Unique Interaction between Layered Black Phosphorus and Nitrogen Dioxide
Air pollution caused by acid gases (NO<sub>2</sub>, SO<sub>2</sub>) or greenhouse gases (CO<sub>2</sub>) is an urgent environmental problem. Two-dimensional nanomaterials exhibit exciting application potential in air pollution control, among which layered black ph...
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MDPI AG
2022-06-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/12/12/2011 |
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| author | Jingjing Zhao Xuejiao Zhang Qing Zhao Xue-Feng Yu Siyu Zhang Baoshan Xing |
| author_facet | Jingjing Zhao Xuejiao Zhang Qing Zhao Xue-Feng Yu Siyu Zhang Baoshan Xing |
| author_sort | Jingjing Zhao |
| collection | DOAJ |
| description | Air pollution caused by acid gases (NO<sub>2</sub>, SO<sub>2</sub>) or greenhouse gases (CO<sub>2</sub>) is an urgent environmental problem. Two-dimensional nanomaterials exhibit exciting application potential in air pollution control, among which layered black phosphorus (LBP) has superior performance and is environmentally friendly. However, the current interaction mechanism of LBP with hazardous gases is contradictory to experimental observations, largely impeding development of LBP-based air pollution control nanotechnologies. Here, interaction mechanisms between LBP and hazardous gases are unveiled based on density functional theory and experiments. Results show that NO<sub>2</sub> is different from other gases, as it can react with unsaturated defects of LBP, resulting in oxidation of LBP and reduction of NO<sub>2</sub>. Computational results indicate that the redox is initiated by p orbital hybridization between one oxygen atom of NO<sub>2</sub> and the phosphorus atom carrying a dangling single electron in a defect’s center. For NO, the interaction mechanism is chemisorption on unsaturated LBP defects, whereas for SO<sub>2</sub>, NH<sub>3</sub>, CO<sub>2</sub> or CO, the interaction is dominated by van der Waals forces (57–82% of the total interaction). Experiments confirmed that NO<sub>2</sub> can oxidize LBP, yet other gases such as CO<sub>2</sub> cannot. This study provides mechanistic understanding in advance for developing novel nanotechnologies for selectively monitoring or treating gas pollutants containing NO<sub>2</sub>. |
| first_indexed | 2024-03-09T22:53:46Z |
| format | Article |
| id | doaj.art-f69da3c8e48445cdb76d8ced0570d248 |
| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-09T22:53:46Z |
| publishDate | 2022-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-f69da3c8e48445cdb76d8ced0570d2482023-11-23T18:16:01ZengMDPI AGNanomaterials2079-49912022-06-011212201110.3390/nano12122011Unique Interaction between Layered Black Phosphorus and Nitrogen DioxideJingjing Zhao0Xuejiao Zhang1Qing Zhao2Xue-Feng Yu3Siyu Zhang4Baoshan Xing5Key Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016, ChinaKey Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016, ChinaKey Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016, ChinaMaterials and Interfaces Center, Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, ChinaKey Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016, ChinaStockbridge School of Agriculture, University of Massachusetts, Amherst, MA 01003, USAAir pollution caused by acid gases (NO<sub>2</sub>, SO<sub>2</sub>) or greenhouse gases (CO<sub>2</sub>) is an urgent environmental problem. Two-dimensional nanomaterials exhibit exciting application potential in air pollution control, among which layered black phosphorus (LBP) has superior performance and is environmentally friendly. However, the current interaction mechanism of LBP with hazardous gases is contradictory to experimental observations, largely impeding development of LBP-based air pollution control nanotechnologies. Here, interaction mechanisms between LBP and hazardous gases are unveiled based on density functional theory and experiments. Results show that NO<sub>2</sub> is different from other gases, as it can react with unsaturated defects of LBP, resulting in oxidation of LBP and reduction of NO<sub>2</sub>. Computational results indicate that the redox is initiated by p orbital hybridization between one oxygen atom of NO<sub>2</sub> and the phosphorus atom carrying a dangling single electron in a defect’s center. For NO, the interaction mechanism is chemisorption on unsaturated LBP defects, whereas for SO<sub>2</sub>, NH<sub>3</sub>, CO<sub>2</sub> or CO, the interaction is dominated by van der Waals forces (57–82% of the total interaction). Experiments confirmed that NO<sub>2</sub> can oxidize LBP, yet other gases such as CO<sub>2</sub> cannot. This study provides mechanistic understanding in advance for developing novel nanotechnologies for selectively monitoring or treating gas pollutants containing NO<sub>2</sub>.https://www.mdpi.com/2079-4991/12/12/2011layered black phosphorusvacancy defectsingle electronnitrogen dioxidehazardous gas pollutants |
| spellingShingle | Jingjing Zhao Xuejiao Zhang Qing Zhao Xue-Feng Yu Siyu Zhang Baoshan Xing Unique Interaction between Layered Black Phosphorus and Nitrogen Dioxide Nanomaterials layered black phosphorus vacancy defect single electron nitrogen dioxide hazardous gas pollutants |
| title | Unique Interaction between Layered Black Phosphorus and Nitrogen Dioxide |
| title_full | Unique Interaction between Layered Black Phosphorus and Nitrogen Dioxide |
| title_fullStr | Unique Interaction between Layered Black Phosphorus and Nitrogen Dioxide |
| title_full_unstemmed | Unique Interaction between Layered Black Phosphorus and Nitrogen Dioxide |
| title_short | Unique Interaction between Layered Black Phosphorus and Nitrogen Dioxide |
| title_sort | unique interaction between layered black phosphorus and nitrogen dioxide |
| topic | layered black phosphorus vacancy defect single electron nitrogen dioxide hazardous gas pollutants |
| url | https://www.mdpi.com/2079-4991/12/12/2011 |
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