Synthesis and Characterization of Novel Triphenylamine-Containing Electrochromic Polyimides with Benzimidazole Substituents.

Two novel electrochromic aromatic polyimides (named as TPA-BIA-PI and TPA-BIB-PI, respectively) with pendent benzimidazole group were synthesized from 1,2-Diphenyl-N,N'-di-4-aminophenyl-5-amino-benzimidazole and 4-Amino-4'-aminophenyl-4″-1-phenyl-benzimidazolyl-phenyl-aniline with 4,4'-(hexafluoroisopropane) phthalic anhydride (6FDA) via two-step polymerization process, respectively. Then, polyimide films were prepared on ITO-conductive glass by electrostatic spraying, and their electrochromic properties were studied. The results showed that due to the π-π* transitions, the maximum UV-Vis absorption bands of TPA-BIA-PI and TPA-BIB-PI films were located at about 314 nm and 346 nm, respectively. A pair of reversible redox peaks of TPA-BIA-PI and TPA-BIB-PI films that were associated with noticeable color changed from original yellow to dark blue and green were observed in the cyclic voltammetry (CV) test. With increasing voltage, new absorption peaks of TPA-BIA-PI and TPA-BIB-PI films emerged at 755 nm and 762 nm, respectively. The switching/bleaching times of TPA-BIA-PI and TPA-BIB-PI films were 13 s/16 s and 13.9 s/9.5 s, respectively, showing that these polyimides can be used as novel electrochromic materials.

A novel porous hollow carboxyl-polysulfone microsphere for selective removal of cationic dyes.

Herein, we obtained porous hollow carboxyl-polysulfone (PH-CPSF) microspheres through non-solvent-induced phase separation (NIPS) method and simple modification, used as highly efficient adsorbents for removing cationic dyes from sewage. The resulting PH-CPSF microspheres possess a hollow core and sponge-like shell structure, with high surface area, durable chemical inertness and structural stability. The as-synthesized PH-CPSF microspheres deliver a desirable adsorption effect after deprotonation treatment, with an adsorption capacity reaching up to 154.5 mg g-1 at 25 °C (pH = 7) of methylene blue (MB). The inter-molecular interactions between MB and the surface of the PH-CPSF, including π-π interaction, hydrogen bonding, strong charge attraction and weak charge attraction endow the adsorption ability of the PH-CPSF. The pseudo-second-order kinetic model pronounces in the adsorption behavior, and the adsorption equilibrium data is fitted to the Langmuir model. Moreover, PH-CPSF microspheres can also be used as adsorption fillers for large-scale water purification, and a removal rate of 94.0% for MB can be achieved under a flow rate of 8000 L m-3 h-1. The reusability of 95.3% removal effect for PH-CPSF microspheres after 20 consecutive cycles can be attained by a simple regeneration treatment. The adsorption efficiency of the PH-CPSF microspheres was evaluated by variety of cationic and anionic dyes, with high adsorption capacity toward cationic dyes (100%) and less than 10% toward anionic dyes. These results manifest that PH-CPSF microspheres are a potential adsorbent with long-term purification capabilities, which are expected to be used in small and large-scale sewage treatment.

Preparation and Characterization of Reduced Graphene Oxide /TiO2 Blended Polyphenylene sulfone Antifouling Composite Membrane With Improved Photocatalytic Degradation Performance.

Nanosized titanium oxide (TiO2)-based photocatalysts have exhibited great potential for the degradation of organic contaminants, while their weak absorption of visible light limits the photocatalytic efficiency. Herein, a novel reduced graphene oxide/TiO2-polyphenylenesulfone (rGO/TiO2-PPSU) hybrid ultrafiltration membrane has been successfully prepared via a non-solvent induced phase-separation method, in which the synergistic coupling between the rGO and TiO2 could endowed the fabricated membranes with visible-light-driven efficient photocatalytically degradation of organic pollutants and outstanding photocatalytic and antifouling properties. Compared with the PPSU membranes prepared with Graphene oxide and TiO2, respectively, the rGO/TiO2-PPSU membrane demonstrated significant photodegradation towards phenazopyridine hydrochloride (PhP) solution under ultraviolet light (improved about 71 and 43%) and visible light (improved about 153 and 103%). The permeability and flux recovery rates of the membrane indicated that the high flux of the rGO/TiO2-PPSU membrane can be greatly restored after fouling, due to the improved self-cleaning properties under visible light static irradiation. With the properties of high performance of photocatalytic degradation and good self-cleaning ability, the rGO/TiO2-PPSU membrane would have great potential in water treatment.

Novel TiO2 Nanoparticles/Polysulfone Composite Hollow Microspheres for Photocatalytic Degradation.

Nanosized titanium oxide (TiO2) material is a promising photocatalyst for the degradation of organic pollutants, whereas the difficulty of its recycling hinders its practical application. Herein, we reported the preparation of a novel titanium oxide/polysulfone (TiNPs/PSF) composite hollow microspheres by the combination of Pickering emulsification and the solvent evaporation technique and their application for the photodegradation of methyl blue (MB). P25 TiO2 nanoparticles dispersed on the surface of PSF microspheres. The porosity, density and photoactivity of the TiNPs/PSF composite microsphere are influenced by the TiO2 loading amount. The composite microsphere showed good methyl blue (MB) removal ability. Compared with TiO2 P25, and PSF, a much higher MB adsorption speed was observed for TiNPs/PSF microspheres benefited from their porous structure and the electrostatic attractions between the MB+ and the negatively charged PSF materials, and showed good degradation efficiency. For TiNPs/PSF composite microsphere with density close to 1, a 100% MB removal (10 mg L-1) within 120 min at a catalyst loading of 2.5 g L-1 can be obtained under both stirring and static condition, due to well dispersing of TiO2 particles on the microsphere surface and its stable suspending in water. For the non-suspended TiNPs/PSF composite microsphere with density bigger than 1, the 100% MB removal can be only obtained under stirring condition. The removal efficiency of MB for the composite microspheres retained 96.5%, even after 20 cycles. Moreover, this composite microsphere also showed high MB removal ability at acidic condition. The high catalysis efficiency, excellent reusability and good stability make this kind of TiNPs/PSF composite microsphere a promising photocatalyst for the water organic pollution treatment.

Design of a novel poly(aryl ether nitrile)-based composite ultrafiltration membrane with improved permeability and antifouling performance using zwitterionic modified nano-silica.

Zwitterionic nano-silica (SiO2 NPs) obtained by lysine surface modification was used as a hydrophilic inorganic filler for preparing a poly(aryl ether nitrile) (PEN) nanocomposite membrane via an immersion precipitation phase inversion method. The effects of zwitterionic SiO2 NPs addition on the morphology, separation and antifouling performance of the synthesized membranes were investigated. Zwitterionic surface modification effectively avoided the agglomeration of SiO2 NPs. The PEN/zwitterionic SiO2 NPs composite membranes exhibited improved porosity, equilibrium water content, hydrophilicity and permeability due to the introduction of hydrophilic SiO2 NPs in the casting solution, and the optimal pure water flux was up to 507.2 L m-2 h-1, while the BSA rejection ratio was maintained at 97.4%. A static adsorption capacity of 72.9 µg cm-2 and the FRR up to 85.3% in the dynamic antifouling experiment proved that the introduction of zwitterionic SiO2 NPs inhibited irreversible fouling and enhanced the antifouling ability of the PEN membrane.

Incorporation of N-phenyl in poly(benzimidazole imide)s and improvement in H2O-absorbtion and transparency.

5-Amine-2-(4-amino-benzene)-1-phenyl-benzimidazole (N-PhPABZ) was successfully synthesized and polymerized with 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA) to obtain a novel N-phenyl-poly(benzimidazole imide) (N-Ph-PBII). The successful incorporation of N-phenyl addressed the issue of high H2O-absorption of traditional PBIIs while retained the superheat resistance property. The resulting N-Ph-PBII possessed a high glass-transition temperature (T g) up to 425 °C and a low affinity for water of 1.4%. Furthermore, the loose molecular packing and noncoplanar structures led to an increase in optical transparency for the modified PBII.

Polyimides containing a novel bisbenzoxazole with high T g and low CTE.

A novel diamine named (2,2'-bibenzoxazole)-5,5'-diamine (DBOA) and derived polyimides (PIs) were successfully synthesized. The rigid, linear, symmetrical molecular structure and the strong charge transfer complex (CTC) were considered to be the reasons for the improved molecular packing and enhanced thermal properties of the polymers. These DBOA based PIs exhibited a higher glass transition temperature (T g) and lower coefficient of thermal expansion (CTE) than traditional benzoxazole (BOA) based PIs. Meanwhile, the PI derived from DBOA and BPDA (3,3',4,4'-biphenyltetracarboxylic dianhydride) exhibited high T g (395 °C) and low CTE (8.9 ppm per °C), and is expected to be applied in organic light-emitting diode (OLED) displays.

Fabrication of ultrafiltration membranes by poly (aryl ether nitrile) with poly (ethylene glycol) as additives.

A new kind of flat sheet ultrafiltration membrane was prepared by a promising membrane material, poly (aryl ether nitrile) (PEN), via non-solvent induced phase separation. The effect of solvents, N-methyl-2-pyrrolidone (NMP) and dimethyl acetamide (DMAc), as well as additive of poly (ethylene glycol) (PEG) with different molecular weights on the structure and permeation performance of synthesized membranes were investigated. Comparing with NMP, DMAc is more suitable for the casting solution preparation due to better solubility. A gradually changing pore from sponge-like to finger-like can be observed when PEG was added with DMAc as solvent, while a finger-like pore structure always appears in the NMP system with or without PEG. In both systems, the formation of macrovoids is effectively promoted by the addition of PEG, and higher porosity membranes can be obtained by PEG with higher molecular weight. With the increase of PEG molecular weight from 400 to 10,000 Da, the permeate flux increases from 74.5 to 114.3 L·m-2·h-1 and from 102.0 to 130.8 L·m-2·h-1 under a 100 kPa pressure-driven when NMP and DMAc were used as solvents, respectively. The membranes prepared by DMAc exhibit outstanding rejection of BSA with rejections all above 96.5%.

Preparation of a Fluorocarbon Polymerizable Surfactant and Its Application in Emulsion Polymerization of Fluorine-Containing Acrylate.

A novel polymerizable fluorocarbon surfactant, perfluoro (4⁻methyl⁻3, 6⁻dioxaoct⁻7⁻ene) sodium sulfonate (PSVNa), was synthesized and characterized. The fluorocarbon surfactant PSVNa and its mixture PSVNa/SDS were used as emulsifiers during the emulsion polymerization of DFHMA/MMA. The investigation of polymerization kinetics, particle size, and stability of the emulsions revealed that PSVNa has excellent emulsifying properties. The NMR spectrum of the copolymer and the detection of residual PSVNa show that more than 95% of the fluorocarbon surfactants have been linked to the polymer chains by radical polymerization, which will greatly reduce the environmental pollution caused by fluorinated surfactants.

A general approach for fabrication of nitrogen-doped graphene sheets and its application in supercapacitors.

In this paper, a general and efficient strategy has been developed to produce nitrogen-doped graphene sheets (NGs) based on hard and soft acids and bases (HSAB) theory. Under hydrothermal conditions, any salt with amphiprotic character have a strong tendency to hydrolysis, it is possible to provide reducing agent and nitrogen source simultaneously. It is worth noting that, NGs can be prepared under hydrothermal conditions by using some common ammonium salts with hard acid-soft base pairs as nitrogen-doping agents. The morphology, structure and composition of the as-prepared NGs were studied in detail. The results demonstrated that large amount of nitrogen was incorporated into the nanocarbon frameworks at the same time as the graphene oxide (GO) sheets were reduced. The electrochemical behavior of the synthesized NGs as supercapacitor electrodes was evaluated in a symmetric two-electrode cell configuration with 1M H2SO4 as the electrolytes. It was found that the nitrogen groups making the as-prepared NGs exhibited remarkably enhanced electrochemical performance when used as electrode materials in supercapacitors. The supercapacitor based on the NGs exhibited a high specific capacitance of 242 F g(-1) at a current density of 1 A g(-1), and remains a relatively high capacitance even at a high current density. This work will put forward to understand and optimize heteroatom-doped graphene in energy storage systems.

Solution processable titanium dioxide precursor and nanoparticulated ink: application in Dye Sensitized Solar Cells.

Colloidal TiO2 anatase nanoparticles of 4-8 nm diameter capped with 3,6,9-trioxadecanoic acid (TODA) were synthesized at low temperature using water and ethanol as the solvents. ATR-FTIR and (1)H NMR characterization showed the capping acid capability of stabilizing the TiO2 nanoparticles through labile hydrogen bonds. The presence of the capping ligand permitted the further preparation of homogeneous and stable colloidal dispersions of the TiO2 powder in aqueous media. Moreover, after solvent evaporation, the ligand could be easily eliminated by soft treatments, such as UV irradiation or low-temperature thermal annealing. These properties have been used in this work to fabricate mesoporous TiO2 electrodes, which can be applied as photoanodes in Dye Sensitized Solar Cells (DSSCs). For the preparation of the electrodes, the as-synthesized mesoporous TiO2 nanoparticles were mixed with commercial TiO2 (Degussa P25) and deposited on FTO substrates by using the doctor blade technique. A mixture of water and ethanol was used as the solvent. A soft thermal treatment at 140 °C for 2h eliminated the organic compound and produced a sintered mesoporous layer of 6 µm thickness. The photovoltaic performance of the DSSCs applying these electrodes sensitized with the N3 dye resulted in 5.6% power conversion efficiency.

A phenyl-capped aniline tetramer for Z907/tert-butylpyridine-based dye-sensitized solar cells and molecular modelling of the device.

Z907-sensitized solar cells incorporating a phenyl-capped aniline tetramer (EPAT) as a substitute of the iodine/iodide redox couple in the electrolytes produce an enhanced open-circuit voltage and short circuit photocurrent density when tert-butylpyridine (TBP) is added to the electrolyte.

New D-π-A-conjugated organic sensitizers based on 4H-pyran-4-ylidene donors for highly efficient dye-sensitized solar cells.

We have synthesized a series of four new promising D-π-A conjugated organic sensitizers with a proaromatic 4H-pyran-4-ylidene as a donor, a thiophene ring in the bridge, and 2-cyanoacrilic acid as acceptor. Comparison between different donor substituents and the modification of the thiophene ring resulted in molar extinction coefficients as high as 36399 M(-1) cm(-1) at 551 nm. The photovoltaic properties of the DSSCs demonstrate power conversion efficiencies as high as 5.4%.

Iodine/iodide-free dye-sensitized solar cells.

Dye-sensitized solar cells (DSSCs) are built from nanocrystalline anatase TiO(2) with a 101 crystal face (nc-TiO(2)) onto which a dye is absorbed, ruthenium complex sensitizers, fluid I(-)/I(3)(-) redox couples with electrolytes, and a Pt-coated counter electrode. DSSCs have now reached efficiencies as high as 11%, and G24 Innovation (Cardiff, U.K.) is currently manufacturing them for commercial use. These devices offer several distinct advantages. On the basis of the electron lifetime and diffusion coefficient in the nc-TiO(2) layer, DSSCs maintain a diffusion length on the order of several micrometers when the dyed-nc-TiO(2) porous layer is covered by redox electrolytes of lithium and/or imidazolium iodide and their polyiodide salts. The fluid iodide/iodine (I(-)/I(3)(-)) redox electrolytes can infiltrate deep inside the intertwined nc-TiO(2) layers, promoting the mobility of the nc-TiO(2) layers and serving as a hole-transport material of DSSCs. As a result, these materials eventually give a respectable photovoltaic performance. On the other hand, fluid I(-)/I(3)(-) redox shuttles have certain disadvantages: reduced performance control and long-term stability and incompatibility with some metallic component materials. The I(-)/I(3)(-) redox shuttle shows a significant loss in short circuit current density and a slight loss in open circuit voltage, particularly in highly viscous electrolyte-based DSSC systems. Iodine can also act as an oxidizing agent, corroding metals, such as the grid metal Ag and the Pt mediator on the cathode, especially in the presence of water and oxygen. In addition, the electrolytes (I(-)/I(3)(-)) can absorb visible light (lambda = approximately 430 nm), leading to photocurrent loss in the DSSC. Therefore, the introduction of iodide/iodine-free electrolytes or hole-transport materials (HTMs) could lead to cost-effective alternatives to TiO(2) DSSCs. In this Account, we discuss the iodide/iodine-free redox couple as a substitute for the fluid I(-)/I(3)(-) redox shuttle. We also review the adaptation of solid-state HTMs to the iodide/iodine-free solid-state DSSCs with an emphasis on their pore filling and charge mobility in devices and the relationship of those values to the performance of the resulting iodide/iodine-free DSSCs. We demonstrate how the structures of the sensitizing dye molecules and additives of lithium or imidazolium salts influence device performance. In addition, the self-organizing molecular interaction for electronic contact of HTMs to dye molecules plays an important role in unidirectional charge diffusion at interfaces. The poly(3,4-ethylenedioxythiophene) (PEDOT)-based DSSCs, which we obtain through photoelectrochemical polymerization (PEP) using 3-alkylthiophen-bearing ruthenium dye, HRS-1, and bis-EDOT, demonstrates the importance of nonbonding interface contact (e.g., pi-pi-stacking) for the successful inclusion of HTMs.

Preparation and characterization of polyaniline microwires containing CdS nanoparticles.

Polyaniline(PANI) microwires containing CdS nanoparticles have been prepared by introducing hydrogen bonding and/or electrostatic interaction between mercaptocarboxylic acid capped CdS nanoparticles and PANI. SEM and TEM proved them to be wire-like structures. PL spectra of the PANI/CdS complex is blue-shifted by 14 nm compared to CdS nanoparticles in N-methylpyrrolidinone(NMP).