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

Rehman, Faisal; Kwon, Soonho; Hossain, Md Delowar; Musgrave III, Charles B.; Goddard, III, William A.; Luo, Zhengtang

doi:10.1039/d2ta06826e

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

Journal Article · Sat Oct 22 00:00:00 EDT 2022 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d2ta06826e· OSTI ID:2421859

^[1]; ^[2]; Hossain, Md Delowar ^[3]; ^[2]; ^[2]; ^[4]

Hong Kong University of Science and Technology (HKUST) (Hong Kong); University of Engineering & Technology Lahore, Faisalabad (Pakistan); California Institute of Technology (CalTech), Pasadena, CA (United States); OSTI
California Institute of Technology (CalTech), Pasadena, CA (United States)
Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis
Hong Kong University of Science and Technology (HKUST) (Hong Kong)

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. In conclusion, we expect that the mechanisms for NRR and HER developed here will help lead to new generations of NRR with high TOF and FE.

View Accepted Manuscript (DOE)

Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0021266

OSTI ID:: 2421859

Alternate ID(s):: OSTI ID: 1894366

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 43 Vol. 10; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
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Energy & Fuels
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N2 reduction
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dual-atom catalyst

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

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