Hybrid Materials Based on Carbon Nanotubes and Tetra- and Octa-Halogen-Substituted Zinc Phthalocyanines: Sensor Response Toward Ammonia from the Quantum-Chemical Point of View
This paper presents the results of quantum-chemical modeling performed by the Density Functional-Based Tight Binding (DFTB) method to investigate the change in the band structure of hybrid materials based on carbon nanotubes and unsubstituted, tetra-, or octa-halogen-substituted zinc phthalocyanines...
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MDPI AG
2024-12-01
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| Online Access: | https://www.mdpi.com/1424-8220/25/1/149 |
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| author | Pavel Krasnov Victoria Ivanova Darya Klyamer Dmitry Bonegardt Aleksandr Fedorov Tamara Basova |
| author_facet | Pavel Krasnov Victoria Ivanova Darya Klyamer Dmitry Bonegardt Aleksandr Fedorov Tamara Basova |
| author_sort | Pavel Krasnov |
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| description | This paper presents the results of quantum-chemical modeling performed by the Density Functional-Based Tight Binding (DFTB) method to investigate the change in the band structure of hybrid materials based on carbon nanotubes and unsubstituted, tetra-, or octa-halogen-substituted zinc phthalocyanines upon the adsorption of ammonia molecules. The study showed that the electrical conductivity of these materials and its changes in the case of interaction with ammonia molecules depend on the position of the impurity band formed by the orbitals of macrocycle atoms relative to the forbidden energy gap of the hybrids. The sensor response of the hybrids containing halogenated phthalocyanines was lower by one or two orders of magnitude, depending on the number of substituents, compared to the hybrid with unsubstituted zinc phthalocyanine. This result was obtained by calculations performed using the nonequilibrium Green’s functions (NEGF) method, which demonstrated a change in the electrical conductivity of the hybrids upon the adsorption of ammonia molecules. The analysis showed that in order to improve the sensor characteristics of CNT-based hybrid materials, preference should be given to those phthalocyanines in which substituents contribute to an increase in HOMO energy relative to the unsubstituted macrocycles. |
| format | Article |
| id | doaj-art-f3d6ee2c8a144d1aa2836609baf93d97 |
| institution | Kabale University |
| issn | 1424-8220 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Sensors |
| spelling | doaj-art-f3d6ee2c8a144d1aa2836609baf93d972025-01-10T13:21:02ZengMDPI AGSensors1424-82202024-12-0125114910.3390/s25010149Hybrid Materials Based on Carbon Nanotubes and Tetra- and Octa-Halogen-Substituted Zinc Phthalocyanines: Sensor Response Toward Ammonia from the Quantum-Chemical Point of ViewPavel Krasnov0Victoria Ivanova1Darya Klyamer2Dmitry Bonegardt3Aleksandr Fedorov4Tamara Basova5International Research Center of Spectroscopy and Quantum Chemistry, Siberian Federal University, 26 Kirensky St., 660074 Krasnoyarsk, RussiaNikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev Pr., 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev Pr., 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev Pr., 630090 Novosibirsk, RussiaKirensky Institute of Physics, Federal Research Center KSC SB RAS, 50/38 Akademgorodok, 660036 Krasnoyarsk, RussiaNikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev Pr., 630090 Novosibirsk, RussiaThis paper presents the results of quantum-chemical modeling performed by the Density Functional-Based Tight Binding (DFTB) method to investigate the change in the band structure of hybrid materials based on carbon nanotubes and unsubstituted, tetra-, or octa-halogen-substituted zinc phthalocyanines upon the adsorption of ammonia molecules. The study showed that the electrical conductivity of these materials and its changes in the case of interaction with ammonia molecules depend on the position of the impurity band formed by the orbitals of macrocycle atoms relative to the forbidden energy gap of the hybrids. The sensor response of the hybrids containing halogenated phthalocyanines was lower by one or two orders of magnitude, depending on the number of substituents, compared to the hybrid with unsubstituted zinc phthalocyanine. This result was obtained by calculations performed using the nonequilibrium Green’s functions (NEGF) method, which demonstrated a change in the electrical conductivity of the hybrids upon the adsorption of ammonia molecules. The analysis showed that in order to improve the sensor characteristics of CNT-based hybrid materials, preference should be given to those phthalocyanines in which substituents contribute to an increase in HOMO energy relative to the unsubstituted macrocycles.https://www.mdpi.com/1424-8220/25/1/149zinc phthalocyaninescarbon nanotubesquantum-chemical calculationsDFTBband structureelectrical conductivity |
| spellingShingle | Pavel Krasnov Victoria Ivanova Darya Klyamer Dmitry Bonegardt Aleksandr Fedorov Tamara Basova Hybrid Materials Based on Carbon Nanotubes and Tetra- and Octa-Halogen-Substituted Zinc Phthalocyanines: Sensor Response Toward Ammonia from the Quantum-Chemical Point of View Sensors zinc phthalocyanines carbon nanotubes quantum-chemical calculations DFTB band structure electrical conductivity |
| title | Hybrid Materials Based on Carbon Nanotubes and Tetra- and Octa-Halogen-Substituted Zinc Phthalocyanines: Sensor Response Toward Ammonia from the Quantum-Chemical Point of View |
| title_full | Hybrid Materials Based on Carbon Nanotubes and Tetra- and Octa-Halogen-Substituted Zinc Phthalocyanines: Sensor Response Toward Ammonia from the Quantum-Chemical Point of View |
| title_fullStr | Hybrid Materials Based on Carbon Nanotubes and Tetra- and Octa-Halogen-Substituted Zinc Phthalocyanines: Sensor Response Toward Ammonia from the Quantum-Chemical Point of View |
| title_full_unstemmed | Hybrid Materials Based on Carbon Nanotubes and Tetra- and Octa-Halogen-Substituted Zinc Phthalocyanines: Sensor Response Toward Ammonia from the Quantum-Chemical Point of View |
| title_short | Hybrid Materials Based on Carbon Nanotubes and Tetra- and Octa-Halogen-Substituted Zinc Phthalocyanines: Sensor Response Toward Ammonia from the Quantum-Chemical Point of View |
| title_sort | hybrid materials based on carbon nanotubes and tetra and octa halogen substituted zinc phthalocyanines sensor response toward ammonia from the quantum chemical point of view |
| topic | zinc phthalocyanines carbon nanotubes quantum-chemical calculations DFTB band structure electrical conductivity |
| url | https://www.mdpi.com/1424-8220/25/1/149 |
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