Conjugated Electron Donor–Acceptor Hybrid Polymeric Carbon Nitride as a Photocatalyst for CO<sub>2</sub> Reduction
This work incorporates a variety of conjugated donor-acceptor (DA) co-monomers such as 2,6-diaminopurine (DP) into the structure of a polymeric carbon nitride (PCN) backbone using a unique nanostructure co-polymerization strategy and examines its photocatalytic activity performance in the field of p...
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| Format: | Article |
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MDPI AG
2019-05-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/24/9/1779 |
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| author | Asif Hayat Mati Ur Rahman Iltaf Khan Javid Khan Muhammad Sohail Humaira Yasmeen Shu-yuan Liu Kezhen Qi Wenxiu Lv |
| author_facet | Asif Hayat Mati Ur Rahman Iltaf Khan Javid Khan Muhammad Sohail Humaira Yasmeen Shu-yuan Liu Kezhen Qi Wenxiu Lv |
| author_sort | Asif Hayat |
| collection | DOAJ |
| description | This work incorporates a variety of conjugated donor-acceptor (DA) co-monomers such as 2,6-diaminopurine (DP) into the structure of a polymeric carbon nitride (PCN) backbone using a unique nanostructure co-polymerization strategy and examines its photocatalytic activity performance in the field of photocatalytic CO<sub>2</sub> reduction to CO and H<sub>2</sub> under visible light irradiation. The as-synthesized samples were successfully analyzed using different characterization methods to explain their electronic and optical properties, crystal phase, microstructure, and their morphology that influenced the performance due to the interactions between the PCN and the DPco-monomer. Based on the density functional theory (DFT) calculation result, pure PCN and CNU-DP<sub>15.0</sub> trimers (interpreted as incorporation of the co-monomer at two different positions) were extensively evaluated and exhibited remarkable structural optimization without the inclusion of any symmetry constraints (the non-modified sample derived from urea, named as CNU), and their optical and electronic properties were also manipulated to control occupation of their respective highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). Also, co-polymerization of the donor−acceptor 2,6-diamino-purine co-monomer with PCN influenced the chemical affinities, polarities, and acid−base functions of the PCN, remarkably enhancing the photocatalytic activity for the production of CO and H<sub>2</sub> from CO<sub>2</sub> by 15.02-fold compared than that of the parental CNU, while also improving the selectivity. |
| first_indexed | 2024-12-22T16:59:32Z |
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| id | doaj.art-d411311227e6400481599f96b42d6af9 |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-22T16:59:32Z |
| publishDate | 2019-05-01 |
| publisher | MDPI AG |
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| series | Molecules |
| spelling | doaj.art-d411311227e6400481599f96b42d6af92022-12-21T18:19:23ZengMDPI AGMolecules1420-30492019-05-01249177910.3390/molecules24091779molecules24091779Conjugated Electron Donor–Acceptor Hybrid Polymeric Carbon Nitride as a Photocatalyst for CO<sub>2</sub> ReductionAsif Hayat0Mati Ur Rahman1Iltaf Khan2Javid Khan3Muhammad Sohail4Humaira Yasmeen5Shu-yuan Liu6Kezhen Qi7Wenxiu Lv8College of Chemistry, Fuzhou University, Fuzhou 350002, ChinaCollege of Chemistry, Fuzhou University, Fuzhou 350002, ChinaKey Laboratory of Functional Inorganic Material Chemistry, School of Chemistry and Materials Science, Heilongjiang University, Harbin 158308, ChinaMOE Key Laboratory of Bioinorganic and Synthetic Chemistry, Key Laboratory of Environment and Energy Chemistry of Guangdong Higher Education Institutes, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, ChinaInstitute for Advanced Study, Shenzhen University, Shenzhen 518060, ChinaKey Laboratory of Bio-Based Material Science and Technology, Ministry of Education, Northeast Forestry University, Harbin 150040, ChinaDepartment of pharmacology, Shenyang Medical College, Shenyang 110034, ChinaInstitute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, ChinaInstitute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, ChinaThis work incorporates a variety of conjugated donor-acceptor (DA) co-monomers such as 2,6-diaminopurine (DP) into the structure of a polymeric carbon nitride (PCN) backbone using a unique nanostructure co-polymerization strategy and examines its photocatalytic activity performance in the field of photocatalytic CO<sub>2</sub> reduction to CO and H<sub>2</sub> under visible light irradiation. The as-synthesized samples were successfully analyzed using different characterization methods to explain their electronic and optical properties, crystal phase, microstructure, and their morphology that influenced the performance due to the interactions between the PCN and the DPco-monomer. Based on the density functional theory (DFT) calculation result, pure PCN and CNU-DP<sub>15.0</sub> trimers (interpreted as incorporation of the co-monomer at two different positions) were extensively evaluated and exhibited remarkable structural optimization without the inclusion of any symmetry constraints (the non-modified sample derived from urea, named as CNU), and their optical and electronic properties were also manipulated to control occupation of their respective highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). Also, co-polymerization of the donor−acceptor 2,6-diamino-purine co-monomer with PCN influenced the chemical affinities, polarities, and acid−base functions of the PCN, remarkably enhancing the photocatalytic activity for the production of CO and H<sub>2</sub> from CO<sub>2</sub> by 15.02-fold compared than that of the parental CNU, while also improving the selectivity.https://www.mdpi.com/1420-3049/24/9/1779polymeric carbon nitridedonor-acceptorphotocatalysisCO<sub>2</sub> reductionDFT calculation |
| spellingShingle | Asif Hayat Mati Ur Rahman Iltaf Khan Javid Khan Muhammad Sohail Humaira Yasmeen Shu-yuan Liu Kezhen Qi Wenxiu Lv Conjugated Electron Donor–Acceptor Hybrid Polymeric Carbon Nitride as a Photocatalyst for CO<sub>2</sub> Reduction Molecules polymeric carbon nitride donor-acceptor photocatalysis CO<sub>2</sub> reduction DFT calculation |
| title | Conjugated Electron Donor–Acceptor Hybrid Polymeric Carbon Nitride as a Photocatalyst for CO<sub>2</sub> Reduction |
| title_full | Conjugated Electron Donor–Acceptor Hybrid Polymeric Carbon Nitride as a Photocatalyst for CO<sub>2</sub> Reduction |
| title_fullStr | Conjugated Electron Donor–Acceptor Hybrid Polymeric Carbon Nitride as a Photocatalyst for CO<sub>2</sub> Reduction |
| title_full_unstemmed | Conjugated Electron Donor–Acceptor Hybrid Polymeric Carbon Nitride as a Photocatalyst for CO<sub>2</sub> Reduction |
| title_short | Conjugated Electron Donor–Acceptor Hybrid Polymeric Carbon Nitride as a Photocatalyst for CO<sub>2</sub> Reduction |
| title_sort | conjugated electron donor acceptor hybrid polymeric carbon nitride as a photocatalyst for co sub 2 sub reduction |
| topic | polymeric carbon nitride donor-acceptor photocatalysis CO<sub>2</sub> reduction DFT calculation |
| url | https://www.mdpi.com/1420-3049/24/9/1779 |
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