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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2025-07-01
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| author | Huimin Guo Yuhan Liu Xin Liu |
| author_facet | Huimin Guo Yuhan Liu Xin Liu |
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| description | 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. |
| format | Article |
| id | doaj-art-b63b188fe5f0449ea25fb3cb3cdc2a6b |
| institution | Kabale University |
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| spelling | doaj-art-b63b188fe5f0449ea25fb3cb3cdc2a6b2025-08-20T03:36:27ZengMDPI AGMolecules1420-30492025-07-013015308510.3390/molecules30153085Phosphorene-Supported Au(I) Fragments for Highly Sensitive Detection of NOHuimin Guo0Yuhan Liu1Xin Liu2School of Chemistry, State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, Dalian Key Laboratory of Intelligent Chemistry, Dalian University of Technology, Dalian 116024, ChinaSchool of Chemistry, State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, Dalian Key Laboratory of Intelligent Chemistry, Dalian University of Technology, Dalian 116024, ChinaSchool of Chemistry, State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, Dalian Key Laboratory of Intelligent Chemistry, Dalian University of Technology, Dalian 116024, ChinaThe 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.https://www.mdpi.com/1420-3049/30/15/3085AuphosphoreneNONO<sub>x</sub> detectionsingle-site heterogeneous catalysis |
| spellingShingle | Huimin Guo Yuhan Liu Xin Liu Phosphorene-Supported Au(I) Fragments for Highly Sensitive Detection of NO Molecules Au phosphorene NO NO<sub>x</sub> detection single-site heterogeneous catalysis |
| title | Phosphorene-Supported Au(I) Fragments for Highly Sensitive Detection of NO |
| title_full | Phosphorene-Supported Au(I) Fragments for Highly Sensitive Detection of NO |
| title_fullStr | Phosphorene-Supported Au(I) Fragments for Highly Sensitive Detection of NO |
| title_full_unstemmed | Phosphorene-Supported Au(I) Fragments for Highly Sensitive Detection of NO |
| title_short | Phosphorene-Supported Au(I) Fragments for Highly Sensitive Detection of NO |
| title_sort | phosphorene supported au i fragments for highly sensitive detection of no |
| topic | Au phosphorene NO NO<sub>x</sub> detection single-site heterogeneous catalysis |
| url | https://www.mdpi.com/1420-3049/30/15/3085 |
| work_keys_str_mv | AT huiminguo phosphorenesupportedauifragmentsforhighlysensitivedetectionofno AT yuhanliu phosphorenesupportedauifragmentsforhighlysensitivedetectionofno AT xinliu phosphorenesupportedauifragmentsforhighlysensitivedetectionofno |