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Modulation of Cu Electronic Structure to Accelerate the Conversion of Key Intermediates for Electrocatalytic Ammonia Synthesis
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DOI：10.1021/acscatal.4c07167.png)
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Abstract
En 中文
Electrochemical nitrate reduction (NO3RR) is primarily hampered by high energy barriers associated with the rate-determining step (RDS), which involves the conversion of *NO3 to *NO2, and the selectivity-determining step (SDS) from *NO to *NHO. Herein, we exhibit a molecular catalyst, Cu(I)-phen-SCN, where the S of the SCN ligand has the highest polarizability and lowest electronegativity compared to C or N. The optimized electronic structure of the catalyst effectively reduces the energy barrier of RDS and SDS simultaneously. In situ impedance and infrared spectroscopy revealed that Cu(I)-phen-SCN exhibits the fastest early reaction kinetics, deeply reducing *NO3 to generate *NO intermediates at an extremely low potential (+0.2 V vs RHE). As a result, the resulting catalyst can achieve ammonia synthesis with Faradaic efficiency and N-selectivity close to similar to 100% and ammonia yields as high as 241.20 +/- 10.82 mg h-1 mgcat -1. In situ X-ray absorption spectroscopy (XAS) and attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) measurements have shown that Cu(I)-phen-SCN is maintained in a dynamically stable state throughout the electrochemical processes, exhibiting excellent catalytic durability. This work proposes a new method to lower the energy barrier in nitrate-based ammonia synthesis reactions, providing an effective strategy to improve the efficiency of ammonia synthesis.
Keywords:
ammonia synthesis
reaction kinetics
rate-determiningstep
selectivity-determining step
structure regulation
Journal
IF:
13.1
Papers:
1.6W
Citations:
15.0W
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Cited Papers