Bio-assisted synthesized Pd nanoparticles supported on ionic liquid decorated magnetic halloysite: an efficient catalyst for degradation of dyes

Using natural materials, i.e. halloysite nanoclay that is a biocompatible naturally occurring clay and Heracleum persicum extract that can serve as a green reducing agent, a novel magnetic catalyst, Fe3O4/Hal-Mel-TEA(IL)-Pd, has been designed and fabricated. To prepare the catalyst, halloysite was first magnetized (magnetic particles with mean diameter of 13.06 +/- 3.1nm) and then surface functionalized with melamine, 1,4 dibromobutane and triethanolamine to provide ionic liquid on the halloysite surface (5wt%). The latter was then used as a support to immobilize Pd nanoparticles that were reduced by Heracleum persicum extract. The characterization of the catalyst established that the loading of Pd in Fe3O4/Hal-Mel-TEA(IL)-Pd was very low (0.93wt%) and its specific surface area was 63 m(2)g(-1). Moreover, the catalyst showed magnetic property (Ms=19.75emug(-1)) and could be magnetically separated from the reaction. The catalytic performance of the magnetic catalyst for reductive degradation of methyl orange and rhodamine B in the presence of NaBH4 in aqueous media was investigated. The activation energy, enthalpy, and entropy for the reduction of methyl orange were estimated as 42.02kJmol(-1), 39.40kJmol(-1), and -139.06Jmol(-1) K-1, respectively. These values for rhodamine B were calculated as 39.97kJmol(-1), 34.33kJmol(-1), and -155.18 Jmol(-1)K(-1), respectively. Notably, Fe3O4/Hal-Mel-TEA(IL)-Pd could be reused for eight reaction runs with negligible loss of the catalytic activity (similar to 3%) and Pd leaching (0.01wt% of the initial loading).