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Kinetic Profile and Catalytic Activity of Transition Metal‐Based Ionic Liquids for Reduction of Nitroarenes via In Situ Formation of Nanoparticles
Author(s) -
Thawarkar Sachin R.,
Khupse Nageshwar D.,
Kumar Anil
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201701601
Subject(s) - ionic liquid , catalysis , chemistry , x ray photoelectron spectroscopy , reaction rate constant , metal , nanoparticle , transition metal , dynamic light scattering , inorganic chemistry , kinetics , materials science , chemical engineering , organic chemistry , nanotechnology , physics , quantum mechanics , engineering
The experimentally determined apparent rate constant ( k app ) shows that the [BmIm] 2 [PdCl 4 ] and [BmIm] 2 [NiCl 4 ] act as effective catalysts for the reduction of nitroarenes to aminoarenes in the presence of NaBH 4 . The TEM, XPS, XRD and dynamic light scattering studies show that there is in situ formation of Pd and Ni metal Nanoparticles (NPs) from the reduction of [BmIm] 2 [PdCl 4 ] and [BmIm] 2 [NiCl 4 ], respectively which are responsible for the enhancement in the catalytic activity. Thus, in the presence of the ionic liquid stabilized metal NPs show higher catalytic activity in comparison to the NPs stabilized with other capping agents as reported. The order of k app as 1) PNP > 2‐BrPNP > 2‐APNP and 2) PNP > ONP > 2‐NR for reduction of nitroarenes using [BmIm] 2 [PdCl 4 ] and [BmIm] 2 [NiCl 4 ] and its correlation explained on the basis of electronic structure and hydrogen bonding ability of nitroarenes. The thermodynamic parameters such as E a , ▵ H # , ▵ S # and ▵ G # are in agreement with the surface catalyzed reduction reaction of PNP in the presence of NPs as catalyst. The k app values illustrated the reduction reaction follow the Langmuir‐Hinshelwood (L‐H) mechanism.