The low temperature (250 ˚C) plasma-enhanced atomic layer deposition of TiZrN alloys yields films with low Zr valence. In optimized Ti-to-Zr-ratio thin films, a high electrochemical surface area remains even after air exposure.
Significance and Impact
Zirconium nitride with a metal valence state of (III) is computationally predicted to be one of the most promising NRR electrocatalysts to generate ammonia at minimal overpotential.
- Zn(III)N is prone to oxidation to the thermodynamically more stable, but catalytically inert and electrically insulating Zr(IV)3N4.
- High temperature (700 ˚C) is required for challenging Zn(III)N conventional synthesis, severely limiting its experimental application as an electrocatalyst.
- At low Zr:Ti ratios, experimentally measured binding energies are consistent with those of Zr(III)N.
Work was performed at Argonne National Laboratory.
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