Abstract
A membrane-like $H_3PMo_{12}O_{40}$-polysulfone film was prepared by blending $H_3PMo_{12}O_{40}$ with polysulfone using dimethylformamide as a common solvent. SEM and EDX analysis showed that $H_3PMo_{12}O_{40}$ was uniformly and finely distributed in the film catalyst. The ESCA measurement also revealed that the oxidation state of Mo was not changed. The $H_3PMo_{12}O_{40}$-polysulfone catalyst showed lower activity for acid-catalyzed reaction and higher activity for oxidation reaction than $H_3PMo_{12}O_{40}$ in ethanol conversion reaction. The oxidation activity of the film catalyst was about 10 times higher than $H_3PMo_{12}O_{40}$. The decrease of acidic activity was due to DMF strongly adsorbed in acid sites of $H_3PMo_{12}O_{40}$, whereas the increase of oxidation activity was mainly due to uniform distribution of $H_3PMo_{12}O_{40}$. Adsorption results showed that the surface character of $H_3PMo_{12}O_{40}$ was drastically increased, while the bulk property of that was almost same after blending. It is suggested that the control of surface/bulk property as well as acid/redox property of heteropoly acid would be possible by blending it with a polymer.
Dimethylformamide를 공통용매로 하여 $H_3PMo_{12}O_{40}$와 polysulfone를 동시에 녹여 분리막 형태의 $H_3PMo_{12}O_{40}$-polysulfone 필름을 제조하였다. SEM 및 EDX 분석 결과 필름 촉매상에서 $H_3PMo_{12}O_{40}$는 매우 고른 상태로 잘 분산되어 있음을 확인되었다. ESCA 분석결과에 의하면 Mo의 산화상태에는 변화가 없었다. 에탄을 전환반응에서 $H_3PMo_{12}O_{40}$-polysulfone 필름 촉매는 $H_3PMo_{12}O_{40}$보다 낮은 산반응특성과 높은 산화반응 특성을 보였으며, 산화반응의 활성은 약 10배 정도 크게 나타났다. 산 특성의 감소는 $H_3PMo_{12}O_{40}$의 산점과 강하게 결합된 dimethylformamide에 기인하여, 산화특성의 증가는 촉매의 고른 분산에 기인하였다. 흡착실험 결과 블랜딩 후 $H_3PMo_{12}O_{40}$의 표면 특성은 크게 증가하였으나 내부 특성은 큰 변화가 없는 것으로 나타났다. 따라서 헤테로폴리산을 고분자와 블랜딩시킬 경우 헤테로폴리산이 지니는 산 및 산화환원 특성의 제어는 물론 촉매의 표면 및 내부 특성 제어가 가능할 것으로 여겨진다.
(Dept. of Chem. Eng., Seoul Nat'l Univ.)