Molar Ratio Research Articles

Identifying Target Molecule and Trace Amount of the Byproduct by Two-Dimensional Self-Assembly with Different Solution Concentrations.

Scanning tunneling microscopy (STM) is a powerful way to realize the recognition of self-assembled nanostructures on the atomic scale. In this article, dihexadecyl 6,9-bis((4-(hexadecyloxy)phenyl)ethynyl) phenanthro[9,10-c]thiophene-1,3-dicarboxylate (D-PT) and dihexadecyl 6-bromo-9-((4-(hexadecyloxy) phenyl)ethynyl)phenanthrol[9,10-c]thiophene-1,3-dicarboxylate (S-BrPT) with different substituents were chosen as the target system. D-PT with four side chains as the target molecule and S-BrPT with three side chains and a bromine substituent as the byproduct were mixed in a molar concentration ratio of 20:1. The effect of solution concentration on the molecular self-assembly of the mixture was investigated by STM at the hexadecane/HOPG interface. At high concentrations, only D-PT molecules formed a dimer pattern resulting from the intermolecular van der Waals force and self-adaption. Further diluting the solution, D-PT formed the coexisting dimer and linear structures, in which the linear pattern was formed via solvent coadsorption. At low concentrations, S-BrPT molecules forming N-shaped dimers appeared and filled the linear structure fabricated by D-PT molecules. With further decrease in the concentration, S-BrPT molecules formed N-shaped dimers covering almost half of the surface area, resulting from the C-Br···π and Br···H-C bonds. At very low concentrations, S-BrPT molecules formed N-shaped dimers to arrange the matrix architecture due to the coadsorption of more hexadecane molecules. Density functional theory (DFT) calculations demonstrated that the stronger intermolecular C-Br···π and Br···H-C bonds were significant factors in determining the formation of N-shaped dimers and the stability of this nanostructure. This work enriches the diversity of self-assembled motifs and provides a strategy to characterize different symmetric molecules with trace amounts in a mixed system by STM.

Environment-benign Colloidal Quantum Dots-modified Dual Photoelectrodes for Self-biased Photoelectrochemical Water Splitting.

Photoelectrochemical (PEC) water splitting based on colloidal quantum dots (QDs) presents a promising approach for utilizing solar energy to produce green hydrogen energy. Previous research has been mainly focused on the single-photoelectrode QDs-PEC device operated under external bias, while the investigation of dual-photoelectrode configuration for self-biased QDs-PEC system is still lacking. In this work, two types of eco-friendly Cu-AISe/ZnSe:Cu (CZAC) and Mn-AIS/ZnS@Cu (MAZC) QDs were used to respectively sensitize the semiconductor n-type TiO2 and p-type Cu2O photoelectrodes, which acted as the photoanode and photocathode to build a heavy metal-free QDs-based bias-free solar water splitting cell, yielding a maximum photocurrent density of 0.47 mA cm-2 and a solar-to-hydrogen (STH) efficiency of 0.4% under 1 sun AM 1.5G illumination (100 mW cm-2). Moreover, approximate 692 nmol of H2 and 355 nmol of O2 with molar ratio of ~2:1 was detected after two hours of continuous light illumination, demonstrating the effective overall water splitting. This work indicates a significant advancement towards the realization of a cost-effective, efficient and "green" QDs-based artificial solar-to-fuel conversion system.

Optimisation of TiO2 synthesis from ilmenite sand and its application in the photocatalytic process

ABSTRACT Iron sand, a mineral, can be extracted to produce titanium dioxide (TiO2). TiO2 is a semiconductor material that is commonly used in photocatalytic applications, as well as electronics, colour pigments, paint manufacturing, and semiconductors. In this study, TiO2 was extracted from Banten ilmenite sand using caustic fusion and hydrometallurgical methods. The TiO2 extraction process was carried out by varying the mole ratio of ilmenite sand to NaOH, which was 1:0, 1:3, and 1:5, and the fusion temperatures were 700°C and 850°C, with time variations of 30, 60, and 90 min. XRF analysis revealed that the highest TiO2 composition was 91.64% in samples with a mole ratio of 1:3 during 30 min of fusion time and 91.14% in samples with a mole ratio of 1:5 during 90 min of fusion time. The XRD data revealed that TiO2 has a rutile phase with a tetragonal structure, while scanning electron microscopy (SEM) analysis revealed that the particle distribution in the sample is not uniform. The UV-Vis measurements revealed that TiO2 has a band gap of 3.10 at 700°C and 3.13 at 850°C. Furthermore, TiO2 degraded Rhodamine B dyes at a rate of 28.266%.

How Does the Powder Mixture of Ibuprofen and Caffeine Attenuate the Solubility of Ibuprofen? Comparative Study for the Xanthine Derivatives to Recognize Their Intermolecular Interactions Using Fourier-Transform Infrared (FTIR) Spectra, Differential Scanning Calorimetry (DSC), and X-ray Powder Diffractometry (XRPD).

Molecular interactions between active pharmaceutical ingredients (APIs) and xanthine (XAT) derivatives were analyzed using singular value decomposition (SVD). XAT derivatives were mixed with equimolar amounts of ibuprofen (IBP) and diclofenac (DCF), and their dissolution behaviors were measured using high-performance liquid chromatography. The solubility of IBP decreased in mixtures with caffeine (CFN) and theophylline (TPH), whereas that of DCF increased in mixtures with CFN and TPH. No significant differences were observed between the mixtures of theobromine (TBR) or XAT with IBP and DCF. Mixtures with various molar ratios were analyzed using differential scanning calorimetry, X-ray powder diffraction, and Fourier-transform infrared spectroscopy to further explore these interactions. The results were subjected to SVD. This analysis provides valuable insights into the differences in interaction strength and predicted interaction sites between XAT derivatives and APIs based on the combinations that form mixtures. The results also showed the impact of the XAT derivatives on the dissolution behavior of IBP and DCF. Although IBP and DCF were found to form intermolecular interactions with CFN and TPH, these effects resulted in a reduction of the solubility of IBP and an increase in the solubility of DCF. The current approach has the potential to predict various interactions that may occur in different combinations, thereby contributing to a better understanding of the impact of health supplements on pharmaceuticals.

Reactive Extrusion Printing of Zeolitic Imidazolate Framework Films.

An outstanding challenge for the field of metal-organic frameworks (MOFs) is structuring to form forms with greater useability. Reactive extrusion printing (REP) is a technique for the direct formation of films from their molecular components on-demand and on-location. Here we apply REP for the first time to zeolitic imidazolate frameworks (ZIFs) and study the interplay of solvent and molarity ratio on the phase distribution between ZIF-8 and ZIF-L in reactive printed films. Our results show that REP controllably directs phase formation between ZIF-L and ZIF-8 and that REP also gives control over crystal size and that high-quality ZIF-8 films, in particular, are produced in low-dispersity interconnected nanoparticulate form. Importantly, we show that REP is responsive to established surface-functionalization techniques to control important printing parameters of line width and thickness. This work expands the repertoire of REP to the important class of ZIFs.

Class II (three-layer system) phenomenological model based on limiting current density and dynamic chelation chemistry for separation of rare earth elements using electrodialysis

This paper presents an in-depth investigation into the optimization of rare earth element (REE) separation through electrodialysis, leveraging a newly developed Class II phenomenological model. This study explores the pivotal roles of the HEDTA/Nd molar ratio and pH of feed solution on enhancing the separation efficiency of neodymium (Nd) and praseodymium (Pr) from lanthanum (La) and cerium (Ce). By integrating expanded Nernst-Planck equations and the concept of limiting current density, the model offers a sophisticated understanding of ion transport dynamics and the impacts of concentration polarization. Experimental validation confirms the model’s predictive accuracy, demonstrating its practical applicability for industrial-scale operations. The research delineates how operational parameters such as chelating agent concentration and pH critically influence the purity and yield of separated REEs. The dynamic nature of chelation chemistry is also examined, highlighting its evolution during the electrodialysis process and its effect on the system’s overall performance. Key findings illustrate that lower HEDTA/Nd molar ratios significantly enhance the purity of Nd + Pr by minimizing the chelation of La and Ce, thus facilitating their migration to the concentrate compartment. Conversely, higher ratios maximize yield by retaining more Nd + Pr in the feed compartment. This dual approach allows for optimized separation based on specific industrial requirements. The outcomes of this study not only advance the field of REE separation but also provide a framework for further research into more efficient and sustainable extraction methods. The developed model and its validation represent a step forward in the practical application of electrodialysis in REE processing, offering substantial benefits for the critical materials sector.

Bioinspired Self-Growing Layered Hydrogel Enabled by Catechol Chemistry-Mediated Interfacial Catalytic System.

Tissue-inspired layered structural hydrogel has attracted increasing attention in artificial muscle, wound healing, wearable electronics, and soft robots. Despite numerous efforts being devoted to developing various layered hydrogels, the rapid and efficient preparation of layered hydrogels remains challenging. Herein, inspired by the self-growth concept of living organisms, an interfacial catalytic self-growth strategy based on catechol chemistry-mediated self-catalytic system of preparing layered hydrogels is demonstrated. Typically, the tannic acid-metal ion (e.g., TA-Fe3+) complex embedded in the hydrogel substrate would catalytically trigger rapid solid-liquid interfacial polymerization to grow the hydrogel layer without bulk solution polymerization. The self-growth process can be finely controlled by changing the growth time, the molar ratio of Fe3+/TA, and so on. The strategy is applicable to prepare various layered hydrogels as well as complex layered hydrogel patterns, allowing the customization of the physicochemical properties of the hydrogel. In addition, the self-adhesive layered hydrogel was prepared and can be utilized as a wearable strain sensor to monitor physiological activities and human motions. The demonstrated interfacial catalytic self-growth strategy will provide a route to design and fabricate layered hydrogel materials.

Syntaxin-6 delays prion protein fibril formation and prolongs presence of toxic aggregation intermediates.

Prions replicate via the autocatalytic conversion of cellular prion protein (PrPC) into fibrillar assemblies of misfolded PrP. While this process has been extensively studied in vivo and in vitro, non-physiological reaction conditions of fibril formation in vitro have precluded the identification and mechanistic analysis of cellular proteins, which may alter PrP self-assembly and prion replication. Here, we have developed a fibril formation assay for recombinant murine and human PrP (23-231) under near-native conditions (NAA) to study the effect of cellular proteins, which may be risk factors or potential therapeutic targets in prion disease. Genetic screening suggests that variants that increase syntaxin-6 expression in the brain (gene: STX6) are risk factors for sporadic Creutzfeldt-Jakob disease (CJD). Analysis of the protein in NAA revealed, counterintuitively, that syntaxin-6 is a potent inhibitor of PrP fibril formation. It significantly delayed the lag phase of fibril formation at highly sub-stoichiometric molar ratios. However, when assessing toxicity of different aggregation time points to primary neurons, syntaxin-6 prolonged the presence of neurotoxic PrP species. Electron microscopy and super-resolution fluorescence microscopy revealed that, instead of highly ordered fibrils, in the presence of syntaxin-6 PrP formed less-ordered aggregates containing syntaxin-6. These data strongly suggest that the protein can directly alter the initial phase of PrP self-assembly and, uniquely, can act as an 'anti-chaperone', which promotes toxic aggregation intermediates by inhibiting fibril formation.

Study on the Pyrolysis and Incineration of Lewisite by Thermodynamic Equilibrium Calculation

AbstractLewisite is a representative chemical warfare agent that contains arsenic. Thermal decomposition is an essential method for Lewisite destruction, and appropriate destruction conditions can enhance the environmental friendliness of this method by minimizing the hazards of destruction products. In this study, the variation of Lewisite during pyrolysis and incineration was calculated, with particular emphasis on the evolution behaviors of arsenic and chloride with temperature, pressure, and molar ratio. The main products identified during pyrolysis were HCl(g), C, As, and AsCl3(g). Under anoxic conditions, AsCl3(g) and As were the dominant species. In oxygen‐enriched conditions, arsenic existed primarily as AsCl3(g), As2O5, As2O4, and AsOCl. Below 600 °C, arsenic predominantly existed in high valence forms such as As2O5. Above 600 °C, the binding capacity of chlorine and arsenic was stronger than that of oxygen, resulting in an AsCl3(g) molar fraction exceeding 75 % at 1200 °C. The primary chlorides in oxygen‐enriched conditions were Cl2(g), HCl(g), AsCl3(g), and Cl(g). Lower incineration temperatures (around 500 °C), sufficient oxygen conditions (molar ratio above 4 : 1), and positive pressures were conducive to reducing the toxicity of destruction products. The results are in good agreement with the experimental data.

ZnO/TiO2 photocatalytic nanocomposite for dye and bacteria removal in wastewater

Abstract The remediation of pollution from textile dyes poses a significant challenge. Recently, photocatalytic nanomaterials derived from semiconductor oxides have garnered attention to address this issue. This study focuses on the synthesis of ZnO/TiO2 nanocomposites with various Zn(II):Ti(IV) molar ratios via the sol-gel method for textile wastewater treatment. The properties of these materials are thoroughly characterized using a suite of analytical techniques, including transmission electron microscopy (TEM), X-ray diffraction (XRD) analysis, X-ray fluorescence (XRF) spectroscopy, Brunauer–Emmett–Teller (BET) surface area analysis, and UV-Vis spectroscopy. Analysis via XRD and XRF confirms the formation of a ZnO/TiO2 heterostructure, while TEM imaging reveals a quasi-spherical morphology with slight agglomeration. Notably, the ZnO/TiO2 nanocomposite with a Zn(II):Ti(IV) molar ratio of 1:5 demonstrates the largest BET surface area (91.345 m2g-1) and the narrowest band gap (Eg = 3.06 eV) as compared to other synthesized compositions. The impact of precursor ratios on photocatalytic activity is assessed through the measurement of methylene blue dye discoloration under sunlight irradiation. Additionally, the antibacterial efficacy against Salmonella typhi and Staphylococcus aureuswas quantitatively evaluated for the ZnO/TiO2 nanocomposites, suggesting potential applications in the treatment of pollutants present in textile wastewater.

Sulfide-enhanced carboxymethyl cellulose stabilised nano zero-valent iron for chromium(VI) mitigation in water: Evidence from batch and column studies

The primary source of chromium pollution in water is industrial operations such as electroplating, leather tanning, and textile manufacture, which use chromium for its ability to resist corrosion. Hexavalent chromium (Cr(VI)), the most detrimental variant, presents significant health hazards, such as cancer. It is crucial to effectively manage and decrease chromium levels to protect human and environmental health, especially in industrial regions where its presence in water is a persistent issue. This work examined the removal of Cr(VI) by sulfidated carboxymethyl cellulose stabilised nano zerovalent iron (S-CMC-nZVI). S-CMC-nZVI exhibited outstanding uniformity and corrosion resistance. Batch experiments revealed that several factors influenced the degree to which S-CMC-nZVI particles eradicated Cr(VI). The parameters to be considered included pH, initial Cr(VI) concentration, coexisting ions, and S/Fe molar ratio. When the sulfur to iron molar ratio was increased from 0 to 0.4, Cr(VI) removal efficiency increased from 73.89 % to 99 %. A pseudo-second-order kinetic model described Cr(VI) removal, and the Langmuir isotherm model determined the highest adsorptive capacity (311.02 mg/g). The presence of bicarbonate and nitrate anions have minimal inhibitory effects on removal of Cr(VI). Experiments on polluted groundwater showed that synthesised nanoparticles may remove Cr(VI) over a long time. Column investigations showed that increasing S-CMC-NZVI concentration increased Cr(VI) removal. The Adsorption, reduction and coprecipitation were major processes responsible for Cr(VI) removal. The research demonstrates that S-CMC-nZVI is a promising material for the in-situ remediation of Cr(VI)-contaminated groundwater.

A novel route to synthesize B6O powder via reaction between CaB6 and B2O3

AbstractA novel approach was applied to synthesize B6O using CaB6 and B2O3 powders as reactants. CaB6 and B2O3 were reacted to generate B6O and CaB2O4 at 1573 K, and the by‐product CaB2O4 was removed by acid leaching. It was found that the samples prepared in this work were oxygen deficient (B6Ox, x ≈ .76–.77). The optimal molar ratio of CaB6 to B2O3 was determined to be 3:5, and excess B2O3 could not lead to a change in the value of oxygen occupancy. Scanning electron microscope images showed that regular holes similar to the morphologies of CaB6 particles were exhibited in the final samples, which could be explained by the diffusion of CaB6 during the reaction process.

Valpalf®: A New Nutraceutical Formulation Containing Bovine Lactoferrin That Exhibits Potentiated Biological Activity

As a nutraceutical, bovine lactoferrin (bLf), an iron-binding glycoprotein involved in innate immunity, is gaining elevated attention for its ability to exert pleiotropic functions and to be exceptionally tolerated even at high dosages. Some of bLf’s activities, including its anti-inflammatory and antioxidant, are tightly linked to its ability to both chelate iron and enter inside the cell nucleus. Here, we present data about Valpalf®, a new formulation containing bLf, sodium citrate, and sodium bicarbonate at a molar ratio of 10−3. In the present study, Valpalf® exhibits superior iron-binding capacity, resistance to tryptic digestion, and a greater capacity to accumulate into the nucleus over time when compared to the native bLf alone. In agreement, Valpalf® effectively reduces interleukin(IL)-6 levels in lipopolysaccharide-stimulated macrophages and modulates the expression of antioxidant enzymes, such as superoxide dismutase 1 and 2, in phorbol-12-myristate-13-acetate-stimulated monocytes. Of note, this potentiated bioactivity was corroborated in a retrospective study on the treatment of anemia of inflammation in hereditary thrombophilic pregnant and non-pregnant women, demonstrating that Valpalf® improves hematological parameters and reduces serum IL-6 levels to a higher extent than bLf alone.

Acidic deep eutectic solvent as a greener medium for highly efficient extraction of anthocyanins from blackberry fruit: Optimization, stability and purification with two-aqueous phase method

Natural deep eutectic solvents (NADESs) are a sustainable and green solution for the recovery of food ingredients such as pigments. In this work, the extraction conditions to obtain the maximum anthocyanins from blackberry fruit were investigated using NADES composed of choline chloride-acetic acid (CHAC) as the green solvent. The central composite design was used conseidering molar ratio, water content, solvent ratio and extraction time as independent variables and total anthocyanin content (TAC), cyanidin-3-glucoside, cyanidin-3-rutinoside, pelargonidin-3-glucoside and cyanidin chloride as responses. The results showed that the independent variables significantly affected the responses. The optimum conditions for CHAC were 1:3.5 M, 40 %, 30 g and 15 min for molar ratio, water content, solvent ratio and extraction time, respectively. Under these conditions, the experimental responses were 131.54 ± 7.89 mg CGE/100 g, 1208.08 ± 13.76 mg/kg, 163.43 ± 1.72 mg/kg, 53.78 ± 1.37 mg/kg and 91.98 ± 0.62 mg/kg for TAC, cyanidin-3-glucoside, cyanidin-3-rutinoside, pelargonidin-3-glucoside and cyanidin chloride, respectively. The pH, viscosity and electric conductivity of CHAC were determined as 1.24 ± 0.03, 1.21 ± 0.17 and 7.50 ± 0.55 mPa and 4675.33 ± 57.74 µS.cm−1, respectively. After storing the NADES extract for 28 days in the dark, cyanidin-3-glucoside, cyanidin-3-rutinoside, pelargonidin-3-glucoside and cyanidin chloride remained 71.57 ± 0.64 %, 75.00 ± 0.26 %, 33.42 ± 0.41 % and 71.45 ± 0.21 %, respectively. Over the 28-day exposure of the NADES extract to light, the cyanidin-3-glucoside, cyanidin-3-rutinoside, pelargonidin-3-glucoside and cyanidin chloride remained 19.09 ± 0.10 %, 34.89 ± 2.28, 13.28 ± 0.25 and 30.97 ± 1.10, respectively. The application of the aqueous two-phase system resulted in the preliminary purification of the NADES extract, providing the highest purity in the top phase for cyanidin-3-glucoside (68.85 ± 1.05 %). The findings revealed that CHAC is a promising green medium for the industrial extraction of anthocyanins, and the aqueous two-phase is suitable for the purification of the anthocyanin-rich extract obtained with NADES.

Effect of combinations of 3,4‐dihydroxyphenylacetic acid and its esters on the oxidative stability of fish oil–containing trace water

AbstractThe current study aims to comprehend the effect of the various combinations of 3,4‐dihydroxyphenylacetic acid (3,4‐DHPA) and its esters in varying molar ratios on retarding oxidation in bulk refined fish oil in the presence of 0.3% w/w water. All the esters and 3,4‐DHPA exhibited better performance than the synthetic antioxidant butylated hydroxytoluene. In the presence of trace water, the parent compound was found to have a synergistic effect with hexyl ester when used at a molar ratio of 2:1, respectively, exhibiting a higher percent reduction among all the esters and their combinations. The study also showed that the presence of extraneous water can significantly accelerate the oxidation (twofold) in a bulk fish oil system. This suggests that the microenvironment of the oil is altered when water is present and that association colloids play a key role in enhancing the rate of oxidation. Thus, while designing a competent mixture of antioxidants, the specific site of oxidation involved and the surface‐active components should be taken into consideration to efficiently retard oxidation.Practical Applications: Analyzing the impact of trace amounts of water on the efficiency of natural antioxidants, including 3,4‐DHPA and its lipophilic esters, helps to comprehend the required optimal antioxidant concentrations for such a dynamic bulk oil system. The study finds application in controlling oxidation in PUFA‐rich oils containing surface‐active minor components that can accelerate oxidation. The results of the study show that 3,4‐DHPA and its esters could be a potential replacement for the synthetic antioxidant BHT in all aspects.

Effect of synthesis conditions on the properties of 13X zeolites for CO2 adsorption

ABSTRACT The 13X zeolites were successfully synthesized from sodium silicate and sodium aluminate via hydrothermal treatment, and applied to the adsorption of carbon dioxide (CO2). The properties of the 13X zeolites were characterized and tested by powder X-ray diffraction (XRD), N2-physisorption measurements, CO2-temperature programmed desorption (CO2-TPD) and CO2 adsorption measurements. The results demonstrate that H2O/Na2O, Na2O/SiO2, and SiO2/Al2O3 molar ratios have an important influence on the adsorption performance of CO2 because of their different physicochemical properties. The pure 13X zeolite can be obtained with the optimal H2O/Na2O, Na2O/SiO2 and SiO2/Al2O3 molar ratios of 60, 4 and 3 in the preparation process, respectively. The 13X sample prepared with suitable synthesis conditions possesses the highest crystallinity, the maximum values of specific surface area (720.8 m2/g) and pore volume (0.458 cm3/g) and moderate strength of the interaction between 13X and CO2, thus presenting the highest adsorption capacity of CO2 (118.3 mg/g).

Nerve-Agent Selective Chemiresistors Fabricated by Oxime Decorated Polypyrrole Layer on Cellulose Paper

In continuous research of detecting highly toxic chemical warfare agents to ensure preparedness for the future battlefield, flexible and wearable sensor platforms with high sensitivity are still demanding. Herein we demonstrate a facile fabrication of polypyrrole-based chemiresistors on cellulose paper for the detection of nerve gas simulants. In order to optimize electrical properties of sensor platform, conducting polymer made of polypyrrole were first synthesized on flexible cellulose paper and interdigitated electrodes were formed thereon. Following confirmation of polypyrrole and/or oxime moiety through FT-IR analyses, electrical characteristics were measured in the various ratio of monomers between simple pyrrole and oxime-modified one. Typically for the optimized chemiresistor(2:8 molar ratio of simple pyrrole and oxime-modified one), eleven species of chemical warfare agents were examined and enhanced conductivity(10<sup>4</sup>~10<sup>5</sup> order) was observed for three simulants(diethyl cyanophosphonate, diisopropyl fluorophosphonate and diethyl chlorophosphonate), which was mainly attributed to intermolecular hydrogen bonding, while no significant responses was recorded against sixteen common volatile organic chemicals.

Molecular Composition of Humic Acids and Soil Organic Matter Stabilization Rate of the First Arctic Carbon Measurement Supersite “Seven Larches”

In the framework of the implementation of the all-Russian climatic project “Carbon measurement test sites”, reference soils of “Seven Larches” carbon supersite, which is a benchmark and the only monitoring site in the Artistic latitudes, were investigated. The morphological structure of representative soils was specified, and it was found that soils are classified as Cryosols of different types (Histic, Stagnic or Gleyic). The basic physico-chemical characteristics of the soils were studied. By means of elemental analysis and 13C NMR spectroscopy, the composition and molecular structure of humic acids from organic and mineral soil horizons were studied. The surface (organic) soil horizons are characterized by high values of H:C molar ratios (1.2–1.3), which indicates a lower degree of the molecular structure aromaticity of humic acids from organic soil horizons. Analysis of the molecular structure of humic acids by 13C NMR spectroscopy showed that humic acids of the studied soils are characterized by the predominance of non-substituted aliphatic (0–47 ppm) and aromatic (108–164 ppm) fragments. Mineral soil horizons are characterized by higher stabilization of organic matter (with lower SOC content—0.5–0.9%) and higher hydrophobicity of humic acid molecules. Comparison of the obtained results with previously published data on the structural and elemental composition of humic acids isolated from soils of similar genesis and geographical location did not reveal any significant differences between the data obtained by us and previously published data. Thus, for “Seven Larches” carbon supersite “reference” parameters of elemental composition of humic acids, their molecular composition and degree of stabilization of soil organic matter were identified.

Delayed ammonia release of ammonia borane hydrolysis by citric acid

Ammonia borane (AB), with high hydrogen density and stability under ambient conditions, readily releases hydrogen via catalyzed hydrolysis. However, ammonia, a byproduct of hydrogen release, limits its utilization. Citric acid, a safe and cost-effective acid catalyst, for the acid catalyst of AB hydrolysis was investigated in this study to mitigate ammonia emissions while enhancing hydrogen release. Maximal hydrogen release (3 eq.H2) and ammonia emission suppression (<0.5 ppm) were achieved using a 2-mol/L AB aqueous solution adding into citric acid powder (molar ratio of AB: citric acid = 1:1). In contrast, the amount of hydrogen release at other concentrations and/or using the mixing method was below 2.7 mol/mol AB within several hours. Ammonia re-released even after hydrogen release in the case of high AB concentration (e.g. >4 mol/L AB aqueous solution with citric acid powder (molar ratio of AB: citric acid = 1:1)) in the solution because of formation of borate ester (1:2 borate–diol molar ratio) via mono-ammonium citrate (a borate-ester precursor), which was revealed by the solution NMR. These results reveal a cost-effective and simple on-way method for hydrogen release with suppressed impurities. Furthermore, understanding impurity generation mechanisms can contribute to utilizing AB-derived hydrogen.

Effect of synthesis conditions on mechanical properties and microstructure of coal gasification slag-based geopolymer

Coal gasification slag (CGS) is an industrial solid waste produced during coal gasification, and it is mostly deposited on the land at present, resulting in serious environmental pollution. In order to promote its resource utilization, geopolymer was synthesized from CGS in this study. The influence of important factors containing the water-solid ratio, alkali activator dosage, activator modulus and curing temperature on the mechanical properties and microstructure of geopolymers were investigated. Micromorphology, chemical composition, mineralogy and chemical bonding of the geopolymer were assessed by scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR), respectively. Results indicate that the compressive strength of geopolymer can be improved by reducing the amount of initial water. The optimal mechanical properties of geopolymer are obtained when the alkali activator dosage is 25 % and the activator modulus is 1. The moderate temperature (e.g. 60 °C) is the most favorable to the compressive strength development of geopolymer. Under these optimal conditions, the 90 days compressive strength of the CGS-based geopolymer (CGSG) can reach 58.3 MPa. The Si/Al molar ratio of the geopolymer gels is between 2.0 and 3.1, and the Al/Na molar ratio is around 1.0. These results can provide a reference for recycling of the CGS and production of eco-friendly building materials.