RESUMO
Porous covalent organic frameworks (COFs), as an emerging material, have the characteristics of high stability, large series of components, easy synthesis, modification, and adjustable amplitude. They have the potential to become good catalysts. Bromine, as a halogen, has attracted intensive interest for the modification of photocatalysts for photocatalytic reactions. It is feasible to enhance the activity and selectivity of the material by facile functionalization of the reticular parent structure's electron-withdrawing groups. In addition, the conjugation effect of bromine, further delocalizing the electrons of the COF, is beneficial to the progress of many photocatalytic reactions. Reports on the modification of COFs by bromine functional groups to improve the catalytic performance have not been found so far. Here, TAPP [5,10,15,20-tetrakis(4-aminophenyl)porphyrin] and 2,5-dibromo-1,4-benzenedialdehyde instead of terephthalaldehyde were chosen to synthesize a porphyrin-based COF (TAPBB-COF) by the solvothermal method. As expected, the valence band (VB) of TAPBB-COF is thus adjusted to a more suitable position. Additionally, the CO production when using TAPBB-COF under full-wavelength light for 12â h was 295.2â µmol g-1 , which was three times that of COF-366, and the new material has good recycling stability and selectivity (95.6 %). Theoretical calculations indicate that the nitrogen of the porphyrin ring and the Schiff base, and the bromine in TAPBB-COF contribute greatly to the activation of H2 O and the conversion of CO2 in the photoreaction.
RESUMO
A covalent organic framework (COF) featuring a unique light porous structure and silver nanoparticles shows high efficiency in the degradation of environmental pollutants. However, the combination of a COF with silver nanoparticles has never been reported until now. Toward this end, 2,4,6-tris-(4-formylphenoxy)-1,3,5-triazine (TPT-CHO) and hydrazine hydrate were selected as the construction units of the COF material (TPHH-COF), which possesses rich nitrogen and oxygen sites. Then a new type of composite catalyst (Ag@TPHH-COF) was successfully obtained by solution infiltration. The obtained materials were also fully characterized by standard methods. The results showed that the silver nanoparticles (with diameters of 5 ± 3 nm) were uniformly dispersed on the surface and in the interlayer gaps of the TPHH-COF substrate. Catalytic studies showed that Ag@TPHH-COF could catalyze the reduction of the various nitroaromatic compounds (NACs) with high efficiency, such as 4-nitrophenol, 2-nitrophenol, 4-nitroaniline, nitrobenzene, 4-nitrotoluene and 1-butyl-4-nitrobenzene. Ag@TPHH-COF could also catalyze the reduction of organic dyes such as Rhodamine B (RhB), Methylene Blue (MB), Methyl Orange (MO) and Congo Red (CR). Moreover, Ag@TPHH-COF has good reusability and high recovery.
RESUMO
A new triazine-based covalent organic polymer (named COP-NT), which showed high catalytic activities for the degradation of acidic and basic dyes, is synthesized. Its structure characteristics were fully investigated, which featured large specific surface area, homogeneous porosity, strong visible light absorption, excellent thermal stability and semiconductor performance. The as-prepared COP-NT exhibits good chemical stability both in acidic and alkaline aqueous solutions, which could be used as an efficient photocatalyst for the degradation of methyl orange (MO), rhodamine B (RhB) and methylene blue (MB). The Ea values for the degradation of MO, RhB or MB are 9.40 kJ mol-1, 30.94 kJ mol-1 or 17.54 kJ mol-1, respectively. Furthermore, COP-NT showed excellent reusability in degrading all the above dyes without obvious performance decay.