Facile and Sustainable Synthesis of ZnO Nanoparticles: Effect of Gelling Agents on ZnO Shapes and Their Photocatalytic Performance.

The present work involves investigating an unexplored soft-chemical method for synthesizing nanostructured ZnO through biopolymer gelation. Our objective was to exploit (i) the difference in the gelation mechanism of four tested biopolymers, namely, alginate, chitosan, carboxymethylcellulose (CMC), and pectin and (ii) numerous experimental parameters that govern this process in order to allow the control of the growth of nanostructured ZnO, with a view to using the prepared oxides as photocatalysts for the oxidation of the Orange G dye. So, the effect of biopolymer's nature on the microstructural, morphological, and textural properties was examined by thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field-emission gun-scanning electron microscopy-high resolution (FEG-SEM) with energy-dispersive spectrometry (SEM-EDS), ultraviolet-visible (UV-vis) spectroscopy, and N2 adsorption/desorption. As-prepared oxides were crystallized in a hexagonal wurtzite structure, with a clear difference in their morphologies. The sample prepared by using chitosan has a specific surface area of around 36.8 m2/g in the form of aggregated and agglomerated nanostructured minirods and thus shows the best photocatalytic performance with 99.3% degradation of the Orange G dye in 180 min.

Sulfated Well-Defined Mesoporous Nanostructured Zirconia for Levulinic Acid Esterification.

Well-organized zirconia (ZrO2) nanoparticles forming mesoporous materials have been successfully synthesized via a facile micelle-templating method using cetyltrimethylammonium bromide as a structure-directing template to control the nucleation/growth process and porosity. The systematic use of such a surfactant in combination with a microwave-assisted solvothermal (cyclohexane/water) reaction enabled the control of pore size in a narrow-size distribution range (3-17 nm). The effect of solvent mixture ratio on the porosity of the synthesized oxide was determined, and the controlled growth of zirconia nanoparticles was confirmed by means of powder X-ray diffraction, small-angle X-ray scattering, transmission electron microscopy, selected area electron diffraction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy as well as N2 physisorption isotherm analysis. Then, the as-prepared nanostructured zirconia oxides were treated with sulfuric acid to have sulfated samples. The catalytic performances of these mesoporous zirconia nanoparticles and their sulfated samples were tested for levulinic acid (LA) esterification by ethanol, with quantitative conversions of LA to ethyl levulinate after 8 h of reaction.

Hybrid Alginate-Brushite Beads Easily Catalyze the Knoevenagel Condensation On-Water.

An innovative hybrid organic-inorganic material composed of alginate-brushite xerogel beads was successfully applied for the catalysis of the Knoevenagel condensation. The catalyst was derived from phosphated alginate xerogel microspheres formed from the ionotropic gelling effect of phosphated alginate. To this end, alginate was phosphated by the addition of diammonium hydrogen phosphate in a 1% w/w alginate gel. The phosphated alginate was subsequently precipitated by chelation of Ca2+ cations, generating a phosphated alginate hydrogel microsphere, which was washed and dried, forming hybrid organic-inorganic xerogel beads as a crystalline phosphate-rich mineral fraction covered by alginate. X-ray diffraction analysis revealed that the crystalline inorganic matrix of the material was composed predominantly of brushite. SEM analysis revealed plate-like, ribbon-like, or needle-like morphologies in the hybrid alginate-brushite beads. The hybrid material was tested as a catalyst for Knoevenagel condensation, which was performed ″on-water″ under mild conditions with aromatic aldehydes and activated methylene compounds, giving high yields (up to 97%). The reaction rate and product yield increased together with the reaction temperature for all reagents. The recyclable solid catalyst was effective for three runs, revealing the potential of the innovative hybrid catalyst as an eco-friendly heterogeneous catalyst.

Effect of coupling alkaline pretreatment and sewage sludge co-digestion on methane production and fertilizer potential of digestate.

This study aims at investigating how organic waste co-digestion coupled with alkaline pretreatment can impact the methane production and agronomic value of produced digestates. For this purpose, sludge alone and mixed with olive pomace or macroalgal residues were subjected to anaerobic digestion with and without alkaline pretreatment. In addition, co-digestion of pretreated sludge with raw substrates was also carried out and compared to the whole mixture pretreatment. KOH pretreatment enhanced methane production by 39%, 15% and 49% from sludge, sludge mixed with olive pomace and sludge mixed with macroalgal residues, respectively. The digestates were characterised according to their physico-chemical and agronomic properties. They were then applied as biofertilizers for tomato growth during the first vegetative stage (28 days of culture). Concentrations in chlorophyll a and carotenoids in tomato plants, following sludge digestate addition, rose by 46% and 41% respectively. Sludge digestate enhanced tomato plant dry weight by 87%, while its nitrogen content increased by 90%. The impact of nitrogen and phosphorus contents in the digestate was strongest on tomato plant dry weight, thus explaining the efficiency of sludge digestate relative to other types of digestate. However, when methane production is considered, the combination of pre-treatment with co-digestion of macroalgal residues and sludge appears most beneficial for maximizing energy recovery and for biofertilizer generation.

Evaluation of agronomic properties of digestate from macroalgal residues anaerobic digestion: Impact of pretreatment and co-digestion with waste activated sludge.

The aim of this paper is to investigate the impact of pretreating macroalgal residue (MAR) from agar-agar extraction and its co-digestion with sewage sludge on methane production and the agronomic quality of the digestates produced. First, different pretreatments were assessed on BMP tests. Among milling technologies used, knife milling with a 4 mm-screen improved methane production by 25%. The MAR was then knife milled before alkaline, acid and thermal pretreatment. KOH pretreatment (5% TS basis, 25 °C for 2 days) led to the highest methane improvement. It was applied to semi-continuous anaerobic digestion and methane production achieved 237 Nml/gVS which was 20% higher than the control (198 Nml/gVS). In comparison to MAR mono-digestion, co-digestion with thickened activated sludge produced less methane (184 Nml/gVS) but reduced H2S emission by 91%. None of the digestates was toxic for the germination or growth of wheat and tomato plants. Particularly, co-digestion had the highest impact on tomato plant dry weight (+94% compared to soil alone) mainly due to the phosphorous brought by sludge. However, the impact of alkaline pretreatment on plant growth was not significant.

Mild microwaves, ultrasonic and alkaline pretreatments for improving methane production: Impact on biochemical and structural properties of olive pomace.

This study aims to investigate the effects of microwaves, ultrasonic and alkaline pretreatments on olive pomace properties and its biomethane potential. Alkaline pretreatment was found to reduce lipid and fiber contents (especially lignin) and to increase soluble matter. The alkali pretreatment at a dose of 8% (w/w TS) under 25 °C and for 1 day removed 96% of initial lipids from the solid olive pomace. Unlike NaOH addition, mild microwaves and ultrasonic pretreatments had no impact on lignin. However, in the case of long microwaves pretreatment (450 W-10 min), cellulose and lignin contents were reduced by 50% and 26% respectively. Similarly, the combination of ultrasonic and alkali reagent showed a positive effect on fiber degradation and lipid solubilization as well as a positive impact on methane production. Statistical analysis highlighted the correlation between NaOH dose, solubilization and methane production. The alkaline pretreatment at ambient temperature appeared the most energetically efficient.

Controlling the growth of nanosized titania via polymer gelation for photocatalytic applications.

Nanocrystalline titania was synthesized by a simple, innovative and eco-friendly gelation method by using biopolymers (polysaccharides). The effect of the gelling agent, such as carboxymethylcellulose (CMC) or alginate (Alg), and the drying routes (conventional drying at room temperature, or freeze-drying) on the properties and photocatalytic performances of nanostructured TiO2 was examined. The crystallographic structures, and textural and morphological characteristics were investigated by thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy with energy dispersive spectrometry (ESEM-FEG-EDS), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (DRS) and N2 adsorption/desorption isotherms. The as-synthesized samples were fully crystallized and appeared to be highly phase-pure anatase or mixed titania polymorphs, and have a quasi-spherical shape with a particle size ranging from 10.34 to 18.07 nm. Phase-pure anatase was obtained by using alginate as the gelling agent, whereas CMC's gelation promotes mixed structures. The presence of rutile phase results in a lower bandgap value of 3.04 eV corresponding to 408 nm. Thus, the material absorption wavelength shifts slightly from the UV (190-380 nm) to visible region (380-750 nm). The drying process also affects TiO2 properties. The lyophilization route improves the oxide's specific surface area, and also its photocatalytic properties verified during Orange G dye photodegradation study.

Combination of Dry Milling and Separation Processes with Anaerobic Digestion of Olive Mill Solid Waste: Methane Production and Energy Efficiency.

This experimental work aims at investigating the effects of milling; sieving; and electrostatic separation on the biochemical methane potential of two olive pomaces from traditional olive oil extraction (M) and from a three-phase system (T). Sieving proved to be efficient for increasing the soluble chemical oxygen demand in the smallest fractions of the sieve of both M (62%) and T (78%) samples. The positive fraction following electrostatic separation also enhanced chemical oxygen demand (COD) solubilisation by 94%, in comparison to sample T milled at 4 mm. Sieve fractions with a size greater than 0.9 mm contained 33% and 47% less lipids for the M and T biomasses; respectively. Dry fractionation modified sample properties as well as lipid and fiber distribution. Concomitantly; milling increased the accessibility and facilitated the release of organic matter. The energy balance was positive after knife milling and sieving; while ball milling and ultrafine milling proved to be inefficient.

Synergistic effect of cellulose nanocrystals/graphene oxide nanosheets as functional hybrid nanofiller for enhancing properties of PVA nanocomposites.

Novel functional hybrid nanofillers composed of cellulose nanocrystals (CNC) and graphene oxide nanosheets (GON), at different weight ratios (2:1, 1:1 and 1:2), were successfully prepared and characterized, and their synergistic effect in enhancing the properties of poly(vinyl alcohol) (PVA) nanocomposites was investigated. Due to the synergistic reinforcement, it was found that the Young's modulus, tensile strength and toughness of the PVA nanocomposite containing 5 wt% hybrid nanofiller (1:2) were significantly improved by 320%, 124% and 159%, respectively; and the elongation at break basically remained compared to the neat PVA matrix. In addition, the glass and melting temperatures as well as the moisture sorption of nanocomposites were also enhanced. This synergistic effect improved the dispersion homogeneity by avoiding the agglomeration phenomenon of nanofillers within the polymer matrix, resulting in nanocomposites with largely enhanced properties compared to those prepared from single nanofiller (CNC or GON). The preparation of these hybrid nanofillers and their incorporation into a polymer provided a novel method for the development of novel multifunctional nanocomposites based on the combination of existing nanomaterials.

Bio-nanocomposite films reinforced with cellulose nanocrystals: Rheology of film-forming solutions, transparency, water vapor barrier and tensile properties of films.

This study was aimed to develop bio-nanocomposite films of carboxymethyl cellulose (CMC)/starch (ST) polysaccharide matrix reinforced with cellulose nanocrystals (CNC) using the solution casting method. The CNC were extracted at the nanometric scale from sugarcane bagasse via sulfuric acid hydrolysis and used as reinforcing phase to produce CMC/ST-CNC bio-nanocomposite films at different CNC loading levels (0.5-5.0 wt%). Steady shear viscosity and dynamic viscoelastic measurements of film-forming solution (FFS) of neat CMC, CMC/ST blend and CMC/ST-CNC bio-nanocomposites were evaluated. Viscosity measurements revealed that a transition from Newtonian behavior to shear thinning occurred when CNC were added. The dynamic tests confirmed that all FFS have a viscoelastic behavior with an entanglement network structure, induced by the hydrogen bonding. In regard to the cast film quality, the rheological data showed that all FFS were suitable for casting of films at ambient temperature. The effect of CNC addition on the optical transparency, water vapor permeability (WVP) and tensile properties of bio-nanocomposite films was studied. It was found that bio-nanocomposite films remain transparent due to CNC dispersion at the nanoscale. The WVP was significantly reduced and the elastic modulus and tensile strength were increased gradually with the addition of CNC. Herein, the steps to form new eco-friendly bio-nanocomposite films were described by taking advantage of the combination of CMC, ST and CNC. The as-produced films exhibited good optical transparency, reduced WVP and enhanced tensile properties, which are the main properties required for packaging applications.

Smart designing of new hybrid materials based on brushite-alginate and monetite-alginate microspheres: bio-inspired for sequential nucleation and growth.

In this report new hybrid materials based on brushite-alginate and monetite-alginate were prepared by self-assembling alginate chains and phosphate source ions via a gelation process with calcium ions. The alginate served as nanoreactor for nucleation and growth of brushite or/and monetite due to its gelling and swelling properties. The alginate gel framework, the crystalline phase and morphology of formed hybrid biomaterials were shown to be strongly dependent upon the concentration of the phosphate precursors. These materials were characterized by thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive x-ray analysis (EDX).