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Designing 3d Transition-Metal Doped g-C3N4 Monolayer for Enhanced Bifunctional Oxygen Evolution/Reduction Reactions Activity: Defect Physics and Constant-Potential Study
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Abstract
En 中文
Graphitic carbon nitride (g-C3N4) doped with 3d transition metals (3d-TM@g-C3N4) has gained attention as a noble metal-free alternative for oxygen evolution and reduction reactions (OER/ORR). Yet the key mechanisms driving its performance remain debated, especially across different charge states. In this study, we investigate the electrocatalytic performance of 3d-TM@g-C3N4 (TM = V, Cr, Mn, Fe, Co, Ni, and Cu) in different charge states using a defect physics method based on density functional theory (DFT). We find that 33 unique charge states of 3d-TM@g-C3N4 are thermodynamically stable. Among them, the Co-substituted nitrogen site in the +1 charge state (CoN 1+@C54N71, eta OER/eta ORR = 0.57/0.50 V) and the Ni interstitial site in the +1 charge state (Niint 1+@C54N72, eta OER/eta ORR = 0.43/0.35 V) exhibit lower overpotentials (eta). Beyond the choice of dopant, key factors influencing the OER/ORR activity of 3d-TM@C3N4 include formation energy, charge state, and the Fermi level of the defective system. Furthermore, machine learning results reveal that the first ionization energy and the atomic radius of TMs are critical descriptors for predicting eta OER and eta ORR, respectively. Constant-potential DFT calculations further confirm that CoN@C54N71 and Niint@C54N72 exhibit excellent bifunctional activity at pH = 0 and U = 0 V versus RHE, with eta OER/eta ORR values of 0.71/0.57 V and 0.72/0.56 V, respectively-demonstrating strong potential for experimental synthesis. The study proposes a new category of bifunctional oxygen catalysts and introduces an innovative approach to optimize their electrocatalytic performance by engineering charge states and electronic structures. 3d(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic) (g-C3N4) (3d-TM@g-C3N4) (sic)(sic)(sic)(sic)(sic)(sic)(sic) (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic) (OER/ORR) (sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic) (DFT), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)3d-TM@g-C3N4 (TM = V,Cr,Mn,Fe,Co,Ni,Cu) (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).(sic)(sic)(sic)(sic), 3d-TM@g-C3N4(sic)(sic)33(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).(sic)(sic),+1(sic)(sic)Co(sic)(sic)N(sic) (sic) (CoN 1+@C54N71, eta OER/eta ORR = 0.57/0.50 V) (sic)+1(sic)(sic)Ni(sic)(sic)(sic) (Niint 1+@C54N72, eta OER/eta ORR = 0.43/0.35 V) (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic) (eta).(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)(sic)3d-TM@g-C3N4(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic),(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)eta OER(sic)eta ORR(sic)(sic)(sic)(sic)(sic)(sic).(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)pH = 0,(sic)(sic)U = 0 V ((sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)) (sic)(sic)(sic), CoN@C54N71(sic)Niint@C54N72(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)eta OER/eta ORR(sic)(sic)(sic)0.71/0.57 V(sic)0.72/0.56 V, (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic).
Keywords:
3d transition metals
bifunctional OER/ORR
charge states
constant-potential
density functional theory
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