Remarkable hydrogen evolution reaction (HER) or superior oxygen evolution reaction (OER) catalyst has been applied in water splitting, however, utilizing a bifunctional catalyst for simultaneously generating H2 and O2 is still a challenging issue, which is crucial for improving the overall efficiency of water electrolysis. Herein, inspired by the superiority of carbon conductivity, the propitious H atom binding energy of metallic cobalt, and better OER activity of cobalt oxide, we synthesized cobalt-cobalt oxide/N-doped carbon hybrids (CoOx@CN) composed of Co(0), CoO, Co3O4 applied to HER and OER by simple one-pot thermal treatment method. CoOx@CN exhibited a small onset potential of 85 mV, low charge-transfer resistance (41 Ω), and considerable stability for HER. Electrocatalytic experiments further indicated the better performance of CoOx@CN for HER can be attributed to the high conductivity of carbon, the synergistic effect of metallic cobalt and cobalt oxide, the stability of carbon-encapsulated Co nanoparticles, and the introduction of electron-rich nitrogen. In addition, when used as catalysts of OER, the CoOx@CN hybrids required 0.26 V overpotential for a current density of 10 mA cm(-2), which is comparable even superior to many other non-noble metal catalysts. More importantly, an alkaline electrolyzer that approached ∼20 mA cm(-2) at a voltage of 1.55 V was fabricated by applying CoOx@CN as cathode and anode electrocatalyst, which opened new possibilities for exploring overall water splitting catalysts.
Despite being promising substitutes for noble metal catalysts used in hydrogen evolution reaction (HER), the nonprecious metal catalysts (NPMCs) based on inexpensive and earth-abundant 3d transition metals (TMs) are still practically unfeasible due mainly to unsatisfactory activity and durability. Herein, a highly active and stable catalyst for HER has been developed on the basis of molybdenum-carbide-modified N-doped carbon vesicle encapsulating Ni nanoparticles (MoxC-Ni@NCV). This MoxC-Ni@NCV material was synthesized simply by the solid-state thermolysis of melamine-related composites of oxalate and molybdate with uniform Ni ions doping (Ni@MOM-com). Notably, the prepared MoxC-Ni@NCV was almost the most efficient NPMCs for HER in acidic electrolyte to date. Besides good long-term stability, MoxC-Ni@NCV exhibited a quiet low overpotential that was comparable to Pt/C. Thus, this work opens a new avenue toward the development of highly efficient, inexpensive HER catalysts.
The earth-abundant nanohybrids Co 0 /Co 3 O 4 @N-doped carbon nanotubes were fabricated via an efficient thermal condensation of D-glucosamine hydrochloride, melamine and Co(NO 3 ) 2 ·6H 2 O. The hybrids furnish excellent catalytic activity and perfect chemoselectivity (>99%) for a wide range of substituted nitroarenes (21 examples) under relatively mild conditions. The high catalytic performance and durability is attributed to the synergistic effects between each component, the unique structure of graphene layers-coated Co 0 and the electronic activation of doped nitrogen. Density functional calculations indicate that the inner Co 0 core and N species on the carbon shell can significantly decrease the dissociation energies of H 2 , giving evidence of the ability of carbon shell in the hybrids to H 2 activation. These results open up an avenue to design more powerful low-cost catalysts for industrial applications.
Porous nitrogen-doped
graphene layers encapsulating cobalt nanoparticles
(NPs) were prepared by the direct pyrolysis process. The resulting
hybrids catalyze the hydrogenation of diverse quinoline compounds
to access the corresponding tetrahydro derivatives (THQs), important
molecules present in fine and bulk chemicals. Near-quantitative yields
of the corresponding THQs were obtained under optimized conditions.
Notably, various useful substituted quinolines and other biologically
important N-heteroarenes are also viable. The enhanced stability of
the catalyst is ascribed to the encapsulation structure, which can
enormously reduce the extent of leaching of base metals and protect
metal NPs from growing larger. The achieved success in the encapsulation
of metal NPs within graphene layers opens an avenue for the design
of highly active and reusable heterogeneous catalysts for more challenging
molecules.
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