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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 30, Number 1
JKCSEZ 30(1)
February 20, 1986 

Studies on the Electrochemical Properties of TiO2-x Thin Films

TiO2-x 박막의 전기화학적 성질에 관한 연구
Q Won Choi, Chu Hyun Choe, Ki Hyung Chjo, Yong Kook Choi

최규원, 최주현, 조기형, 최용국
공기산화와 수증기 산화법에 의하여 TiO2-x박막을 만들었고, 알곤 기체속에서 TiO2단결정을 환원하였다. TiO2x박막의 전극 특성은 환원된 단결정 rutile의 특성과 거의 같았다. 산소가 용해된 전해질용액에서 측정된 TiO2-x전극들의 전류-전압 곡선으로 부터 음극전류의 peak는 -0.8V ~ -1.0V에서 나타났으며, 영볼트 근처의 TiO2-x전극들의 음극전류는 공기로 포화된 용액에서 보다 질소로 포화된 용액에서 더 크게 나타났다. 시간에 따르는 전류 (i)의 변화는 i0e-kt식에 의존하였고 이때의 속도상수(k)는 k0[H+]n exp(Aη+Ea/RT)로 나타낼 수 있었다. 여기서 활성화에너지 Ea는 0.035∼0.145V의 과전압에서는 4.6∼4.8kcal/mole, 0.2∼0.5V의 과전압에서는 1.6kcal/mole이고, 위식중의 n과 A는 0.035∼0.145V에서 0.1과, 5.4∼5.6/V, 0.2∼0.5V에서는 0.04와 1.3/V이었다. 산소의 환원반응은 전체적으로 비가역 반응임을 알았다.

A titanium oxide thin films were prepared by air oxidation and vapour oxidation and a TiO2 single crystal was reduced by heating in an argon atmosphere. All the electrode characteristics of the TiO2-x, thin films are not different from those of slightly reduced single crystal rutile. In cyclic voltammogram of oxygen containing electrolyte solution at TiO2-x electrodes, cathodic peaks were observed at between -0.8V and -1.0V vs. SCE. The cathodic current near 0V vs. SCE in saturated solution with nitrogen was observed to be greater than in saturated solution with air. The chronoamperogram was represented by the equation of i = i0e-kt, when the rate constant k was represented by the equation of k =k0[H+]n exp(Aη+Ea/RT). The values of activation energy Ea were found to be 4.6∼4.8kcal/mole in overpotential range of 0.035∼0.145 V and 1.6kcal/mole in overpotential range of 0.2∼0.5V. The values of n and A were found to be 0. 1 and 5.4∼5.6/V in range of 0.035∼0.145V, and in range of 0.2∼0.5V, to be 0.04 and 1.3/V, respectively. This can be interpreted as an totally irreversible reduction of oxygen.

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