Hydrolysis of cellulose by the heteropoly acid H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript>

The potential of heteropoly acid H₃PW₁₂O₄₀ to catalyze the hydrolysis of cellulose to glucose under hydrothermal conditions was explored. This technology could contribute to sustainable societies in the future by using cellulose biomass. A study to optimize the reaction conditions, such as the amount of catalyst, reaction time, temperature, and the amount of cellulose used, was performed. A remarkably high yield of glucose (50.5%) and selectivity higher than 90% at 453 K for 2 h with a mass ratio of cellulose to H₃PW₁₂O₄₀ of 0.42 were achieved. This was attributed to the high hydrothermal stability and the excellent catalytic properties, such as the strong Brønsted acid sites. This homogeneous catalyst can be recycled for reuse by extraction with diethyl ether. The results illustrate that H₃PW₁₂O₄₀ is an environmentally benign acid catalyst for the hydrolysis of cellulose.     

Oxidant Effect of H2O2 for the Syntheses of Quinoline Derivatives via One-Pot Reaction of Aniline and Aldehyde

A convenient one-pot method for the synthesis of substituted quinolines via the reaction of aniline and aldehyde in the presence of a Lewis acid (AlCl₃) and an oxidant (H₂O₂) has been developed. Hydrogen peroxide was found to promote the reaction by its function as a hydrogen hunter, hindering the formation of by-product N-alkylaniline. The effect of the oxidant on the yield and selectivity was studied. When the molar ratio of aniline, n-butyraldehyde, and H₂O₂ was 1:3:0.5 at 25 °C, the yield of 3-ethyl-2-propylquinoline was improved from 64% (reaction without H₂O₂) to 84% (with H₂O₂), and the quinoline selectivity was improved to almost 100%. Moreover, the reaction time was obviously reduced. The substituent effect was also investigated in this work.     

Production of formic and acetic acids from phenol by hydrothermal oxidation

Hydrothermal technology is a core environmental-protection technique which can be used for waste water treatment and biomass conversion. In this paper a novel idea, alkaline hydrothermal oxidation, is proposed for producing formic and acetic acids from wastewater containing phenolic compounds. The effects of the most important conditions??reaction temperature, reaction time, oxygen supply, and type of alkaline catalyst??on yields of formic and acetic acids were investigated. The results indicated that the optimum conditions for production of formic and acetic acids were: reaction temperature 300???C, reaction time 90?s, H₂O₂ equivalent to 60% oxygen, and NaOH concentration 1.5?mmol. Under the optimum conditions the yields of formic and acetic acids reached 4.8 and 23.5%, respectively. In addition, the effect of different alkalis on yields of formic and acetic acids was also investigated. The results showed that compared with use of NaOH addition of KOH had a more pronounced effect on improving the yield of acetic acid. This research indicated that high-value-added formic and acetic acids can be recovered as resources by hydrothermal oxidation of phenolic wastewater, and thus hydrothermal oxidation has high potential for converting phenolic compounds in wastewater into value-added products.     

Selective oxidation of light alkanes over Mo-based oxide catalysts

A highly reduced Keggin-type heteropolymolybdophosphate, H₃PMo₁₂O₄₀(Py), which was formed by the heat-treatment of pyridinium salt of H₃PMo₁₂O₄₀, can catalyze the propane oxidation to acrylic acid and acetic acid selectively. We propose a possible reaction mechanism for alkane oxidation, where protons and electrons on the reduced H₃PMo₁₂O₄₀ catalyst cooperate for activating molecular oxygen to form electrophilic oxygen species for alkane oxidation. It is also reported that Anderson-type heteropolycompounds linked with vanadyl cations VO²⁺ were able to be synthesized by hydrothermal reaction and showed good catalytic activity for the ethene oxidation to acetic acid.     

Synthesis, structure and catalytic activity of an oxo-bridged dinuclear oxovanadium complex of an isonicotinohydrazide ligand

A mononuclear dioxo vanadium(V) complex of a hydrazone ONO donor ligand, [V^VO₂(L¹)] (1), was synthesized by the reaction of V₂O₅ and terephthalic acid with H₂L¹ in 1:1:1 mol ratio, while an oxo-bridged bis(vanadium(IV)oxo) complex, [μ ₂–O–{V^IVO(L²)}₂] (2), was synthesized by the treatment of isonicotinic acid hydrazide, salicylaldehyde and CoSO₄·7H₂O with bis(acetylacetonato)oxovanadium(IV) (H₂L¹ = isonicotinic acid(2-hydroxy-benzylidene)-hydrazide, H₂L² = isonicotinic acid (1-methyl-3-oxo-butylidene)-hydrazide). The complexes were characterized by elemental analyses and spectroscopic methods. The crystal structure of complex 2 was determined by X-ray analysis. The complexes were tested as catalysts for the oxidation of cycloalkenes and benzyl alcohol using H₂O₂ as terminal oxidant. Excellent selectivity was achieved in the oxidation of cyclohexene.     

The synthesis of a lanthanum metal–organic framework and its sensitivity electrochemical detection of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

A lanthanum metal–organic framework, [La(BTC)(H₂O)(DMF)] (H₃BTC = 1, 3, 5-benzenetricarboxylic acid), was synthesized under mild hydrothermal conditions. The synthesized [La(BTC)(H₂O)(DMF)] was characterized by scanning electron microscopy in combination with energy dispersive X-ray spectroscopy (SEM/EDS), transmission electron microscopy (TEM), X-ray diffraction (XRD), and fourier transform infrared spectroscopy (FT-IR). Its electrochemical properties and electrocatalytic activity towards H₂O₂ reduction in acidic media were studied by cyclic voltammetry (CV) and amperometric current–time response. The [La(BTC)(H₂O)(DMF)] modified electrode shows good electrochemical behavior and performs well electrocatalytic activity towards hydrogen peroxide (H₂O₂) reduction at ca. ?0.7 V. The modified electrode displays a linear range from 5 μM to 2.67 mM and a limit of detection of 0.73 μM to H₂O₂. The [La(BTC)(H₂O)(DMF)] modified electrode also possesses good selectivity and stability. Thus, [La(BTC)(H₂O)(DMF)] will be a promising material for non-enzymatic H₂O₂ sensor.     

The Optimization of Dilute Acid Hydrolysis of Cotton Stalk in Xylose Production

Cotton stalk, a lignocellulosic waste material, is composed of xylose that can be used as a raw material for production of xylitol, a high-value product. There is a growing interest in the use of lignocellulosic wastes for conversion into various chemicals because of their low cost and the fact that they are renewable and abundant. The objective of the study was to determine the effects of H₂SO₄ concentration, temperature, and reaction time on the production of sugars (xylose, glucose, and arabinose) and on the reaction by-products (furfural and acetic acid). Response surface methodology was used to optimize the hydrolysis process in order to obtain high xylose yield and selectivity. The optimum reaction temperature, reaction time, and acid concentration were 140 °C, 15 min, and 6%, respectively. Under these conditions, xylose yield and selectivity were found to be 47.88% and 2.26 g g⁻¹, respectively.     

Dichromate dosimetry: The effect of acetic acid on the radiolytic reduction yield

The radiation chemical yield for the reduction of dichromate, Cr(VI) → Cr³⁺, in an acidic aqueous perchloric acid solution of potassium dichromate, may be increased from 0.04 to >0.2 μ mol J^-1 by adding acetic acid. The increased yield, G[-(Cr₂O₇)^2-] is about the same in N_2- and O₂-saturated solutions. The molar linear absorption coefficient at 350 nm also is the same in both solutions (ϵ_m = 2800 M^-1cm^-1) at pH 0.4. The proposed mechanism to explain the enhanced response in N₂-saturated solutions involves the efficient reaction of acetic acid with hydroxyl radicals by the abstraction of H from the methyl group; the resulting acid radicals react with relatively high yield to reduce Cr(VI). In O₂-saturated solution, the acetic acid radical apparently goes through an acetic acid peroxyl radical by a bimolecular reaction to the tetroxide intermediate of acetic acid, which releases H₂O₂ with relatively high yield by a Bennett-type reaction. This additional H₂O₂, as a reducing agent, reacts slowly with dichromate and boosts the value of G[-(Cr₂O₇)^2-]. The negative slope of the response (ΔA vs dose) continues to increase during the period immediately after irradiation of oxygenated solution, due to slow reaction of radiolytically-produced H₂O₂ with dichromate. There is also in both O₂- and N₂-saturated solution a long-term slow reaction involving oxidation of the organic substrate (in this case, acetic acid). Because of these instabilities, the solutions cannot readily be used for dosimetry without the presence of silver ions, which in the oxidized state, Ag²⁺, act to stabilize the solution after irradiation. The addition of silver dichromate at a concentration of 0.1 mM decreases the yield to G[-(Cr₂O₇)^2-] = 0.17 μmolJ^-1, but greatly improves the stability of the solution after irradiation. The absorbed dose range for the modified dichromate dosimeter when analyzed spectrophotometrically at 350 nm wavelength is approx. 2 × 10²-2 × 10³ Gy.     

高效锂离子筛吸附剂MnO2•0.5H2O的软化学合成及吸附性能研究

以MnCl₂•4H₂O, LiOH•H₂O等试剂为初始原料, 采用溶胶-凝胶、水热处理、固化等软化学合成步骤制备了锂离子筛前驱体Li_1.6Mn_1.6O₄, 并经稀盐酸抽锂后得到了高选择性锂离子筛吸附剂MnO₂•0.5H₂O. 着重对合成过程中锂锰比, 氧化剂用量等因素影响进行了探讨, 并对所制备吸附剂的吸附性能进行了研究. 结果表明, 经软化学合成步骤制备的锂离子筛对Li^＋有良好的吸附量和选择性, 在未来从海水、卤水等液态锂资源富集或提取锂的应用中具有很大的潜力.     

Synthesis of nanometric β-barium metaborate powder from different borate solutions by ultrasound-assisted precipitation

In this study, the synthesis of barium metaborate powder (BaB₂O₄) was carried out by ultrasound-assisted precipitation using different borate solutions. Different solutions such as borax (Na₂B₄O₇, BD), boric acid (H₃BO₃, BA), and sodium metaborate (NaBO₂, SMB) were used in the synthesis and an ultrasonic immersion horn probe was used as the major source of ultrasound. The effect of reaction temperature and time, pH, and crystallization time on the BaB₂O₄ yield (%) was investigated. The ultrasound-assisted synthesis up to 90 % yield could be achieved using a 0.2 M BD solution at 80 °C, reacting for 5 min at pH 13 followed by 2 h of crystallization. Following crystallization, the obtained powder was heated up to 140, 250, 650, and 750 °C for 2.5 h, and it was shown that β-BaB₂O₄ nanometric powders were obtained after the 750 °C heat treatment.     

Design of a Highly Efficient Indium-Exchanged Heteropolytungstic Acid for Glycerol Esterification with Acetic Acid

A series of highly active, selective, and stable solid indium-exchanged tungstophosphoric acid catalysts had been prepared, characterized and evaluated for bio-derived glycerol esterification with acetic acid to produce valuable biofuel additives. It was found that the In_x/3H_3?xPW with nanotube structure owns Lewis acidity and Brønsted acidity in one, which favors for the efficient esterification of glycerol into monoglycerides with higher selectivity. Among all, In_0.8H_0.6PW presented exceptionally high activity with 88 % conversion and 96 % selectivity to MAG within 30 min of reaction time at 120 °C using 4:1 molar ratio. The better performance came from its remarkable stability, due to the unique Keggin structure, high acidity as well as nanotube structure. In addition, this In_0.8H_0.6PW catalyst did not suffer from deactivation of water in the six consecutive reaction tests.     

Gold nanoparticles supported on cellulose aerogel as a new efficient catalyst for epoxidation of styrene

A new efficient heterogeneous catalyst was introduced for the epoxidation of styrene. The catalyst was obtained from deposition of gold nanoparticles on the cellulose aerogel. The catalyst was characterized with XRD, TGA, EDX, BET, FAAS and SEM. High yield and excellent selectivity were achieved for the epoxidation of styrene in solvent-free conditions at room temperature using H₂O₂ as a green oxidant during 1 h. The reaction has some advantages such as solvent-free and mild reaction conditions, low catalyst loading, high yield, excellent selectivity, green oxidant and short reaction duration. In addition, the catalyst is recyclable and applicable for six times without decrease in yield.     

Novel hybrid process for the conversion of microcrystalline cellulose to value-added chemicals: part 2: effect of constant voltage on product selectivity

In this study, electrochemical degradation of microcrystalline cellulose (MCC) under hot-compressed water was investigated via application of constant voltage on reaction medium. Constant voltage ranges from 2.5 to 8.0 V was applied between anode (Titanium) and cathode (reactor wall). As an electrolyte and proton source 5–25 mM of H₂SO₄ was used. Reactions were carried out in a specially designed batch reactor (450 mL) made of T316 for 240 min at temperature of 200 °C.MCC decomposition products such as glucose, fructose, furfural, 5-HMF and levulinic acid were detected and quantified by High Performance Liquid Chromatography (HPLC). In the absence of electrolyte, applied voltage (2.5 and 4.0 V) decreased the total organic carbon (TOC) yield, in contrast at 8.0 V, TOC yield increased to 13%. Application of 8.0 V in hydrothermal conditions alter MCC decomposition pathway selectively to furfural (15%). Addition of electrolyte (5 mM, H₂SO₄) and application of 2.5 V potential increased TOC (54%) and changed the decomposition pathway in favor of 5-HMF (30%) and levulinic acid (21%). The structural changes in solid residues of electrochemically reacted MCC was analyzed by Fourier Transform Infrared Spectroscopy (FTIR) and found that MCC particles functionalized by carboxylic acid and sulfonated groups by the application of constant voltage to reaction medium. In the presence of electrolyte, under certain voltage (2.5 V), functionalization of solid particles became more obvious in FTIR spectrum results. Therefore, change in the selectivity values of degradation products were conducted with the functionalization of MCC particles due to applied voltage under sub-critical conditions.     

Effect of Hydrothermal Time,pH, and Alkali on Crystal Phase and Morphology of Manganese Oxides

γ‐MnOOH nanowires and Mn₃O₄ nanoparticles were prepared in the hydrothermal process. The effect of hydrothermal time, pH, and alkali on morphology and composition of manganese oxides was investigated. The results of XRD, TEM, and SEM showed that the γ‐MnOOH prepared in shorter hydrothermal time was a mixture of nanocubes and nanowires, while in longer hydrothermal time was pure nanowires. Interestingly, increasing the pH of the reaction system from 8 to 10, the mixture of γ‐MnOOH nanowires and Mn₃O₄ nanoparticles was obtained. Alkali types also were discussed in directing the reaction and crystallization of manganese oxides. The product was pure γ‐MnOOH when using NaOH in the system, but a mixture of Mn₃O₄ and γ‐MnOOH was obtained when using NH₃ · H₂O.     

The Process of Acetonitrile Synthesis over γ-Al2O3 Promoted by Phosphoric Acid Catalysts

The influence of principal parameters (reaction temperature, ratio of acetic acid and ammonia, composition of reactionary mixture and promotion of catalysts) on the selectivity and yield of the desired product was studied in the reaction of catalytic acetonitrile synthesis by ammonolysis of acetic acid. The processing of γ-Al₂O₃ by phosphoric acid increases amount of the centers, on which carries out reaction of acetamide dehydration. The kinetic model of a limiting stage of reaction – the acetamide dehydration to acetonitrile was suggested. In the process of ammonolysis of acetic acid it was demonstrated that the use of catalysts promoted by phosphoric acid and ratio NH₃:CH₃COOH=(3-4):1 at temperatures of a reactor 360-390°С leads to the increase of acetonitrile productivity to 0.7-0.8 g/cm³·h and allows to minimize formation of by-products.     

On the Modification of Chitosan Through Grafting

Abstract

The feasibility of grafting poly(methyl acrylate) and poly[1-(methoxycarbonyl) ethylene] onto chitosan, poly-β(1←-4)-2-amino-2-deoxy-d-glucose, was investigated. The grafting reaction was carried out in aqueous solution by using ferrous ammonium sulfate (FAS) in combination with H₂O₂ as redox initiator. The effects of such reaction variables as chitosan, monomer and initiator concentrations, reaction time, and reaction temperature were determined. Through this study the grafting reaction could be optimized. The grafting yield reached its maximum value of 332% when 0.3 g chitosan was copolymerized with 3 mL monomer at 70°C for 120 minutes with [FAS] = 6 × 10^?5 M, [H₂O₂] = 6 × 10^?3 M, and 8 mL water. The grafted chitosan was found to be insoluble in solvents for chitosan and solvents for poly(methyl acrylate), but did show swelling in dilute acetic acid, methanol, acetone, and in an ethanol/2% acetic acid 1:1 mixture. The thermal stability of chitosan and grafted chitosan were studied by dynamic thermogravimetric analysis. The results show that the graft copolymer is thermally more stable than pure chitosan. The overall activation energy for graft copolymerization was estimated to be 32.8 kcal/mol.     

Dynamic hydrothermal synthesis of Al-substituted 11 Å tobermorite from solid waste fly ash residue-extracted Al2O3

Fly ash residue (hereafter, FAR) is the by-product of pulverized coal combustion fly ash-extracted Al₂O₃. It results in a hazardous industrial solid waste if it does not have appropriate treatment and utilization. Al-substituted 11 Å tobermorite is successfully synthesized from FAR/SiO₂ mixture by dynamic hydrothermal treatment at 220 °C for 6 h. FAR and its hydrothermal reaction products are studied by chemical analysis, XRD, SEM, FTIR, and BET methods. The XRD results show that dicalcium silicate existing in FAR has been converted into tobermorite after the hydrothermal treatment. The main crystalline phases of product are Al-substituted 11 Å tobermorite and minor calcite. SEM results show that the hydrothermal products of the FAR/SiO₂ mixture consist of many tiny needlelike and platy crystals which form micro-porous spherical particles, ranging in size from a few microns to dozens of microns, and have a specific surface area of 49.004 m²/g. The Al-substituted tobermorite-bearing products have a high performance of exclusion of Cr³⁺ from acidified aqueous media, and the adsorption efficiency of Cr³⁺ is 98 %. The exclusion reaction proceeds rapidly, reaching equilibria within 1 h. The results show that this product has a potential to be used in industrial processes for adsorption of heavy metal cations from wastewater.     

Aqueous Reactive Oxygen Species Induced by He + O<Subscript>2</Subscript> Plasmas: Chemistry Pathways and Dosage Control Approaches

Plasma–liquid interaction has already been a hotspot in the research field of plasma medicine. Aqueous reactive oxygen species (ROS) generated in this process are widely accepted playing a crucial role in plasma biomedical effects. In this paper, chemistry pathways among various aqueous ROS induced by He + O₂ plasmas are investigated by a numerical model. Simulation results show that these aqueous ROS can be classified into two groups according to their production ways: the group of species including O, ¹O₂ and e directly produced in plasma, and the other group of species including O₂ ^?, H₂O₂, O₃, etc. produced by liquid reactions. A key reaction chain of e → O₂ ^? → HO₂(→ HO₂ ^?) → H₂O₂ is found to be important in the plasma-induced liquid chemistry. Furthermore, impacts of changes in plasma and solution conditions on aqueous ROS concentrations are studied as well. It is found that changes in plasma conditions (O₂ ratio in the discharge gas/power density) can globally influence the concentrations of almost every aqueous ROS, while conditions changes of the treated liquid (pH/dissolved oxygen) only partially influence the concentrations of some specific species including O₂ ^?/HO₂, O₃ ^?/HO₃ and H₂O₂. The revelations of the liquid chemistry pathways and the dependence of ROS dosage on the treatment conditions offer a better understanding on the plasma–liquid interactions, as well as provide optimized dosage control approaches for biomedical applications.     

Continuous Flow Reduction of Artemisinic Acid Utilizing Multi‐Injection Strategies—Closing the Gap Towards a Fully Continuous Synthesis of Antimalarial Drugs

One of the rare alternative reagents for the reduction of carbon–carbon double bonds is diimide (HN?NH), which can be generated in situ from hydrazine hydrate (N₂H₄ ? H₂O) and O₂. Although this selective method is extremely clean and powerful, it is rarely used, as the rate‐determining oxidation of hydrazine in the absence of a catalyst is relatively slow using conventional batch protocols. A continuous high‐temperature/high‐pressure methodology dramatically enhances the initial oxidation step, at the same time allowing for a safe and scalable processing of the hazardous reaction mixture. Simple alkenes can be selectively reduced within 10–20 min at 100–120 °C and 20 bar O₂ pressure. The development of a multi‐injection reactor platform for the periodic addition of N₂H₄ ? H₂O enables the reduction of less reactive olefins even at lower reaction temperatures. This concept was utilized for the highly selective reduction of artemisinic acid to dihydroartemisinic acid, the precursor molecule for the semisynthesis of the antimalarial drug artemisinin. The industrially relevant reduction was achieved by using four consecutive liquid feeds (of N₂H₄ ? H₂O) and residence time units resulting in a highly selective reduction within approximately 40 min at 60 °C and 20 bar O₂ pressure, providing dihydroartemisinic acid in ≥93 % yield and ≥95 % selectivity.     

Iron Incorporated Mesoporous Molecular Sieves Synthesized by a Microwave-Hydrothermal Process and Their Application in Catalytic Oxidation

Fe-FSM-16 and Fe-containing mesoporous materials (Fe-JLU-15) prepared by using semifluorinated surfactant as a template, have been synthesized by microwave-hydrothermal (M-H) process and characterized by several spectroscopic techniques. The catalytic activity of these materials was tested for the phenol hydroxylation and wet phenol oxidation with H₂O₂ under mild reaction conditions. The effect of pH, H₂O₂/PhOH molar ratio and stability of the catalyst on the oxidation process was also investigated. Phenol oxidation and H₂O₂ decomposition show that the Fe-JLU-15 is more active than Fe-FSM-16 and more stable in aqueous solution. The total amount of dissolved iron is less than 5 wt% of the iron initially contained in the catalyst. In phenol hydroxylation, these two solids can effectively catalyze the phenol hydroxylation. Catechol and hydroquinone were observed as the major products, with a difference in the product distribution for these solids. The Fe-JLU-15 has a high selectivity for catechol (63.5 % phenol conversion, CAT/HQ = 2.7) while the Fe-FSM-16 shows a high selectivity for hydroquinone (56.8 % phenol conversion, CAT/HQ < 1) under the same reaction conditions.