4.8 Article

Nanoparticulate WN/Ni3C Coupling in Ceramic Coatings for Boosted Urea Electro-Oxidation

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ADVANCED ENERGY MATERIALS
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WILEY-V C H VERLAG GMBH
DOI: 10.1002/aenm.202302452

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ceramic coatings; DFT calculations; electrolysis; urea oxidation reaction; WN/Ni3C coupling

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A novel ceramic coating with coupled tungsten nitride/nickel carbide nanoparticles has been developed for urea electrolysis. The coupled effect enables valence-stable catalytic sites, leading to enhanced electron transfer and improved kinetics of the urea oxidation reaction. The ceramic coating shows outstanding performance as a urea oxidation reaction electrocatalyst, making it a promising candidate for advanced electrocatalytic applications.
Urea electrolysis can convert urea from urea-rich wastewater to hydrogen for environmental protection and sustainable energy production. However, the sluggish kinetics of urea oxidation reaction (UOR) requires valence-variable sites that are generally active at high anodic overpotentials. Herein, a robust ceramic coating is constructed with coupled tungsten nitride (WN)/nickel carbide (Ni3C) nanoparticles to achieve valence-stable catalytic sites with outstanding UOR performance. Various characterization results indicate strong interfacial electron transfer from WN to Ni3C in coupled nanoparticles, which enables reservation of Ni2+ sites without self-oxidation during UOR, quite distinct from the kinetically slow Ni3+ OOH-catalyzed UOR pathway. Theoretical calculations show that the coupled effect in WN/Ni3C leads to enhanced electron transfer from catalytic sites to adsorbed urea, and W sites are thermodynamically favorable for UOR. This efficiently lowers the barrier of rate-determining step (RDS: *CO-N-2.-> *CO center dot OH), thus enabling fast UOR kinetics and a low potential of 1.336 V at 100 mAcm(-2), which identifies this ceramic coating as one of the best UOR electrocatalysts. This work opens a new avenue for design of stable and active sites in ceramics coatings toward advanced electrocatalytic applications.

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