Conjugated porous organic polymers have sparked growing research attention as photocatalysts owing to their high surface area, tunable pores, and capacity to collect and transfer light energy via their delocalized backbone. However, the synthesis methods for preparing these polymers require difficult experimental setups, such as high polymerization temperature, inert atmosphere, and use of transition metal catalysts. In the present work, a triphenylamine-based conjugated porous polymer (TPA-BPA) has been synthesized employing tris(4-aminophenyl)amine (TPA) and biphenyldicarboxaldehyde (BPA) as precursors via a one-pot Schiff base reaction in ambient conditions in the absence of the metal catalyst. The synthesized TPA-BPA polymer has been characterized using Fourier transform infrared spectroscopy, C cross-polarization magic angle spinning nuclear magnetic resonance, Brunauer-Emmett-Teller (BET), thermogravimetric analysis, field emission scanning electron microscopy, high-resolution transmission electron microscopy, valence band X-ray photoelectron spectroscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, powder X-ray diffraction, electron paramagnetic resonance (EPR), and diffuse reflectance spectroscopy (DRS) techniques. The DRS analysis revealed that TPA-BPA has an optical band gap of 2.1 eV, demonstrating its semiconductive nature. The EPR study has shown that the synthesized polymer exhibits an intense radical signal at = 2.00, confirming free radical generation upon photoexcitation and facilitating the breakdown of organic contaminants by photocatalysis. TPA-BPA possesses an exceptional porous structure with a surface area of 36 m/g, as confirmed by BET studies, and high thermal stability up to 420 °C. It has been confirmed by photocatalytic studies that TPA-BPA shows effective degradation of methyl orange (92%), Congo red (91.5%), tobramycin (96%), and hydroquinone (85%) under visible light irradiation in 60 min. Owing to these observations, TPA-BPA can be an excellent candidate as a photocatalyst for environmental remediation. These findings pave the way for large-scale manufacturing of metal-free conjugated porous polymers as photocatalysts with variable photoelectrical characteristics.
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http://dx.doi.org/10.1021/acs.langmuir.4c03461 | DOI Listing |
Int J Biol Macromol
January 2025
Textile Innovation R&D Department, Korea Institute of Industrial Technology, Ansan 15588, Republic of Korea. Electronic address:
Artificial vascular grafts, as blood vessel substitutes, are a prime challenge in tissue engineering and biomaterial research. An ideal artificial graft must have physiological and mechanical properties similar to those of a natural blood vessel, and hemocompatibility on its surface. We designed and fabricated artificial grafts by applying 3D printing and templated technology, which is endowed with morphologically patient-specific vascular reconstruction.
View Article and Find Full Text PDFChem Asian J
January 2025
Qingdao University of Science and Technology, College of Polymer Science and Engineering, 53 ZHENGZHOU ROAD, 266000, Qingdao, CHINA.
Constructing highly conjugated three-dimensional covalent organic frameworks (3D COFs), particularly those with luminescent features, remains a significant challenge. In this work, we successfully synthesized a 3D COF, named 3D-Py-SP-COF, using a rigid and orthogonal spirobifluorene building block for the spatial 3D structure construction and planar pyrene as luminescent units. The incorporation of the pyrene and the unique rigid 3D network structure endow 3D-Py-SP-COF with fluorescent properties.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Advanced Membranes and Porous Materials Center, Division of Physical Science and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900, Kingdom of Saudi Arabia.
Understanding how structural modifications affect the photophysics of organic linkers is crucial for their integration into metal-organic frameworks (MOFs) for light-driven applications. This study explores the impact of varying the amine functional group position on two terephthalic acid derivatives─linker and linker ─by investigating their photophysics through a combination of steady-state and ultrafast laser spectroscopy and time-dependent density functional theory (TD-DFT) calculations. With tetrahydrofuran as the solvent, time-correlated single-photon counting revealed a 2-fold increase in the S excited-state lifetime of the molecule with the amine group at the meta position compared with that of the molecule with the amine group at the ortho position.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Tsinghua University, Institute of Nuclear and New Energy Technology, Room A320, Nengke Building, Qinghua Yuan No.1, Beijing, CHINA.
Exploiting supramolecular secondary building units (SSBUs) for developing porous crystalline materials represents an exciting breakthrough that extends the boundaries of reticular chemistry. However, shaping polynuclear clusters sustained by non-covalent interactions for the assembly of hydrogen-bonded frameworks remains a critical challenge. This study presents a novel strategy to stabilize SSBUs by tuning the π-stacking geometry of conjugated building blocks, facilitating the creation of hydrogen-bonded frameworks with tailored architectures for demanding gas separation.
View Article and Find Full Text PDFNanoscale
January 2025
Department of Chemistry, Netaji Subhas University of Technology, Delhi, India.
Nanoporous organic polymers (NPOPs) have emerged as versatile materials with robust thermal stability, large surface area (up to 2500 m g), and customizable porosity, making them ideal candidates for advanced hydrogen (H) storage applications. This review provides a comprehensive analysis of various NPOPs, including covalent organic frameworks (COFs), hypercrosslinked polymers (HCLPs), conjugated microporous polymers (CMPs), and porous aromatic frameworks (POAFs). Notably, these materials demonstrate superior H storage capacities, achieving up to 10 wt% at cryogenic temperatures, which is essential for applying H as a clean energy carrier.
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