Search Results (10)

Vacancy defect graphitic carbon nitride (g-C₃N₄) and conjugated polyimide (PI) polymer photocatalysts have become increasingly recognized as metal-free photocatalysts featuring an appropriate bandgap. The narrow absorption spectrum of visible light and the rapid recombination rate of the photoexcited charge carriers in PI polymers and g-C₃N₄ impede its photocatalytic performance. The presence of oxygen vacancies (OVs) in PI polymer photocatalysts, as well as nitrogen vacancies (NVs) and carbon vacancies (CVs) in g-C₃N₄, can significantly enhance the migration of photogenerated electrons. Adding vacancies to improve the electronic structure and band gap width can greatly enhance the photocatalytic efficiency of PI polymers and g-C₃N₄. Defect engineering is important for increasing the photocatalytic ability of PI-polymer and g-C₃N₄. There remains a notable absence of thorough review papers covering the synthesis, characterization, and applications of vacancy-rich PI-polymer and g-C₃N₄ in photocatalysis. This review paper examines the roles of OVs in PI-polymer, NVs, and CVs in g-C₃N₄ and thoroughly summarizes the preparation approaches employed before and after, as well as during polymerization. This review scrutinizes spectroscopic characterization techniques, such as EPR, XPS, PAS, XRD, FTIR, and NMR, for vacancy defect analysis. We also reviewed the role of vacancies, which include light absorption, photogenerated charge carrier separation, and transfer dynamics. This review could serve as a comprehensive understanding, a vacancy-engineered design framework, and a practical guide for synthesizing and characterizing. Full article

Non-conjugated polymer-derived functional nanocomposites are one of the important ways to develop multifunctional hybrids. By increasing the degree of crosslinking, their photophysical properties can be improved. PbS is a class of narrow bandgap infrared active materials. To avoid aggregation and passivation of the surface defects of PbS nanomaterials, a large number of organic and inorganic ligands are usually used. In this study, PbS/C composite nanosheets were synthesized with Pb²⁺ ion-crosslinked sodium alginate gel by one-pot carbonization. The resulting nanosheets were coated on untreated A4 printing paper, and the electrodes were the graphite electrodes with 5B pencil drawings. The photocurrent signals of the products were measured using typical 650, 808, 980, and 1064 nm light sources. The results showed that the photocurrent switching signals were effectively extracted in the visible and near-infrared regions, which was attributed to the mutual passivation of defects during the in situ preparation of PbS and carbon nanomaterials. At the same time, the resulting nanocomposite exhibited electrical switching responses to the applied strain to a certain extent. The photophysical and defect passivation mechanisms were discussed based on the aggregation state of the carbon hybrid and the interfacial electron interaction. This material would have potential applications in broadband flexible photodetectors, tentacle sensors, or light harvesting interdisciplinary areas. This study provided a facile approach to prepare a low-cost hybrid with external stimulus response and multifunctionality. These results show that the interfacial charge transfer is the direct experimental evidence of interfacial interaction, and the regulation of interfacial interaction can improve the physical and chemical properties of nanocomposites, which can meet the interdisciplinary application. The interdisciplinary and application of more non-conjugated polymer systems in some frontier areas will be expanded upon. Full article

In this study, polyvinylidene fluoride (PVDF) fibers doped with hydrated calcium nitrate were prepared using electrospinning. The samples were analyzed using scanning electron microscopy (SEM), X-ray diffraction (XRD), optical spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR), Raman, and photoluminescence (PL) spectroscopy. The results are complementary and confirm the presence of chemical hydrogen bonding between the polymer and the dopant. Additionally, there was a significant increase in the proportion of the electroactive polar beta phase from 72 to 86%. It was shown that hydrogen bonds acted as a transport pathway for electron capture by the conjugated salt, leading to more than a three-fold quenching of photoluminescence. Furthermore, the optical bandgap of the composite material narrowed to the range of visible light energies. For the first time, it the addition of the salt reduced the energy of the PVDF exciton by a factor of 17.3, initiating photocatalytic activity. The calcium nitrate-doped PVDF exhibited high photocatalytic activity in the degradation of methylene blue (MB) under both UV and visible light (89 and 44%, respectively). The reaction rate increased by a factor of 2.4 under UV and 3.3 under visible light during piezophotocatalysis. The catalysis experiments proved the efficiency of the membrane design and mechanisms of catalysis are suggested. This study offers insight into the nature of chemical bonds in piezopolymer composites and potential opportunities for their use. Full article

Bandgap energy is one of the most important properties for developing electronic devices because of its influence on the electrical conductivity of substances. Many methods have been developed to control bandgap, one of which is the realization of conducting polymers using narrow-bandgap polymers; however, the preparation of these polymers is complex. In this study, water-soluble, narrow-bandgap polymers with reactive groups were prepared by the addition–condensation reaction of pyrrole (Pyr), benzaldehyde-2-sulfonic acid sodium salt (BS), and aldehyde-containing reactive groups (aldehyde and pyridine) for post-crosslinking. Two types of reactions, aldehyde with p-phenylenediamine and pyridine with 1,2-dibromoethylene, were carried out for the π-conjugated post-crosslinking between polymers. The polymers were characterized by proton nuclear magnetic resonance (¹H-NMR), thermogravimetric/differential thermal analysis (TG/DTA), UltraViolet-Visible-Near InfraRed spectroscopy (UV-Vis-NIR), and other analyses. The bandgaps of the polymers, calculated from their absorption, were less than 0.5 eV. Post-crosslinking prevents resolubility and develops electron-conducting routes between the polymer chains for π-conjugated systems. Moreover, the post-crosslinked polymers maintain their narrow bandgaps. The electrical conductivities of the as-prepared polymers were two orders of magnitude higher than those before the crosslinking. Full article

Conjugated polymers with narrower bandgaps usually induce higher carrier mobility, which is vital for the improved thermoelectric performance of polymeric materials. Herein, two indacenodithiophene (IDT) based donor–acceptor (D-A) conjugated polymers (PIDT-BBT and PIDTT-BBT) were designed and synthesized, both of which exhibited low-bandgaps. PIDTT-BBT showed a more planar backbone and carrier mobility that was two orders of magnitude higher (2.74 × 10⁻² cm²V⁻¹s⁻¹) than that of PIDT-BBT (4.52 × 10⁻⁴ cm²V⁻¹s⁻¹). Both exhibited excellent thermoelectric performance after doping with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, where PIDTT-BBT exhibited a larger conductivity (0.181 S cm⁻¹) and a higher power factor (1.861 μW m⁻¹ K⁻²) due to its higher carrier mobility. The maximum power factor of PIDTT-BBT reached 4.04 μW m⁻¹ K⁻² at 382 K. It is believed that conjugated polymers with a low bandgap are promising in the field of organic thermoelectric materials. Full article

Two two-dimensional (2D) donor–acceptor (D-A) type conjugated polymers (CPs), namely, PBDT-TVT-BT and PBDT-TVT-FBT, in which two ((E)-(4,5-didecylthien-2-yl)vinyl)- 5-thien-2-yl (TVT) side chains were introduced into 4,8-position of benzo[1,2-b:4,5-bʹ]dithiophene (BDT) to synthesize the highly conjugated electron-donating building block BDT-TVT, and benzothiadiazole (BT) and/or 5,6-difluoro-BT as electron-accepting unit, were designed to systematically ascertain the impact of fluorination on thermal stability, optoelectronic property, and photovoltaic performance. Both resultant copolymers exhibited the lower bandgap (1.60 ~ 1.69 eV) and deeper highest occupied molecular orbital energy level (E_HOMO, –5.17 ~ –5.37 eV). It was found that the narrowed absorption, deepened E_HOMO and weakened aggregation in solid film but had insignificant influence on thermal stability after fluorination in PBDT-TVT-FBT. Accordingly, a PBDT-TVT-FBT-based device yielded 16% increased power conversion efficiency (PCE) from 4.50% to 5.22%, benefited from synergistically elevated V_OC, J_SC, and FF, which was mainly originated from deepened E_HOMO, increased μ_h, μ_e, and more balanced μ_h/μ_e ratio, higher exciton dissociation probability and improved microstructural morphology of the photoactive layer as a result of incorporating fluorine into the polymer backbone. Full article

The B←N is isoelectronic to the C–C, with the former having stronger dipole moment and higher electron affinity. Replacing the C–C bonds in conjugated polymers with B←N bonds is an effective pathway toward novel polymers with strong electron affinity and adjustable optoelectronic properties. In this work, we synthesize a conjugated copolymer, namely, BNIDT-DPP, based on a B←N embedded unit, BNIDT, and a typical electron-deficient unit, diketopyrrolopyrrole (DPP). For comparison, the C–C counterpart, i.e., IDT-DPP, is also synthesized. In contrast to IDT-DPP, the B←N embedded polymer BNIDT-DPP shows an extended absorption edge (836 versus 978 nm), narrowed optical bandgap (1.48 versus 1.27 eV), and higher electron affinity (3.54 versus 3.74 eV). The Gaussian simulations reveal that the B←N embedded polymer BNIDT-DPP is more electron-deficient in contrast to IDT-DPP, supporting the decreased bandgap and energy levels of BNIDT-DPP. Organic thin-film transistor (OTFT) tests indicate a well-defined p-type characteristic for both IDT-DPP and BNIDT-DPP. The hole mobilities of IDT-DPP and BNIDT-DPP tested by OTFTs are 0.059 and 0.035 cm²/V·s, respectively. The preliminary fabrication of all-polymer solar cells based on BNIDT-DPP and PBDB-T affords a PCE of 0.12%. This work develops a novel B←N embedded polymer with strong electron affinity and extended absorption, which is potentially useful for electronic device application. Full article

To investigate the influence of fluoride phenyl side-chains onto a quinoxaline (Qx) unit on the photovoltaic performance of the narrow bandgap (NBG) photovoltaic polymers, herein, two novel NBG copolymers, PBDTT-DTQx and PBDTT-DTmFQx, were synthesized and characterized. 2-ethylhexylthiothiophene-substituted benzodithiophene (BDTT), 2,3-diphenylquinoxaline (DQx) [or 2,3-bis(3-fluorophenyl)quinoxaline (DmFQx)] and 2-ethylhexylthiophene (T) were used as the electron donor (D) unit, electron-withdrawing acceptor (A) unit and π-bridge, respectively. Compared to non-fluorine substituted PBDTT-DTQx, fluoride PBDTT-DTmFQx exhibited a wide UV-Vis absorption spectrum and high hole mobility. An enhanced short-circuit current (J_sc) and fill factor (FF) simultaneously gave rise to favorable efficiencies in the polymer/PC₇₁BM-based polymer solar cells (PSCs). Under the illumination of AM 1.5G (100 mW cm⁻²), a maximum power conversion efficiency (PCE) of 6.40% was achieved with an open-circuit voltage (V_oc) of 0.87 V, a J_sc of 12.0 mA cm⁻² and a FF of 61.45% in PBDTT-DTmFQx/PC₇₁BM-based PSCs, while PBDTT-DTQx-based devices also exhibited a PCE of 5.43%. The excellent results obtained demonstrate that PBDTT-DTmFQx by fluorine atom engineering could be a promising candidate for organic photovoltaics. Full article

Novel two-dimensional conjugated copolymer, abbreviated as PDTBSeVTT-2TF, containing electron-deficient 4,7-di(thiophen-2-yl)benzo[c][1,2,5]selenodiazole (DTBSe) unit, conjugated vinyl-terthiophene (VTT) side chain and 3,3′-difluoro-2,2′-bithiophene (2TF) was designed and synthesized using microwave-assisted Stille cross-coupling polymerization. UV–visible absorption and cyclic voltammetry studies revealed that this copolymer possesses a strong and broad absorption in the range of 300–800 nm and a narrow optical bandgap (E_g) of 1.57 eV with low-lying HOMO and LUMO energy levels. Further, the bulk heterojunction polymer solar cells (PSCs) were fabricated using PDTBSeVTT-2TF as donor and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) as acceptor with an inverted device structure of ITO/ZnO/PDTBSeVTT-2TF:PC₇₁BM/V₂O₅/Ag. The processing temperature of blend solution for preparing PDTBSeVTT-2TF:PC₇₁BM active layer showed obvious impact on the photovoltaic performance of solar devices. The cell fabricated from the blend solution at 65 °C exhibited enhanced power conversion efficiencies (PCE) of 5.11% with a J_sc of 10.99 mA/cm⁻² compared with the one at 50 °C, which had a PCE of 4.69% with a J_sc of 10.10 mA/cm⁻². This enhancement is due to the dissolution of PDTBSeVTT-2TF clusters into single molecules and small aggregates, improving the miscibility between the polymer and PC₇₁BM and thus increasing the donor/acceptor interface. Full article

There have been exciting developments in the field of polymer solar cells (PSCs) as the potential competitor to the traditional silicon-based solar cells in the past decades. The most successful PSCs are based on the bulk hetero-junction (BHJ) structure, which contains a bicontinuous nanoscale interpenetrating network of a conjugated polymer and a fullerene blend. The power conversion efficiencies (PCEs) of BHJ PSCs have now exceeded 11%. In this review, we present an overview of recent emerging developments of narrow bandgap conjugated polymers for PSCs. We focus on a few important acceptors used in the donor-acceptor type conjugated polymers for highly efficient PSCs. We also reviewed the emerged donor-π-acceptor (D-π-A) side chains polymers. The band-gaps and energy levels as well as the photovoltaic performances of conjugated polymers are discussed. Full article