Stabilization effects in binary colloidal Cu and Ag nanoparticle electrodes under electrochemical CO2 reduction conditions.

Nanoparticle modified electrodes constitute an attractive way to tailor-make efficient carbon dioxide (CO2) reduction catalysts. However, the restructuring and sintering processes of nanoparticles under electrochemical reaction conditions not only impedes the widespread application of nanoparticle catalysts, but also misleads the interpretation of the selectivity of the nanocatalysts. Here, we colloidally synthesized metallic copper (Cu) and silver (Ag) nanoparticles with a narrow size distribution (<10%) and utilized them in electrochemical CO2 reduction reactions. Monometallic Cu and Ag nanoparticle electrodes showed severe nanoparticle sintering already at low overpotential of -0.8 V vs. RHE, as evidenced by ex situ SEM investigations, and potential-dependent variations in product selectivity that resemble bulk Cu (14% for ethylene at -1.3 V vs. RHE) and Ag (69% for carbon monoxide at -1.0 V vs. RHE). However, by co-deposition of Cu and Ag nanoparticles, a nanoparticle stabilization effect was observed between Cu and Ag, and the sintering process was greatly suppressed at CO2 reducing potentials (-0.8 V vs. RHE). Furthermore, by varying the Cu/Ag nanoparticle ratio, the CO2 reduction reaction (CO2RR) selectivity towards methane (maximum of 20.6% for dense Cu2.5-Ag1 electrodes) and C2 products (maximum of 15.7% for dense Cu1-Ag1 electrodes) can be tuned, which is attributed to a synergistic effect between neighbouring Ag and Cu nanoparticles. We attribute the stabilization of the nanoparticles to the positive enthalpies of Cu-Ag solid solutions, which prevents the dissolution-redeposition induced particle growth under CO2RR conditions. The observed nanoparticle stabilization effect enables the design and fabrication of active CO2 reduction nanocatalysts with high durability.

Electrochemical and electrocatalytic properties of thin films of poly(3,4-ethylenedioxythiophene) grown on basal plane platinum electrodes.

The first part of this communication studies the electrochemical properties of thin films of poly(3,4-ethylenedioxythiophene) (PEDOT) grown on the three basal plane platinum electrodes via cyclic voltammetry, chronoamperometry, electrochemical impedance spectroscopy and in situ FTIR spectroelectrochemistry. In the second part of this work the redox reaction of 2,5-dimercapto-1,3,4-thiadiazole (DMcT) at these platinum modified electrodes is investigated via cyclic voltammetry and electrochemical impedance spectroscopy in order to elucidate the effect of some polymer properties on its electrocatalytic behavior, such as the ionic resistance, nature of the doping ion and the structure. First of all, it was found that the ionic resistance of the PEDOT films electrochemically synthesized on platinum electrodes increases in the order Pt(100) < Pt(110) < Pt(111) and the advantages of using single crystal platinum electrodes coated with PEDOT for the IR study of individual mobile species flux and the evolution of charge carriers during the reduction process of p-doped PEDOT were proven. On the other hand, it was found that compact, rigid and low resistance PEDOT films show higher standard charge transfer rates for the DMcT redox reaction than those that have a more porous structure and higher ionic resistance. Finally, PEDOT films doped with alkaline ions are more electrocatalytic for the oxidation process of the protonated form of DMcT.

Voltammetry of basal plane platinum electrodes in acetonitrile electrolytes: effect of the presence of water.

The first part of this report studies the electrochemical properties of single-crystal platinum electrodes in acetonitrile electrolytes by means of cyclic voltammetry. Potential difference infrared spectroscopy in conjunction with linear voltammetry was used to obtain a molecular-level picture of this interface. The second part of this report studies the hydrogen evolution and the hydrogen oxidation reactions on the three low-index faces of Pt electrodes in acetonitrile electrolytes. The data (CVs and IR spectra) strongly suggest that acetonitrile and CN(-) molecules are adsorbed on single-crystal platinum electrodes in the range of -1.5 to 0.3 V versus Ag/AgCl. Those species block part of the adsorption sites for hydrogen adatoms, and they decompose on the surface in the presence of water. The nature of the cation and the presence of water strongly affect the onset of acetonitrile electrolysis and the kinetics and stability of the adsorbed species on the electrode. Finally, the hydrogen evolution and the hydrogen oxidation reactions on platinum single-crystal surfaces in acetonitrile electrolytes are strongly affected by the surface-energy state of Pt electrodes.