Manipulating the surface composition of Pt-Ru bimetallic nanoparticles to control the methanol oxidation reaction pathway.

The rational manipulation of reaction intermediates is crucial for achieving high-performance heterogeneous catalysis. Herein, using in situ Fourier transform infrared-diffuse reflection (FTIR) analysis, we report that the methanol oxidation reaction (MOR) intermediates can be controlled by precisely tuning the location and content of Ru on the Pt-Ru alloy surface.

High temperature self-assembly one-step synthesis of a structurally ordered PtFe catalyst for the oxygen reduction reaction.

Herein, we present a high-temperature self-assembly strategy that directly allows the transformation of adsorbed Pt(NH3)42+ and Fe3+ sources into structurally ordered face-centered tetragonal (fct)-PtFe alloy NPs (2.6 ± 0.2 nm) by integrating reduction and phase transformation. The small-size and ordered atomic arrangement of the fct-PtFe alloy NPs, together with their robust NC protective shell, make these NPs exhibit excellent catalytic activity and stability for the oxygen reduction reaction.

NaCl protected synthesis of 3D hierarchical metal-free porous nitrogen-doped carbon catalysts for the oxygen reduction reaction in acidic electrolyte.

A high-performance 3D hierarchical porous metal-free N-doped carbon catalyst toward the oxygen reduction reaction (ORR) in acidic medium was successfully synthesized by employing ZnO as a mesoporous template and NaCl as both a macroporous template and a structure protective agent. The resultant improved active site density and diffusion efficiency lead to a superior ORR activity with a half-wave potential high up to 0.755 V in 0.1 M HClO4.

Ultrahigh-Loading Zinc Single-Atom Catalyst for Highly Efficient Oxygen Reduction in Both Acidic and Alkaline Media.

Atomically dispersed Zn-N-C nanomaterials are promising platinum-free catalysts for the oxygen reduction reaction (ORR). However, the fabrication of Zn-N-C catalysts with a high Zn loading remains a formidable challenge owing to the high volatility of the Zn precursor during high-temperature annealing. Herein, we report that an atomically dispersed Zn-N-C catalyst with an ultrahigh Zn loading of 9.33 wt % could be successfully prepared by simply adopting a very low annealing rate of 1° min-1 . The Zn-N-C catalyst exhibited comparable ORR activity to that of Fe-N-C catalysts, and significantly better ORR stability than Fe-N-C catalysts in both acidic and alkaline media. Further experiments and DFT calculations demonstrated that the Zn-N-C catalyst was less susceptible to protonation than the corresponding Fe-N-C catalyst in an acidic medium. DFT calculations revealed that the Zn-N4 structure is more electrochemically stable than the Fe-N4 structure during the ORR process.

Controlled synthesis of single cobalt atom catalysts via a facile one-pot pyrolysis for efficient oxygen reduction and hydrogen evolution reactions.

Metal-nitrogen doped carbon catalysts (M-N/C) with abundantly accessible M-Nx sites, particularly single metal atom M-N/C (SAM-N/C), have been developed as a substitute for expensive Pt-based catalysts. These catalysts are used to increase the efficiency of otherwise sluggish oxygen reduction reactions (ORR) and hydrogen evolution reactions (HER). However, although the agglomerated metal nanoparticles are usually easy to form, they are very difficult to remove due to the protective surface-coating carbon layers, a factor that significantly hampers SAM-N/C fabrication. Herein, we report a one-step pyrolysis approach to successfully fabricate single cobalt atom Co-N/C (SACo-N/C) by using a Co2+-SCN- coordination compound as the metal precursor. Thanks to the decomposition of Co2+-SCN- compound at lower temperature than that of carbon layer deposition, Co-rich particles grow up to larger ones before carbon layers formation. Even though encapsulated by the carbon layers, it is difficult for the large Co-rich particle to be completely sealed. And thus, it makes the Co atoms possible to escape from incomplete carbon layer, to coordinate with nitrogen atoms, and to form SACo-N/C catalysts. This SACo-N/C exhibits excellent performances for both ORR (half-wave potential of 0.878 V) and HER (overpotential at 10 mA/cm2 of 178 mV), and is thus a potential replacement for Pt-based catalysts. When SACo-N/C is integrated into a Zn-O2 battery, battery with high open-circuit voltage (1.536 V) has high peak power density (266 mW/cm2) and large gravimetric energy density (755 mA h/gZn) at current densities of 100 mA/cm2. Thus, we believe that this strategy may offer a new direction for the effective generation of SAM-N/C catalysts.

Preparation of Hollow Nitrogen Doped Carbon via Stresses Induced Orientation Contraction.

Hollow structured materials are widely applicable in various fields. Although many routes have been explored for getting such materials, a strategy mainly based on physical effect is still deficient. Herein, a "stresses induced orientation contraction" mechanism for preparation of hollow structures is reported. The composites constructed by zeolite imidazolate framework-8 (ZIF8) cores and polymerized dopamine (PDA) shells, upon annealing, form intensive interfacial interactions, which drag the ZIF8 cores outward to restrain their shrinkage. The gradually accumulated stresses in the central position of ZIF8 dodecahedron nanoparticles, then destroy the ZIF8 crystalline cores to form the hollow structures. In this stress-based route for creating hollow interiors with core-shell composites as the starting materials, three critical factors are necessary: 1) an intensive core-shell interfacial interaction; 2) the distinctly higher shrinkage degree of the cores than the shells; and 3) the relatively loose core structures. In oxygen reduction reaction (ORR) tested with three-electrode solution system and Zn-O2 battery, the achieved hollow nitrogen doped carbon (NC) demonstrates ultrahigh catalytic activities. This work gives an absolutely novel strategy for preparation of hollow structures, which may afford the exploration of a wider range of materials system with hollow interiors.

Exploring Fe-Nx for Peroxide Reduction: Template-Free Synthesis of Fe-Nx Traumatized Mesoporous Carbon Nanotubes as an ORR Catalyst in Acidic and Alkaline Solutions.

Fe-based electrocatalysts are elegant due to their better performance towards the oxygen reduction reaction. Nevertheless, they commonly contain different moieties, for example Fe-Nx , Fe, Fe3 C and N-doped carbon, primarily the debatable assistance of these components towards ORR electrocatalysis, specifically for intermediate peroxide reduction reactions (PRR). In this paper, to explore the role of Fe-Nx centres for PRR, a Fe-N-C electrocatalyst rooted in nitrogen-doped carbon nanotubes with mesoporous structures was synthesized from a Fe/Zn-dicyanoimidazolate framework. The use of dicyanoimidazole coordinated with iron can introduce the Fe-Nx active sites as well as directional N-doped carbon nanotubes, which is good for enhancing electronic conductance of the catalyst. The attained electrocatalyst shows tremendous enactment to ORR, being comparable to the activity of Pt/C in acidic and better in alkaline electrolytes. This study also reveals that Fe-Nx active centres are responsible for less H2 O2 production. Though the Fe-Nx moieties and Fe3 C/Fe particles encapsulated N-doped carbon, both are active centres for ORR, however, Fe-Nx sites are more active than others for peroxide reduction reaction. These perceptions suggest rational methodologies for more active and consequently further durable Fe-N-C catalysts.