Substitutional Coinage Metals as Promising Defects for Adsorption and Detection of Gases on MoS<sub>2</sub> Monolayers: A Computational Approach
Defective molybdenum disulfide (MoS<sub>2</sub>) monolayers (MLs) modified with coinage metal atoms (Cu, Ag and Au) embedded in sulfur vacancies are studied at a dispersion-corrected density functional level. Atmospheric constituents (H<sub>2</sub>, O<sub>2</sub>...
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| Format: | Article |
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MDPI AG
2023-06-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/24/12/10284 |
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| author | Josue Gutierrez-Rodriguez Miguel Castro Jose Manuel Nieto-Jalil Dora Iliana Medina Saul Montes de Oca José Andrés García-González Eduardo Rangel-Cortes Alan Miralrio |
| author_facet | Josue Gutierrez-Rodriguez Miguel Castro Jose Manuel Nieto-Jalil Dora Iliana Medina Saul Montes de Oca José Andrés García-González Eduardo Rangel-Cortes Alan Miralrio |
| author_sort | Josue Gutierrez-Rodriguez |
| collection | DOAJ |
| description | Defective molybdenum disulfide (MoS<sub>2</sub>) monolayers (MLs) modified with coinage metal atoms (Cu, Ag and Au) embedded in sulfur vacancies are studied at a dispersion-corrected density functional level. Atmospheric constituents (H<sub>2</sub>, O<sub>2</sub> and N<sub>2</sub>) and air pollutants (CO and NO), known as secondary greenhouse gases, are adsorbed on up to two atoms embedded into sulfur vacancies in MoS<sub>2</sub> MLs. The adsorption energies suggest that the NO (1.44 eV) and CO (1.24 eV) are chemisorbed more strongly than O<sub>2</sub> (1.07 eV) and N<sub>2</sub> (0.66 eV) on the ML with a cooper atom substituting for a sulfur atom. Therefore, the adsorption of N<sub>2</sub> and O<sub>2</sub> does not compete with NO or CO adsorption. Besides, NO adsorbed on embedded Cu creates a new level in the band gap. In addition, it was found that the CO molecule could directly react with the pre-adsorbed O<sub>2</sub> molecule on a Cu atom, forming the complex OOCO, via the Eley–Rideal reaction mechanism. The adsorption energies of CO, NO and O<sub>2</sub> on <i>Au<sub>2S2</sub></i>, <i>Cu<sub>2S2</sub></i> and <i>Ag<sub>2S2</sub></i> embedded into two sulfur vacancies were competitive. Charge transference occurs from the defective MoS<sub>2</sub> ML to the adsorbed molecules, oxidizing the later ones (NO, CO and O<sub>2</sub>) since they act as acceptors. The total and projected density of states reveal that a MoS<sub>2</sub> ML modified with copper, gold and silver dimers could be used to design electronic or magnetic devices for sensing applications in the adsorption of NO, CO and O<sub>2</sub> molecules. Moreover, NO and O<sub>2</sub> molecules adsorbed on MoS<sub>2</sub>-<i>Au<sub>2</sub>s<sub>2</sub></i> and MoS<sub>2</sub>-<i>Cu<sub>2</sub>s<sub>2</sub></i> introduce a transition from metallic to half-metallic behavior for applications in spintronics. These modified monolayers are expected to exhibit chemiresistive behavior, meaning their electrical resistance changes in response to the presence of NO molecules. This property makes them suitable for detecting and measuring NO concentrations. Also, modified materials with half-metal behavior could be beneficial for spintronic devices, particularly those that require spin-polarized currents. |
| first_indexed | 2024-03-11T02:20:11Z |
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| issn | 1661-6596 1422-0067 |
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| last_indexed | 2024-03-11T02:20:11Z |
| publishDate | 2023-06-01 |
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| spelling | doaj.art-373cb06cc178410f88325f206b1f755f2023-11-18T10:51:21ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672023-06-0124121028410.3390/ijms241210284Substitutional Coinage Metals as Promising Defects for Adsorption and Detection of Gases on MoS<sub>2</sub> Monolayers: A Computational ApproachJosue Gutierrez-Rodriguez0Miguel Castro1Jose Manuel Nieto-Jalil2Dora Iliana Medina3Saul Montes de Oca4José Andrés García-González5Eduardo Rangel-Cortes6Alan Miralrio7Escuela de Ingeniería y Ciencias, Tecnologico de Monterrey, Ave. Eugenio Garza Sada 2501, Monterrey 64849, MexicoDepartamento de Física y Química Teórica, Division de Estudios de Posgrado, Facultad de Química, Universidad Nacional Autónoma de México (UNAM), Del. Coyoacán, Ciudad de México 04510, MexicoDepartamento de Física y Química Teórica, Division de Estudios de Posgrado, Facultad de Química, Universidad Nacional Autónoma de México (UNAM), Del. Coyoacán, Ciudad de México 04510, MexicoTecnologico de Monterrey, Institute of Advanced Materials for Sustainable Manufacturing, Monterrey 64849, MexicoEscuela de Ingeniería y Ciencias, Tecnologico de Monterrey, Ave. Eugenio Garza Sada 2501, Monterrey 64849, MexicoEscuela de Ingeniería y Ciencias, Tecnologico de Monterrey, Ave. Eugenio Garza Sada 2501, Monterrey 64849, MexicoEscuela de Ingeniería y Ciencias, Tecnologico de Monterrey, Ave. Eugenio Garza Sada 2501, Monterrey 64849, MexicoEscuela de Ingeniería y Ciencias, Tecnologico de Monterrey, Ave. Eugenio Garza Sada 2501, Monterrey 64849, MexicoDefective molybdenum disulfide (MoS<sub>2</sub>) monolayers (MLs) modified with coinage metal atoms (Cu, Ag and Au) embedded in sulfur vacancies are studied at a dispersion-corrected density functional level. Atmospheric constituents (H<sub>2</sub>, O<sub>2</sub> and N<sub>2</sub>) and air pollutants (CO and NO), known as secondary greenhouse gases, are adsorbed on up to two atoms embedded into sulfur vacancies in MoS<sub>2</sub> MLs. The adsorption energies suggest that the NO (1.44 eV) and CO (1.24 eV) are chemisorbed more strongly than O<sub>2</sub> (1.07 eV) and N<sub>2</sub> (0.66 eV) on the ML with a cooper atom substituting for a sulfur atom. Therefore, the adsorption of N<sub>2</sub> and O<sub>2</sub> does not compete with NO or CO adsorption. Besides, NO adsorbed on embedded Cu creates a new level in the band gap. In addition, it was found that the CO molecule could directly react with the pre-adsorbed O<sub>2</sub> molecule on a Cu atom, forming the complex OOCO, via the Eley–Rideal reaction mechanism. The adsorption energies of CO, NO and O<sub>2</sub> on <i>Au<sub>2S2</sub></i>, <i>Cu<sub>2S2</sub></i> and <i>Ag<sub>2S2</sub></i> embedded into two sulfur vacancies were competitive. Charge transference occurs from the defective MoS<sub>2</sub> ML to the adsorbed molecules, oxidizing the later ones (NO, CO and O<sub>2</sub>) since they act as acceptors. The total and projected density of states reveal that a MoS<sub>2</sub> ML modified with copper, gold and silver dimers could be used to design electronic or magnetic devices for sensing applications in the adsorption of NO, CO and O<sub>2</sub> molecules. Moreover, NO and O<sub>2</sub> molecules adsorbed on MoS<sub>2</sub>-<i>Au<sub>2</sub>s<sub>2</sub></i> and MoS<sub>2</sub>-<i>Cu<sub>2</sub>s<sub>2</sub></i> introduce a transition from metallic to half-metallic behavior for applications in spintronics. These modified monolayers are expected to exhibit chemiresistive behavior, meaning their electrical resistance changes in response to the presence of NO molecules. This property makes them suitable for detecting and measuring NO concentrations. Also, modified materials with half-metal behavior could be beneficial for spintronic devices, particularly those that require spin-polarized currents.https://www.mdpi.com/1422-0067/24/12/10284molybdenum disulfide monolayermolecular adsorptionhalf-metallic behaviorgreenhouse gaseschemiresistive sensorsmagnetic sensors |
| spellingShingle | Josue Gutierrez-Rodriguez Miguel Castro Jose Manuel Nieto-Jalil Dora Iliana Medina Saul Montes de Oca José Andrés García-González Eduardo Rangel-Cortes Alan Miralrio Substitutional Coinage Metals as Promising Defects for Adsorption and Detection of Gases on MoS<sub>2</sub> Monolayers: A Computational Approach International Journal of Molecular Sciences molybdenum disulfide monolayer molecular adsorption half-metallic behavior greenhouse gases chemiresistive sensors magnetic sensors |
| title | Substitutional Coinage Metals as Promising Defects for Adsorption and Detection of Gases on MoS<sub>2</sub> Monolayers: A Computational Approach |
| title_full | Substitutional Coinage Metals as Promising Defects for Adsorption and Detection of Gases on MoS<sub>2</sub> Monolayers: A Computational Approach |
| title_fullStr | Substitutional Coinage Metals as Promising Defects for Adsorption and Detection of Gases on MoS<sub>2</sub> Monolayers: A Computational Approach |
| title_full_unstemmed | Substitutional Coinage Metals as Promising Defects for Adsorption and Detection of Gases on MoS<sub>2</sub> Monolayers: A Computational Approach |
| title_short | Substitutional Coinage Metals as Promising Defects for Adsorption and Detection of Gases on MoS<sub>2</sub> Monolayers: A Computational Approach |
| title_sort | substitutional coinage metals as promising defects for adsorption and detection of gases on mos sub 2 sub monolayers a computational approach |
| topic | molybdenum disulfide monolayer molecular adsorption half-metallic behavior greenhouse gases chemiresistive sensors magnetic sensors |
| url | https://www.mdpi.com/1422-0067/24/12/10284 |
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