The interface [BuMeIm][Tf2N]/electrode, where [BuMeIm][Tf2N] stands for the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, was characterized by electrochemical impedance spectroscopy at different temperatures and for different electrode materials: platinum (Pt, metallic), glassy carbon (GC, high conductivity), carbon nitride (a-CNx, mean conductivity), and boron-doped diamond (BDD, semiconducting with a quasimetallic character). For Pt, GC, and a-CNx, the behavior of the interface could be described by the same equivalent electrical circuit. In the case of BDD, a parallel combination of Rsc and Csc was introduced into the circuit to take into account the potential drop due to the development of a space charge region within the material. The Mott-Schottky plots have confirmed the polycrystalline semiconductor character of the BDD material, and the boron concentration estimated is fully consistent with the B amount introduced for the synthesis. The variations of the double-layer capacitance as a function of potential were found to be camel shaped for all electrode materials at the highest studied temperature. This is consistent with the prediction of Kornyshev's theory as low values of the packing parameter γ were estimated by simulation (lower than 0.33). An increase of the double-layer capacitance is found with the temperature similarly to most of the results obtained for molten salts.
Pd@PPy hybrid catalytic materials are synthesized in water via redox polymerization reaction of pyrrole with [Pd(NH3)4Cl2]. The nanocomposites formed are composed of highly dispersed palladium particles which are either zerovalent or easily reducible, and are embedded in spherical polypyrrole globules. A unique combination of high palladium dispersion (NP size: 2.4 nm) and elevated palladium content (35 wt%) is obtained. The components of these novel nanocomposites are characterized by means of FTIR, XPS, XRD, SEM, and TEM microscopy techniques. The process of formation in solution is also monitored using UV‐visible and DLS techniques. The application of these novel hybrid nanomaterials in the palladium‐catalyzed direct arylation of heteroaromatics is reported. High efficiency in C–C bond formation is obtained using these materials. Furans and thiophenes are arylated by using bromoarenes. Pd@PPy nanocomposites can efficiently couple n‐butyl furan and n‐butyl thiophene with bromobenzene and bromoquinoline, as well as with activated or deactivated electron‐poor and electron‐rich functionalized bromoarenes. Thus, a clean reaction process is developed that combines the absence of organic ligand in catalytic reactions and easy recovery of Pd@PPy nanocomposite via simple filtration. Preliminary kinetic and post‐catalysis studies suggest a molecular or colloidal soluble active species. These very active species are efficiently delivered by the nanocomposites and susceptible to a surprisingly uniform back redeposition within the polypyrrole support.
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