Novel amino-functionalized lignin microspheres: High performance biosorbent with enhanced capacity for heavy metal ion removal.

Novel highly effective amino-functionalized lignin-based biosorbent in the microsphere geometry (A-LMS) for removal of heavy metal ions, was synthesized via inverse suspension copolymerization of kraft lignin with poly(ethylene imine) grafting-agent and epoxy chloropropane cross-linker. Optimization of A-LMS synthesis, performed with respect to the quantity of sodium alginate emulsifier (1, 5 and 10 wt%), provides highly porous microspheres A-LMS_5, using 5 wt% emulsifier, with 800 ± 80 µm diameter, 7.68 m2 g-1 surface area and 7.7 mmol g-1 of terminal amino groups. Structural and surface characteristics were obtained from Brunauer-Emmett-Teller method, Fourier Transform-Infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and porosity determination. In a batch test, the influence of pH, A-LMS_5 dose, temperature, contact time on adsorption efficiency of Ni2+, Cd2+, As(V) and Cr(VI) ions were studied. The adsorption is spontaneous and feasible with maximum adsorption capacity of 74.84, 54.20, 53.12 and 49.42 mg g-1 for Cd2+, Cr(VI), As(V) and Ni2+ ions, respectively, obtained by using Langmuir model. Modeling of kinetic data indicated fast adsorbate removal rate with pore diffusional transport as rate limiting step (pseudo-second order model and Weber-Morris equations), thus further confirming high performances of produced bio-adsorbent for heavy metal ions removal.

Controllable synthesis of Fe3O4-wollastonite adsorbents for efficient heavy metal ions/oxyanions removal.

Iron oxide, in the form of magnetite (MG)-functionalized porous wollastonite (WL), was used as an adsorbent for heavy metal ions (cadmium and nickel) and oxyanions (chromate and phosphate) removal from water. The porous WL was synthesized from calcium carbonate and siloxane by controlled sintering process using low molecular weight submicrosized poly(methyl methacrylate) as a pore-forming agent. The precipitation of MG nanoparticles was carried out directly by a polyol-medium solvothermal method or via branched amino/carboxylic acid cross-linker by solvent/nonsolvent method producing WL/MG and WL-γ-APS/MG adsorbents, respectively. The structure/properties of MG functionalized WL was confirmed by applying FTIR, Raman, XRD, Mössbauer, and SEM analysis. Higher adsorption capacities of 73.126, 66.144, 64.168, and 63.456 mg g-1 for WL-γ-APS/MG in relation to WL/MG of 55.450, 52.019, 48.132, and 47.382 mg g-1 for Cd2+, Ni2+, phosphate, and chromate, respectively, were obtained using nonlinear Langmuir model fitting. Adsorption phenomena were analyzed using monolayer statistical physics model for single adsorption with one energy. Kinetic study showed exceptionally higher pseudo-second-order rate constants for WL-γ-APS/MG, e.g., 1.17-13.4 times, with respect to WL/MG indicating importance of both WL surface modification and controllable precipitation of MG on WL-γ-APS.

Novel modified nanocellulose applicable as reinforcement in high-performance nanocomposites.

The influence of modification and vacuum/supercritical CO2 (scCO2) drying methods on the surface properties, morphology and thermal stability of cellulose nanocrystals (NC) was presented in this study. Introduction of reactive vinyl groups on NC surface was performed by either direct esterification with oleic acid, linseed or sunflower oil fatty acids; or by amidation of maleic acid/ethylene diamine with methyl ester of fatty acid. Obtained modified NC (m-NC) were characterized using FTIR and Raman spectroscopy; and by determination of acid, iodine and ester values. Structural analysis of m-NC showed varieties of forms, from spongy to nanostructural non-uniform layered morphology with observable agglomeration, which confirmed morphology dependence on modification/processing methods Thermogravimetry-MS spectrometry showed different thermal stability and degradation pathways of NC/m-NC. Incorporation of 1 wt% of reactive m-NC in unsaturated polyester lead to high performance nanocomposites and contributed to increase of stress at break in the range from 76 to 93%.