Xin-Gui Li

Strong adsorbability of mercury ions on aniline/sulfoanisidine copolymer nanosorbents.

The highest Hg-ion adsorbance so far, namely up to 2063 mg g(-1), has been achieved by poly(aniline-co-5-sulfo-2-anisidine) nanosorbents. Sorption of Hg ions occurs mainly by redox and chelation mechanisms (see scheme), but also by ion exchange and physisorption.Poly(aniline (AN)-co-5-sulfo-2-anisidine (SA)) nanoparticles were synthesized by chemical oxidative copolymerization of AN and SA monomers, and their extremely strong adsorption of mercury ions in aqueous solution was demonstrated. The reactivity ratios of AN and SA comonomers were found to be 2.05 and 0.02, respectively. While AN monomer tends to homopolymerize, SA monomer tends to copolymerize with AN monomer because of the great steric hindrance and electron-attracting effect of the sulfo groups, despite the effect of conjugation of the methoxyl group with the benzene ring. The effects of initial mercury(II) concentration, sorption time, sorption temperature, ultrasonic treatment, and sorbent dosage on mercury-ion sorption onto AN/SA (50/50) copolymer nanoparticles with a number-average diameter of around 120 nm were significantly optimized. The results show that the maximum Hg-ion sorption capacity on the particulate nanosorbents can even reach 2063 mg of Hg per gram of sorbent, which would be the highest Hg-ion adsorbance so far. The sorption data fit to the Langmuir isotherm, and the process obeys pseudo-second-order kinetics. The IR and UV/Vis spectral data of the Hg-loaded copolymer particles suggest that some mercury(II) was directly reduced by the copolymer to mercury(I) and even mercury(0). A mechanism of sorption between the particles and Hg ions in aqueous solution is proposed, and a physical/ion exchange/chelation/redox sorption ratio of around 2/3/45/50 was found. Copolymer nanoparticles may be one of the most powerful and cost-effective sorbents of mercury ions, with a wide range of potential applications for the efficient removal and even recovery of the mercury ions from aqueous solution.

Self‐Stabilized Nanoparticles of Intrinsically Conducting Copolymers from 5‐Sulfonic‐2‐Anisidine

Novel copolymer nanoparticles with inherent self-stability, narrow size distribution, and high electrical conductivity are facilely and productively synthesized by the oxidative precipitation polymerization of 5-sulfonic-2-anisidine and aniline in acidic medium without any external stabilizer. The structures of the copolymer particles are systematically characterized by IR and UV/Vis spectroscopy, X-ray diffraction, laser particle-size analysis, atomic force microscopy, field-emission scanning electron microscopy, and high-resolution transmission electron microscopy. The comonomer ratio, oxidant/monomer ratio, and polymerization temperature and medium can be used to optimize the size and conductivity of the nanoparticles. It is found that the nanoparticles exhibit a minimal size and polydispersity index of around 53 nm and 1.045, respectively. Nanocomposite films of the nanoparticles with diacetyl and ethyl celluloses show good thermostability and a low percolation threshold of 0.08 wt%, at which the films retain 89% of the transparency, 96-98% of the strength, and 10(8) times the conductivity of the matrix film. The synthesis of sulfoanisidine copolymer nanoparticles is thus achieved without the use of external stabilizer, which opens up a simple and general route to the fabrication of nanostructured polymer materials with controllable size, narrow size distribution, intrinsic self-stability, strong dispersibility, high purity, and optimizable electroconductivity.

Facile Optimal Synthesis of Inherently Electroconductive Polythiophene Nanoparticles

The straight dope: Polythiophene (PTh) nanoparticles with a narrow size distribution were successfully synthesized by a chemical oxidative polymerization (see image). The highest conductivity of virgin PTh is 3.1x10(-4) S cm(-1) and can be dramatically enhanced to 50 S cm(-1) by doping in iodine vapor.Polythiophene (PTh) nanoparticles were successfully synthesized by a simple chemical oxidative polymerization in the presence of a very small amount of cetyltrimethylammonium bromide (CTAB). The polymerization yield, particle size, bulk electrical conductivity, and solubility of the PTh nanoparticles have been optimized by adjusting the CTAB/FeCl(3) oxidant/thiophene monomer ratio, thiophene concentration, polymerization temperature, and reaction time. The structure of the PTh nanoparticles was systematically characterized by IR and UV/Vis spectroscopy, wide-angle X-ray diffraction, laser particle-size analysis, field-emission scanning electron microscopy (SEM), and transmission electron microscopy (TEM). It was found that the number-average diameter (D(n)) and size polydispersity index (PDI) of the particles decrease significantly from 4.19 microm and 1.21 to 203 nm and 1.056, respectively, with a slightly increasing CTAB concentration. SEM and TEM reveal that the PTh particle size is reduced to 67 and 36 nm, respectively. The conductivity increases on raising the FeCl(3)/thiophene ratio or on lowering the CTAB concentration and polymerization temperature. A moderate monomer concentration and polymerization time are very beneficial for achieving highly conducting PTh. The highest conductivity of virgin PTh is 3.1x10(-4) S cm(-1) and can be further elevated to 50 S cm(-1) by doping in iodine vapor. Under optimized polymerization conditions, the significant variation of the conductivity of the PTh particles in virgin and doped states was well confirmed by the intensity and wavelength of the UV/Vis spectral band owing to the large pi conjugation. The PTh particles demonstrate uncommon characteristics including easy synthesis, low cost of production, large pi-conjugated structure, high conductivity, solution processability, and extensive potential for further application.

Interfacial Synthesis and Widely Controllable Conductivity of Polythiophene Microparticles

Fine polythiophene (PTh) microparticles were successfully synthesized by a novel interfacial polymerization at a dynamic interface between two immiscible solvents, i.e., n-hexane and acetonitrile or nitromethane containing thiophene and oxidant, respectively. The polymerization yield, size, and electrical conductivity of the microparticles are optimized by facilely regulating the medium species, oxidant species, oxidant/monomer ratio, monomer concentration, and polymerization temperature. The microparticles were thoroughly characterized by IR, UV-vis spectroscopy, wide-angle X-ray diffractometry, laser particle-size analyzer, and simultaneous TG-DSC technique. The yield rises with increasing oxidant/monomer ratio, monomer concentration, and polymerization temperature. However, low monomer concentration, low polymerization temperature, and modest oxidant/monomer ratio are all favorable for the formation of the PTh with good, large pi-conjugation and high conductivity. With decreasing the thiophene concentration from 200 to 50 mM at a fixed FeCl3/thiophene molar ratio of 3 at 0 degrees C in hexane/nitromethane biphase system, the PTh obtained exhibits a steadily enhanced conductivity from 10(-12) to 0.01 S cm(-1) and gradually darkening color from crimson to black. Under the same conditions, the PTh obtained in hexane/acetonitrile usually possesses lower yield but higher conductivity than that in hexane/nitromethane. The conductivity will be further enhanced to 1.1 and 4.4 S cm(-1) if the PTh powders are doped in iodine vapor and simply carbonized at 25 through 999 degrees C in nitrogen, respectively. The PTh is fine particles with the number-average diameter of 2.67-3.95 microm and low size polydispersity index between 1.12 and 1.23. The black particles carbonized at 25 to 999 degrees C are much smaller than original PTh particles, with the number-average diameter of 279 nm and size polydispersity index of 1.09. This interfacial approach provides an optimal synthesis of unique PTh microparticles with large pi-conjugation, high conductivity, black color, uniform size, good insolubility, excellent infusibility, high thermostability, and high yield of electrically conducting char at 999 degrees C.

Facile High‐Yield Synthesis of Polyaniline Nanosticks with Intrinsic Stability and Electrical Conductivity

Chemical oxidative polymerization at 15 degrees C was used for the simple and productive synthesis of polyaniline (PAN) nanosticks. The effect of polymerization media on the yield, size, stability, and electrical conductivity of the PAN nanosticks was studied by changing the concentration and nature of the acid medium and oxidant and by introducing organic solvent. Molecular and supramolecular structure, size, and size distribution of the PAN nanosticks were characterized by UV/Vis and IR spectroscopy, X-ray diffraction, laser particle-size analysis, and transmission electron microscopy. Introduction of organic solvent is advantageous for enhancing the yield of PAN nanosticks but disadvantageous for formation of PAN nanosticks with small size and high conductivity. The concentration and nature of the acid medium have a major influence on the polymerization yield and conductivity of the nanosized PAN. The average diameter and length of PAN nanosticks produced with 2 M HNO(3) and 0.5 M H(2)SO(4) as acid media are about 40 and 300 nm, respectively. The PAN nanosticks obtained in an optimal medium (i.e., 2 M HNO(3)) exhibit the highest conductivity of 2.23 S cm(-1) and the highest yield of 80.7 %. A mechanism of formation of nanosticks instead of nanoparticles is proposed. Nanocomposite films of the PAN nanosticks with poly(vinyl alcohol) show a low percolation threshold of 0.2 wt %, at which the film retains almost the same transparency and strength as pure poly(vinyl alcohol) but 262 000 times the conductivity of pure poly(vinyl alcohol) film. The present synthesis of PAN nanosticks requires no external stabilizer and provides a facile and direct route for fabrication of PAN nanosticks with high yield, controllable size, intrinsic self-stability, strong redispersibility, high purity, and optimizable conductivity.

Redox sorption and recovery of silver ions as silver nanocrystals on poly(aniline-co-5-sulfo-2-anisidine) nanosorbents.

Poly[aniline(AN)-co-5-sulfo-2-anisidine(SA)] nanograins with rough and porous structure demonstrate ultrastrong adsorption and highly efficient recovery of silver ions. The effects of five key factors-AN/SA ratio, Ag(I) concentration, sorption time, ultrasonic treatment, and coexisting ions-on Ag(I) adsorbability were optimized, and AN/SA (50/50) copolymer nanograins were found to exhibit much stronger Ag(I) adsorption than polyaniline and all other reported sorbents. The maximal Ag(I) sorption capacity of up to 2034 mg g(-1) (18.86 mmol g(-1)) is the highest thus far and also much higher than the maximal Hg-ion sorption capacity (10.28 mmol g(-1)). Especially at <or=2 mM Ag(I), the nanosorbents exhibit >or=99.98 % adsorptivity, and thus achieve almost complete Ag(I) sorption. The sorption fits the Langmuir isotherm well and follows pseudo-second-order kinetics. Studies by IR, UV/Vis, X-ray diffraction, polarizing microscopy, centrifugation, thermogravimetry, and conductivity techniques showed that Ag(I) sorption occurs by a redox mechanism mainly involving reduction of Ag(I) to separable silver nanocrystals, chelation between Ag(I) and -NH-/-N=/-NH(2)/-SO(3)H/-OCH(3), and ion exchange between Ag(I) and H(+) on -SO(3) (-)H(+). Competitive sorption of Ag(I) with coexisting Hg, Pb, Cu, Fe, Al, K, and Na ions was systematically investigated. In particular, the copolymer nanoparticles bearing many functional groups on their rough and porous surface can be directly used to recover and separate precious silver nanocrystals from practical Ag(I) wastewaters containing Fe, Al, K, and Na ions from Kodak Studio. The nanograins have great application potential in the noble metals industry, resource reuse, wastewater treatment, and functional hybrid nanocomposites.

Synthesis, Properties and Application of Conducting PPY Nanoparticles

The successful fabrication, various structure, unique properties, and wide application potential of novel conducting polypyrrole (PPY) nanoparticles and nanocomposites with an intrinsically electrical conductivity have been systematically reviewed. Wholly new pyrrole (PY) copolymer nanoparticles were synthesized by a chemical oxidative precipitation polymerization from 20 mol% PY and 80 mol% 4-sulfonic diphenylamine (SD) in HCl aqueous solution without any external stabilizer. Their structure and morphology were characterized by laser particle-size analyzer and transmission electron microscopy. Unique effects of polymerization temperature on the polymerization yield, particle size, and bulk electrical conductivity were systematically studied. The number-average diameter of the particles in water depends on the polymerization temperature from 0 to 25°C, reaching a minimum of 78 nm with an extremely low polydispersity index of 1.033 by laser particle-size analyzer. Dry particles exhibit much smaller size of around 10 nm based on a high-resolution transmission electron microscopy observation. The PY/SD (20/80) copolymer has a gradually increased conductivity from 1 × 10−4 to 5 × 10−3 S/cm with lowering polymerization temperature from 25 °C to 0°C. The relatively low purity, poor self-stability, and high cost of the nanoscale PPYs with intrinsic electroconductivity could be overcome by effortlessly incorporating a certain amount of SD comonomer as internal emulsifier during PY polymerization in emulsifier-free HCl aqueous solution.