Strain Engineering of Cu<sub>2</sub>O@C<sub>2</sub>N for Enhanced Methane-to-Methanol Conversion
Inspired by the active site of methane monooxygenase, we designed a Cu<sub>2</sub>O cluster anchored in the six-membered nitrogen cavity of a C<sub>2</sub>N monolayer (Cu<sub>2</sub>O@C<sub>2</sub>N) as a stable and efficient enzyme-like catalyst. Dens...
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MDPI AG
2025-07-01
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| author | Shuxin Kuai Bo Li Jingyao Liu |
| author_facet | Shuxin Kuai Bo Li Jingyao Liu |
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| description | Inspired by the active site of methane monooxygenase, we designed a Cu<sub>2</sub>O cluster anchored in the six-membered nitrogen cavity of a C<sub>2</sub>N monolayer (Cu<sub>2</sub>O@C<sub>2</sub>N) as a stable and efficient enzyme-like catalyst. Density functional theory (DFT) calculations reveal that the bridged Cu-O-Cu structure within C<sub>2</sub>N exhibits strong electronic coupling, which is favorable for methanol formation. Two competing mechanisms—the concerted and radical-rebound pathways—were systematically investigated, with the former being energetically preferred due to lower energy barriers and more stable intermediate states. Furthermore, strain engineering was employed to tune the geometric and electronic structure of the Cu-O-Cu site. Biaxial strain modulates the Cu-O-Cu bond angle, adsorption properties, and d-band center alignment, thereby selectively enhancing the concerted pathway. A volcano-like trend was observed between the applied strain and the methanol formation barrier, with 1% tensile strain yielding the overall energy barrier to methanol formation (ΔG<sub>overall</sub>) as low as 1.31 eV. N<sub>2</sub>O effectively regenerated the active site and demonstrated strain-responsive kinetics. The electronic descriptor Δε (ε<sub>d</sub> − ε<sub>p</sub>) captured the structure–activity relationship, confirming the role of strain in regulating catalytic performance. This work highlights the synergy between geometric confinement and mechanical modulation, offering a rational design strategy for advanced C1 activation catalysts. |
| format | Article |
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| institution | Kabale University |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-07-01 |
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| spelling | doaj-art-cc28ace74b60464f8ed29ccf898833a22025-08-20T03:36:27ZengMDPI AGMolecules1420-30492025-07-013015307310.3390/molecules30153073Strain Engineering of Cu<sub>2</sub>O@C<sub>2</sub>N for Enhanced Methane-to-Methanol ConversionShuxin Kuai0Bo Li1Jingyao Liu2Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130023, ChinaInstitute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, ChinaInstitute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130023, ChinaInspired by the active site of methane monooxygenase, we designed a Cu<sub>2</sub>O cluster anchored in the six-membered nitrogen cavity of a C<sub>2</sub>N monolayer (Cu<sub>2</sub>O@C<sub>2</sub>N) as a stable and efficient enzyme-like catalyst. Density functional theory (DFT) calculations reveal that the bridged Cu-O-Cu structure within C<sub>2</sub>N exhibits strong electronic coupling, which is favorable for methanol formation. Two competing mechanisms—the concerted and radical-rebound pathways—were systematically investigated, with the former being energetically preferred due to lower energy barriers and more stable intermediate states. Furthermore, strain engineering was employed to tune the geometric and electronic structure of the Cu-O-Cu site. Biaxial strain modulates the Cu-O-Cu bond angle, adsorption properties, and d-band center alignment, thereby selectively enhancing the concerted pathway. A volcano-like trend was observed between the applied strain and the methanol formation barrier, with 1% tensile strain yielding the overall energy barrier to methanol formation (ΔG<sub>overall</sub>) as low as 1.31 eV. N<sub>2</sub>O effectively regenerated the active site and demonstrated strain-responsive kinetics. The electronic descriptor Δε (ε<sub>d</sub> − ε<sub>p</sub>) captured the structure–activity relationship, confirming the role of strain in regulating catalytic performance. This work highlights the synergy between geometric confinement and mechanical modulation, offering a rational design strategy for advanced C1 activation catalysts.https://www.mdpi.com/1420-3049/30/15/3073methane monooxygenaseC<sub>2</sub>N monolayermethane conversionstrain engineeringdensity functional theory |
| spellingShingle | Shuxin Kuai Bo Li Jingyao Liu Strain Engineering of Cu<sub>2</sub>O@C<sub>2</sub>N for Enhanced Methane-to-Methanol Conversion Molecules methane monooxygenase C<sub>2</sub>N monolayer methane conversion strain engineering density functional theory |
| title | Strain Engineering of Cu<sub>2</sub>O@C<sub>2</sub>N for Enhanced Methane-to-Methanol Conversion |
| title_full | Strain Engineering of Cu<sub>2</sub>O@C<sub>2</sub>N for Enhanced Methane-to-Methanol Conversion |
| title_fullStr | Strain Engineering of Cu<sub>2</sub>O@C<sub>2</sub>N for Enhanced Methane-to-Methanol Conversion |
| title_full_unstemmed | Strain Engineering of Cu<sub>2</sub>O@C<sub>2</sub>N for Enhanced Methane-to-Methanol Conversion |
| title_short | Strain Engineering of Cu<sub>2</sub>O@C<sub>2</sub>N for Enhanced Methane-to-Methanol Conversion |
| title_sort | strain engineering of cu sub 2 sub o c sub 2 sub n for enhanced methane to methanol conversion |
| topic | methane monooxygenase C<sub>2</sub>N monolayer methane conversion strain engineering density functional theory |
| url | https://www.mdpi.com/1420-3049/30/15/3073 |
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