Catalysis Division, CSIR-National Chemical Laboratory, Pune, 411008, India.
Academy of Scientific and Innovative Research, CSIR, Ghaziabad, 201002, India.
Chem Asian J. 2023 Jun 1;18(11):e202300119. doi: 10.1002/asia.202300119. Epub 2023 May 2.
Hydrogenation of phenol to cyclohexanone/cyclohexanol is an important reaction in production of nylon-6, nylon-66 and in petroleum industry. Liquid phase phenol hydrogenation over Pd-CuO/CeO was carried out under mild conditions. Palladium impregnated over CuO/CeO synthesized by co-precipitation method showed excellent catalytic activity for phenol hydrogenation (99% conversion with 80% cyclohexanol yield) at 90 °C and 10 bar H pressure in water. Commercial 10%Pd/C showed only 8% phenol conversion under identical conditions. The detailed characterization revealed significant improvement in surface area of ceria after addition of CuO and decrease in crystallite size with creation of defects in CeO lattice. XPS analysis showed Pd loading on CuO/CeO to cause hydrogen spillover on the surface leading to increase in the oxygen vacancies. The interaction of phenol with catalyst surface studied by detailed FTIR analysis, revealed activation of phenol on oxygen vacancy of ceria as phenoxide ion with perpendicular orientation of aromatic ring on catalyst surface.
苯酚加氢生成环己酮/环己醇是尼龙-6、尼龙-66 生产和石油工业中的重要反应。在温和条件下,采用共沉淀法合成的负载钯的氧化铜/氧化铈(Pd-CuO/CeO)进行了液相苯酚加氢反应。在 90°C 和 10 bar H 压力下,负载钯的氧化铜/氧化铈在水中表现出优异的苯酚加氢活性(转化率为 99%,环己醇收率为 80%)。而在相同条件下,商业的 10%Pd/C 仅显示 8%的苯酚转化率。详细的表征表明,添加氧化铜后氧化铈的表面积显著提高,晶粒度减小,CeO 晶格中产生缺陷。XPS 分析表明,Pd 在 CuO/CeO 上的负载导致表面上的氢溢出,从而增加氧空位。通过详细的傅里叶变换红外(FTIR)分析研究了苯酚与催化剂表面的相互作用,结果表明,苯酚在氧化铈的氧空位上被活化,形成苯酚氧离子,其芳环在催化剂表面呈垂直取向。