Specificity of the Thermal Stability and Reactivity of Two-Dimensional Layered Cu-Fe Sulfide-Mg-Based Hydroxide Compounds (Valleriites).

We recently synthesized prospective new materials composed of alternating quasi-atomic sheets of brucite-type hydroxide (Mg, Fe)(OH)2 and CuFe1-xS2 sulfide (valleriites). Herein, their thermal behavior important for many potential applications has been studied in inert (Ar) and oxidative (20% O2) atmospheres using thermogravimetry (TG) and differential scanning calorimetry (DSC) analyses and characterization with X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX). In the Ar media, the processes are determined by the dehydroxylation of the hydroxide layers forming MgO, with the temperature of the major endothermic maximum of the mass loss at 413 °C. Sulfide sheets start to degrade below 500 °C and melt at nearly 800 °C, with bornite, chalcopyrite, and troilite specified as the final products. In the oxidative atmosphere, the exothermic reactions with the mass increase peaked at 345 and 495 °C, corresponding to the partial and major oxidations of Cu-Fe sulfide layers. Sulfur oxides captured in magnesium hydroxide layers to form MgSO4 compromised the layer integrity and promoted the oxidation of the sulfide entities. The final products also contained minor MgO, Cu2MgO3, Fe3O4, and MgFe2O4 phases. Samples doped with Al, which decreases the content of Fe in hydroxide layers, show notably impeded decay of valleriite in argon but facilitated the oxidation of Cu-Fe sulfides, while the impact of Li (it slightly increases the number of the Fe-OH sites) was less expressed. The mutual stabilization of the two-dimensional (2D) hydroxide and sulfide layers upon heating in an inert atmosphere but not in oxygen as compared with bulk brucite and chalcopyrite was suggested to explain high thermal resistance across the stacked incommensurate sheets, which slows down the endothermic reactions and accelerates the exothermic oxidation; the high number of Fe atoms in the hydroxide sheets are expected to promote the phonon exchange and heat transfer between the layers.

Fractionation of Aspen Wood to Produce Microcrystalline, Microfibrillated and Nanofibrillated Celluloses, Xylan and Ethanollignin.

A new method for extractive-catalytic fractionation of aspen wood to produce microcrystalline (MCC), microfibrillated (MFC), nanofibrilllated (NFC) celluloses, xylan, and ethanollignin is suggested in order to utilize all of the main components of wood biomass. Xylan is obtained with a yield of 10.2 wt.% via aqueous alkali extraction at room temperature. Ethanollignin was obtained with a yield of 11.2 wt.% via extraction with 60% ethanol from the xylan-free wood at 190 °C. The lignocellulose residue formed after the extraction of xylan and ethanollignin was subjected to catalytic peroxide delignification in the acetic acid-water medium at 100 °C in order to obtain microcrystalline cellulose. MCC is hydrolyzed with 56% sulfuric acid and treated with ultrasound to produce microfibrillated cellulose and nanofibrillated cellulose. The yields of MFC and NFC were 14.4 and 19.0 wt.%, respectively. The average hydrodynamic diameter of NFC particles was 36.6 nm, the crystallinity index was 0.86, and the average zeta-potential was 41.5 mV. The composition and structure of xylan, ethanollignin, cellulose product, MCC, MFC, and NFC obtained from aspen wood were characterized using elemental and chemical analysis, Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) analyses, Gas chromatography (GC), Gel permeation-chromatography (GPC), Scanning electron microscopy (SEM), Atomic force microscopy (AFM), Dynamic light scattering (DLS), Thermal gravimetric analysis (TGA).

Preparation and Characterization of di- and Tricarboxylic Acids-Modified Arabinogalactan Plasticized Composite Films.

To ensure the high quality of water, it is necessary to remove toxic pollutants. At present, purification of water is implemented using various sorbents. The efficient sorption materials are modified polysaccharides. In this study, we report on a new environmentally friendly method for modifying larch hemicellulose-arabinogalactan (AG)-with polybasic carboxylic acids (citric, succinic, oxalic, and adipic) to obtain composite materials. The synthesized AG derivatives have been explored by a complex of physicochemical methods, including gel permeation chromatography (GPC), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffractometry (XRD), scanning electron microscopy (SEM), and sorption capacity investigations. It is shown that the heat treatment results in the formation of additional inter- and intramolecular bonds between carboxylic acids and polysaccharide molecules. The formation of ester bonds has been confirmed by the appearance of absorption bands in the IR spectra in the range of 1750-1690 cm-1. It has been found, using the TGA study, that the most thermally stable (up to 190 °C) sample is arabinogalactan oxalate obtained under heat treatment. The SEM study of the synthesized AG films has shown that the modified samples have the homogeneous film surface ensured by cross-linking. It has been established, when studying the sorption properties of the AG derivatives, that AG succinate (82.52%) obtained by lyophilization has the highest sorption capacity, due to the developed mesoporous surface, which, in turn, makes the synthesized films promising eco-friendly materials for use as drug carriers, sorbents, and water treatment agents.

Sulfation of Birch Wood Microcrystalline Cellulose with Sulfamic Acid Using Ion-Exchange Resins as Catalysts.

Cellulose sulfates are important biologically active substances with a wide range of useful properties. The development of new methods for the production of cellulose sulfates is an urgent task. In this work, we investigated ion-exchange resins as catalysts for the sulfation of cellulose with sulfamic acid. It has been shown that water-insoluble sulfated reaction products are formed in high yield in the presence of anion exchangers, while water-soluble products are formed in the presence of cation exchangers. The most effective catalyst is Amberlite IR 120. According to gel permeation chromatography, it was shown that the samples sulfated in the presence of the catalysts KU-2-8, Purolit s390 plus, and AN-31 SO42- underwent the greatest degradation. The molecular weight destribution profiles of these samples are noticeably shifted to the left towards low-molecular-weight compounds with an increase in fractions in the regions Mw ~2.100 g/mol and ~3.500 g/mol, indicating the growth of microcrystalline cellulose depolymerization products. The introduction of a sulfate group into the cellulose molecule is confirmed using FTIR spectroscopy by the appearance of absorption bands at 1245-1252 cm-1 and 800-809 cm-1, which correspond to the vibrations of the sulfate group. According to X-ray diffraction data, amorphization of the crystalline structure of cellulose is observed during sulfation. Thermal analysis has shown that with an increase in the content of sulfate groups in cellulose derivatives, thermal stability decreases.

Microfibrillated Cellulose with a Lower Degree of Polymerization; Synthesis via Sulfuric Acid Hydrolysis under Ultrasonic Treatment.

A new approach is being considered for obtaining microfibrillated cellulose with a low degree of polymerization by sulfuric acid hydrolysis with simultaneous ultrasonic treatment under mild conditions (temperature 25 °C, 80% power control). Samples of initial cellulose, MCC, and MFC were characterized by FTIR, XRF, SEM, DLS, and TGA. It was found that a high yield of MFC (86.4 wt.%) and a low SP (94) are observed during hydrolysis with ultrasonic treatment for 90 min. It was shown that the resulting microfibrillated cellulose retains the structure of cellulose I and has an IC of 0.74. It was found that MFC particles are a network of fibrils with an average size of 91.2 nm. ζ-potential of an aqueous suspension of MFC equal to -23.3 mV indicates its high stability. It is noted that MFC has high thermal stability, the maximum decomposition temperature is 333.9 °C. Simultaneous hydrolysis process with ultrasonic treatment to isolate MFC from cellulose obtained by oxidative delignification of spruce wood allows to reduce the number of stages, reduce energy costs, and expand the scope.

Comprehensive Study of the Ammonium Sulfamate-Urea Binary System.

The physicochemical properties of binary systems are of great importance for the application of the latter. We report on the investigation of an ammonium sulfamate-urea binary system with different component ratios using a combination of experimental (FTIR, XRD, TGA/DSC, and melting point) and theoretical (DFT, QTAIM, ELF, RDG, ADMP, etc.) techniques. It is shown that, at a temperature of 100 °C, the system under study remains thermally and chemically stable for up to 30 min. It was established using X-ray diffraction analysis that the heating time barely affects the X-ray characteristics of the system. Data on the aggregate states in specified temperature ranges were obtained with thermal analysis and determination of the melting point. The structures of the ammonium sulfamate-urea system with different component ratios were optimized within the density functional theory. The atom-centered density matrix propagation calculation of the ammonium sulfamate-urea system with different component ratios was performed at temperatures of 100, 300, and 500 K. Regardless of the component ratio, a regular increase in the potential energy variation (curve amplitude) with an increase in temperature from 100 to 500 K was found.

An Efficient Method of Birch Ethanol Lignin Sulfation with a Sulfaic Acid-Urea Mixture.

For the first time, the process of birch ethanol lignin sulfation with a sulfamic acid-urea mixture in a 1,4-dioxane medium was optimized experimentally and numerically. The high yield of the sulfated ethanol lignin (more than 96%) and containing 7.1 and 7.9 wt % of sulfur was produced at process temperatures of 80 and 90 °C for 3 h. The sample with the highest sulfur content (8.1 wt %) was obtained at a temperature of 100 °C for 2 h. The structure and molecular weight distribution of the sulfated birch ethanol lignin was established by FTIR, 2D 1H and 13C NMR spectroscopy, and gel permeation chromatography. The introduction of sulfate groups into the lignin structure was confirmed by FTIR by the appearance of absorption bands characteristic of the vibrations of sulfate group bonds. According to 2D NMR spectroscopy data, both the alcohol and phenolic hydroxyl groups of the ethanol lignin were subjected to sulfation. The sulfated birch ethanol lignin with a weight average molecular weight of 7.6 kDa and a polydispersity index of 1.81 was obtained under the optimum process conditions. Differences in the structure of the phenylpropane units of birch ethanol lignin (syringyl-type predominates) and abies ethanol lignin (guaiacyl-type predominates) was manifested in the fact that the sulfation of the former proceeds more completely at moderate temperatures than the latter. In contrast to sulfated abies ethanol lignin, the sulfated birch ethanol lignin had a bimodal and wider molecular weight distribution, as well as less thermal stability. The introduction of sulfate groups into ethanol lignin reduced its thermal stability.

Sulfation of Wheat Straw Soda Lignin with Sulfamic Acid over Solid Catalysts.

Soda lignin is a by-product of the soda process for producing cellulose from grassy raw materials. Since a method for the industrial processing of lignin of this type is still lacking, several research teams have been working on solving this problem. We first propose a modification of soda lignin with sulfamic acid over solid catalysts. As solid catalysts for lignin sulfation, modified carbon catalysts (with acid sites) and titanium and aluminum oxides have been used. In the elemental analysis, it is shown that the maximum sulfur content (16.5 wt%) was obtained with the Sibunit-4® catalyst oxidized at 400 °C. The incorporation of a sulfate group has been proven by the elemental analysis and Fourier-transform infrared spectroscopy. The molecular weight distribution has been examined by gel permeation chromatography. It has been demonstrated that the solid catalysts used in the sulfation process causes hydrolysis reactions and reduces the molecular weight and polydispersity index. It has been established by the thermal analysis that sulfated lignin is thermally stabile at temperatures of up to 200 °C. According to the atomic force microscopy data, the surface of the investigated film consists of particles with an average size of 50 nm. The characteristics of the initial and sulfated ß-O-4 lignin model compounds have been calculated and recorded using the density functional theory.

Molecular Characteristics and Antioxidant Activity of Spruce (Picea abies) Hemicelluloses Isolated by Catalytic Oxidative Delignification.

Spruce (Piceaabies) wood hemicelluloses have been obtained by the noncatalytic and catalytic oxidative delignification in the acetic acid-water-hydrogen peroxide medium in a processing time of 3-4 h and temperatures of 90-100 °C. In the catalytic process, the H2SO4, MnSO4, TiO2, and (NH4)6Mo7O24 catalysts have been used. A polysaccharide yield of up to 11.7 wt% has been found. The hemicellulose composition and structure have been studied by a complex of physicochemical methods, including gas and gel permeation chromatography, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. The galactose:mannose:glucose:arabinose:xylose monomeric units in a ratio of 5:3:2:1:1 have been identified in the hemicelluloses by gas chromatography. Using gel permeation chromatography, the weight average molar mass Mw of hemicelluloses has been found to attain 47,654 g/mol in noncatalytic delignification and up to 42,793 g/mol in catalytic delignification. Based on the same technique, a method for determining the α and k parameters of the Mark-Kuhn-Houwink equation for hemicelluloses has been developed; it has been established that these parameters change between 0.33-1.01 and 1.57-472.17, respectively, depending on the catalyst concentration and process temperature and time. Moreover, the FTIR spectra of the hemicellulose samples contain all the bands characteristic of heteropolysaccharides, specifically, 1069 cm-1 (C-O-C and C-O-H), 1738 cm-1 (ester C=O), 1375 cm-1 (-C-CH3), 1243 cm-1 (-C-O-), etc. It has been determined by the thermogravimetric analysis that the hemicelluloses isolated from spruce wood are resistant to heating to temperatures of up to ~100 °C and, upon further heating, start destructing at an increasing rate. The antioxidant activity of the hemicelluloses has been examined using the compounds simulating the 2,2-diphenyl-2-picrylhydrazyl free radicals.

Food Xanthan Polysaccharide Sulfation Process with Sulfamic Acid.

Xanthan is an important polysaccharide with many beneficial properties. Sulfated xanthan derivatives have anticoagulant and antithrombotic activity. This work proposes a new method for the synthesis of xanthan sulfates using sulfamic acid. Various N-substituted ureas have been investigated as process activators. It was found that urea has the greatest activating ability. BBD of xanthan sulfation process with sulfamic acid in 1,4-dioxane has been carried out. It was shown that the optimal conditions for the sulfation of xanthan (13.1 wt% sulfur content) are: the amount of sulfating complex per 1 g of xanthan is 3.5 mmol, temperature 90 °C, duration 2.3 h. Sulfated xanthan with the maximum sulfur content was analyzed by physicochemical methods. Thus, in the FTIR spectrum of xanthan sulfate, in comparison with the initial xanthanum, absorption bands appear at 1247 cm-1, which corresponds to the vibrations of the sulfate group. It was shown by GPC chromatography that the starting xanthan gum has a bimodal molecular weight distribution of particles, including a high molecular weight fraction with Mw > 1000 kDa and an LMW fraction with Mw < 600 kDa. It was found that the Mw of sulfated xanthan gum has a lower value (~612 kDa) in comparison with the original xanthan gum, and a narrower molecular weight distribution and is characterized by lower PD values. It was shown by thermal analysis that the main decomposition of xanthan sulfate, in contrast to the initial xanthan, occurs in two stages. The DTG curve has two pronounced peaks, with maxima at 226 and 286 °C.

Colloidal and Immobilized Nanoparticles of Lead Xanthates.

Although nanoparticles of heavy metal xanthates and their hydrosols can play important roles in froth flotation, environmental issues, analytics, and manufacturing of metal sulfide nanocomposites, they have received little attention. We studied colloidal solutions and immobilized particles prepared via interaction of aqueous lead nitrate with alkyl xanthates applying UV-vis absorption spectroscopy, dynamic light scattering, zeta potential measurement, thermogravimetry analysis, Fourier transform infrared spectroscopy, Raman scattering, X-ray photoelectron spectroscopy, atomic force microscopy, and transmission electron microscopy. The hydrodynamic diameter of colloidal particles of Pb(SSCOR)2 decreased from 500 to 50 nm with an increase in the alkyl radical length and the initial xanthate to lead ratio (X/Pb); the zeta potential magnitude varied similarly, although it remained negative. The effect of pH in the range of 4.5-11 was minor, but the colloids produced using excess of Pb2+ in alkaline media were close to PbX and decomposed much easier than PbX2. The uptake of lead xanthates on supports was generally low because of negative charges of the colloids; however, 50-100 nm thick PbX2 films were deposited on PbS and SiO2 from the media of X/Pb < 2 and pH < 9 because of preadsorption of Pb2+, while nanorods formed on highly oriented pyrolytic graphite.