Abstract
Hierarchical porous carbon-encapsulated ultrasmall PtCu (UsPtCu@C) nanoparticles (NPs) were constructed based on segmentation and re-encapsulation of porous PtCu NPs by using glucose as a green biomass carbon source. The synergistic electronic effect from the bimetallic elements can enhance the catalytic activity by adjusting the surface electronic structure of Pt. Most importantly, the generated porous carbon shell provided a large contact surface area, excellent electrical conductivity, and structural stability, and the ultrasmall PtCu NPs exhibited an increased electrochemical performance compared with their PtCu matrix because of the exposure of more catalytically active centers. This synergistic relationship between the components resulted in enhanced catalytic activity and better stability of the obtained UsPtCu@C for ethylene glycol oxidation reaction and the oxygen-reduction reaction in alkaline electrolyte, which was higher than the PtCu NPs and commercial Pt/C (20 wt % Pt on Vulcan XC-72). The electrochemically active surface areas of the UsPtCu@C, PtCu NPs, and commercial Pt/C were calculated to be approximately 230.2, 32.8, and 64.0 m2/gPt, respectively; the mass activity of the UsPtCu@C for the ethylene glycol oxidation reaction was 8.5 A/mgPt, which was 14.2 and 8.5 times that of PtCu NPs and commercial Pt/C, respectively. The specific activity of UsPtCu@C was 3.7 mA/cmpt2, which was 2.1 and 2.3 times that of PtCu NPs and commercial Pt/C, respectively. The onset potential (Eon-set) of UsPtCu@C for the oxygen-reduction reaction was 0.96 V (vs reversible hydrogen electrode, RHE), which was 110 and 60 mV higher than PtCu and commercial Pt/C, respectively. The half-wave potentials (E1/2) of UsPtCu@C, PtCu, and Pt/C were 0.88, 0.56, and 0.82 V (vs RHE), respectively, which indicated that the UsPtCu@C catalyst had an excellent bifunctional electrocatalytic activity.
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