Redox Behavior of Chromium Oxide-Zirconia Catalyst

산화크롬-질코니아 촉매의 산화-환원거동

Chromium oxide/zirconia catalysts were prepared by dry impregnation of $Zr(OH)_4$ powder with aqueous solution of $(NH_4)_2CrO_4$ followed by calcining in air. The redox behavior of prepared catalysts were investigated by reacting cumene as test material over catalysts. As a result it was found that $Cr^{6+}$ species(as chromate) on the surface of catalyst was responsible for the formation of strong acid site and the catalytic activity for the dealkylation of cumene. However, much of the $Cr^{6+}$ species was reduced to $Cr^{3+}$ species by $H_2$ formed during the catalytic reaction of cumene and the reduced $Cr^{3+}$ species was an active site for dehydrogenation of cumene to form ${\alpha}$-methyl styrene. The reduced $Cr^{3+}$ species was also reoxidized to a $Cr^{6+}$ species after treatment with $O_2$ and consequently the deoxidized catalyst exhibited catalytic activity for the dealkylation reaction of cumene.

분말의 $Zr(OH)_4$를 $(NH_4)_2CrO_4$수용액에 함침시킨 후 공기중에 소성하여 질코니아에 담지된 산화크롬 촉매를 제조하였다. 제조된 $CrO_x/ZrO_2$ 촉매상에 cumene을 반응시켜 산화-환원 거동을 연구한 결과 크롬의 산화상태가 +6인 chromate형태로 질코니아 표면에 존재할 때는 강한 산점이 생성되어 cumene의 탈알킬화 반응에 촉매활성을 나타내었다. 그러나 많은 양의 $Cr^{6+}$종은 반응중에 탈수소로 생성된 $H_2$에 의하여 환원되어 $Cr^{3+}$종으로 변환되었으며 $Cr^{3+}$종은 cumene을 탈수소화시켜 ${\alpha}$-methyl styrene을 생성하는 반응에 활성점으로 작용하였다. 환원된 $Cr^{3+}$종은 $O_2$로 처리하면 다시 $Cr^{6+}$종으로 되고 따라서 산화된 촉매는 cumene의 탈알킬화 반응에 활성을 나타내었다.