Electrocatalytic effect of Ag and Cd bimetallic nanoparticles towards the reduction of nitrate and/or nitrite ions
ABSTRACT The electrocatalytic effect of Cd-Ag bimetallic nanoparticles supported on highly oriented pyrolytic graphite (HOPG) and vitreous carbon (VC) substrates was evaluated for the nitrate and/or nitrite ions reduction reaction. For this, in a first stage, the metallic and bimetallic deposits were obtained on the carbonaceous substrates (CS) using the electrochemical technique of the single potentiostatic pulse. In the case of the bimetallic pair, the amount of Cd was selectively deposited on the Ag nanoparticles previously supported on HOPG or CV, due to the strong interaction between the two metals, using different polarization times. Potentiodynamic studies of the system Cd-Ag/(CS) indicated that, for relatively large polarization times, it is feasible the formation of a surface alloy between Ag and Cd atoms, due to an interdiffusion process between them, which may affect its catalytic activity. The generated particles on HOPG, were characterized by ex-situ AFM and XPS analysis, corroborating the latter the formation of a Cd-Ag alloy. Subsequently, the electrodes modified with metallic and bimetallic nanoparticles, and also the substrates free of deposits, were analysed by cyclic voltammetry in solutions containing nitrate ions. It was found that the reduction of nitrate and/or nitrite ions processes begin at more positive potential values in the case of bimetallic deposits, corresponding to a more pronounced catalytic effect by the presence of Cd and Ag, which could be alloyed in the surface, producing a synergistic effect for the reduction of the anions. Even, a change in the catalytic performance by using longer polarization times for the deposition of Cd on supported Ag nanoparticles was verified, that could be related with that alloyed phase. The reaction products were analyzed by colorimetry and ion exchange chromatography for determining nitrate, nitrite and ammonium amounts in solution.