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Optimizing Nitrate Reduction to Ammonia via Modulating Adsorption-Desorption Dynamics with High-Entropy CuNiCoZnMn
Kun Zhang1, Zunjie Zhang2, Tianfang Yang2
1School of Materials Science and Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. China.
A novel quinary CuNiCoZnMn alloy catalyst significantly enhances ammonia synthesis from nitrate reduction. This high entropy alloy optimizes adsorption and desorption, achieving high ammonia yield and Faraday efficiency.
Area of Science:
- Materials Science
- Electrochemistry
- Catalysis
Background:
- Nitrate reduction reaction (NO3RR) to ammonia is an eight-electron process.
- Efficient NO3RR requires catalysts with optimal NO3- adsorption and NH3 desorption.
- Cu-based catalysts show promise for NO3RR due to their surface properties.
Purpose of the Study:
- To develop a high entropy quinary alloy catalyst for efficient nitrate reduction to ammonia.
- To tune the electronic structure of catalytic sites for optimized reaction pathways.
- To investigate the effect of Zn and Mn elements on adsorption and desorption properties.
Main Methods:
- Synthesis of CuNiCoZnMn high entropy quinary alloy.
- Electrochemical evaluation of catalytic performance for NO3RR.
- Density Functional Theory (DFT) calculations to analyze adsorption and desorption energies.
Main Results:
- The quinary CuNiCoZnMn alloy catalyst achieved an NH3 yield of 723.7 μmol h-1 cm-2 and 96.6% Faraday efficiency at -0.35 V vs RHE.
- DFT calculations revealed significantly improved NO3- adsorption (-2.50 eV) and NH3 desorption (0.072 eV) for the quinary alloy compared to ternary and quaternary alloys.
- Zn addition reduced desorption energy barrier, while Mn addition enhanced initial adsorption energy.
Conclusions:
- The CuNiCoZnMn quinary alloy demonstrates superior catalytic activity for ammonia synthesis via nitrate reduction.
- The high entropy alloy design effectively optimizes the adsorption-desorption dynamics crucial for efficient NO3RR.
- This catalyst presents a promising pathway for sustainable ammonia production.
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