Edge-doped substituents as an rising atomic-level technique for enhancing M–N4–C single-atom catalysts in electrocatalysis of the ORR, OER, and HER

M–N₄–C single-atom catalysts (MN₄) have gained consideration for his or her environment friendly use on the atomic degree and adjustable properties in electrocatalytic reactions just like the ORR, OER, and HER. But, understanding MN₄‘s exercise origin and enhancing its efficiency stays difficult. Edge-doped substituents profoundly have an effect on MN₄‘s exercise, explored on this research by investigating their interplay with MN₄ metallic facilities in ORR/OER/HER catalysis (Sub@MN₄, Sub = B, N, O, S, CH₃, NO₂, NH₂, OCH₃, SO₄; M = Fe, Co, Ni, Cu). The outcomes present overpotential variations (0 V to 1.82 V) primarily based on Sub and metallic facilities. S and SO₄ teams optimize FeN₄ for peak ORR exercise (overpotential at 0.48 V) and cut back OER overpotentials for NiN₄ (0.48 V and 0.44 V). N considerably reduces FeN₄‘s HER overpotential (0.09 V). Correlation evaluation highlights the metallic middle’s key function, with ΔG_*H and ΔG_*OOH displaying mutual predictability (R² = 0.92). E_g proves a dependable predictor for Sub@CoN₄ (ΔG_*OOH/ΔG_*H, R² = 0.96 and 0.72). Machine studying with the KNN mannequin aids catalyst efficiency prediction (R² = 0.955 and 0.943 for ΔG_*OOH/ΔG_*H), emphasizing M–O/M–H and the d band middle as essential elements. This research elucidates edge-doped substituents’ pivotal function in MN₄ exercise modulation, providing insights for electrocatalyst design and optimization.