Computational insights and strategic choices of nitrate and nitric oxide electroreduction to ammonia

doi:10.1016/S1872-2067(25)64776-0

Abstract

Abstract:

Electrochemical nitrate reduction (eNO₃RR) and nitric oxide reduction (eNORR) to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production, particularly within the recently proposed reverse artificial nitrogen cycle route: N₂ → NO_x → NH₃. Notably, experimental studies have demonstrated that eNORR exhibits superior performance over eNO₃RR on Cu₆Sn₅ catalysts. However, the fundamental mechanisms underlying this difference remain poorly understood. Herein, we performed systematic theoretical calculations to explore the reaction pathways, electronic structure effects, and potential-dependent Faradic efficiency associated with ammonia production via these two distinct electrochemical pathways (eNORR and eNO₃RR) on Cu₆Sn₅. By implementing an advanced ‘adaptive electric field controlled constant potential (EFC-CP)’ methodology combined with microkinetic modeling, we successfully reproduced the experimental observations and identified the key factors affecting ammonia production in both reaction pathways. It was found that eNORR outperforms eNO₃RR because it circumvents the ^*NO₂ dissociation and ^*NO₂ desorption steps, leading to distinct surface coverage of key intermediates between the two pathways. Furthermore, the reaction rates were found to exhibit a pronounced dependence on the surface coverage of ^*NO in eNORR and ^*NO₂ in eNO₃RR. Specifically, the facile desorption of ^*NO₂ on the Cu₆Sn₅ surface in eNO₃RR limits the attainable surface coverage of ^*NO, thereby impeding its performance. In contrast, the eNORR can maintain a high surface coverage of adsorbed ^*NO species, contributing to its enhanced ammonia production performance. These fundamental insights provide valuable guidance for the rational design of catalysts and the optimization of reaction routes, facilitating the development of more efficient, sustainable, and scalable techniques for ammonia production.

Key words: Reverse ammonia production, Electrocatalysis, Nitric oxide reduction, Nitrate reduction, Constant potential, Density functional theory calculation, Microkinetic modeling

Pu Guo, Shaoxue Yang, Huijuan Jing, Dong Luan, Jun Long, Jianping Xiao. Computational insights and strategic choices of nitrate and nitric oxide electroreduction to ammonia[J]. Chinese Journal of Catalysis, 2025, 77: 220-226.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64776-0

https://www.cjcatal.com/EN/Y2025/V77/I10/220

Figures/Tables 4

Fig. 1. (a) Computational model. (b) The free energies of the Volmer reaction at different potentials and dielectric constants. (c) Fitting results of slopes for εHP, Volmer reaction as a model system. (d) Linear relationships of ?G(HER) vs. ?M.

Fig. 2. (a) Free energy diagram for eNO3RR and eNORR to NH3 on the bare surface of Cu6Sn5 (22-) at 0 V vs. RHE. (b) Geometries for the intermediates in the optimal pathway. The red, blue, white, purple, dark grayish cyan and soft red colors denote the oxygen, nitrogen, hydrogen, potassium, tin and copper atoms, respectively.

Fig. 3. (a) Desorption energy for nitrite ion and the corresponding electron transfer during NO2 desorption. (b) Density of states of Cu6Sn5 at 0 V vs. RHE and ?0.22 V vs. RHE. Note that the fermi level at ?0.22 V vs. RHE is respect to that at 0 V vs. RHE. $\Delta N=\int_{-\infty}^{E f} \operatorname{DOS}(E) d E(-0.22 V)-\int_{-\infty}^{E f} \operatorname{DOS}(E) d E(0 V)$ (c) Activation energy barriers for *NO2 dissociation, *NO2 protonation and *NO protonation. (d) Charge transfer coefficients β [β = 1 - (qTS - qFS)] for *NO2 protonation (top) and *NO protonation (bottom) over Cu6Sn5 at different potentials. (e) Geometries of the transition states for *NO2 protonation (top) and *NO protonation (bottom) on Cu6Sn5 at 0 V vs. RHE. (f) ?COHP and ?ICOHP analyses for *NO2 protonation (left) and *NO protonation (right) at 0 V vs. RHE. The ?ICOHP at the Fermi level is indicated. (g) ?ICOHP of O?H bond at initial state for *NO2 protonation and NO protonation over Cu6Sn5 at different potentials. (h) Activation energy barrier for the Volmer and Heyrovsky reactions at 0 V vs. RHE over Cu6Sn5. (i) Charge transfer coefficients (top) and activation energy barriers (bottom) for the Volmer and Heyrovsky reactions over Cu6Sn5 at different potentials. The red, blue, white, purple, dark grayish cyan and soft red colors denote the oxygen, nitrogen, hydrogen, potassium, tin and copper atoms, respectively. IS, TS and FS denote the initial state, transition state and final state.

Fig. 4. (a) Simulated and experimental Faradaic efficiencies for ammonia in eNORR and eNO3RR on bare Cu6Sn5 at various potentials. (b) Simulated and experimental Faradaic efficiency for eNORR on bare Cu6Sn5 (top) and eNO3RR on semi-covered Cu6Sn5 (bottom) at 0 V vs. RHE. Degree of rate control for different elementary steps (c) and surface coverage of intermediates (d) in eNORR and eNO3RR over the Cu6Sn5 at different potentials. (R1: *NO + H2O + e- ? *NOH + OH?, R2: *NO2 + e- ? NO2? + *, R3: *NO2 + * ? *NO + *O, R4: NO3? + * ? *NO3 + e-).

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