The influence of sodium alginate on the structural and adsorption properties of resorcinol-formaldehyde resins and their porous carbon derivatives.

A series of carbon composites were synthesised by carbonisation of resorcinol-formaldehyde resin mixtures with the addition of different amounts of sodium alginate (SA) and compared with a composite prepared using Na2 CO3 as a catalyst for the polymerisation reaction. The effect of operating parameters such as SA concentration and polycondensation time on the structural and morphological properties of resorcinol-formaldehyde resins (RFR) and carbon-derived composites was investigated for further use as adsorbents. The synthesised composites were characterised by FTIR, SEM, Raman spectroscopy and N2 adsorption/desorption techniques. It was found that the morphology, specific surface area (SBET ~347-559 m2 /g), volume and particle size distribution (~0.5-4 µm) and porosity (Vpor =0.178-0.348 cm3 /g) of the composites were influenced by the concentration of SA and the synthesis technique and determined the adsorption properties of the materials. It was found that the surface of the filled chars was found to have an affinity for heavy metals and has the ability to form chemical bonds with cadmium ions. The maximum sorption capacities for Cd(II), i. e. 13.28 mg/g, were observed for the sample synthesised with the highest SA content. This confirms the statement that as-synthesised materials are promising adsorbents for environmental applications.

Comparison of Structural, Water-Retaining and Sorption Properties of Acrylamide-Based Hydrogels Cross-Linked by Physical and Chemical Methods.

Two series of hydrogels based on acrylamide and its copolymers with acrylonitrile and acrylic acid were synthesized by two cross-linking methods - chemical (using N,N'-methylene bis-acrylamide) and physical (using montmorillonite (MMT)) ones. The structure of the gels was characterized by Fourier Transform Infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The swelling and sorption properties were analyzed as a function of both the monomer composition and the cross-linking method. The shift of the band corresponding to Si-O (995-1030 cm-1 ) confirmed the formation of intercalation structures for MMT-cross-linked gels. Moreover, physically cross-linked gels demonstrated a non-monotonic dependence of the swelling degree on the MMT concentration, and acrylamide-acrylic acid copolymer MMT-cross-linked gels showed pH sensitivity and the highest swelling degree of 150 g/g. The highest sorption capacity towards cadmium(II) ions was demonstrated by acrylamide-acrylic acid copolymer gels, both covalently cross-linked (30 mg/g) and MMT-cross-linked (8.9 mg/g).

NiFe and CoFe nanocatalysts supported on highly dispersed alumina-silica: Structure, surface properties, and performance in CO2 methanation.

The hydrogenation of CO2 to CH4 has gained considerable interest in terms of sustainable energy and environmental mitigation. In this regard, the present work aims to investigate the adsorptive concentration and CO2 methanation performance over CoFe and NiFe bimetallic catalysts supported on fumed alumina-silica SA96 support at 170-450 °C and under atmospheric pressure. The catalysts were prepared by wet impregnation method, subjected to calcination and further reduced with hydrogen, and their performance in CO2 methanation was investigated in a hydrogen-rich 2%CO2-55%H2-43%He gas mixture. In this study, we describe the crystal and mesoporous structures of the prepared catalysts by in-situ XRD and ex-situ nitrogen adsorption, evaluate the NiFe and CoFe metal surface states before and after catalysis by XPS, visualize the surface morphology by SEM, estimate the catalytic activity by gas chromatography, and investigate the adsorbed surface species, showing the presence of *HCOO/*HCO and *CO intermediates, determine two possible pathways of CH4 formation on the studied catalysts by temperature-programmed desorption mass spectrometry, and correlate the structural and surface properties with high CO2 conversions up to 100% and methanation selectivities up to 72%. The latter is related to changes in the elemental chemical states and surface composition of CoFe and NiFe nanocatalysts induced by treatment under reaction conditions, and the surface reconstruction during catalysis transfers the part of active 3d transition metals into the pores of the SA96 support. Our thorough characterization study with complementary techniques allowed us to conclude that this high activity is related to the formation of catalytically active Ni/Ni3Fe and Co/CoFeOx nanoscale crystallites under H2 reduction and their maintenance under CO2 methanation conditions. The successfully applied combination of CO2 chemisorption and thermodesorption techniques demonstrates the ability to adsorb the CO2 molecules by supported NiFe and CoFe nanocatalysts and the pure alumina-silica SA96 support.

Cross-Linked Hydrogels Based on PolyNIPAAm and Acid-Activated Laponite RD: Swelling and Tunable Thermosensitivity.

The effects of acid activation of Laponite RD (Lap) on the structure and properties of activated Lap nanoparticles (aLap) and the properties of polyNIPAAm hydrogels physically cross-linked by aLap have been studied. The acid activation of Lap by the sulfuric acid was done using the concentration of sulfuric acid within the interval Ca = 0.525-14.58% for 10 h. For slightly activated samples (Ca ≤ 1.25 wt %), the significant increase of the specific surface area (by ≈1.56 times) was accompanied with a significant decrease in both the values of the specific heat of immersion in water and n-decane. However, the hydrophilic properties of all samples S0-S5 were still observed. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) data, Fourier transform infrared (FTIR) spectra, and X-ray diffraction (XRD) patterns demonstrated that the acid activation resulted in the destruction of the crystal lattice of Lap, leaching of magnesium and lithium, and formation of the amorphous phases. Moreover, the acid activation significantly affected aggregation and negative surface charges of the aLap faces in aqueous suspension. The effects of aLap on the swelling properties and cooperativity in the phase transitions of polyNIPAAm hydrogels cross-linked by aLap are also discussed. It was demonstrated that an increase in Ca resulted in a significant increase in the equilibrium degree of swelling of the hydrogels and a decrease in the hydrogel phase-transition temperature from the swollen phase to the shrunken phase.

Thermoresponsive hydrogels physically crosslinked with magnetically modified LAPONITE® nanoparticles.

Recently, considering the potential applications of hydrogel nanocomposites in biomedical engineering, there has been a growing interest in the synthesis of hydrogels with improved mechanical properties. Among magnetic materials, iron oxides are of particular interest due to their magnetic properties and biocompatibility. At the same time, LAPONITE®, a synthetic clay, can be used to improve the mechanical properties of polymer-based nanocomposites. In this study we report the effects of hydrogel composition and structure on its thermoresponsive properties and hydrogel sorption and release of a model anticancer drug - 5-fluorouracil. Using one-step coprecipitation method we synthesized magnetic LAPONITE® (LAM) nanoparticles with magnetite-to-LAPONITE® weight ratios from 2 : 1 to 1 : 8. With increase in magnetite concentration the ferrofluidic properties of LAM nanoparticles are getting improved, while fluorouracil absorptivity - decreases. Exfoliation of the clay is observed when the magnetite content exceeds the LAPONITE® content. Physical crosslinking of poly(N-isopropylacrylamide) with LAM nanoparticles yields magnetic thermosensitive hydrogel nanocomposites with controllable temperature-induced drug release. All hydrogel nanocomposites have a distinct volume phase transition from a swollen state to a collapsed state upon heating within the physiologically acceptable temperature range of 33-36 °C.

Novel granular bentonite-carbon sorbents: textural characterization, adsorption-desorption isotherm, kinetics, and cost estimation.

This research focuses on the synthesis of novel low-cost granular sorbents based on bentonite clay of the Navbahor deposit, dust fraction of Angren brown coal, and agricultural wastes such as straw and sawdust to meet the internal needs of the Republic of Uzbekistan. The impact of the initial mixture ingredients on the structural and textural properties of bentonite-coal sorbents (BCSs) has been studied using X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectroscopy, optical microscopy, and nitrogen adsorption-desorption analysis. For determining the sorption capacity of BCSs, a standard model substance methylene blue (MB), was applied. It was revealed that the maximum adsorption amount of MB was 5.3 mg∙g-1 during 2 h of contact. Prolonging the contact time to 24 h allowed for more extensive diffusion of dye molecules into the sorbent's pores, increasing the adsorption capacity to 13 mg∙g-1. It was demonstrated that BCSs could be regenerated by strong oxidizing agents such as sulfuric acid and hydrogen peroxide, with sulfuric acid proving more effective. Regeneration fully restores sorption properties, particularly at low dye concentrations (up to 0.2 mg∙ml-1). Despite slight reductions in adsorption capacity over multiple regeneration cycles, the sorbents maintain their structural integrity and durability. It is shown that compared to imported expensive activated carbon, the gross profitability of the in-house production of such granular BCSs within the territory of Uzbekistan increases from 48 to 78%, while the net income increases almost three times.

Separation of plant protection products from complex aqueous bodies using carbon-mineral composites incorporated with double metals (Ni/Mn or Ni/Fe).

Due to the extensive application of pesticides and their hazardous effects on organisms, there is an urgent need to remove them effectively from wastewater. Metal-incorporated carbon-mineral composites (Ni/Mn-CMC and Ni/Fe-CMC) described in this paper can certainly be applied for this purpose. They were synthesized by combining mechanochemical and pyrolytic processes and their physicochemical properties were investigated using numerous methods (SEM-EDS, N2 adsorption/desorption, XRD, surface charge, FTIR). Adsorption capacity towards diuron and carboxin with and without impurities commonly detected in natural ecosystems, cadmium ions or arsenite, was measured. The obtained results indicated that Ni/Fe-CMC is more efficient adsorbent of pesticides due to its well-developed surface. It was able to bind 158.34 mg g-1 of diuron and 133.58 mg g-1 of carboxin in the solutions, where only one pesticide was present. In turn, these values for the Ni/Mn-CMC sample were 126.49 mg g-1 and 102.08 mg g-1, respectively. It should be noted that the composites maintained their high adsorption capacity in the multicomponent solutions, i.e., containing both pesticide and metal ions. Then, the maximum reduction in pesticide adsorption was only 8.36. Ni/Mn-CMC and Ni/Fe-CMC were successfully regenerated with ethanol without changing their structure and adsorption capacity. Also, the extracts from investigated materials did not have negative impact on plant growth. This confirmed suitability of carbon-mineral composites for repeated multiple use without toxic effects to organisms.

Synthesis, characterization and biocompatibility of hybrid hydrogels based on alginate, κ-carrageenan, and chitosan filled with montmorillonite clay.

New hybrid hydrogel composites based on a mixture of natural polysaccharides (sodium alginate, κ-carrageenan, and chitosan) filled with the clay mineral of natural origin, montmorillonite (MMT), were studied. The structure of intercalated/flocculated MMT distribution in the interpenetrating network of polysaccharide matrix was characterized using FTIR, X-ray diffraction, and SEM techniques. Swelling kinetics was investigated using the weight analysis, whereas the phase transition of water in the composition of hybrid hydrogels, by DSC method. Their biosafety was estimated using the Nelyubov method, germination test on cress (L. sativum) seeds, and metabolic fingerprinting of microbial communities and dehydrogenase assay. The obtained results indicated promising water-retaining properties of the synthesized materials. The hydrogels had a good sorption affinity for cadmium (Cd) ions confining bioavailability of the selected toxic heavy metal. They were safe for soil microorganisms and did not generate metabolic stress for them. Moreover, they did not reduce the viability of pea seeds. Thus, the development of biosafe hybrid hydrogel composites with a comprehensive, good effect on the environment could be considered as successful.

Interfacial behavior of n-decane bound to weakly hydrated silica gel and nanosilica over a broad temperature range.

The interfacial and temperature behavior of n-decane bound to weakly hydrated nanosilica A-400 (initial, heated, or compacted) or silica gel Si-60 was studied using low-temperature (1)H NMR spectroscopy applied to static samples that allowed us to observe signals only of mobile decane and unfrozen water molecules. For deeper insight into the phenomena studied, interactions of n-decane, 1-decanol, and water with a set of nanosilicas and silica gels were analyzed using DSC and thermoporometry. Both NMR and DSC results demonstrated that during heating of frozen samples at a heating rate of 5 K/min a portion of decane or decanol remained frozen at temperature higher than the freezing point of bulk liquid (Tf). For decane and decanol adsorbed onto silica gels Si-40, Si-60, and Si-100, the number, position, and intensity of freezing and melting peaks observed in the DSC thermograms over the 170-300 K range during cooling and heating of samples depended on the pore size distribution of silicas as well as on the amounts and type of adsorbates. The position of the main freezing peak of decane for all samples was close to Tf because the alkane amount was greater than the pore volume; i.e., a fraction of decane was bulk liquid. According to (1)H NMR data, a portion of decane, which was in a quasi-crystalline solid state characterized by fast molecular exchange (i.e., short transverse relaxation time) and not observed in the spectra, was greater than a portion of decane frozen at temperatures close to Tf during cooling that appears in the DSC endotherms of heated samples.

Polyacrylamide Hydrogel Enriched with Amber for In Vitro Plant Rooting.

In this work, a new material for in vitro plant rooting based on highly dispersed polyacrylamide hydrogel (PAAG) enriched with amber powder was synthesized and investigated. PAAG was synthesized by homophase radical polymerization with ground amber addition. Fourier transform infrared spectroscopy (FTIR) and rheological studies were used to characterize the materials. They showed that the synthesized hydrogels have physicochemical and rheological parameters similar to those of the standard agar media. The acute toxicity of PAAG-amber was estimated based on the influence of washing water on the viability of plant seeds (pea and chickpea) and Daphnia magna. It proved its biosafety after four washes. The impact on plant rooting was studied using the propagation of Cannabis sativa on synthesized PAAG-amber and compared with agar. The developed substrate stimulated the rooting of the plants to more than 98% in comparison to standard agar medium (95%). Additionally, the use of PAAG-amber hydrogel markedly enhanced metric indicators of seedlings: root length increased by 28%, stem length-by 26.7%, root weight-by 167%, stem weight-by 67%, root and stem length-by 27%, root and stem weight-by 50%. This means that the developed hydrogel significantly accelerates reproduction and allows obtaining a larger amount of plant material within a shorter period of time than the standard agar substrate.

Nanooxide/Polymer Composites with Silica@PDMS and Ceria-Zirconia-Silica@PDMS: Textural, Morphological, and Hydrophilic/Hydrophobic Features.

SiO2@PDMS and CeO2-ZrO2-SiO2@PDMS nanocomposites were prepared and studied using nitrogen adsorption-desorption, Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), measurements of advancing and receding contact angles with water, and microcalorimetry. The pore size distributions indicate that the textural characteristics change after oxide modification by poly(dimethylsiloxane) (PDMS). Composites are characterized by mainly mesoporosity and macroporosity of aggregates of oxide nanoparticles or oxide@PDMS nanoparticles and their agglomerates. The FT-IR spectra show that PDMS molecules cover well the oxide surface, since the intensity of the band of free silanols at 3748 cm-1 decreases with increasing PDMS concentration and it is absent in the IR spectrum at C PDMS ≥ 20 wt% that occurs due to the hydrogen bonding of the PDMS molecules to the surface hydroxyls. SEM images reveal that the inter-particle voids are gradually filled and aggregates are re-arranged and increase from 20 to 200 nm in size with the increasing polymer concentration. The highest hydrophobicity (contact angle θ = 140° at C PDMS = 20-40 wt%) is obtained for the CeO2-ZrO2-SiO2@PDMS nanocomposites. The heat of composite immersion in water shows a tendency to decrease with increasing PDMS concentration.

Synthesis, Structural, and Adsorption Properties and Thermal Stability of Nanohydroxyapatite/Polysaccharide Composites.

A series of composites based on nanohydroxyapatite (nHAp) and natural polysaccharides (PS) (nHAp/agar, nHAp/chitosan, nHAp/pectin FB300, nHAp/pectin APA103, nHAp/sodium alginate) was synthesized by liquid-phase two-step method and characterized using nitrogen adsorption-desorption, DSC, TG, FTIR spectroscopy, and SEM. The analysis of nitrogen adsorption-desorption data shows that composites with a nHAp: PS ratio of 4:1 exhibit a sufficiently high specific surface area from 49 to 82 m2/g. The incremental pore size distributions indicate mainly mesoporosity. The composites with the component ratio 1:1 preferably form a film-like structure, and the value of S BET varies from 0.3 to 43 m2/g depending on the nature of a polysaccharide. Adsorption of Sr(II) on the composites from the aqueous solutions has been studied. The thermal properties of polysaccharides alone and in nHAp/PS show the influence of nHAp, since there is a shift of characteristic DSC and DTG peaks. FTIR spectroscopy data confirm the presence of functional groups typical for nHAp as well as polysaccharides in composites. Structure and morphological characteristics of the composites are strongly dependent on the ratio of components, since nHAp/PS at 4:1 have relatively large S BET values and a good ability to adsorb metal ions. The comparison of the adsorption capacity with respect to Sr(II) of nHAp, polysaccharides, and composites shows that it of the latter is higher than that of nHAp (per 1 m2 of surface).

Silica-Supported Titania-Zirconia Nanocomposites: Structural and Morphological Characteristics in Different Media.

A series of TiO2-ZrO2/SiO2 nanocomposites were synthesized using a liquid-phase method and characterized by various techniques, namely, nitrogen adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, high-resolution transmission electron microscopy, and photon correlation spectroscopy (PCS). It was revealed that the component ratio and calcination temperature affect the phase composition of nanocomposites. Composites TiZrSi1 (TiO2:ZrO2:SiO2 = 3:10:87) and TiZrSi2 (10:10:80) calcined at 1100 °Ð¡ demonstrate the presence of t-ZrO2 crystallites in TiZrSi1 and ZrTiO4 phase in TiZrSi2. The samples calcined at 550 °Ð¡ were amorphous as it was found from XRD data. According to the Raman spectra, the bands specific for anatase are observed in TiZrSi2. According to XPS data, Zr and Ti are in the highest oxidation state (+4). Textural analysis shows that initial silica is mainly meso/macroporous, but composites are mainly macroporous. The particle size distributions in aqueous media showed a tendency of increasing particle size with increasing TiO2 content in the composites.