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Kinetic investigation for the catalytic reduction of nitrophenol using ionic liquid stabilized gold nanoparticles

Thawarkar, Sachin R., Thombare, Balu, Munde, Bhaskar S., Khupse, Nageshwar D.
RSC advances 2018 v.8 no.67 pp. 38384-38390
activation energy, ambient temperature, borohydrides, bromides, catalysts, catalytic activity, enthalpy, entropy, hydrogen bonding, ionic liquids, nanogold, p-nitrophenol, reaction mechanisms, reducing agents
We demonstrate the synthesis of gold nanoparticles (AuNP) stabilized by 1-butyl-3-hexadecyl imidazolium bromide (Au@[C₄C₁₆Im]Br) and their use as a catalyst for the reduction of nitrophenol. The AuNPs show excellent stability in presence of [C₄C₁₆Im]Br ionic liquids for the reduction of 4-nitrophenol and 2-nitrophenol using NaBH₄ as a reducing agent. The detailed kinetics for the reduction of 4-nitrophenol and 2-nitrophenol were investigated and the catalytic activity of Au@[C₄C₁₆Im]Br was evaluated. The pseudo first-order rate constant (kₐₚₚ) values for 4-nitrophenol was observed to be greater than that of 2-nitrophenol and explained on the basis of hydrogen bonding present in 2-nitrophenol. Au@[C₄C₁₆Im]Br showed good separability and reusability and hence, it can be used for the complete reduction of nitrophenols in multiple cycles. The Langmuir–Hinshelwood reaction mechanism is elucidated for reduction of 4-nitrophenol by Au@[C₄C₁₆Im]Br nanocatalyst on the basis of the kₐₚₚ values. The thermodynamic activation parameters such as activation energy, enthalpy of activation and entropy of activation were determined and explained using the temperature dependent kinetics for the reduction of nitrophenol using Au@[C₄C₁₆Im]Br. The above results reveal that the Au@[C₄C₁₆Im]Br nanocatalyst demonstrates excellent catalytic performance for the reduction of nitrophenol by NaBH₄ at room temperature.