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Reaction mechanism and kinetics for N₂ reduction to ammonia on the Fe-Ru based dual-atom catalyst

Rehman, Faisal and Kwon, Soonho and Hossain, Md Delowar and Musgrave, Charles B., III and Goddard, William A., III and Luo, Zhengtang (2022) Reaction mechanism and kinetics for N₂ reduction to ammonia on the Fe-Ru based dual-atom catalyst. Journal of Materials Chemistry A, 10 (43). pp. 23323-23331. ISSN 2050-7488. doi:10.1039/d2ta06826e.

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Environmental and energy considerations demand that the Haber-Bosch process for reducing N₂ to NH₃ be replaced with electrochemical ammonia synthesis where the H atoms come from water instead of from H₂. But a practical realization of electrochemical N₂ reduction reaction (NRR) requires the development of new generation electrocatalysts with low overpotential and high Faraday efficiency (FE). A major problem here is that the hydrogen evolution reaction (HER) competes with NRR. Herein, we consider new generation dual-site catalysts involving two different metals incorporated into a novel two-dimensional C₃N–C₂N heterostructure that provides a high concentration of well-defined but isolated active sites that bind two distinct metal atoms in a framework that facilitates electron transfer. We report here the mechanism and predicted kinetics as a function of applied potential for both NRR and HER for the (Fe–Ru)/C₃N–C₂N dual atom catalyst. These calculations employ the grand canonical potential kinetics (GCP-K) methodology to predict reaction free energies and reaction barriers as a function of applied potential. The rates are then used in a microkinetic model to predict the turn-over-frequencies (TOF) as a function of applied potential. At U = 0 V, the FE for NRR is 93%, but the current is only 2.0 mA cm⁻². The onset potential (at 10 mA cm⁻²) for ammonia on Fe–Ru/C₃N–C₂N is −0.22 V_(RHE). This leads to a calculated TOF of 434 h⁻¹ per Fe–Ru site. We expect that the mechanisms for NRR and HER developed here will help lead to new generations of NRR with high TOF and FE.

Item Type:Article
Related URLs:
URLURL TypeDescription
Rehman, Faisal0000-0002-2524-8681
Kwon, Soonho0000-0002-9225-3018
Hossain, Md Delowar0000-0003-3440-8306
Musgrave, Charles B., III0000-0002-3432-0817
Goddard, William A., III0000-0003-0097-5716
Luo, Zhengtang0000-0002-5134-9240
Alternate Title:Reaction mechanism and kinetics for N2 reduction to ammonia on the Fe–Ru based dual-atom catalyst
Additional Information:Z. L. acknowledge supports by the RGC (16304421), the Innovation and Technology Commission (ITC-CNERC14SC01), Guangdong Science and Technology Department (Project No. 2020A0505090003), Research Fund of Guangdong-Hong Kong-Macao Joint Laboratory for Intelligent Micro-Nano Optoelectronic Technology (No. 2020B1212030010), IER Foundation (HT-JD-CXY-201907), and Shenzhen Special Fund for Central Guiding the Local Science and Technology Development (2021Szvup136). F. R. appreciates financial support from the Higher Education Commission (HEC) of Pakistan. S. K. and C. B. M. and W. A. G. acknowledge support by the Liquid Sunlight Alliance, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award Number DE-SC0021266. All results and findings in this work reflect solely the opinions of the author and does not represent the views of the U.S. government.
Group:Liquid Sunlight Alliance
Funding AgencyGrant Number
Research Grants Council of Hong Kong16304421
Innovation and Technology Commission (Hong Kong)ITC-CNERC14SC01
Guangdong Science and Technology Department2020A0505090003
Guangdong-Hong Kong-Macao Joint Laboratory for Intelligent Micro-Nano Optoelectronic Technology2020B1212030010
IER FoundationHT-JD-CXY-201907
Shenzhen Special Fund for Central Guiding the Local Science and Technology Development2021Szvup136
Higher Education Commission (Pakistan)UNSPECIFIED
Department of Energy (DOE)DE-SC0021266
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Issue or Number:43
Record Number:CaltechAUTHORS:20221103-652750400.32
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:117708
Deposited By: Donna Wrublewski
Deposited On:03 Dec 2022 22:21
Last Modified:03 Dec 2022 22:21

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