Self-assembled poly(N-methylaniline)-lignosulfonate spheres: from silver-ion adsorbent to antimicrobial material.

Self-assembled poly(N-methylaniline)-lignosulfonate (PNMA-LS) composite spheres with reactive silver-ion adsorbability were prepared from N-methylaniline by using lignosulfonate (LS) as a dispersant. The results show that the PNMA-LS composite consisted of spheres with good size distribution and an average diameter of 1.03-1.27 µm, and the spheres were assembled by their final nanofibers with an average diameter of 19-34 nm. The PNMA-LS composite spheres exhibit excellent silver-ion adsorption; the maximum adsorption capacity of silver ions is up to 2.16 g g(-1) at an adsorption temperature of 308 K. TEM and wide-angle X-ray results of the PNMA-LS composite spheres after absorption of silver ions show that silver ions are reduced to silver nanoparticles with a mean diameter of about 11.2 nm through a redox reaction between the PNMA-LS composite and the silver ions. The main adsorption mechanism between the PNMA-LS composite and the silver ions is chelation and redox adsorption. In particular, a ternary PNMA-LS-Ag composite achieved by using the reducing reaction between PNMA-LS composite spheres and silver ions can be used as an antibacterial material with high bactericidal rate of 99.95 and 99.99% for Escherichia coli and Staphylococcus aureus cells, respectively.

Controlled preparation and reactive silver-ion sorption of electrically conductive poly(N-butylaniline)-lignosulfonate composite nanospheres.

Electroconductive poly(N-butylaniline)-lignosulfonate (PBA-LS) composite nanospheres were prepared in a facile way by in situ, unstirred polymerization of N-butylaniline with lignosulfonate (LS) as a dispersant and dopant. The LS content was used to optimize the size, structure, electroconductivity, solubility, and silver ion adsorptive capacity of the PBA-LS nanospheres. Uniform PBA-LS10 nanospheres with a minimal mean diameter of 375 nm and high stability were obtained when the LS content was 10 wt %. The PBA-LS10 nanospheres possess an increased electroconductivity of 0.109 S cm(-1) compared with that of poly(N-butylaniline) (0.0751 S cm(-1)). Furthermore, the PBA-LS10 nanospheres have a maximal silver-ion sorption capacity of 815.0 mg g(-1) at an initial silver ion concentration of 50 mmol L(-1) (25 °C for 48 h), an enhancement of 70.4% compared with PBA. Moreover, a sorption mechanism of silver ions on the PBA-LS10 nanospheres is proposed. TEM and wide-angle X-ray diffraction results showed that silver nanoparticles with a diameter size range of 6.8-55 nm was achieved after sorption, indicating that the PBA-LS10 nanospheres had high reductibility for silver ions.

Enzymatic hydrolysis lignin functionalized Ti3C2Tx nanosheets for effective removal of MB and Cu2+ ions.

Functionalized two-dimensional Ti3C2Tx (TN-EHL) was prepared as an effective adsorbent for removal of methylene blue dye (MB) and copper ions (Cu2+). Enzymatic hydrolysis lignin (EHL), a reproducible natural resource, was used to functionalize the Ti3C2Tx nanosheets. EHL can not only introduce active functional groups into TN-EHL but also prevent the oxidation of Ti3C2Tx, thus promoting the adsorption performance of TN-EHL. The maximum adsorption capacities of TN-EHL50 (in which the EHL content is 50 wt%) for MB and Cu2+ were 293.7 mg g-1 and 49.96 mg g-1, respectively. The higher correlation coefficients (R2) of MB (0.9996) and Cu2+ (0.9995) indicating that their adsorption processes can be described by the pseudo-second-order kinetic model. The MB adsorption data fit the Freundlich isotherm with R2 of 0.9953, whereas the Cu2+ ions adsorption data fit the Langmuir isotherm with R2 of 0.9998. The thermodynamic analysis indicates that the adsorption process of MB and Cu2+ on TN-EHL50 is spontaneous and endothermic. Significantly, the Cu2+ ions were reduced to Cu2O and CuO particles during the adsorption process. Therefore, TN-EHL has a great potential as an environmentally friendly adsorbent for MB removal and recovery of Cu2+ ions from wastewater.

Efficient adsorption of methylene blue and lead ions in aqueous solutions by 5-sulfosalicylic acid modified lignin.

As a kind of biomass that exists widely in plants, lignin shows much diversity as a functional material. In order to improve the adsorption ability, lignin was chemically modified by 5-sulfosalicylic acid and then used to adsorb methylene blue (MB) and Pb2+ from aqueous solutions. The results showed that the 5-sulfosalicylic acid modified lignin exhibited a high adsorption ability for dyes or heavy metals. The maximum adsorption capacity of the adsorbent approached 83.2 mg/g for MB and 39.3 mg/g for Pb2+ with the adsorbent dosage of 5 g/L at pH 5.85 or 5.35 (corresponding to MB or Pb2+, respectively), initial adsorbate concentration of 200 mg/L, temperature of 318 K and contact time of 12 h. The adsorption kinetics and isotherm studies indicated that both the adsorption of MB and Pb2+ onto SSAL followed the pseudo-second-order model and Langmuir isotherm model. It means that the adsorption process fits the model of mono-layer adsorption and it was mainly chemical process and accompanied with surface adsorption. The proposed SSAL is low-cost, eco-friendly and highly efficient therefore a promising material for adsorptive removal of MB and Pb2+ from wastewater.

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.

Preparation and application of porous nitrogen-doped graphene obtained by co-pyrolysis of lignosulfonate and graphene oxide.

Nitrogen-doped graphene with in-plane porous structure was fabricated by simple co-pyrolysis of lignosulfonate and graphene oxide in the presence of urea. Lignosulfonate first performs as a dispersant adsorbed on the surface of graphene oxide to prevent the aggregation of graphene oxide sheets for preparing homogeneous nitrogen-containing precursor, and then acts as a porogen to render graphene sheets with nanopores in the pyrolysis process of the nitrogen-containing precursor. Urea was used as a nitrogen source to incorporate nitrogen atoms into graphene basal plane. The special nanoporous structure combined with nitrogen content of 7.41at.% endows the nitrogen-doped graphene electrode material with super capacitance up to 170Fg(-1), high rate performance, and excellent cycling stability.

Fabrication, characterization and application of nitrogen-containing carbon nanospheres obtained by pyrolysis of lignosulfonate/poly(2-ethylaniline).

Lignosulfonate/poly(2-ethylaniline) (LS-PEA) composite nanospheres were prepared via in situ polymerization of 2-ethylaniline (EA) with lignosulfonate (LS) as a dispersant. LS-PEA nanospheres with an average diameter of 155 nm were obtained at an optimal LS concentration of 20 wt.%. Subsequently, nitrogen-containing carbon nanospheres were fabricated via direct pyrolysis of the LS-PEA composite nanospheres at 600-800 °C. The carbon nanospheres prepared by pyrolysis were used as anodes of lithium-ion batteries. The first charge and discharge capacity of carbon nanospheres prepared at 700 °C at current densities of 60 and 100 mA g(-1) were 980 and 432 mAh g(-1), and 764 and 342 mAh g(-1), respectively. The batteries still owned a high capacity of 353 and 296 mAh g(-1) after 20 cycles. The results indicated that these nitrogen-containing carbon nanospheres could be used as a promising candidate for electrode materials of lithium-ion batteries.

Preparation and heavy metal ions biosorption of graft copolymers from enzymatic hydrolysis lignin and amino acids.

Novel biosorbents, graft copolymers, were prepared via Mannich reaction from enzymatic hydrolysis lignin with glycine and cystine, respectively. The element content, FT-IR and fluorescence spectra, relative viscosity, and particle size of the copolymers were systematically investigated. Furthermore, effects of initial pH, ionic strength, temperature, contact time and initial metal ion concentration on the biosorption capacities of Cu(II) and Co(II) ions onto the copolymers were studied using batch sorption technique. It was found that the copolymers exhibited excellent biosorption characteristics for Cu(II) and Co(II) ions. The sorption kinetic data can be described well with a pseudo-second-order model, and the equilibrium data can be fitted well to the Langmuir and Freundlich isotherm for Cu(II) and Co(II) biosorption process, respectively. Surface complexation and ion-exchange modeling were performed to elucidate the biosorption mechanism involved because surfaces of the copolymers contained three main types of acid/base sites from the amino acid grafted copolymer units.

Facile preparation of hierarchical polyaniline-lignin composite with a reactive silver-ion adsorbability.

A hierarchical polyaniline-lignin (PANI-EHL) composite was facilely prepared from aniline and enzymatic hydrolysis lignin in an aqueous solution of ammonia. The morphology, FTIR, UV-vis spectra, thermogravimetric analysis, and wide-angle X-ray diffraction analyses of the composite were systematically investigated. Furthermore, the sorption property of the PANI-EHL composite for silver ions in aqueous solution was studied via a static sorption technique. The result demonstrated that the PANI-EHL composite possessed a strongly reactive sorption characteristic for silver ions. Serrated silver threads with length up to 10 mm were obtained by using the PANI-EHL composite as a low-cost adsorbent. Moreover, the role of EHL and polyaniline in the PANI-EHL composite for silver ions sorption was investigated. The investigation indicated that the EHL unit could play a vital role in the chelation of silver ions, whereas the polyaniline unit played a leading role in redox sorption.

Fabrication of poly(N-ethylaniline)/lignosulfonate composites and their carbon microspheres.

Novel poly(N-ethylaniline)/lignosulfonate (PNA-LS) composites were prepared via an in situ polymerization of N-ethylaniline (NA) with lignosulfonate (LS) as a dispersant. Nitrogen-containing carbon materials were obtained by direct pyrolysis of the PNA-LS composites at the pyrolytic temperatures ranging from 300°C to 1200°C. The as-prepared PNA-LS composites and their carbon materials were investigated by TGA, SEM, TEM, FTIR and UV-vis spectra, XRD and elemental analysis. The results showed that the morphology, structure and properties of the PNA-LS composites were depended on the LS:NA mass ratio. PNA-LS microspheres with an average diameter of 1300 nm could be fabricated when the LS:NA mass ratio was 2.5:97.5, while regular hexagon sheets of PNA-LS composite were obtained with the LS:NA mass ratio above 5:95. Furthermore, nitrogen-containing carbon nanospheres with an average diameter of 820 nm were achieved at the carbonization temperature of 800°C.