A Feasible Strategy for Identifying Single‐Atom Catalysts Toward Electrochemical NO‐to‐NH₃ Conversion

Abstract

Combining NO removal and NH3 synthesis, electrochemical NO reduction reaction (NORR) toward NH3 is considered as a novel and attractive approach. However, exploring suitable catalysts for NO‐to‐NH3 conversion is still a formidable task due to the lack of a feasible method. Herein, utilizing systematic first‐principles calculations, a rational strategy for screening efficient single‐atom catalysts (SACs) for NO‐to‐NH3 conversion is reported. This strategy runs the gamut of stability, NO adsorbability, NORR activity, and NH3 selectivity. Taking transition metal atom embedded in C2N (TM‐C2N) as an example, its validity is demonstrated and Zr‐C2N is selected as a stable NO‐adsorbable NORR catalyst with high NH3 selectivity. Therefore, this work has established a theoretical landscape for screening SACs toward NO‐to‐NH3 conversion, which will contribute to the application of SACs for NORR and other electrochemical reactions.

Confinement catalysis of a single atomic vacancy assisted by aliovalent ion doping enabled efficient NO electroreduction to NH3

“…74 This NO adsorption model will restrict the reaction to occur only through the distal pathway among various ones. 27,29 More importantly, the conned space of SAVs will effectively prevent the approaching of two NO molecules and thus the N-N bond coupling to form N 2 O 2 , and the under-coordinated active sites in the vacancy can strongly bind the N atom to prevent *N diffusion. Consequently, due to spatial connement, N 2 formation can be excluded and there is only one pathway for N 2 O formation, i.e., the coupling of the N-N bond between *N and the incoming NO, which will guarantee the high selectivity of NO-to-NH 3 .…”

“…14,15 However, up to now, only a few electrocatalysts have been reported from experiments [16][17][18][19][20][21] or theories. [22][23][24][25][26][27][28][29][30][31][32][33] Undoubtedly, designing NORR electrocatalysts with higher performance poses a great challenge for this emerging reaction.…”

“…However, the competitive hydrogen evolution reaction (HER) and the broad spectrum of reductive products make the ve-electron NO-NH 3 transformation process rather challenging. [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] For the NORR, N 2 and N 2 O are the main possible byproducts, and especially N 2 formation is the most thermodynamically favorable. 9,22,26,34 For the formation of N 2 O and N 2 , the NO dimer (N 2 O 2 ) is considered as a pivotal precursor with the cis form being the most stable.…”

Coupling denitrification and ammonia synthesis via selective electrochemical reduction of nitric oxide over Fe2O3 nanorods

“…For this, the pivotal precursor is the NO dimer (N 2 O 2 ), whose cis form is the most stable with the structure of O]N-N]O. 61,62 As shown in Fig. S33, † This journal is © The Royal Society of Chemistry 2022 (110) and (012) surfaces, as shown in Fig.…”

Highly Efficient Electrocatalytic Upgrade of n‐Valeraldehyde to Octane over Au SACs–NiMn2O4 Spinel Synergetic Composites

“…However, the one-step electrocatalytic upgrade of n-valeraldehyde to high-value-added octane has remained unexplored. In recent years, single-atom catalysts have been gradually utilized in the elimination of inorganic and organic pollutants, such as NO, [40] carbon monoxide, [41] carbon dioxide, [42] nitrate, [43,44] 1, 2-dichloroethane, [34] and upgrade of N 2 and 1, 2-dichloroethane, [34,45] and good results are obtained. Herein, we fabricate an Au SACs-NiMn 2 O 4 spinel synergetic composites via simple and feasible adsorption-deposition method and apply it in the one-step electrocatalytic upgrade of n-valeraldehyde to octane.…”