Theoretical Insights into the Mechanism of Selective Nitrate‐to‐Ammonia Electroreduction on Single‐Atom Catalysts

Abstract

Selective nitrate‐to‐ammonia electrochemical conversion is an efficient pathway to solve the pollution of nitrate and an attractive strategy for low‐temperature ammonia synthesis. However, current studies for nitrate electroreduction (NO3RR) mainly focus on metal‐based catalysts, which remains challenging because of the poor understanding of the catalytic mechanism. Herein, taking single transition metal atom supported on graphitic carbon nitrides (g‐CN) as an example, the NO3RR feasibility of single‐atom catalysts (SACs) is first demonstrated by using density functional theory calculations. The results reveal that highly efficient NO3RR toward NH3 can be achieved on Ti/g‐CN and Zr/g‐CN with low limiting potentials of −0.39 and −0.41 V, respectively. Furthermore, the considerable energy barriers are observed during the formation of byproducts NO2, NO, N2O, and N2 on Ti/g‐CN and Zr/g‐CN, guaranteeing their high selectivity. This work provides a new route for the application of SACs and paves the way to the development of NO3RR.

Theoretical Inspection of TM-P4C Single-Atom Electrocatalyst: Ultra-High Performance for bifunctional Oxygen Reduction and Evolution Reactions

“…For the all TMP4 catalysts, CoP4 exhibits the best OER, ORR and bifunctional catalytic activities with 𝐸 𝑂𝐸𝑅 = 1.55 𝑉, 𝐸 𝑂𝑅𝑅 = 0.86 𝑉 and ∆𝐸 = 0.69𝑉, respectively, which are better than that of Ni-SAC reported recently by Zhang and co-workers [52] (𝐸 𝑂𝐸𝑅 = 1.62 𝑉, 𝐸 𝑂𝑅𝑅 = 0.59 𝑉 and ∆𝐸 = 1.03𝑉). Followed by the PdP4 (𝐸 𝑂𝐸𝑅 = 1.98 𝑉, 𝐸 𝑂𝑅𝑅 = 0.69 𝑉 and ∆𝐸 = 1.29𝑉), RhP4 (𝐸 𝑂𝐸𝑅 = 1.73 𝑉, 𝐸 𝑂𝑅𝑅 = 0.07 𝑉 and ∆𝐸 = 1.66𝑉), PtP4 (𝐸 𝑂𝐸𝑅 = 1.79 𝑉, 𝐸 𝑂𝑅𝑅 = 0.12 𝑉 and ∆𝐸 = 1.67𝑉 ), AuP4 ( 𝐸 𝑂𝐸𝑅 = 1.9 𝑉 , 𝐸 𝑂𝑅𝑅 = 0.21 𝑉 and ∆𝐸 = 1.69𝑉 ) and NiP4 ( 𝐸 𝑂𝐸𝑅 = 2.07 𝑉 , 𝐸 𝑂𝑅𝑅 = 0.36 𝑉 and ∆𝐸 = 1.71𝑉 ).…”

Engineering Single Atom Catalysts to Tune Properties for Electrochemical Reduction and Evolution Reactions

“…Thus, SACs integrate benefits that include high catalytic activity, stability, selectivity, and reusability to sustainably synthesize fine chemicals. [ 30–34 ]…”

Tunable Schottky Barrier and Interfacial Electronic Properties in Graphene/ZnSe Heterostructures

“…Ever since graphene was exfoliated experimentally in 2004Novoselov et al (2004, owing to its unique advantages, such as high charge mobility at room temperature and excellent Hall effect Novoselov et al (2005), Zhang et al (2005), it has attracted many theoretical and experimental attentions (Olabi et al, 2021;cao et al, 2018;Wang et al, 2020;Niu et al, 2020). Nevertheless, ZnSe as a zero bandgap material was not well-developed in graphene photonics and optoelectronics (Bonaccorso et al, 2010).…”