First-Principles Study on the CO<sub>2</sub> Reduction Reaction (CO<sub>2</sub>RR) Performance of h-BN-Based Single-Atom Catalysts Modified with Transition Metals
The reasonable design of low-cost, high-activity single-atom catalysts (SACs) is crucial for achieving highly efficient electrochemical CO<sub>2</sub>RR. In this study, we systematically explore, using density functional theory (DFT), the performance of transition metal (TM = Mn, Fe, Co,...
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| Main Authors: | , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-04-01
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| Series: | Nanomaterials |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2079-4991/15/8/628 |
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| Summary: | The reasonable design of low-cost, high-activity single-atom catalysts (SACs) is crucial for achieving highly efficient electrochemical CO<sub>2</sub>RR. In this study, we systematically explore, using density functional theory (DFT), the performance of transition metal (TM = Mn, Fe, Co, Ni, Cu, Zn)-doped defect-type hexagonal boron nitride (h-BN) SACs TM@B<sub>−1</sub>N (B vacancy) and TM@BN<sub>−1</sub> (N vacancy) in both CO<sub>2</sub>RR and the hydrogen evolution reaction (HER). Integrated crystal orbital Hamiltonian population (ICOHP) analysis reveals that these catalysts weaken the sp orbital hybridization of CO<sub>2</sub>, which promotes the formation of radical-state intermediates and significantly reduces the energy barrier for the hydrogenation reaction. Therefore, these theoretical calculations indicate that the Mn, Fe, Co@B<sub>−1</sub>N, and Co@BN<sub>−1</sub> systems demonstrate excellent CO<sub>2</sub> chemical adsorption properties. In the CO<sub>2</sub>RR pathway, Mn@B<sub>−1</sub>N exhibits the lowest limiting potential (<i>U<sub>L</sub></i> = −0.524 V), and its higher d-band center (−0.334 eV), which aligns optimally with the adsorbate orbitals, highlights its excellent catalytic activity. Notably, Co@BN<sub>−1</sub> exhibits the highest activity in HER, while <i>U<sub>L</sub></i> is −0.217 V. Furthermore, comparative analysis reveals that Mn@B<sub>−1</sub>N shows 16.4 times higher selectivity for CO<sub>2</sub>RR than for HER. This study provides a theoretical framework for designing bifunctional SACs with selective reaction pathways. Mn@B<sub>−1</sub>N shows considerable potential for selective CO<sub>2</sub> conversion, while Co@BN<sub>−1</sub> demonstrates promising prospects for efficient hydrogen production. |
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| ISSN: | 2079-4991 |