Electrocatalytic Reduction of Nitrogen to Ammonia Using Tiara‐like Phenylethanethiolated Nickel Cluster

The fixing of N2 to NH3 is challenging due to the inertness of the N≡N bond. Commercially, ammonia production depends on the energy‐consuming Haber‐Bosch (H−B) process, which emits CO2 while using fossil fuels as the sources of hydrogen and energy. An alternative method for NH3 production is the ele...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-07, Vol.62 (27), p.e202305462-n/a
Main Authors: Maman, Manju P., Gurusamy, Tamilselvi, Pal, Arun K., Jana, Rajkumar, Ramanujam, Kothandaraman, Datta, Ayan, Mandal, Sukhendu
Format: Article
Language:English
Subjects:
Alternative energy sources
Ammonia
Ammonia Synthesis
Atom-Precise Cluster
Carbon dioxide
Catalysts
Chemical reduction
Clusters
DFT
Electrocatalysis
Electrochemistry
Fossil fuels
Nickel
Nitrogen
Nitrogen Reduction Reaction
Renewable energy sources
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Summary:The fixing of N2 to NH3 is challenging due to the inertness of the N≡N bond. Commercially, ammonia production depends on the energy‐consuming Haber‐Bosch (H−B) process, which emits CO2 while using fossil fuels as the sources of hydrogen and energy. An alternative method for NH3 production is the electrochemical nitrogen reduction reaction (NRR) process as it is powered by renewable energy sources. Here, we report a tiara‐like nickel‐thiolate cluster, [Ni6(PET)12] (where, PET=2‐phenylethanethiol)] as an efficient electro‐catalyst for the electrochemical NRR at ambient conditions. Ammonia (NH3: 16.2±0.8 μg h−1 cm−2) was the only nitrogenous product over the potential of −2.3 V vs. Fc+/Fc with a Faradaic efficiency of 25%±1.7. Based on theoretical calculations, NRR by [Ni6(PET)12] proceeds through both the distal and alternating pathways with an onset potential of −1.84 V vs. RHE (i.e., −2.46 V vs. Fc+/Fc) which corroborates with the experimental findings. Atom‐precise nickel‐thiolate clusters activate dinitrogen electrochemically and selectively transform it to ammonia with 25 % Faradaic efficiency. A combined approach based on experimental results and theoretical calculations sheds light on the mechanism of this electrochemical nitrogen reduction reaction.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202305462