More Ganesh Sunil, Kushwaha Nidhi, Bal Rajaram, Srivastava Rajendra
Catalysis Research Laboratory, Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar, Punjab 140001, India.
Nanocatalysis Area Conversion and Catalysis Division, CSIR-Indian Institute of Petroleum, Dehradun 248005, India.
J Colloid Interface Sci. 2022 Aug;619:14-27. doi: 10.1016/j.jcis.2022.03.093. Epub 2022 Mar 24.
The use of a single catalyst to perform thermal and photochemical N-alkylation of amine is challenging work. Herein, Pd decorated MOF-derived CeO was prepared for the cascade one-pot synthesis of secondary amine by thermal and photocatalytic routes. Among the designed catalysts, Pd(0.5%)/CeO-300 exhibited the best activity for thermal and photocatalytic one-pot secondary amine synthesis involving benzyl alcohol and aniline. The physicochemical characteristics of Pd(0.5%)/CeO-300 suited for the oxidation of benzyl alcohol followed by condensation with aniline to form an imine. Further, reduction of imine over Pd NPs decorated on CeO-300 took place to form secondary amine. An excellent conversion of benzyl alcohol and secondary amine selectivity was observed thermally at 100 °C in 26 h. The Pd(0.5%)/CeO-300 exhibited excellent activity in white LED. Interestingly, more activity was achieved in sunlight. The Pd(0.5%)/CeO-300 demonstrated excellent stability under thermal and photocatalytic conditions and was recycled 5 times without losing any significant activity. The surface area, acidity, and elemental compositions were characterized by various physicochemical techniques. The light absorption property, bandgap, charge carrier separation, and photocurrent measurements were carried out by photoelectrochemical and optoelectronic analysis. The reaction mechanism and structural activity relationship correlated with control experiments, catalytic activity data, physicochemical, and optoelectronic characterization. One catalyst affording efficient activity in conventional thermal and photocatalytic conditions, especially sunlight, would be exciting to researchers and industrial practitioners.
使用单一催化剂进行胺的热化学和光化学N-烷基化是一项具有挑战性的工作。在此，制备了钯修饰的MOF衍生CeO，用于通过热催化和光催化途径级联一锅法合成仲胺。在所设计的催化剂中，Pd(0.5%)/CeO-300在涉及苯甲醇和苯胺的热催化和光催化一锅法仲胺合成中表现出最佳活性。Pd(0.5%)/CeO-300的物理化学特性适合苯甲醇氧化，随后与苯胺缩合形成亚胺。此外，在CeO-300上修饰的钯纳米颗粒上亚胺发生还原反应形成仲胺。在100℃下热反应26小时，观察到苯甲醇的转化率和仲胺选择性都非常好。Pd(0.5%)/CeO-300在白色发光二极管照射下表现出优异的活性。有趣的是，在阳光下活性更高。Pd(0.5%)/CeO-300在热催化和光催化条件下表现出优异的稳定性，可循环使用5次而不会损失任何显著活性。通过各种物理化学技术对其表面积、酸度和元素组成进行了表征。通过光电化学和光电子分析进行了光吸收性能、带隙、电荷载流子分离和光电流测量。通过对照实验、催化活性数据以及物理化学和光电子表征，关联了反应机理和结构活性关系。一种催化剂能在传统热催化和光催化条件下，尤其是在阳光下提供高效活性，这将令研究人员和工业从业者兴奋不已。
