Conjugated Electron Donor–Acceptor Hybrid Polymeric Carbon Nitride as a Photocatalyst for CO2 Reduction

Molecules

Asif Hayat¹  MatiUr Rahman¹  Shu-yuan Liu²  Muhammad Sohail³  Kezhen Qi⁴  Wenxiu Lv⁴  Humaira Yasmeen⁵  Iltaf Khan⁶  Javid Khan⁷ 

[1] College of Chemistry, Fuzhou University, Fuzhou 350002, China;Department of pharmacology, Shenyang Medical College, Shenyang 110034, China;Institute for Advanced Study, Shenzhen University, Shenzhen 518060, China;Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China;Key Laboratory of Bio-Based Material Science and Technology, Ministry of Education, Northeast Forestry University, Harbin 150040, China;Key Laboratory of Functional Inorganic Material Chemistry, School of Chemistry and Materials Science, Heilongjiang University, Harbin 158308, China;MOE 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, China;

关键词: polymeric carbon nitride;    donor-acceptor;    photocatalysis;    CO₂ reduction;    DFT calculation;   

DOI  :  10.3390/molecules24091779

来源: DOAJ

【 摘 要 】

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 CO₂ reduction to CO and H₂ 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_15.0 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 H₂ from CO₂ by 15.02-fold compared than that of the parental CNU, while also improving the selectivity.

【 授权许可】

Unknown