Computational insights on potential dependence of electrocatalytic synthesis of ammonia from nitrate

doi:10.1016/S1872-2067(23)64413-4

Abstract

Abstract:

Electrochemical nitrate reduction reaction (eNO₃RR) has been considered as an alternative route for decentralized ammonia (NH₃) synthesis. However, a major challenge is products selectivity at low overpotentials, namely, the competition between nitrite (HNO₂) and ammonia. Herein, we employed a single-atom catalyst (FeN₄) as model to study the competitive mechanism of NH₃ and HNO₂ by density functional theory calculations. It was found the optimal paths for ammonia and nitrite productions share a key intermediate (NO₂*), whose adsorption structures and preference in the following conversion determines the selectivity. We have incorporated potential-dependent barriers and microkinetic modeling to understand the Faradaic efficiency at different potentials. Our results are in good agreement with the experimental trend of Faradaic efficiencies of NH₃ and HNO₂, which can be rationalized well by the charge transfer coefficient (β) for NO₂* protonation to cisHNO₂* with respect to that to HNO₂. A low selectivity of ammonia production at small overpotentials can be ascribed to a kinetic issue. The electron localization function and crystal orbital Hamilton population were analyzed on the initial and transition states for NO₂* protonation to cisHNO₂* and HNO₂. The computational mechanistic insights can help to design new catalyst for eNO₃RR highly active and selective to NH₃.

Key words: Electrochemical ammonia synthesis, Density functional theory calculation, Reaction phase diagram, Activity, Selectivity

Huijuan Jing, Jun Long, Huan Li, Xiaoyan Fu, Jianping Xiao. Computational insights on potential dependence of electrocatalytic synthesis of ammonia from nitrate[J]. Chinese Journal of Catalysis, 2023, 48: 205-213.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64413-4

https://www.cjcatal.com/EN/Y2023/V48/I5/205

Figures/Tables 5

Scheme 1. (a) A complex reaction network for eNO3RR to nitrite and ammonia, constructed from the elementary steps listed in Table S1. (b) A scheme of global energy optimization to search optimal pathway, where the rA, rB and rC are the elementary steps with the largest ΔGRPD in given paths; (c) The green and red arrows connect a specific pathway of eNO3RR to ammonia and nitrite over FeN4 catalyst.

Fig. 1. The 2D (quasi) activity maps as a function of NH* [Gad(NH*)] and HNO2* [Gad(HNO2*)] adsorption free energies for eNO3RR to NH3 (a) and HNO2 (b). (c) The 2D (quasi) activity and selectivity map for eNO3RR to NH3 and HNO2, the areas marked by the black line represent the border of different selectivity. The 2D maps are shown at -0.55 V vs. RHE, marked with a standard error bar of 0.2 eV. (d) The limiting (solid black line) and path-selective steps (solid color line) for eNO3RR to NH3 and HNO2. For the one-dimensional reaction phase diagram, the shadow (light green) and blank background represent selective NH3 and HNO2 production, respectively.

Fig. 2. Kinetic barriers on FeN4 for eNO3RR to NH3 and HNO2 at -0.50 V vs. RHE (in eV). The most feasible pathways to produce NH3 and HNO2 are highlighted with green and red lines, respectively. The pink, red, light blue, brown and bright yellow represent H, O, N, C and Fe atoms, respectively.

Fig. 3. (a) Free energy diagram of eNO3RR to NH3 on FeN4 at three different potentials (-0.50, -0.66 and -0.85 V vs. RHE). (b) Free energy diagram of eNO3RR to HNO2 on FeN4 at three different potentials (-0.50, -0.66 and -0.85 V vs. RHE). (c) FE trend of NH3 and HNO2 as a function of potential by microkinetic simulations. (d) FE trend of NH3 and HNO2 as a function of potential by experiment from Ref. [14]. (e) The kinetic barriers of key elementary steps at various potentials. (f) Comparison between theoretical activity (logTOFNH3) and experimental partial current density of NH3 (logjNH3) at each applied potential ranging from -0.50 to -0.85 V vs. RHE.

Fig. 4. (a) (1-4) The geometry and ELF of key initial states for R4: NO2* → cisHNO2* and R7: NO2* → HNO2. (b) (1-4) The geometry and ELF of key transition states for R4: NO2* → cisHNO2* and R7: NO2* → HNO2. (c) The COHP analysis for the interaction of Fe-N bond in the optimized initial states for (1) R4: NO2* → cisHNO2* and (2) R7: NO2* → HNO2. (d) The COHP analysis for the interaction of H???O bond in the optimized transition states for (1) R4: NO2* → cisHNO2* and (2) R7: NO2* → HNO2. (As shown in Fig. 4(a) (1 and 2) and Fig. 4(b) (1 and 2), the pink, green, red, light blue, brown and bright yellow represent H, transferred H, O, N, C and Fe atoms, respectively.)

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