Phosphorene-Supported Au(I) Fragments for Highly Sensitive Detection of NO
The fabrication and application of single-site heterogeneous reaction centers are new frontiers in chemistry. Single-site heterogeneous reaction centers are analogous to metal centers in enzymes and transition-metal complexes: they are charged and decorated with ligands and would exhibit superior re...
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| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-07-01
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| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/30/15/3085 |
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| Summary: | The fabrication and application of single-site heterogeneous reaction centers are new frontiers in chemistry. Single-site heterogeneous reaction centers are analogous to metal centers in enzymes and transition-metal complexes: they are charged and decorated with ligands and would exhibit superior reactivity and selectivity in chemical conversion. Such high reactivity would also result in significant response, such as a band gap or resistance change, to approaching molecules, which can be used for sensing applications. As a proof of concept, the electronic structure and reaction pathways with NO and NO<sub>2</sub> of Au(I) fragments dispersed on phosphorene (Pene) were investigated with first-principle-based calculations. Atomic-deposited Au atoms on Pene (Au<sub>1</sub>-Pene) have hybridized Au states in the bulk band gap of Pene and a decreased band gap of 0.14 eV and would aggregate into clusters. Passivation of the Au hybrid states with -OH and -CH<sub>3</sub> forms thermodynamically plausible HO-Au<sub>1</sub>-Pene and H<sub>3</sub>C-Au<sub>1</sub>-Pene and restores the band gap to that of bulk Pene. Inspired by this, HO-Au<sub>1</sub>-Pene and H<sub>3</sub>C-Au<sub>1</sub>-Pene were examined for detection of NO and NO<sub>2</sub> that would react with -OH and -CH<sub>3</sub>, and the resulting decrease of band gap back to that of Au<sub>1</sub>-Pene would be measurable. HO-Au<sub>1</sub>-Pene and H<sub>3</sub>C-Au<sub>1</sub>-Pene are highly sensitive to NO and NO<sub>2</sub>, and their calculated theoretical sensitivities are all 99.99%. The reaction of NO<sub>2</sub> with HO-Au<sub>1</sub>-Pene is endothermic, making the dissociation of product HNO<sub>3</sub> more plausible, while the barriers for the reaction of CH<sub>3</sub>-Au<sub>1</sub>-Pene with NO and NO<sub>2</sub> are too high for spontaneous detection. Therefore, HO-Au<sub>1</sub>-Pene is not eligible for NO<sub>2</sub> sensing and CH<sub>3</sub>-Au<sub>1</sub>-Pene is not eligible for NO and NO<sub>2</sub> sensing. The calculated energy barrier for the reaction of HO-Au-Pene with NO is 0.36 eV, and the reaction is about thermal neutral, suggesting HO-Au-Pene is highly sensitive for NO sensing and the reaction for NO detection is spontaneous. This work highlights the potential superior sensing performance of transition-metal fragments and their potential for next-generation sensing applications. |
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| ISSN: | 1420-3049 |