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Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
Published on: April 10, 2018
A Zn-modulated NiFeCoCuZn high-entropy alloy for efficient electrocatalytic nitrate reduction to ammonia
Jiahui Wang1, Peihan Yan1, Yaqin Li1
1School of Materials Science, Shanghai Dianji University, 300 Shuihua Road, Pudong New Area, Shanghai 201306, China. zhiyahan@sdju.edu.cn.
Abstract:
Electrocatalytic nitrate reduction to ammonia offers a promising route for coupling nitrate-contaminated wastewater remediation with value-added ammonia production, yet efficient catalysts with high selectivity and stability remain difficult to develop. Herein, a Zn-modulated NiFeCoCuZn high-entropy alloy catalyst was constructed, with Zn-free NiFeCoCu as the control. Structural and compositional characterization confirmed the near-equimolar multicomponent nature of NiFeCoCuZn, while Zn incorporation altered the particle-stacking morphology and surface core-level electronic states of the NiFeCoCu matrix. XPS analysis reveals negative shifts in the Ni, Fe, Co, and Cu core-level binding energies together with clear Zn 2p signals, indicating Zn-associated local electronic perturbation and multimetallic coupling. Benefiting from this regulated high-entropy alloy environment, NiFeCoCuZn delivers an NH3 yield rate of approximately 151.9 mg h-1 mg_cat-1 and an NH3 faradaic efficiency of approximately 91.2% at -0.5 V vs. RHE, outperforming the NiFeCoCu control. Chronoamperometry, UV-vis colorimetry, and 1H NMR cross-validation further verify its nitrate-to-ammonia conversion capability. Auxiliary free-energy calculations suggest that Zn incorporation optimizes nitrate-intermediate adsorption, lowers the initial nitrate-activation energy barrier, and maintains manageable competition from the hydrogen-evolution pathway, thereby promoting selective ammonia production.
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