The Use of Metal Nanoparticle-Embedded Poly(ethyleneimine) Composite Microgel in the Reduction of Nitrophenols

Abstract

Metal nanoparticles such as Ni, Cu, and Co were prepared within polyethyleneimine (PEI) microgels and were used in the reduction of 4-nitrophenol (4-NP) and 2-nitrophenol (2-NP) to 4-aminophenol (4-AP) and 2-aminophenol (2-AP). The metal nanoparticle content of the prepared PEI-M composite catalyst system (M = Co, Ni, and Cu) was increased by multiple loading and reduction cycles into PEI microgels to provide faster and better reduction of 4-NP and 2-NP. The TOF value increased to 1.48 from 0.353 (mol 4-NP (mol catalyst min)−1) for 4-NP reduction catalyzed by PEI-Ni after three cycles of metal loading and reduction. The effect of temperature on 4-NP and 2-NP reductions catalyzed by PEI-M illustrated that higher temperature resulted in very fast reductions, e.g., at 70 °C 4-NP and 2-NP reduction by PEI-Ni resulted in very fast reduction times of 1.2 and 0.67 min to 4-AP and 2-AP, respectively. The activation parameters, such as energy, entropy, and enthalpy, were also calculated and mild activation energies of 38.8 and 46.0 kJ mol−1 for 4-NP and 2-NP catalyzed by PEI-Ni were found, respectively, in comparison to similar studies in the literature. Moreover, it was demonstrated that PEI-Ni microgels are reusable five times consecutively, with almost 100 % conversion and 100 % of their catalytic activity.