Preparation of CuO-CeO₂ mixed oxide catalyst by sol-gel method and its application to preferential oxidation of CO

졸-겔법에 의한 CuO-CeO₂ 복합 산화물 촉매의 제조 및 CO의 선택적 산화반응에 응용

For the preferential oxidation of CO contained in the fuel of polymer electrolyte membrane fuel cell (PEMFC), CuO-$CeO_2$ mixed oxide catalysts were prepared by the sol-gel and co-precipitation methods to replace noble metal catalysts. In the catalyst preparation by the sol-gel method, Cu/Ce ratio and hydrolysis ratio were changed. The catalytic activity of the prepared catalysts was compared with the catalytic activity of the noble metal catalyst($Pt/{\gamma}-Al_2O_3$). Among the catalysts prepared with different Cu/Ce ratios, the catalyst whose Cu/Ce ratio was 4:16 showed the highest CO conversion (90%) and selectivity (60%) at $150^{\circ}C$. As the hydrolysis ratio was increased in the catalyst preparation, surface area increased, and catalytic activity also increased. The highest CO conversions with the CuO-$CeO_2$ mixed oxide catalyst prepared by the co-precipitation method and the noble metal catalyst (1wt% $Pt/{\gamma}-Al_2O_3$) were 82 and 81% at $150^{\circ}C$, respectively, whereas the highest CO conversion with the CuO-$CeO_2$ mixed oxide catalyst prepared by the sol-gel method was 90% at the same temperature. This indicates that the catalyst prepared by the sol-gel method shows higher catalytic activity than the catalysts prepared by the co-precipitation method and the noble metal catalyst. From the CO-TPD experiment, it was found that the catalyst having CO desorption peak at a lower temperature ($140^{\circ}C$) revealed higher catalytic activity.

고분자 전해질 연료전지의 연료에 포함된 일산화탄소의 선택적 산화를 위하여, 귀금속 촉매를 대체하기 위한 CuO-$CeO_2$ 복합 산화물 촉매를 졸-겔법과 공침법으로 제조하였다. 졸-겔법으로 촉매 제조 시 Cu/Ce의 비와 가수분해 비를 변화시켰다. 제조한 촉매의 활성은 귀금속 촉매($Pt/{\gamma}-Al_2O_3$)와 비교하였다. Cu/Ce의 비를 변화시키면서 제조한 촉매 중 Cu/Ce의 비가 4:16인 촉매가 가장 높은 CO 전환율(90%)과 선택도(60%)를 나타내었다. 촉매의 제조에서 가수분해 비가 증가할수록 촉매 표면적이 증가하였고, 아울러 촉매 활성 또한 증가하였다. 공침법으로 제조한 촉매와 1wt% $Pt/{\gamma}-Al_2O_3$ 촉매의 가장 높은 CO 전환율은 각각 82% 및 81%인 반면, 졸-겔법으로 제조한 촉매의 경우는 90%가 얻어졌다. 이는 졸-겔법으로 제조한 촉매가 공침법으로 제조한 촉매나 귀금속 촉매보다 더 높은 촉매활성을 보임을 의미한다. CO-TPD 실험을 통하여, 낮은 온도($140^{\circ}C$)에서 CO를 탈착하는 촉매가 본 반응에서 더 높은 촉매활성을 보임을 알 수 있었다.