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Electrocatalytic Reduction of Nitrogen to Ammonia Using Tiara-like Phenylethanethiolated Nickel Cluster |
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| Authors: | Dr Manju P Maman Dr Tamilselvi Gurusamy Dr Arun K Pal Dr Rajkumar Jana Dr Kothandaraman Ramanujam Dr Ayan Datta Dr Sukhendu Mandal |
| Institution: | 1. School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram Maruthamala P. O., Vithura, Thiruvananthapuram, Kerala, 695551 India
These authors contributed equally to this work.;2. Department of Chemistry, Advanced Centre for Energy Storage and Conversion—The Energy Consortium, Indian Institute of Technology Madras, Chennai, Tamil Nadu, 600036 India These authors contributed equally to this work.;3. School of Chemical Sciences, Indian Association for the Cultivation of Science, Kolkata, 700032 India;4. Department of Chemistry, Advanced Centre for Energy Storage and Conversion—The Energy Consortium, Indian Institute of Technology Madras, Chennai, Tamil Nadu, 600036 India;5. School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram Maruthamala P. O., Vithura, Thiruvananthapuram, Kerala, 695551 India |
| Abstract: | 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. |
| Keywords: | Ammonia Synthesis Atom-Precise Cluster DFT Electrocatalysis Nitrogen Reduction Reaction |