고분자와의 블랜딩에 의한 헤테로폴리산의 촉매 특성 제어

송인규; 이종국; 이화영

Journal of the Korean Industrial and Engineering Chemistry, Vol.5, No.5, 819-824, October, 1994

Export Citation

고분자와의 블랜딩에 의한 헤테로폴리산의 촉매 특성 제어

Control of Catalytic Properties of Heteropoly Acid by Blending it with a Polymer

송인규, 이종국, 이화영

초록

Dimethylformamide를 공통용매로 하여 H₃PMo₁₂O₄₀와 polysulfone를 동시에 녹여 분리막 형태의 H₃PMo₁₂O₄₀-polysulfone 필름을 제조하였다. SEM 및 EDX 분석 결과 필름 촉매상에서 H₃PMo₁₂O₄₀는 매우 고른 상태로 잘 분산되어 있음을 확인되었다. ESCA 분석결과에 의하면 Mo의 산화상태에는 변화가 없었다. 에탄을 전환반응에서 H₃PMo₁₂O₄₀-polysulfone 필름 촉매는 H₃PMo₁₂O₄₀보다 낮은 산반응특성과 높은 산화반응 특성을 보였으며, 산화반응의 활성은 약 10배 정도 크게 나타났다. 산 특성의 감소는 H₃PMo₁₂O₄₀의 산점과 강하게 결합된 dimethylformamide에 기인하여, 산화특성의 증가는 촉매의 고른 분산에 기인하였다. 흡착실험 결과 블랜딩 후 H₃PMo₁₂O₄₀의 표면 특성은 크게 증가하였으나 내부 특성은 큰 변화가 없는 것으로 나타났다. 따라서 혜테로폴리산을 고분자와 블랜딩시킬 경우 혜테로폴리산이 지니는 산 및 산화환원 특성의 제어는 물론 촉매의 표면 및 내부 특성 제어가 가능할 것으로 여겨진다.

A membrane-like H₃PMo₁₂O₄₀-polysulfone film was prepared by blending H₃PMo₁₂O₄₀ with polysulfone using dimethylformamide as a common solvent. SEM and EDX analysis showed that H₃PMo₁₂O₄₀ was uniformly and finely distributed in the film catalyst. The ESCA measurement also revealed that the oxidation state of Mo was not changed. The H₃PMo₁₂O₄₀-polysulfone catalyst showed lower activity for acid-catalyzed reaction and higher activity for oxidation reaction than H₃PMo₁₂O₄₀ in ethanol conversion reaction. The oxidation activity of the film catalyst was about 10 times higher than H₃PMo₁₂O₄₀. The decrease of acidic activity was due to DMF strongly adsorbed in acid sites of H₃PMo₁₂O₄₀, whereas the increase of oxidation activity was mainly due to uniform distribution of H₃PMo₁₂O₄₀. Adsorption results showed that the surface character of H₃PMo₁₂O₄₀ 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.

[References]

Komata T, Misono M, Chem. Lett., 1177 (1983)
Yoshida S, Niiyama H, Echigoya E, J. Phys. Chem., 86, 3150 (1982)
Mizuno N, Watanabe T, Misono M, J. Phys. Chem., 89, 80 (1985)
Seo G, Lim JW, Kim JT, J. Catal., 114, 469 (1988)
Tsigdinos GA, Topics Curr. Chem., 76, 1 (1978)
Misono M, Mater. Chem. Phys., 17, 103 (1987)
Misono M, Catal. Rev.-Sci. Eng., 29, 269 (1987)
Misono M, Sakata K, Yoneda Y, Lee WY, Proc. 7th Int. Cong. Catal., Tokyo (Kodansha-Elsevier, Amsterdam), 1047 (1981)
Okuhara T, Hayashimoto T, Misono M, Yoneda Y, Chem. Lett., 573 (1983)
Saito Y, Cook PN, Niiyama H, Echigoya E, J. Catal., 95, 49 (1985)
Song IK, Lee WY, Kim JJ, Catal. Lett., 9, 339 (1991)
Song IK, Shin SK, Lee WY, J. Catal., 144, 348 (1993)
Tsigdinos GA, Ind. Eng. Chem. Prod. Res. Dev., 13, 267 (1974)
Okuhara T, Kaisai A, Hayakawa N, Misono M, Yoneda Y, Chem. Lett., 391 (1981)

[Referenced By]

[1] Komata T, Misono M, Chem. Lett., 1177 (1983)

[2] Yoshida S, Niiyama H, Echigoya E, J. Phys. Chem., 86, 3150 (1982)

[3] Mizuno N, Watanabe T, Misono M, J. Phys. Chem., 89, 80 (1985)

[4] Seo G, Lim JW, Kim JT, J. Catal., 114, 469 (1988)

[5] Tsigdinos GA, Topics Curr. Chem., 76, 1 (1978)

[6] Misono M, Mater. Chem. Phys., 17, 103 (1987)

[7] Misono M, Catal. Rev.-Sci. Eng., 29, 269 (1987)

[8] Misono M, Sakata K, Yoneda Y, Lee WY, Proc. 7th Int. Cong. Catal., Tokyo (Kodansha-Elsevier, Amsterdam), 1047 (1981)

[9] Okuhara T, Hayashimoto T, Misono M, Yoneda Y, Chem. Lett., 573 (1983)

[10] Saito Y, Cook PN, Niiyama H, Echigoya E, J. Catal., 95, 49 (1985)

[11] Song IK, Lee WY, Kim JJ, Catal. Lett., 9, 339 (1991)

[12] Song IK, Shin SK, Lee WY, J. Catal., 144, 348 (1993)

[13] Tsigdinos GA, Ind. Eng. Chem. Prod. Res. Dev., 13, 267 (1974)

[14] Okuhara T, Kaisai A, Hayakawa N, Misono M, Yoneda Y, Chem. Lett., 391 (1981)