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Coralloid-Pt nanodendrites decorated nanoporous gold films (NPG-Ptx) were fabricated through underpotential deposition/in-situ reduction replacement (UPD/IRR) strategy and exhibit significantly enhanced ORR activities. Ab initio density functional theory (DFT) studies further demonstrate the ORR mechanism of NPG-Ptx. [Display omitted] • Coralloid-Pt nanodendrites decorated nanoporous gold films (NPG-Ptx) were fabricated through underpotential deposition/in-situ reduction replacement (UPD/IRR) strategy. • The NPG-Ptx (x = 1 ∼ 4) exhibit significantly enhanced ORR activities in acidic media. • The DFT studies demonstrate the ORR mechanism and rate-determining step of NPG-Ptx follow the free energy diagrams. • The PDOS results indicate a relatively stronger O 2 reaction capacity on Pt side than Pt top. Deposition of trace amounts of Pt onto nanoporous gold ligaments (NPG-Pt) has demonstrated promising performance of low-Pt electrocatalysts for oxygen reduction reaction (ORR); however, improving the activity of ORR remains challenging because of the difficulty in understanding the electronic effect between Pt and NPG as well as the absence of ORR mechanism studies on NPG-Pt. Here we show that NPG-Ptx (x = 1 ∼ 4), unique coralloid-Pt nanodendrites decorated nanoporous gold films through underpotential deposition/in-situ reduction replacement (UPD/IRR) strategy, exhibit significantly enhanced ORR activities. Among them, NPG-Pt3 exhibits the best ORR activity compared with the others and Pt/C in acidic media. Density functional theory (DFT) studies demonstrate the ORR mechanism and rate-determining step of NPG-Ptx follow the free energy diagrams. Furthermore, the projected density of state (PDOS) results reveal a relatively weaker O 2 reaction capacity on the top side of Pt (Pt top) than the side site (Pt side) for NPG-Ptx. The increase of d -band center for NPG-Ptx pushes up the energy of the antibonding state above the Fermi level, and then the backflow of electrons into the system makes the energy more stable, optimizing the ORR activity. These results provide new inspirations for the development of low-Pt electrocatalysts for energy technologies in a rational manner. [ABSTRACT FROM AUTHOR]

[Display omitted] • Hierarchical NiC 2 O 4 /Ni(OH) 2 nanospheres are synthesized via a simple two-step hydrothermal method as the positive electrode. • The porous biomass-derived carbon with the honeycomb structure is obtained from pine petals as the negative electrode. • Hierarchical NiC 2 O 4 /Ni(OH) 2 nanospheres and the porous biomass-derived carbon possess a high specific capacity. • The hybrid supercapacitor exhibits excellent energy and power density. The high-performance hybrid supercapacitor (HSC) with high power capability and stable cyclability is intensively pursued as a next-generation energy storage device. Here, a kind of hierarchical NiC 2 O 4 /Ni(OH) 2 nanospheres, consisting of subunits of NiC 2 O 4 nanorods and Ni(OH) 2 nanospheres, are synthesized via a two-step hydrothermal method. The hierarchical NiC 2 O 4 /Ni(OH) 2 nanosphere positive electrode, benefiting from the synergistic effect of unique hierarchical structure and built-in electric fields, significantly boosting electron transmission capability and accelerating the ion/electron transfer rate, delivers an excellent specific capacity of 668 C g−1 at 1 A g−1. In addition, the porous biomass-derived carbon (PBC) with the honeycomb structure from pine petals as the negative electrode shows a remarkable electrochemical performance, exhibiting a specific capacitance of 249.7 F g−1 at 1 A g−1. As such, an assembled HSC of NiC 2 O 4 /Ni(OH) 2 ||PBC based on hierarchical NiC 2 O 4 /Ni(OH) 2 nanospheres positive electrode and PBC negative electrode display a conspicuous energy density of 31.07 Wh kg−1, and a power density of 833.47 W kg−1 at a maximum potential window of 1.7 V. This innovative hierarchical engineering of double nickel-based composites with bio-carbon provides an advanced enlightenment for high-performance HSCs. [ABSTRACT FROM AUTHOR]