Cathodic Corrosion of Cu Substrates as a Route to Nanostructured Cu/M (M=Ag, Au, Pd) Surfaces

Abstract

The electrochemical formation of nanostructured materials is generally achieved by reduction of a metal salt onto a substrate that does not influence the composition of the deposit. In this work, we report that Ag, Au and Pd electrodeposited onto Cu under conditions where galvanic replacement is not viable and hydrogen gas is evolved results in the formation of nanostructured surfaces that unexpectedly incorporate a high concentration of Cu in the final material. Under cathodic polarisation conditions, the electrodissolution/corrosion of Cu occurs, which provides a source of ionic copper that is reduced at the surface–electrolyte interface. The nanostructured Cu/M (M=Ag, Au and Pd) surfaces are investigated for their catalytic activity for the reduction of 4‐nitrophenol by NaBH4, where Cu/Ag was found to be extremely active. This work indicates that a substrate electrode can be utilised in an interesting manner to make bimetallic nanostructures with enhanced catalytic activity.

Robust Electroreduction of CO2 at a Poly(4‐vinylpyridine)–Copper Electrode

“…The above results indicate that the cathodic corrosion of the copper support during CO 2 reduction (the so‐called anomalous dissolution) is instrumental for the catalytic activity of P4VP/Cu. Although the exact mechanism of this effect is unknown, it is likely to have the same ligand‐promoted origin as the cathodic corrosion of copper during oxygen reduction, as well as the copper alloying upon cathodic electrodeposition of metals on copper . Namely, copper cathodes dissolve when the attacking oxidant forms strong charge‐transfer complexes with copper.…”

Cathodic Corrosion of Metal Electrodes—How to Prevent It in Electroorganic Synthesis

“…Cathodic etching is another mechanism that can corrode cathodes, and it has been documented in both aqueous ( Scheme 5 , up, a–c) and anhydrous aprotic solvents ( Scheme 5 , down, d–f) for a range of metals including Pt, 75 , 79 , 80 , 97 − 116 Rh, 75 , 97 , 98 , 101 , 102 , 117 Ir, 101 Pd, 98 , 101 , 106 , 107 , 118 , 119 Au, 75 , 97 , 98 , 101 , 117 Ag, 75 , 98 , 101 Cu, 75 , 98 , 101 , 120 Re, 98 Fe, 98 Ni, 75 , 98 , 101 Nb, 75 , 98 Ru, 75 Ti, 98 , 121 − 123 V, 121 W, 121 Si, 75 , 98 Nb, 75 Ru, 75 Al, 98 Pb, 56 , 57 , 124 − 131 Sn, 125 , 127 − 133 Sb, 83 , 91 , 129 , 134 Bi,…”

“…To date, pure Pt, 75 , 76 , 79 , 80 , 97 − 103 , 114 − 116 Rh, 75 , 76 , 97 , 98 , 101 , 102 , 117 Pd, 98 , 101 Au, 75 , 97 , 98 , 101 , 117 Ag, 75 , 101 Ir, 101 Cu, 75 , 98 , 101 , 120 Re, 98 Ru, 75 , 101 Ir, 101 Fe, 98 Ni, 75 , 98 , 101 Nb, 75 , 98 Ti, 98 , 121 − 123 V, 121 W, 121 Si, 75 , 98 Sb, 91 and Al 98 electrodes have been reported to cathodically corrode through etching mechanism in aqueous media. Regarding alloys, Pt 90 Rh 10 , 76 , 98 Pt 70 Rh 30 , 76 , 98 Pt 55 Rh 45 , 102 Pt 20 Rh 80 , 76 , 98 Pt 12 Rh 88 , 102 Pt 80 Ir 20 , 76 Pt 95 ...…”

Local structure and composition of PtRh nanoparticles produced through cathodic corrosion

“…Among the various chemical, [10][11][12][13][14] biochemical 15 and physical [16][17][18] processes used to create metal alloy nanoparticles, a promising candidate is cathodic corrosion. This method, which was first observed by Haber, 19 revisited by Kabanov et al 20 and studied again more recently, [21][22][23][24][25][26] involves making nanoparticles by applying a cathodic voltage to a sacrificial electrode. During this cathodic polarization, nanoparticles will form near and on the electrode.…”