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,...
Saved in:
| Main Authors: | , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-04-01
|
| Series: | Nanomaterials |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2079-4991/15/8/628 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1850180476401090560 |
|---|---|
| author | Xiansheng Yu Can Zhao Qiaoyue Chen Lai Wei Xucai Zhao Lili Zhang Liqian Wu Yineng Huang |
| author_facet | Xiansheng Yu Can Zhao Qiaoyue Chen Lai Wei Xucai Zhao Lili Zhang Liqian Wu Yineng Huang |
| author_sort | Xiansheng Yu |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-7e657a88e5ab46138e6ee2fe9ccc37d8 |
| institution | OA Journals |
| issn | 2079-4991 |
| language | English |
| publishDate | 2025-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Nanomaterials |
| spelling | doaj-art-7e657a88e5ab46138e6ee2fe9ccc37d82025-08-20T02:18:10ZengMDPI AGNanomaterials2079-49912025-04-0115862810.3390/nano15080628First-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 MetalsXiansheng Yu0Can Zhao1Qiaoyue Chen2Lai Wei3Xucai Zhao4Lili Zhang5Liqian Wu6Yineng Huang7Xinjiang Laboratory of Phase Transitions and Microstructures in Condensed Matters, College of Physical Science and Technology, Yili Normal University, Yining 835000, ChinaXinjiang Laboratory of Phase Transitions and Microstructures in Condensed Matters, College of Physical Science and Technology, Yili Normal University, Yining 835000, ChinaXinjiang Laboratory of Phase Transitions and Microstructures in Condensed Matters, College of Physical Science and Technology, Yili Normal University, Yining 835000, ChinaXinjiang Laboratory of Phase Transitions and Microstructures in Condensed Matters, College of Physical Science and Technology, Yili Normal University, Yining 835000, ChinaXinjiang Laboratory of Phase Transitions and Microstructures in Condensed Matters, College of Physical Science and Technology, Yili Normal University, Yining 835000, ChinaXinjiang Laboratory of Phase Transitions and Microstructures in Condensed Matters, College of Physical Science and Technology, Yili Normal University, Yining 835000, ChinaMicro-Electronics Research Institute, Hangzhou Dianzi University, Hangzhou 310018, ChinaXinjiang Laboratory of Phase Transitions and Microstructures in Condensed Matters, College of Physical Science and Technology, Yili Normal University, Yining 835000, ChinaThe 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.https://www.mdpi.com/2079-4991/15/8/628first principlesh-BNSACsHERCO<sub>2</sub>RR |
| spellingShingle | Xiansheng Yu Can Zhao Qiaoyue Chen Lai Wei Xucai Zhao Lili Zhang Liqian Wu Yineng Huang 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 Nanomaterials first principles h-BN SACs HER CO<sub>2</sub>RR |
| title | 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 |
| title_full | 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 |
| title_fullStr | 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 |
| title_full_unstemmed | 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 |
| title_short | 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 |
| title_sort | 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 |
| topic | first principles h-BN SACs HER CO<sub>2</sub>RR |
| url | https://www.mdpi.com/2079-4991/15/8/628 |
| work_keys_str_mv | AT xianshengyu firstprinciplesstudyonthecosub2subreductionreactioncosub2subrrperformanceofhbnbasedsingleatomcatalystsmodifiedwithtransitionmetals AT canzhao firstprinciplesstudyonthecosub2subreductionreactioncosub2subrrperformanceofhbnbasedsingleatomcatalystsmodifiedwithtransitionmetals AT qiaoyuechen firstprinciplesstudyonthecosub2subreductionreactioncosub2subrrperformanceofhbnbasedsingleatomcatalystsmodifiedwithtransitionmetals AT laiwei firstprinciplesstudyonthecosub2subreductionreactioncosub2subrrperformanceofhbnbasedsingleatomcatalystsmodifiedwithtransitionmetals AT xucaizhao firstprinciplesstudyonthecosub2subreductionreactioncosub2subrrperformanceofhbnbasedsingleatomcatalystsmodifiedwithtransitionmetals AT lilizhang firstprinciplesstudyonthecosub2subreductionreactioncosub2subrrperformanceofhbnbasedsingleatomcatalystsmodifiedwithtransitionmetals AT liqianwu firstprinciplesstudyonthecosub2subreductionreactioncosub2subrrperformanceofhbnbasedsingleatomcatalystsmodifiedwithtransitionmetals AT yinenghuang firstprinciplesstudyonthecosub2subreductionreactioncosub2subrrperformanceofhbnbasedsingleatomcatalystsmodifiedwithtransitionmetals |