Dariusz Moszyński

Modification of Chitin with Kraft Lignin and Development of New Biosorbents for Removal of Cadmium(II) and Nickel(II) Ions

Novel, functional materials based on chitin of marine origin and lignin were prepared. The synthesized materials were subjected to physicochemical, dispersive-morphological and electrokinetic analysis. The results confirm the effectiveness of the proposed method of synthesis of functional chitin/lignin materials. Mechanism of chitin modification by lignin is based on formation of hydrogen bonds between chitin and lignin. Additionally, the chitin/lignin materials were studied from the perspective of waste water treatment. The synthetic method presented in this work shows an attractive and facile route for producing low-cost chitin/lignin biosorbents with high efficiency of nickel and cadmium adsorption (88.0% and 98.4%, respectively). The discovery of this facile method of synthesis of functional chitin/lignin materials will also have a significant impact on the problematic issue of the utilization of chitinous waste from the seafood industry, as well as lignin by-products from the pulp and paper industry.

Adsorption of anionic azo-dyes from aqueous solutions onto graphene oxide: Equilibrium, kinetic and thermodynamic studies

In the present study, graphene oxide (GO) was used for the adsorption of anionic azo-dyes such as Acid Orange 8 (AO8) and Direct Red 23 (DR23) from aqueous solutions. GO was characterized by Fourier Transform-Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS), Thermogravimetric Analysis (TGA), Atomic Force Microscopy (AFM), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), High-Resolution Transmission Electron Microscopy (HRTEM) and zeta potential measurements. The influence of dye initial concentration, temperature and pH on AO8 and DR23 adsorption onto GO was investigated. Equilibrium data were analyzed by model equations such as Langmuir Freundlich, Temkin, Dubinin-Radushkevich and Redlich-Peterson isotherms and were best represented by Langmuir and Redlich-Peterson isotherm model. Kinetic adsorption data were analyzed using the pseudo-first-order kinetic model, the pseudo-second-order kinetic model and the intraparticle diffusion model. The adsorption kinetics well fitted using a pseudo-second-order kinetic model. Thermodynamics parameters, ΔG°, ΔH° and ΔS°, were calculated, indicating that the adsorption of AO8 and DR23 onto GO was spontaneous process. The adsorption process of AO8 onto GO was exothermic, while the adsorption of DR23 onto GO was endothermic in nature.

Chitin-Lignin Material as a Novel Matrix for Enzyme Immobilization

Innovative materials were made via the combination of chitin and lignin, and the immobilization of lipase from Aspergillus niger. Analysis by techniques including FTIR, XPS and 13C CP MAS NMR confirmed the effective immobilization of the enzyme on the surface of the composite support. The electrokinetic properties of the resulting systems were also determined. Results obtained from elemental analysis and by the Bradford method enabled the determination of optimum parameters for the immobilization process. Based on the hydrolysis reaction of para-nitrophenyl palmitate, a determination was made of the catalytic activity, thermal and pH stability, and reusability. The systems with immobilized enzymes were found to have a hydrolytic activity of 5.72 mU, and increased thermal and pH stability compared with the native lipase. The products were also shown to retain approximately 80% of their initial catalytic activity, even after 20 reaction cycles. The immobilization process, using a cheap, non-toxic matrix of natural origin, leads to systems with potential applications in wastewater remediation processes and in biosensors.

Chlorination of carbon nanotubes obtained on the different metal catalysts

In this paper, a chlorination method is proposed for simultaneous purification and functionalization of carbon nanotubes, thus increasing their ability to use. Carbon nanotubes were obtained by CVD method through ethylene decomposition on the nanocrystalline iron or cobalt or bimetallic iron-cobalt catalysts. The effects of temperature (50, 250, and 450°C) in the case of carbon nanotubes obtained on the Fe-Co catalyst and type of catalyst (Fe, Co, Fe/Co) on the effectiveness of the treatment and functionalization were tested. The phase composition of the samples was determined using the X-ray diffraction method. The quantitative analysis of metal impurity content was validated by means of the thermo gravimetric analysis. Using X-ray Photoelectron Spectroscopy (XPS), Energy Dispersive Spectroscopy (EDS) analysis, and also Mohr titration method, the presence of chlorine species on the surface of chlorinated samples was confirmed.

The transformation of α–Fe into γ′–Fe4N in nanocrystalline Fe–N system: Influence of Gibbs–Thomson effect

A nanocrystalline iron sample of non-uniform grain size distribution was nitrided at 500 °C under gas atmosphere with gradually increased nitriding potential. Mixtures of α–Fe and γ′–Fe4N phases were observed at a broad range of the nitriding potential. Unexpectedly, the mean size of the products crystallites at small conversion degrees was much higher than the one observed initially for the substrate and gradually decreased with the advancement of the reaction. The observed behavior was explained by the reaction mechanism regarding the influence of the Gibbs–Thomson effect.

Magnetic properties of ZnFe2O4 nanoparticles

Fine particles of ZnFe2O4 were synthesized by a wet chemical method in the (80 wt.% Fe2O3 + 20 wt.% ZnO) system. The morphological and structural properties of the mixed system were investigated by scanning electron microscopy, X-ray diffraction, inductively coupled plasma atomic emission, and X-ray photoelectron spectroscopy. The major phase was determined to be the ZnFe2O4 spinel with particle size of 11 nm. The magnetic properties of the material were investigated by ferromagnetic resonance (FMR) in the temperature range from liquid helium to room temperature. A very intense, asymmetric FMR signal from ZnFe2O4 nanoparticles was recorded, which has been analyzed in terms of two Callen-lineshape lines. Temperature dependence of the FMR parameters was obtained from fitting the experimental lines with two component lines. Analysis of the FMR spectra in terms of two separate components indicates the presence of strongly anisotropic magnetic interactions.

Aqueous processable WO3−x nanocrystals with solution tunable localized surface plasmon resonance

Heavily doped tungsten oxide nanoparticles with localized surface plasmon resonances (LSPRs) were recently highlighted as potential substitutes for noble metals in the field of plasmonic applications. Herein, oxygen deficient, spherically shaped WO3−x nanocrystals (NCs) were synthesized with a pronounced visible LSPR absorbance peak instead of a broadband tail usually observed for WO3−x nanowires. Although the tuning of the plasmon resonances was achieved mainly by changing the nanocrystals composition or solvent refraction index, we demonstrate this via the interfacial charge donation/extraction. In an aqueous NCs dispersion, the LSPR peak was either blue shifted in an acidic solution up to 80 nm or bleached by a basic solution making the NCs appropriate for sensing applications.

Candida antarctica Lipase B Immobilized onto Chitin Conjugated with POSS® Compounds: Useful Tool for Rapeseed Oil Conversion

A new method is proposed for the production of a novel chitin-polyhedral oligomeric silsesquioxanes (POSS) enzyme support. Analysis by such techniques as X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed the effective functionalization of the chitin surface. The resulting hybrid carriers were used in the process of immobilization of the lipase type b from Candida antarctica (CALB). Fourier transform infrared spectroscopy (FTIR) confirmed the effective immobilization of the enzyme. The tests of the catalytic activity showed that the resulting support-biocatalyst systems remain hydrolytically active (retention of the hydrolytic activity up to 87% for the chitin + Methacryl POSS® cage mixture (MPOSS) + CALB after 24 h of the immobilization), as well as represents good thermal and operational stability, and retain over 80% of its activity in a wide range of temperatures (30–60 °C) and pH (6–9). Chitin-POSS-lipase systems were used in the transesterification processes of rapeseed oil at various reaction conditions. Produced systems allowed the total conversion of the oil to fatty acid methyl esters (FAME) and glycerol after 24 h of the process at pH 10 and a temperature 40 °C, while the Methacryl POSS® cage mixture (MPOSS) was used as a chitin-modifying agent.

Synthesis and antibacterial properties of Fe3O4-Ag nanostructures

Abstract Superparamagnetic iron oxide nanoparticles were obtained in the polyethylene glycol environment. An effect of precipitation and drying temperatures on the size of the prepared nanoparticles was observed. Superparamagnetic iron oxide Fe3O4, around of 15 nm, was obtained at a precipitation temperature of 80°C and a drying temperature of 60°C. The presence of functional groups characteristic for a polyethylene glycol surfactant on the surface of nanoparticles was confirmed by FTIR and XPS measurements. Silver nanoparticles were introduced by the impregnation. Fe3O4-Ag nanostructure with bactericidal properties against Escherichia coli species was produced. Interesting magnetic properties of these materials may be helpful to separate the bactericidal agent from the solution.

Effect of a Barium Promoter on the Stability and Activity of Carbon‐Supported Cobalt Catalysts for Ammonia Synthesis

Samples of barium‐promoted carbon‐supported cobalt catalysts for ammonia synthesis were prepared; the cobalt content was constant (27.4 wt %) and the amount of barium introduced differed within the range of 0–0.88 mmol gC+Co−1. Turbostratic carbon was used as the support. Several techniques, including X‐ray powder diffraction, TEM, Thermogravimetric analysis–mass spectrometry (methanation studies) and H2 temperature‐programmed desorption were used to examine the properties of the carbon support or catalytic materials. The reaction rate measurements were performed under the following conditions: T=400 °C, p=9.0 MPa, x  NH 3 =8.5 mol %, H2/N2=3:1. It was found that barium is an important component of the cobalt catalysts supported on activated carbon for ammonia synthesis. Barium inhibits the process of carbon support methanation, which also results in a decrease in the sintering of the active phase (cobalt). Moreover, even a small amount of barium significantly activates the cobalt surface in ammonia synthesis, suggesting that barium locates primarily on the surface of cobalt.