Zinc-Mediated Template Synthesis of Hierarchical Porous N-Doped Carbon Electrocatalysts for Efficient Oxygen Reduction.

The development of highly active and low-cost catalysts for use in oxygen reduction reaction (ORR) is crucial to many advanced and eco-friendly energy techniques. N-doped carbons are promising ORR catalysts. However, their performance is still limited. In this work, a zinc-mediated template synthesis strategy for the development of a highly active ORR catalyst with hierarchical porous structures was presented. The optimal catalyst exhibited high ORR performance in a 0.1 M KOH solution, with a half-wave potential of 0.89 V vs. RHE. Additionally, the catalyst exhibited excellent methanol tolerance and stability. After a 20,000 s continuous operation, no obvious performance decay was observed. When used as the air-electrode catalyst in a zinc-air battery (ZAB), it delivered an outstanding discharging performance, with peak power density and specific capacity as high as 196.3 mW cm-2 and 811.5 mAh gZn-1, respectively. Its high performance and stability endow it with potential in practical and commercial applications as a highly active ORR catalyst. Additionally, it is believed that the presented strategy can be applied to the rational design and fabrication of highly active and stable ORR catalysts for use in eco-friendly and future-oriented energy techniques.

Bean Pod-Like SbSn/N-Doped Carbon Fibers toward a Binder Free, Free-Standing, and High-Performance Anode for Sodium-Ion Batteries.

Bimetallic SbSn alloy stands out among the anode materials for sodium-ion batteries (SIBs) because of its high theoretical specific capacity (752 mAh g-1 ) and good electrical conductivity. However, the major challenge is the large volume change during cycling processes, bringing about rapid capacity decay. Herein, to cope with this issue, through electrostatic spinning and high temperature calcination reduction, the unique bean pod-like free-standing membrane is designed initially, filling SbSn dots into integrated carbon matrix including hollow carbon spheres and nitrogen-doped carbon fibers (B-SbSn/NCFs). Significantly, the synergistic carbon matrix not only improves the conductivity and flexibility, but provides enough buffer space to alleviate the large volume change of metal particles. More importantly, the B-SbSn/NCFs free-standing membrane can be directly used as the anode without polymer binder and conductive agent, which improves the energy density and reaction kinetics. Satisfyingly, the free-standing BSbSn/NCFs membrane anode shows excellent electrochemical performance in SIB. The specific capacity of the membrane electrode can maintain 486.9 mAh g-1 and the coulombic efficiency is close to 100% after 400 cycles at 100 mA g-1 . Furthermore, the full cell based on B-SbSn/NCFs anode also exhibits the good electrochemical performance.

Metal-Organic-Framework-Derived Carbons: Applications as Solid-Base Catalyst and Support for Pd Nanoparticles in Tandem Catalysis.

The facile pyrolysis of a bipyridyl metal-organic framework, MOF-253, produces N-doped porous carbons (Cz-MOF-253), which exhibit excellent catalytic activity in the Knoevenagel condensation reaction and outperform other nitrogen-containing MOF-derived carbons. More importantly, by virtue of their high Lewis basicity and porous nature, Cz-MOF-253-supported Pd nanoparticles (Pd/Cz-MOF-253-800) show excellent performance in a one-pot sequential Knoevenagel condensation-hydrogenation reaction.

Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO2 Electroreduction to CO and Hydrocarbons.

This study explores the kinetics, mechanism, and active sites of the CO2 electroreduction reaction (CO2RR) to syngas and hydrocarbons on a class of functionalized solid carbon-based catalysts. Commercial carbon blacks were functionalized with nitrogen and Fe and/or Mn ions using pyrolysis and acid leaching. The resulting solid powder catalysts were found to be active and highly CO selective electrocatalysts in the electroreduction of CO2 to CO/H2 mixtures outperforming a low-area polycrystalline gold benchmark. Unspecific with respect to the nature of the metal, CO production is believed to occur on nitrogen functionalities in competition with hydrogen evolution. Evidence is provided that sufficiently strong interaction between CO and the metal enables the protonation of CO and the formation of hydrocarbons. Our results highlight a promising new class of low-cost, abundant electrocatalysts for synthetic fuel production from CO2 .

Selective Electrocatalytic H2 O2 Generation by Cobalt@N-Doped Graphitic Carbon Core-Shell Nanohybrids.

Electrocatalytic oxygen reduction (ORR) is an emerging synthetic strategy to prepare H2 O2 in a sustainable fashion. N-doped graphitic carbon with embedded cobalt nanoparticles was selected as an advanced material able to selectively trigger the ORR to form H2 O2 with a faradaic efficiency of almost 100 % at very positive applied potentials. The production of H2 O2 proceeded with high rates as calculated by bulk electrolysis (49 mmol g-1 h-1 ) and excellent current densities (≈-0.8 mA cm-2 at 0.5 V vs. reversible hydrogen electrode). The totally selective behavior depended on the combination of concomitant material features, such as the textural properties, the nature of the metal, the distribution of N moieties, the acidic environment, and the applied potential.

Synergistic Effects of Active Sites' Nature and Hydrophilicity on the Oxygen Reduction Reaction Activity of Pt-Free Catalysts.

This work highlights the importance of the hydrophilicity of a catalyst's active sites on an oxygen reduction reaction (ORR) through an electrochemical and physico-chemical study on catalysts based on nitrogen-modified carbon doped with different metals (Fe, Cu, and a mixture of them). BET, X-ray Powder Diffraction (XRPD), micro-Raman, X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Scanning Transmission Electron Microscopy (STEM), and hydrophilicity measurements were performed. All synthesized catalysts are characterized not only by a porous structure, with the porosity distribution centered in the mesoporosity range, but also by the presence of carbon nanostructures. In iron-doped materials, these nanostructures are bamboo-like structures typical of nitrogen carbon nanotubes, which are better organized, in a larger amount, and longer than those in the copper-doped material. Electrochemical ORR results highlight that the presence of iron and nitrogen carbon nanotubes is beneficial to the electroactivity of these materials, but also that the hydrophilicity of the active site is an important parameter affecting electrocatalytic properties. The most active material contains a mixture of Fe and Cu.

Synthesis, characterization and dye removal capacities of N-doped mesoporous carbons.

Nitrogen-doped ordered mesoporous carbons were synthesized by chemical vapor deposition, using acetonitrile as carbon and nitrogen source and SBA-15 as mesoporous silica template. Their porous texture, structural order and surface chemistry were studied as a function of the experimental conditions (acetonitrile stream concentration and deposition time). A non-doped ordered mesoporous carbon was also prepared by the same procedure using propylene as carbon source. Methylene blue, methyl orange and fuchsin acid were selected as probe molecules to investigate the dye adsorption behavior on the ordered mesoporous carbons. Both N-doped and non-doped ordered mesoporous carbons adsorbed large amounts of these three dyes demonstrating the importance of mesoporosity, especially for the adsorption of larger dyes (e.g. fuchsin acid). The presence of nitrogen functional groups was detrimental for the adsorption of the basic dye (methylene blue). On the other hand, the nitrogen functionalities improved the adsorption kinetics for both acid and basic dyes, and the N-doped samples achieved 100% of their maximum adsorption capacities in less than 15 min.