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Matched Kinetics Process Over Fe2O3-Co/NiO Heterostructure Enables Highly Efficient Nitrate Electroreduction to
Qiang Yang1,2, Yongguang Bu3, Shuailei Pu1,2
1State Key Laboratory of Soil and Sustainable Agriculture, Institute of Soil Science, Chinese Academy of Sciences, Nanjing, 210008, China.
This study introduces a new electrocatalyst for green ammonia synthesis via nitrate electroreduction. Nickel-substituted cobalt-iron layered double oxides significantly improve ammonia selectivity and yield.
Area of Science:
- Electrochemistry
- Materials Science
- Green Chemistry
Background:
- Tandem nitrate electroreduction (NO₃⁻RR) is a promising route for green ammonia (NH₃) synthesis.
- Mismatched kinetics in NO₃⁻RR lead to poor NH₃ selectivity and nitrite (NO₂⁻) byproduct formation.
Purpose of the Study:
- To design and investigate Ni²⁺-substituted Co/Fe layered double oxides (LDOs) as tandem electrocatalysts for NO₃⁻RR.
- To enhance NH₃ selectivity and yield by addressing kinetic mismatches in the NO₃⁻RR process.
Main Methods:
- Synthesis of Ni²⁺-substituted Co/Fe LDOs.
- Electrochemical testing of NO₃⁻RR using pulsed electrolysis.
- In situ/operando characterization and theoretical calculations.
Main Results:
- The (Co₀.₈₃Ni₀.₁₆)₂Fe catalyst achieved a high NH₃ yield rate (50.4 mg·cm⁻²·h⁻¹) and Faradaic efficiency (97.8%).
- Ni substitution enhanced NH₃ selectivity by modifying Co electronic behavior and providing active hydrogen (*H) sites.
- Optimized adsorption and hydrogenation of *NO₂ on Co sites were observed.
Conclusions:
- Ni substitution in Co/Fe LDOs effectively promotes NO₃⁻RR kinetics and selectivity for NH₃ evolution.
- The findings offer insights into designing advanced tandem electrocatalysts for sustainable ammonia synthesis.
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