As low-cost electrocatalysts for oxygen reduction reaction applied to fuel cells and metal-air batteries, atomic-dispersed transition metal-nitrogen-carbon materials are emerging, but the genuine mechanism thereof is still arguable. Herein, by rational design and synthesis of dual-metal atomically dispersed Fe,Mn/N-C catalyst as model object, we unravel that the O2 reduction preferentially takes place on FeIII in the FeN4 /C system with intermediate spin state which possesses one eg electron (t2g4eg1) readily penetrating the antibonding π-orbital of oxygen. Both magnetic measurements and theoretical calculation reveal that the adjacent atomically dispersed Mn-N moieties can effectively activate the FeIII sites by both spin-state transition and electronic modulation, rendering the excellent ORR performances of Fe,Mn/N-C in both alkaline and acidic media (halfwave positionals are 0.928 V in 0.1 M KOH, and 0.804 V in 0.1 M HClO4), and good durability, which outperforms and has almost the same activity of commercial Pt/C, respectively. In addition, it presents a superior power density of 160.8 mW cm−2 and long-term durability in reversible zinc–air batteries. The work brings new insight into the oxygen reduction reaction process on the metal-nitrogen-carbon active sites, undoubtedly leading the exploration towards high effective low-cost non-precious catalysts.
Crystal phase regulations may endow materials with enhanced or new functionalities. However, syntheses of noble metal-based allomorphic nanomaterials are extremely difficult, and only a few successful examples have been found. Herein, we report the discovery of hexagonal close-packed Pt–Ni alloy, despite the fact that Pt–Ni alloys are typically crystallized in face-centred cubic structures. The hexagonal close-packed Pt–Ni alloy nano-multipods are synthesized via a facile one-pot solvothermal route, where the branches of nano-multipods take the shape of excavated hexagonal prisms assembled by six nanosheets of 2.5 nm thickness. The hexagonal close-packed Pt–Ni excavated nano-multipods exhibit superior catalytic property towards the hydrogen evolution reaction in alkaline electrolyte. The overpotential is only 65 mV versus reversible hydrogen electrode at a current density of 10 mA cm−2, and the mass current density reaches 3.03 mA μgPt−1 at −70 mV versus reversible hydrogen electrode, which outperforms currently reported catalysts to the best of our knowledge.
Driven by the persisting poor understanding of the sluggish kinetics of the hydrogen evolution reaction (HER) on Pt in alkaline media, a direct correlation of the interfacial water structure and activity is still yet to be established. Herein, using Pt and Pt–Ni nanoparticles we first demonstrate a strong dependence of the proton donor structure on the HER activity and pH. The structure of the first layer changes from the proton acceptors to the donors with increasing pH. In the base, the reactivity of the interfacial water varied its structure, and the activation energies of water dissociation increased in the sequence: the dangling O−H bonds < the trihedrally coordinated water < the tetrahedrally coordinated water. Moreover, optimizing the adsorption of H and OH intermediates can re‐orientate the interfacial water molecules with their H atoms pointing towards the electrode surface, thereby enhancing the kinetics of HER. Our results clarified the dynamic role of the water structure at the electrode–electrolyte interface during HER and the design of highly efficient HER catalysts.
The application of Pt alloy catalysts for oxygen reduction reactions (ORRs) in proton-exchange membrane fuel cells is severely impeded by base metal leaching, since the produced metal ions can result in the degradation of a Nafion membrane by replacing H + and inducing a Fenton reaction. Doping Pt with nonmetal elements can significantly mitigate such problems due to the relative harmlessness of the corrosion products of anions. Herein, we developed a phosphorus-doping strategy, which can greatly boost the ORR performance of Pt. Phosphorus was introduced into the near-surface of commercial Pt/C (denoted as P NS -Pt/C) via a surfactant-free method. Highangle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray photoelectron spectrum (XPS) tests indicate that the introduction of phosphorus induced distortion of the Pt lattice and the downshift of the d-band center. In situ electrochemical Fourier transform infrared (FTIR) spectroscopy with adsorbed CO as a molecule probe further revealed that the introduction of phosphorus can lower the adsorption ability. The ORR mass activity of P NS -Pt/C is as high as 1.00 mA μg Pt −
Precise tuning of the chemical environment of neighboring atomic FeN 4 sites is extremely important for optimizing Fe−N−C catalysts to produce the fast oxygen reduction reaction (ORR) kinetics both in acidic and alkaline media, but it is actually very challenging. Heteroatoms could affect the metal charge of the active center through long-range electron delocalization; however, there are a few studies on it. Herein, density functional theory (DFT) calculations demonstrate that the addition of long-range P into edge-type FeN 4 can drive the electron delocalization and decrease the band gap of the FeN 4 center, leading to a substantial decrease in the free energy barrier to direct four-electron ORR kinetics compared to P-free edge-type FeN 4 , indicating superior intrinsic ORR activity. Experimentally, by incorporating P in edge-rich FeN 4 supported on N,P-doped carbon (Fe−N−C−P/N,P−C), the created Fe−N−C catalyst presents the greatly increased acidic ORR activity, with a half-wave potential (E 1/2 ) of 0.80 V (vs a reversible hydrogen electrode), which approaches that of commercial Pt/C and also has a high half-wave potential of 0.87 V, beyond Pt/C for alkaline ORR. In addition, it shows higher proton exchange membrane fuel cell and Zn-air battery performances than the pristine Fe−C−N catalyst (Fe−N−C/ N−C). This work will guide the rational design of highly active metal atomic scale catalysts with optimized chemical surroundings in terms of P incorporation as a chemically tunable method.
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