NiO surfaces seems to be the controlling factor in determining the rates of oxidation of carbon monoxide.

Kinetics of the Oxidation of Carbon Monoxide on NiO at Low Temperature

최재시(Jae Shi Choi),김규홍(Keu Hong Kim) 대한화학회 1974 대한화학회지 Vol.18 No.2

산화망간-이산화티탄계의 결함구조 및 전기전도메카니즘

김규홍,최재시,Keu Hong Kim,Jae Shi Choi 대한화학회 1982 대한화학회지 Vol.26 No.3

0.40, 0.80 및 1.60 mol %의 산화망간을 함유한 이산화티탄의 전기전도도를 $10^{-8}\;to\;10^{-1}$ atm의 산소분압하에서 100 ~ 400$^{\circ}$C 및 1100 ~ 1300$^{\circ}$C의 온도에서 측정하였다. 일정한 산소분압하에서 측정된 전기전도도 값을 온도의 역수에 대하여 도시한 결과 저온 및 고온 영역에서 직선관계를 나타내었으며 활성화에너지는 각각 0.18 및 3.70eV이다. 전기전도도의 산소분압 의존성은 저온영역에서 -1/6이며 고온 영역에서 -1/4이다. 저온 영역과 고온영역에서의 결함구조가 각각(Vo-2e') 및 $Ti^3$임을 밝혔으며 전기전도 메카니즘과 가능한 전도띠 모델이 제안되었다. The electrical conductivity of n-type polycrystalline MnOx-Ti$O_2$ system containing 0.40, 0.80, and 1.60 mol % of manganese oxide has been measured from 100 to 400$^{\circ}$C and 1100 to 1300$^{\circ}$C under oxygen partial pressures of$10^{-8}\;to\;10^{-1}$ atm. Plots of log conductivity vs. reciprocals of absolute temperature at constant $Po_2$'s are found to be linear with an inflection, and the activation energies obtained from the slopes appear to be an enough average 0.18eV for the extrinsic and 3.70eV for the intrinsic. The log $\sigma$ vs. log $Po_2$ are found to be linear at $Po_2$'s of $10^{-8}\;to\;10^{-1}$atm. The conductivity dependences on $Po_2$at the two temperature regions are closely approximated by $\sigma{\propto}$Po_2$-1}6$ for the extrinsic and $${\sigma}{\propto}Po_2^{-1}4}$$ for the intrinsic, respectively. The predominant defects are believed to be Vo-2e' and $Ti^3$${\cdot}$interstitial at the extrinsic and intrinsic. From the interpretations of conductivity dependences on temperature and$Po_2$ , the conduction mechanisms and possible band models are proposed.

$ZnCe_{1+y}O_2$상에서 일산화탄소의 산화반응 메카니즘

김규홍,최재시,Kim Keu Hong,Jae Shi Choi 대한화학회 1984 대한화학회지 Vol.28 No.2

$ZnCe_{1+y}O_2$상에서 CO산화반응 속도가 $300{\sim}500^{\circ}C$영역에서 측정되었다. 산화반응 속도는 CO에 1차 O2에 0.5차를 나타내는 속도식에 따랐으며 격자점의 산소와 Zn 도프에 기인되어 생성된 Vo-2e' 결함이 CO 및 O2의 활성화 sites로 작용되었다. 전기전도도 데이타와 rate law로 부터 산화반응 메카니즘이 규명되었으며 율속과정이 제안되었다 The catalytic oxidation of CO has been investigated on $ZnCe_{1+y}O_2$ at temperatures from 300 to $500^{\circ}C$ under various P_{CO} and PO_2 conditions. The oxidation rates have been correlated with 1.5-order kinetics: first order with respect to CO and 0.5 order with respect to O2. CO appears to be absorbed essentially on the O lattice of $ZnCe_{1+y}O_2$ as a molecular species, while $O_2$ adsorbs on an O vacancy as an ionic species. The conductivity data show that CO adsorption contributes electron to the conduction band and the adsorption process of $O_2$ withdraws it from an O vacancy. The oxidation mechanism and the defect model of $ZnCe_{1+y}O_2$ are inferred at given temperature and $PO_2'$s from the agreement between the conductivities and kinetic data. It is suggested that CO absorption is the rate-controlling.