Fig. 2. a) XRD patterns of Pt/C and Pt–Ag/C electrocatalysts synthesized by ultrasound. b) comparison of XRDs in 36–43° region for both samples. Transmission electron micrograph (TEM)
of c) Pt/C and d) Pt–Ag/C.
peaks toward the Pt position. Fig. 2c and d shows the TEM images of Pt/C and Pt–Ag/C, respectively. Two samples show the metal nanoparticles with a particle size less than 10 nm in the form of spherical agglomerates shape of around 25 and 50 nm for mono- and bi-metallic catalysts, respectively.
3.2. Electrochemical characterization results
Fig. 3 exhibits the CV curves of a) Pt–Ag/C, b) Pt/C and c) Ag/V catalysts in N2 saturated 0.5 M H2SO4 at room time (RT). The curves of the samples are compared at the 1st and 20th cycles. Fig. 3a shows that the first CV cycle of Pt–Ag/C in acid medium exhibits two anodic peaks in the potential range of 0.4–0.9 V associated to the oxidative dissolution/leaching of Ag that decayed rapidly with increasing the number of CVs [2,12]. After 5 cycles of potential scans, Pt–Ag exhibits similar electrochemical characteristics as the Pt/C sample with different intensity current density due to a rearrangement of the platinum surface caused by the dissolution of Ag [27]. In the CVs of Pt/C (Fig. 3b) no remarkable change in the CV features was observed, indicating more stability as compared to the silver sample. The CVs of Ag/C in Fig. 3c exhibit two peaks associated to the oxidative Ag that decrease with the number of scans associated to silver dissolution. The electrochemical surface area (ESA) of samples was estimated by integrating the cyclic voltammograms corresponding to the hydrogen adsorption– desorption area. For calculation of ESA a value of 210 μC cm−2 was assumed as a monolayer charge of H2 [28]. The ESA of real area per milligram of metal obtained for the bimetallic sample Pt–Ag/C (256 cm2 mg−1 metal) is higher than that of Pt/C (246.6 cm2 mg−1 metal) and Ag/C (33.33 cm2 mg−1 metal). The incorporation of Ag in the bimetallic sample modified the electronic properties of Pt–Ag, increasing the quantity of hydrogen adsorption–desorption. EAS data in this work were different from those reported previously, due to differences in the preparation of the working electrodes [12]. The commercial Pt/C sample has an ESA of 500 cm2 mg−1 metal, the large exposed area
corresponds to the high dispersion of platinum on the carbon of the commercial sample compared to the low dispersion obtained in the synthesized materials.
Fig. 2. a) XRD patterns of Pt/C and Pt–Ag/C electrocatalysts synthesized by ultrasound. b) comparison of XRDs in 36–43° region for both samples. Transmission electron micrograph (TEM) of c) Pt/C and d) Pt–Ag/C.peaks toward the Pt position. Fig. 2c and d shows the TEM images of Pt/C and Pt–Ag/C, respectively. Two samples show the metal nanoparticles with a particle size less than 10 nm in the form of spherical agglomerates shape of around 25 and 50 nm for mono- and bi-metallic catalysts, respectively.3.2. Electrochemical characterization resultsFig. 3 exhibits the CV curves of a) Pt–Ag/C, b) Pt/C and c) Ag/V catalysts in N2 saturated 0.5 M H2SO4 at room time (RT). The curves of the samples are compared at the 1st and 20th cycles. Fig. 3a shows that the first CV cycle of Pt–Ag/C in acid medium exhibits two anodic peaks in the potential range of 0.4–0.9 V associated to the oxidative dissolution/leaching of Ag that decayed rapidly with increasing the number of CVs [2,12]. After 5 cycles of potential scans, Pt–Ag exhibits similar electrochemical characteristics as the Pt/C sample with different intensity current density due to a rearrangement of the platinum surface caused by the dissolution of Ag [27]. In the CVs of Pt/C (Fig. 3b) no remarkable change in the CV features was observed, indicating more stability as compared to the silver sample. The CVs of Ag/C in Fig. 3c exhibit two peaks associated to the oxidative Ag that decrease with the number of scans associated to silver dissolution. The electrochemical surface area (ESA) of samples was estimated by integrating the cyclic voltammograms corresponding to the hydrogen adsorption– desorption area. For calculation of ESA a value of 210 μC cm−2 was assumed as a monolayer charge of H2 [28]. The ESA of real area per milligram of metal obtained for the bimetallic sample Pt–Ag/C (256 cm2 mg−1 metal) is higher than that of Pt/C (246.6 cm2 mg−1 metal) and Ag/C (33.33 cm2 mg−1 metal). The incorporation of Ag in the bimetallic sample modified the electronic properties of Pt–Ag, increasing the quantity of hydrogen adsorption–desorption. EAS data in this work were different from those reported previously, due to differences in the preparation of the working electrodes [12]. The commercial Pt/C sample has an ESA of 500 cm2 mg−1 metal, the large exposed areacorresponds to the high dispersion of platinum on the carbon of the commercial sample compared to the low dispersion obtained in the synthesized materials.
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