Institute of Chemistry, University of Miskolc, Miskolc-Egyetemváros, 3515 Miskolc, Hungary.
Institute of Mineralogy and Geology, University of Miskolc, Miskolc-Egyetemváros, 3515 Miskolc, Hungary.
Int J Mol Sci. 2022 Oct 30;23(21):13197. doi: 10.3390/ijms232113197.
2,4-diaminotoluene (TDA) is one of the most important polyurethane precursors produced in large quantities by the hydrogenation of 2,4-dinitrotoluene using catalysts. Any improvement during the catalysis reaction is therefore of significant importance. Separation of the catalysts by filtration is cumbersome and causes catalyst loss. To solve this problem, we have developed magnetizable, amine functionalized ferrite supported palladium catalysts. Cobalt ferrite (CoFeO-NH), nickel ferrite (NiFeO-NH), and cadmium ferrite (CdFeO-NH) magnetic catalyst supports were produced by a simple coprecipitation/sonochemical method. The nanospheres formed contain only magnetic (spinel) phases and show catalytic activity even without noble metals (palladium, platinum, rhodium, etc.) during the hydrogenation of 2,4-dinitrotoluene, 63% (/) conversion is also possible. By decorating the supports with palladium, almost 100% TDA selectivity and yield were ensured by using Pd/CoFeO-NH and Pd/NiFeO-NH catalysts. These catalysts possess highly favorable properties for industrial applications, such as easy separation from the reaction medium without loss by means of a magnetic field, enhanced reusability, and good dispersibility in aqueous medium. Contrary to non-functionalized supports, no significant leaching of precious metals could be detected even after four cycles.
2,4-二氨基甲苯(TDA)是最重要的聚氨酯前体之一,大量生产是通过使用催化剂将 2,4-二硝基甲苯加氢得到的。因此,任何催化反应的改进都具有重要意义。过滤分离催化剂繁琐且会导致催化剂损失。为了解决这个问题,我们开发了可磁化的、胺功能化的铁氧体负载钯催化剂。通过简单的共沉淀/超声化学方法制备了磁性钴铁氧体(CoFeO-NH)、镍铁氧体(NiFeO-NH)和镉铁氧体(CdFeO-NH)磁性催化剂载体。形成的纳米球仅包含磁性(尖晶石)相,即使在没有贵金属(钯、铂、铑等)的情况下,在 2,4-二硝基甲苯的加氢反应中也具有催化活性,转化率可达 63%(/)。通过在载体上修饰钯,使用 Pd/CoFeO-NH 和 Pd/NiFeO-NH 催化剂可以确保几乎 100%的 TDA 选择性和收率。这些催化剂具有工业应用的有利特性,例如可以通过磁场轻松分离而不会损失,可重复使用性增强,以及在水介质中的良好分散性。与非功能化载体相反,即使经过四个循环也检测不到贵金属的明显浸出。