Bhattacharjee Samiran, Kim Jun, Ahn Wha-Seung
J Nanosci Nanotechnol. 2014 Mar;14(3):2546-52. doi: 10.1166/jnn.2014.8535.
Pd nanoparticles supported on the chromium terephthalate metal organic framework MIL-101 (Pd/MIL-101) in different loadings (0.9 and 4.5 wt%) have been successfully prepared through a simple Pd-acetate adsorption and reduction in acetone, and tested as catalyst for selected liquid phase oxidation and hydrogenation reactions. The materials were characterized by XRD, N2 adsorption--desorption isotherm, TEM, SEM-EDX and ICP analysis. The parent MIL-101 structure was found well preserved after formation of Pd nanoparticles and after catalytic reaction runs. The present catalyst afforded good activity and selectivity for the oxidation of benzyl alcohol to benzaldehyde with 85% conversion and 97% selectivity using air (1 atm) at 85 degrees C after 14 h. The catalyst also showed good activity in the hydrogenation of the C=C bond in alkenes to corresponding alkanes and also benzaldehyde to benzyl alcohol at room temperature using H2 (1 atm). Rigorous test results confirmed that Pd-nanoparticles supported on MIL-101 are responsible for the catalytic reactions occurred. Pd/MIL-101 was reusable several times without losing the structural integrity and initial activity, and demonstrated significantly higher catalytic activities than those by a commercial Pd catalyst supported on activated carbon.
通过在丙酮中简单地吸附醋酸钯并进行还原，成功制备了负载在对苯二甲酸铬金属有机骨架MIL-101上的不同负载量（0.9和4.5 wt%）的钯纳米颗粒（Pd/MIL-101），并将其作为选定的液相氧化和氢化反应的催化剂进行了测试。通过XRD、N2吸附-脱附等温线、TEM、SEM-EDX和ICP分析对材料进行了表征。发现在形成钯纳米颗粒后以及催化反应运行后，母体MIL-101结构保存完好。在85℃下使用空气（1 atm）反应14小时后，本催化剂对苯甲醇氧化为苯甲醛具有良好的活性和选择性，转化率为85%，选择性为97%。该催化剂在室温下使用H2（1 atm）将烯烃中的C=C键氢化为相应的烷烃以及将苯甲醛氢化为苯甲醇的反应中也表现出良好的活性。严格的测试结果证实，负载在MIL-101上的钯纳米颗粒是发生催化反应的原因。Pd/MIL-101可以重复使用多次而不会失去结构完整性和初始活性，并且显示出比负载在活性炭上的商业钯催化剂显著更高的催化活性。
