Electrochemical Activation of Carbon–Halogen Bonds: Electrocatalysis at Palladium–Copper Nanoparticles

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Abstract
Palladised Cu nanoparticles (Pd–Cu NPs) supported on glassy carbon are synthesised through electrolytic deposition of Cu followed by galvanic displacement of Cu with Pd. The electrodes are characterised by using X‐ray photoelectron spectroscopy and energy‐dispersive X‐ray spectroscopy, which show that although the composition of the NPs depends on the deposition time of Pd, Cu is always the main component, whereas Pd is preferentially limited to the uppermost layer of the nanoparticle surface. The reductive cleavage of a series of organic chlorides is investigated at Cu, Pd, Cu NPs and Pd–Cu NPs both in N,N‐dimethylformamide (DMF) and DMF/H2O (3:1 v/v). A strong dependence of the electrocatalytic properties of the electrodes on the mechanism of dissociative electron transfer (DET) is observed in pure DMF; moderate electrocatalysis is found for the reduction of all alkyl halides undergoing concerted DET, whereas no appreciable catalysis is observed for the reduction of aromatic chlorides, which undergo stepwise DET. However, addition of H2O remarkably enhances the catalytic activity of the metals. In DMF/H2O, all investigated compounds are catalytically reduced at Cu, Cu NPs and Pd–Cu NPs with good‐to‐excellent catalytic activities.

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