Adenine-functionalized conjugated polymer as an efficient photocatalyst for hydrogen evolution from water

Conjugated polymers have emerged as a promising class of organic photocatalysts for photocatalytic hydrogen evolution from water splitting due to their adjustable chemical structures and electronic properties. However, developing highly efficient organic polymer photocatalysts with high photocatalytic activity for hydrogen evolution remains a significant challenge. Herein, we present an efficient approach to enhance the photocatalytic performance of linear conjugated polymers by modifying the surface chemistry via introducing a hydrophilic adenine group into the side chain. The adenine unit with five nitrogen atoms could enhance the interaction between the surface of polymer photocatalyst and water molecules through the formation of hydrogen bonding, which improves the hydrophilicity and dispersity of the resulting polymer photocatalyst in the photocatalytic reaction solution. In addition, the strong electron-donating ability of adenine group with plentiful nitrogen atoms could promote the separation of light-induced electrons and holes. As a result, the adenine-functionalized conjugated polymer PF6A-DBTO2 shows a high photocatalytic activity with a hydrogen evolution rate (HER) of 25.21 mmol g^?1 h^?1 under UV-Vis light irradiation, which is much higher than that of its counterpart polymer PF6-DBTO2 without the adenine group (6.53 mmol g^?1 h^?1). More importantly, PF6A-DBTO2 without addition of a Pt co-catalyst also exhibits an impressive HER of 21.93 mmol g^?1 h^?1 under visible light (λ > 420 nm). This work highlights that it is an efficient strategy to improve the photocatalytic activity of conjugated polymer photocatalysts by the modification of surface chemistry.     

Toward High-Performance Dihydrophenazine-Based Conjugated Microporous Polymer Cathodes for Dual-Ion Batteries through Donor–Acceptor Structural Design

Recent studies have demonstrated that dihydrophenazine (Pz) with high redox-reversibility and high theoretical capacity is an attractive building block to construct p-type polymer cathodes for dual-ion batteries. However, most reported Pz-based polymer cathodes to date still suffer from low redox activity, slow kinetics, and short cycling life. Herein, a donor–acceptor (D–A) Pz-based conjugated microporous polymer (TzPz) cathode is constructed by integrating the electron-donating Pz unit and the electron-withdrawing 2,4,6-triphenyl-1,3,5-triazine (Tz) unit into a polymer chain. The D–A type structure enhances the polymer conjugation degree and decreases the band gap of TzPz, facilitating electron transportation along the polymer skeletons. Therefore the TzPz cathode for dual-ion battery shows a high reversible capacity of 192 mAh g⁻¹ at 0.2 A g⁻¹ with excellent rate performance (108 mAh g⁻¹ at 30 A g⁻¹), which is much higher than that of its counterpart polymer BzPz produced from 1,3,5-triphenylbenzene (Bz) and Pz (148 and 44 mAh g⁻¹ at 0.2 and 10 A g⁻¹, respectively). More importantly, the TzPz cathode also shows a long and stable cyclability of more than 10 000 cycles. These results demonstrate that the D–A structural design is an efficient strategy for developing high-performance polymer cathodes for dual-ion batteries.     

Unusual Two-Step Assembly of a Minimalistic Dipeptide-Based Functional Hypergelator

Self-assembled peptide hydrogels represent the realization of peptide nanotechnology into biomedical products. There is a continuous quest to identify the simplest building blocks and optimize their critical gelation concentration (CGC). Herein, a minimalistic, de novo dipeptide, Fmoc-Lys(Fmoc)-Asp, as an hydrogelator with the lowest CGC ever reported, almost fourfold lower as compared to that of a large hexadecapeptide previously described, is reported. The dipeptide self-assembles through an unusual and unprecedented two-step process as elucidated by solid-state NMR and molecular dynamics simulation. The hydrogel is cytocompatible and supports 2D/3D cell growth. Conductive composite gels composed of Fmoc-Lys(Fmoc)-Asp and a conductive polymer exhibit excellent DNA binding. Fmoc-Lys(Fmoc)-Asp exhibits the lowest CGC and highest mechanical properties when compared to a library of dipeptide analogues, thus validating the uniqueness of the molecular design which confers useful properties for various potential applications.     

High performance lead-free Na0.5K0.5NbO3 piezoelectric ceramics obtained via oscillatory hot-pressing

Lead-free Na_0.5K_0.5NbO₃ (KNN) piezoelectric ceramics is regarded as a potential candidate for PZT material, while high performance is difficult to be obtained due to its poor sinterability and non-stoichiometric component. In this work, oscillatory pressure-assisted hot pressing (OPAHP) is utilized to fabricate KNN ceramics with high density. The KNN ceramics sintered at 860 °C exhibits superior performance with piezoelectric parameter (d₃₃) of 142 pC/N, electromechanical coupling factors (k_p) of 0.41, and relative permittivity (ε^T₃₃/ε₀) of 472–620. Additionally, hardness and flexural strength are measured as 3.55 GPa and 99.13 MPa, respectively. This work indicates that OPAHP technique is effective for fabricating KNN piezoelectric ceramics with high performance.     

Highly textured and strongly anisotropic TiB2 ceramics prepared using magnetic field alignment (9T)

Highly textured TiB₂ ceramics were prepared by slip casting an aqueous suspension in a magnetic field of 9 T, followed by sintering using Field Assisted Sintering Technology (FAST). Particle size refinement by ball milling improved both the degree of texturing and densification of the material (RD > 98 %). The sintered material exhibited a Lotgering orientation factor of 0.90, with the c-axis of TiB₂ oriented parallel to the magnetic field and FAST pressing direction. The texturing effect induced by the uniaxial pressing was negligible. The textured TiB₂ material exhibited a significant anisotropy in mechanical properties; the values of hardness and indentation elastic modulus measured along directions transverse to the c-axis of TiB₂ were 37 % and 13 % higher than the ones measured along the c-axis direction. Moreover, the specific wear rate of a surface of textured TiB₂ parallel to the field was one order of magnitude lower than a surface perpendicular to the field.     

Reinforcement and toughening mechanisms in polymer nanocomposites – Carbon nanotubes and aluminum oxide

The addition of nanoparticles has been reported as an option to increase the fracture toughness of thermosetting polymers without compromising the stiffness. In this paper, alumina or carbon nanotubes (CNTs), in three different concentrations, were dispersed in an epoxy resin. Mechanical properties were measured through tensile test and the results indicate increases for all nanocomposites, with a maximum for the addition of 0.5% of CNTs (17% in elastic modulus and 22% in ultimate stress). Using TEM images, it was possible to identify the nanostructures and mechanisms that lead to improved stiffness. Fracture toughness tests and SEM images showed that cavitation – shear yielding (for epoxy/alumina nanocomposites) and crack bridging – pull-out (for epoxy/CNTs nanocomposites) are the predominant mechanisms.     

Dielectric response and energy storage efficiency of low content TiO2-polymer matrix nanocomposites

TiO₂/epoxy nanocomposites were prepared at different filler concentrations varying from 3 to 12 phr (parts per hundred resin per weight). The dispersion of TiO₂ was examined by Scanning Electron Microscopy and proved to be adequate. Differential Scanning Calorimetry was implemented to determine the glass to rubber transition temperature of the polymer matrix. The dielectric analysis was performed via Broadband Dielectric Spectroscopy in a wide frequency and temperature range. Five different mechanisms were observed in the spectra of the examined composites which are identified, in terms of increasing temperature at constant frequency, as γ, β, Intermediate Dipolar Effect (IDE), α and Interfacial Polarization (IP) relaxation modes. The activation energies of all relaxation modes were calculated. Finally, the dielectric response of the TiO₂ nanocomposites compared to that of the TiO₂ microcomposites reveals that the former exhibit significantly higher energy storage efficiency even at lower TiO₂ concentration than the corresponding of the microcomposites.     

Synthesis and characterization of copolymers with the same proportions of polystyrene and poly(ethylene oxide) compositions but different connection sequence by the efficient Williamson reaction

The AB type diblock PS‐b‐PEO and ABA type triblock PS‐b‐PEO‐b‐PS copolymers containing the same proportions of polystyrene (PS) and poly(ethylene oxide) (PEO) but different connection sequence were synthesized and investigated. Using the sequential living anionic polymerization and ring‐opening polymerization mechanisms, diblock PS‐b‐PEO copolymers with one hydroxyl group at the PEO end were obtained. Then, using the classic and efficient Williamson reaction (realized in a ‘click’ style), triblock PS‐b‐PEO‐b‐PS copolymers were achieved by a coupling reaction between hydroxyl groups at the PEO end of PS‐b‐PEO. The PS‐b‐PEO and PS‐b‐PEO‐b‐PS copolymers were well characterized by ¹H NMR spectra and SEC measurements. The critical micelle concentration (CMC) and thermal behaviors were also investigated by steady‐state fluorescence spectra and DSC, respectively. The results showed that, because the PEO segment in triblock PS‐b‐PEO‐b‐PS was more restricted than that in diblock PS‐b‐PEO copolymer, the former PS‐b‐PEO‐b‐PS copolymer always gave higher CMC values and lower crystallization temperature (T_c), melting temperature (T_m) and degree of crystallinity (X_c) parameters. © 2015 Society of Chemical Industry