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Research Article | Open Access

Enhanced N2 electroreduction activity of single-atom catalysts: Modulating the linear scaling relationship by coordination engineering and dual-site strategies

Renyi Li1, Caimu Wang1, Jiao Zhang1, Wei Guo1,2 ()
Centre for Quantum Physics, Key Laboratory of Advanced Optoelectronic Quantum Architecture and Measurement (MOE), School of Physics, Beijing Institute of Technology, Beijing 100081, China
Frontiers Science Center for High Energy Material (MOE), Beijing Institute of Technology, Beijing 100081, China
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The linear scaling relationship between ∆G(*N2→*N2H) and ∆G(*NH2→*NH3) of TM@WS2 single-atom catalysts (SACs) can be optimized by coordination engineering and dual-site strategies, bringing the modulated catalyst closer to the ideal active space of electrocatalytic nitrogen reduction reaction (eNRR).

Abstract

The volcano plot is widely used to elucidate the activity trends among different catalysts, thereby effectively screening and guiding catalyst design. However, the inherent linear scaling relationship (LSR) constrains the breakthrough in the activity of catalysts, and the understanding of the activity limit in volcano plot is still ambiguous. In this work, by employing first-principles calculations and microkinetic modeling, we proposed coordination engineering (CE) and dual-site (DS) strategies to surpass the Sabatier’s limitation of WS2-supported TM (TM@WS2) single-atom catalysts (SACs) for electrocatalytic nitrogen reduction reaction (eNRR). We found that the LSR between ΔG(*N2→*N2H) and ΔG(*NH2→*NH3) was optimized to be closer to the ideal space of eNRR activity after modulating TM@WS2 SACs by these two design strategies. By combining the reaction selectivity trend plot, we picked out N-Os@WS2, C-Ir@WS2, Fe2@WS2, and Ru2@WS2 as optimal eNRR catalysts with low limiting potential (UL), and N-Os@WS2 SAC (UL: –0.28 V) outperforms the best eNRR catalyst among TM@WS2 SACs. By constructing explicit solvent models, we conducted a detailed study on the reaction kinetics of proton transfer over these four catalysts. We propose that the activity enhancement in TM@WS2 SACs for eNRR can be attributed to the ligand effect and geometric effect brought about by CE and DS strategies, improving the donation-backdonation process of electron transfer between N2 and the active sites. The designed catalyst has certain resistance to demetallization and agglomeration under simulated solvent environment. This work provides a feasible design strategy for the activity enhancement of SACs and brings a new perspective to deeply understanding the volcano plot in heterogeneous catalysis.

Keywords

linear scaling relationshipvolcano plotsingle-atom catalystsdensity functional theory (DFT)electrochemical nitrogen reduction

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Nano Research
Volume 18 Issue 3,
March 2025
Article number: 94907212
DOI: 10.26599/NR.2025.94907212
Cite this article:
Li R, Wang C, Zhang J, et al. Enhanced N2 electroreduction activity of single-atom catalysts: Modulating the linear scaling relationship by coordination engineering and dual-site strategies. Nano Research, 2025, 18(3): 94907212. https://doi.org/10.26599/NR.2025.94907212
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