Embedding Group VIII Elements into a 2D Rigid pc-C3N2 Monolayer to Achieve Single-Atom Catalysts with Excellent OER Activity: A DFT Theoretical Study
Abstract
:1. Introduction
2. Calculation Method
3. Results and Discussion
3.1. Geometric Structure, Stability and Electronic Properties for TM@C3N2
3.2. OER Catalytic Activity of the TM@C3N2 Systems
3.3. Mechanism Analysis of OER
4. Conclusions
- (1)
- All these TM@C3N2 systems can exhibit high structural stability, wherein the TM atoms are stably anchored in small and large cavities of a pc-C3N2 monolayer to form two different kinds of TMN4 units. Compared with the pristine pc-C3N2 with metallic characteristics, the conductivity of these doped systems can be further enhanced. All these advantages are conducive to the OER catalytic performance of the materials.
- (2)
- Through a calculation screening of the TM atoms in group VIII, it is found that four new TM@C3N2 systems doped with Co/Rh/Ir/Ru atoms can possess very low overpotential (0.33~0.48 V), indicating the considerably high OER catalytic activity, where the adsorption sites including Co@S-C3N2, Rh@S-C3N2, Ru@L-C3N2, Rh@L-C3N2 and Ir@L-C3N2 can be used as the active sites. As a result, the Rh@C3N2 system can exhibit higher OER catalytic performance, due to the higher density of active sites.
- (3)
- It is found that ∆GO* can be used as an effective descriptor of the OER catalytic activity of TM@C3N2 systems. The number of outer electrons, the periodic number of doped TM atoms and the cavity size can be the crucial factors in determining the ∆GO* value, and the effective cooperation between them can lead to moderate ∆GO* values, bringing about excellent OER catalytic performance in these SAC catalysts.
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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a = b (Å) | DS-TM-N (Å) | DL-TM-N (Å) | |
---|---|---|---|
pc-C3N2 | 16.580 | --- | --- |
Fe@C3N2 | 16.345 | 1.914 | 2.356 |
Co@C3N2 | 16.385 | 1.952 | 2.333 |
Ni@C3N2 | 16.234 | 1.889 | 2.321 |
Ru@C3N2 | 16.261 | 1.889 | 2.331 |
Rh@C3N2 | 16.370 | 1.951 | 2.342 |
Pd@C3N2 | 16.300 | 1.942 | 2.294 |
Os@C3N2 | 16.244 | 1.891 | 2.323 |
Ir@C3N2 | 16.505 | 1.981 | 2.409 |
Pt@C3N2 | 16.400 | 1.971 | 2.350 |
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Wang, Q.; Yang, E.; Liu, R.; Lv, M.; Zhang, W.; Yu, G.; Chen, W. Embedding Group VIII Elements into a 2D Rigid pc-C3N2 Monolayer to Achieve Single-Atom Catalysts with Excellent OER Activity: A DFT Theoretical Study. Molecules 2023, 28, 254. https://doi.org/10.3390/molecules28010254
Wang Q, Yang E, Liu R, Lv M, Zhang W, Yu G, Chen W. Embedding Group VIII Elements into a 2D Rigid pc-C3N2 Monolayer to Achieve Single-Atom Catalysts with Excellent OER Activity: A DFT Theoretical Study. Molecules. 2023; 28(1):254. https://doi.org/10.3390/molecules28010254
Chicago/Turabian StyleWang, Qingxian, E Yang, Ran Liu, Mingyue Lv, Wei Zhang, Guangtao Yu, and Wei Chen. 2023. "Embedding Group VIII Elements into a 2D Rigid pc-C3N2 Monolayer to Achieve Single-Atom Catalysts with Excellent OER Activity: A DFT Theoretical Study" Molecules 28, no. 1: 254. https://doi.org/10.3390/molecules28010254