H2O System Research Articles

Phase equilibria of ternary systems: LiCl–MClx (M = Na+, Mg2+, Sr2+)–H2O systems at 1 bar and volume properties investigating from 1 to 1000 bar (T = 298.2 K)

There are abundant lithium resources in seawater and brines. The thermodynamic phase equilibria of salt-water systems containing lithium have significant advantages to separation lithium from brines. Consequently, measurement and prediction of phase equilibria of LiCl–MClx (M = Na+, Mg2+, Sr2+)–H2O ternary systems are investigated at 298.2 K and 1 bar. The phase equilibria are determined using the isothermal dissolution equilibrium method and the solubilities of salts in the ternary systems are predicted using the Pitzer model. The predicted solubilities agree well with experimental data at 298.2 K and 1 bar.Then, the changes of volume properties (ΔV¯dis0) and compressibility (Δκ¯dis0) of three ternary solutions at high pressure of 1–1000 bars were obtained in this work. The solubility product constants Ksp of salts at high pressure are calculated in detail. The thermodynamic prediction model of the phase equilibria is developed at high pressure of 1–1000 bar accordingly. The predicted phase equilibria at high pressure of 1–1000 bar are discussed and compared detailly.

Growth, structure and optical properties of Rb2CоCl4·2H2O crystals

Phase equilibria in the RbCl–CoCl2·2H2O–H2O system were investigated, single crystals of double rubidium–cobalt chloride dihydrate were obtained, and its structure and optical properties were studied. The regions of crystallization of compounds in the three-component system under study were delimited. Rb2CoCl4·2H2O crystals were grown by controlled decrease in the temperature of a saturated aqueous solution. Using X-ray diffraction analysis, the crystal lattice parameters of Rb2CoCl4·2H2O were obtained and the structure of the crystals was refined. The spectral characteristics of the obtained crystals and the corresponding aqueous solution were studied in the λ range 200–800 nm.

Mixed quantum/classical theory for rotationally inelastic scattering of identical collision partners revised.

Mixed quantum/classical theory (MQCT) for the treatment of rotationally inelastic transitions during collisions of two identical molecules, described either as indistinguishable or distinguishable partners, is reviewed. The treatment of two molecules as indistinguishable includes symmetrization of rotational wavefunctions, introduces exchange parity, and leads to state-to-state transition matrix elements different from those in the straightforward treatment of molecules as distinguishable. Moreover, the treatment of collision partners as indistinguishable is eight times faster. Numerical results presented herein for H2 + H2, CO + CO and H2O + H2O systems indicate good agreement of MQCT calculations with full-quantum calculations from the literature and show that an a posteriori correction, applied after treatment of the collision partners as distinguishable, generally produces good results that agree well with the rigorous treatment of collision partners as indistinguishable. This correction for the cross section includes either multiplication by 2 or a summation over physically indistinguishable processes, depending on the transition type. After this correction, the results of the two treatments agree within 5% for most but may reach 10-20% for some transitions. At low collision energies dominated by scattering resonances, these differences can be larger, but they tend to decrease as collision energy is increased. It is also shown that if the system is artificially forced to follow the same collision path in the indistinguishable and distinguishable treatments, then all differences between the results of the two treatments disappear. This interesting finding gives new insight into the collision process and indicates that the indistinguishability of identical collision partners comes into play through the collision path itself, rather than through matrix elements of inelastic transitions.

Hydrothermal precipitation of copper from leaching solutions of metallurgical dusts

In this work, we aim to establish the main regularities of hydrothermal precipitation of copper from the previously unstudied sulfuric-nitric acid and sulfate solutions of atmospheric and autoclave processing of metallurgical dusts. Pyrite was used as a sulfidizer. The elemental composition of the products was determined by X-ray fluorescence, inductively coupled plasma atomic emission spectrometry, and atomic absorption analysis. It was found that copper precipitation by the proposed technology enables its recovery at a level of more than 95%. For sulfate solutions with a high arsenic concentration, a two-stage scheme of oxidation-hydrothermal treatment with the following parameters was proposed: temperature 180°С, duration 2 h, oxygen consumption 0.026 dm3/g pyrite (for the 1st stage), and 200°С and 2 h (for the 2nd stage). Extraction in the cake amounted to 95.4% of copper (in the form of Cu2S) and 91.4% of arsenic (in the form of FeAsO4), which allowed further separation of these metals by flotation. An autoclave treatment of a Cu–Zn–Fe–As–NO3 solution in the presence of pyrite at 180–220°С produced the activation energy values (kJ/mol) corresponding to the kinetic regime calculated by the two methods: 64.6 by the conventional method and 60.5 by the shrinking core model. The kinetic parameters of CuSO4–H2SO4–FeS2–H2O and CuNO3–H2SO4–FeS2–H2O systems were also determined. Flotation enrichment of copper autoclave precipitation cake was shown to result in a high degree of Cu and As separation, with the recovery amounting to Cu ˃ 95% and As ˂ 5%. Precious metals contained in pyrite are transferred to a flotation concentrate by 92.7% (Au) and 96.5% (Ag). The composition of the resulting flotation concentrate comprised (%): 12 Cu; 37 Fe; 38 S; 13 other elements. It is shown that, in order to obtain a product with the required content of copper, flotation concentrate should be separated into pyrite and copper concentrates followed by an additional flotation of primary copper concentrate in an alkaline medium in the presence of lime. Hence, our study has established the main regularities of hydrothermal precipitation of copper from the sulfuric-nitric acid and sulfate solutions of atmospheric and autoclave processing of metallurgical dusts.

Efficient synthesis of highly hydrophobic lignin nanoparticles and their application as nano fillers for multifunctional composite membranes

Controlling the hydrophobic behaviors of lignin nanoparticles (LNPs) is crucial and advantageous for their application as film Nano Fillers, yet it poses a significant challenge. Herein, we successfully developed a novel method for the preparation of LNPs with highly hydrophobic behaviors using ternary deep eutectic solution (DES)-H2O systems. The resulting LNPs exhibit a significantly reduced content of hydrophilic groups on their outer surface, leading to a zeta potential value of only −4.9 mV, and up to 140.0° of water contact angle (WCA). Afterwards, a “Dissolution-Restructuration” mechanism was proposed to explain the formation of the prepared LNPs. Firstly, DES demonstrates superior H-bonding capabilities, facilitating the complete disruption of inter- and intramolecular H-bonding in lignin, and resulting in the formation of a highly homogenized lignin network. Subsequently, the DES system undergoes compromise after adding water, triggering the reformation of both inter- and intramolecular H-bonding and π-π interactions. Consequently, lignin orderly self-assembles into LNPs with highly hydrophobic characteristics. Especially, using the as-prepared LNPs as Nano fillers, a series of LNPs-containing polyvinyl alcohol (PVA) films were successfully fabricated, exhibiting exceptional hydrophobic behaviors (with contact angles reaching up to 124.0°). Furthermore, the mechanical strength, UV-shielding capabilities, and biodegradability of the PVA films are significantly enhanced. This study introduces a sustainable and efficient approach for the synthesis of hydrophobic LNPs, thereby facilitating the broadening of applications for lignin-based functional composite film materials.

Fluid evolution and genesis of the Shipenggou gold deposit in Central Jilin Province, China: Constraints from C–H–O and in–situ sulphur isotopes of pyrite and fluid inclusions

The origin and evolution of the Shipenggou gold deposit in the Shipenggou–Jiapigou–Jinchengdong (SJJ) gold belt in Jilin Province, Northeast China, remain poorly understood. In this study, fluid inclusion and C–H–O–S isotopes from the Shipenggou deposit were investigated to clarify the fluid evolution and mineralisation process. The gold mineralisation is hosted in the biotite plagiogneiss of the Archaean Sandaogou Formation and is dominated by gold–bearing quartz veins. The orebodies are controlled by NNE– and NEE–striking brittle–ductile structures. Four stages of mineralisation have been identified: (I) milky quartz–minor pyrite, (II) quartz–pyrite–minor gold, (III) gold–quartz–polymetallic sulphide, and (IV) quartz–carbonate. Fluid inclusions were identified as four types: aqueous (VL–type), CO2–bearing (CL–type), CO2–rich (LC–type), and carbonic (PC–type). VL–, CL–, LC–, and PC–type FIs were developed within quartz from Stages I–II. Stage III quartz contains both CL– and VL–type FIs. Only VL–type FIs were observed in calcite from Stage IV. The total homogenisation temperatures (Tht) of FIs in Stages I, II, III, and IV are of 281.5–324.8, 215.5–269.1, 151.2–198.3, and 125.4–149.5 °C with salinities of 2.8–13.2, 2.8–9.6, 3.2–8.4, and 3.0–5.9 wt% NaCl eqv. Laser Raman spectroscopy analysis indicated the CL– and PC–type FIs from Stages I and II contain CO2 and minor quantities of CH4. The ore–forming fluids have developed from a medium temperature, low–medium salinity immiscible NaCl–H2O–CO2 ± CH4 system to a low temperature, low salinity homogeneous NaCl–H2O system. The HO isotopic compositions indicate that the initial ore–forming fluids were mantle–derived magmatic water. Subsequently, the ore–forming fluids were gradually joined by meteoric water. δ13C values indicate C in the fluids have originated from organic matter. Organic matter may have originated from the mantle, which mixed crust materials influenced by the subduction of the Palaeo–Pacific slab. In–situ, S isotope data of pyrite indicate that the origin of sulphur at the Shipenggou deposit is the mantle containing a crust component. Based on the above analysis results, the Shipenggou gold deposit is a mesothermal magma-hydrothermal vein–type gold deposit.

Investigation of Metal–H2O Systems at Elevated Temperatures: Part I. Development of a Solubility Apparatus Specialized for Super-Ambient Conditions

Abstract Metals used in aqueous environments where high temperatures and pressures are present are susceptible to corrosion. This is the case for nuclear power plants, especially CANDUTM reactors, where the liquid water systems can reach over 300 °C at pressures well above 101.325 kPa (1 atm). In such situations, failure to control corrosion has economic and safety consequences. To extend corrosion modeling tools, such as Pourbaix diagrams, to harsh aqueous conditions, there is a need for experimental thermochemical data performed at elevated temperatures. This is particularly true for metal and alloy systems where such information is unavailable or unreliable. A relatively simple approach to obtaining temperature dependent thermodynamic properties is the investigation of solid–liquid phase, or solubility, equilibria. However, this requires specially designed instrumentation that can withstand harsh temperatures and extreme pH conditions, while providing accurate data. In this work, an apparatus developed for super-ambient highly acidic and alkaline solubility experiments is presented. Solubility measurements were made in the zinc oxide system, which has been extensively studied. Using these equilibrium data and comparing to the literature, allowed the instrumentation and analysis process to be validated. In situ pH measurements using a constant volume, batch reactor system are described along with a brief presentation of the ZnO dissolution equilibria results at 85 °C (358.15 K).

Utilizing environment-friendly eugenol as a diluent with trioctylamine for the reactive extraction of aqueous levulinic acid

This paper focuses on the reactive extraction of levulinic acid (LA) from aqueous solution by reactive extraction. This goal is achieved using eugenol, a green alternative in the industry, as a solvent in the liquid-liquid equilibrium (LLE) measurements for the ternary system of LA + Eugenol + H2O and quaternary systems of LA + Eugenol/ Methanol (MeOH) + H2O + Tri-n-octylamine (TOA) at T = 293.15 K. Additionally, the distribution coefficients (KD) were calculated for LA using the two diluents. Also, the ability of different diluents with TOA, in the extraction of LA were compared. The distribution coefficient of eugenol with TOA (KD = 9.44) is compared with other organic diluents which indicated that eugenol is a suitable option. MeOH, being the shortest chain alcohol, also turned out to be a diluent that could be utilized for extraction of LA with TOA. Furthermore, the Non-Random Two-Liquid (NRTL) excess Gibbs energy model was applied to correlate the measured phase equilibria. The obtained parameters were further validated using a decanter model.

Simultaneous precipitation removal of fluoride ion and chloride ion from smelting waste acid using renewable remover

Purification and reuse is a potential method of smelting waste acid disposal. High concentrations of fluoride and chloride in waste acid are harmful impurity and must be removed. Previous studies have shown that fluoride removal with rare earth and chloride removal with bismuth have similar cyclic process of "precipitation removal-agent regeneration" and similar reaction conditions. In this paper, a method of simultaneous precipitation removal of F− and Cl− from waste acid using La(OH)3 and Bi2O3 as a mixed remover was proposed, and the mixed remover is regenerated by sodium hydroxide solution for the recycling of the remover. Thermodynamic analysis of La3+-Bi3+-F−-Cl−-H2O system verified the feasibility of simultaneous removal. The experimental results showed that under the optimum reaction conditions, the removal efficiencies of F− and Cl− were 93.67 % and 96.47 %, respectively, and the concentrations of F− and Cl− in the solution after removal were 66.70 mg/L and 71.10 mg/L, respectively. Under the optimum conditions, the regeneration efficiencies of La(OH)3 and Bi2O3 were 96.80 % and 96.95 %, respectively. The proposed process has the advantages of no waste output, short process, and low energy consumption and provides an environmentally friendly method of removing fluoride and chloride from waste acid.

Coupling rare-earth metal introduction and alkali oxide addition to achieve efficient regeneration of LiBH4 by reacting hydrous LiBO2 with Al

The lack of cost-effective regeneration techniques for LiBH4 limits its large-scale applications for supplying hydrogen via hydrolysis. Now, we report a facile method to regenerate LiBH4 by ball milling its real hydrolytic byproduct (LiBO2·xH2O) with cheap Al based reducing agents, instead of traditional Mg. Effective strategies are developed to promote the formation of LiBH4 by introducing Li2O to enable the dense Al2O3 to convert into LiAlO2 on Al surface and break up passivation layers, and by partially replacing Al with Al-RE alloy to improve grinding and contacting efficiency of raw materials and facilitate the conversion from initial H+ in LiBO2·2H2O to final H¯ in LiBH4. A yield of 10.4 % can be obtained for a relatively short ball milling time (10 h) for the Al-Al2Ce-Li2O-LiBO2·2H2O system. Another advantage of this method is that the utilization of H+ source in LiBO2·2H2O improves energy efficiency and reduces the cost. This work broadens the species of reducing agents for borohydride regeneration and enriches its regeneration methods.

The precipitation mechanisms of scheelite from CO2-rich hydrothermal fluids: Insight from thermodynamic modeling

Scheelite and wolframite are two main tungsten-bearing ore minerals in tungsten deposits. Compared to wolframite formed mostly by NaCl–H2O fluids, scheelite in many but not all tungsten deposits is associated with CO2–bearing hydrothermal fluids, but its precipitation mechanisms from these fluids are poorly understood. The replacement of wolframite by scheelite is common among tungsten deposits where these two tungstates coexist, but how CO2, as the pH-buffering agent, affects their replacement remains unclear. To answer these questions, we first tested the pH-buffering effect of CO2 by comparing available experimental pH values of H2O–CO2±NaCl solutions at 200–280 °C and the corresponding thermodynamic modeling results. The mean absolute errors between the calculated and experimental pH values are 0.14 log units in H2O–CO2 solutions and 0.13 log units in H2O–CO2–NaCl solutions, indicating that the calculated acitivities of H+ in CO2-bearing solutions are reliable. Then, the solubilities of scheelite, scheelite-ferberite, and scheelite-hübnerite in NaCl–H2O–CO2 systems were modeled in this study. Our modeling results suggest that scheelite solubility in CO2-rich fluids is highly dependent on fluid pressure but is insensitive to fluid temperature. A decrease in fluid pressure from lithostatic to hydrostatic levels at a depth of 3–8 km causes CO2 escape and pH rise and precipitates over 70 % of tungsten contents in fluids on average. Therefore, CO2 escape is an efficient mechanism for precipitating scheelite from CO2–rich hydrothermal fluids. The independence of scheelite solubility on temperature at high pressures and the slightly retrograde solubility at low pressures allows CO2–rich hydrothermal fluids to carry a great amount of tungsten far away from its sources. This may be one of reasons why some scheelite deposits occur at greater distances (>500 m) from the granite or extend along its strike for several kilometers. Similar to the cases in NaCl–H2O systems, two mechanisms for scheelite replacing wolframite in CO2–rich fluids are identified, a single decrease in fluid pressure or simple cooling plus an increase in the ratios of total Ca contents to total Fe (or Mn) contents in fluids.

Corrosion behavior and mechanism of Cr10Mo1 steel subjected to different corrosive ions in simulated concrete pore solution

The corrosion of pre-passivated Cr10Mo1 steels in simulated concrete pore solution of saturated Ca(OH)2 induced by different corrosive ions were investigated, namely Cl−, SO2- 4, and combination of Cl− and SO2- 4. Electrochemical methods, Pourbaix analysis of Fe–Cr–H2O system and DFT calculation were adopted to characterize corrosion behavior and reveal underlying mechanism. Results showed that while sulfate may induce corrosion at higher threshold value, the scenario of chloride alone leads to lowest corrosion potential, linear polarization resistance and highest corrosion rate, and the presence of SO2- 4 ions mitigate corrosion risk under the coexistence condition of chloride and sulfate. A two-step reaction model of competitive adsorption-catalytic corrosion was proposed based on theoretical analysis and DFT calculation results.

Separation and extraction of NH4Br and (K,NH4)2SO4 from 1-Bromooctane production wastewater by crystallization method

This work provides a method for the separation and extraction of bromine salts from bromine-containing wastewater by crystallization. Wastewater from the production of 1-Bromooctane is rich in potassium and bromine salts. This will allow for the recycling of chemical resources in this aqueous salt system. Based on the need for the process design of the new method, the solubility phase equilibrium of the quaternary K+,NH4+//SO42-,Br-–H2O system at 298.15 K and 323.15 K was investigated in this paper by using the isothermal dissolution equilibrium method, and the dry basis phase diagrams were plotted using the experimental data. And the equilibrium solid phase composition was determined by X-ray diffraction. At 298.15 K, the dry phase diagram of the quaternary system K+,NH4+//SO42-,Br-–H2O consists of three invariant points and five crystalline regions (K2SO4, (NH4)2SO4, (K,NH4)2SO4, (K,NH4)Br, (NH4,K)Br). At 323.15 K, there is one invariant point in the phase diagram of this quaternary system and three crystalline regions((K,NH4)2SO4, (K,NH4)Br, (NH4,K)Br). The (K,NH4)Br crystallization zone grows while the (NH4,K)Br crystallization zone decreases with increasing temperature, according to comparisons of the dry basis phase diagrams of this quaternary system at different temperatures. Crystallization zones of solid solution (K,NH4)2SO4 replaced the K2SO4 and (NH4)2SO4 single salt crystallization zones at the same time. The Pitzer model was used to calculate the solubility of this quaternary system at 298.15 K. The results showed that the experimental values were in good agreement with the calculated values. Based on the theoretical analysis of the dry phase diagram of the quaternary system K+,NH4+//SO42-,Br-–H2O, a process route for salt extraction using bromine-containing wastewater generated from the production of 1-Bromooctane was proposed and designed. The new process was experimentally verified to be technically feasible to obtain NH4Br with 99.01 % purity and (K,NH4)2SO4. The process has significant advantages, such as production safety, low input costs and no three-waste emissions.

Thermodynamic evaluation of the aerial and aqueous oxidation of Al – Mg, Al – Si and Al – Mg – Si system alloys at 298 K

Aluminum and magnesium are the lightest structural metals, and therefore, various alloys based on them are widely used in both, automotive and aerospace industries. However, aluminum and magnesium are very easily affected by atmospheric and aqueous corrosion, and, therefore, the alloying elements should enhance their corrosion stability. In this work, the thermodynamic analysis of phase and chemical equilibria involving aluminum and magnesium alloys doped with silicon in oxygen–containing air environments, as well as the analysis of chemical and electrochemical equilibria involving these alloys in aqueous environments is conducted. The phase and chemical equiliibria in the Al–Mg, Al–Si, Mg–Si, and Al–Mg–Si systems at 298 K are considered, and the thermodynamic activities of the components of common Al–Mg–Si system alloys are calculated. The invariant chemical equilibria in the systems Al–Mg–O, Al–Si–O, Mg–Si–O at 298 K are considered, the isothermal section of the state diagrams of these systems are plotted, and the oxidation scheme of the Al–Mg–Si system alloys in excess oxygen is proposed. The chemical and electrochemical equilibria in the Al–Mg–Si–H2O system at 298 K are considered and presented in form of the activity – pH and the potential – pH diagrams, and the oxidation of the Al–Mg–Si system alloys in aqueous environments is discussed.

Phase Equilibria in the Na+,K+//Cl–,NO$$_{3}^{ - }$$–H2O System near Boiling Temperatures. I. Modeling of Ternary Systems

Phase Equilibria in the Na+,K+//Cl–,NO$$_{3}^{ - }$$–H2O System near Boiling Temperatures. I. Modeling of Ternary Systems

Corundum-quartz metastability: the role of silicon diffusion in corundum

The synthesis of the Al2SiO5 polymorphs kyanite, sillimanite and andalusite in a pure Al2O3–SiO2–H2O (ASH) system has long been known to be impeded. In order to decipher individual aspects of the reaction: corundum + SiO2aq, which repeatedly fails to produce thermodynamically stable Al2SiO5, we conducted experiments within the stability fields of kyanite and sillimanite (500–800 ℃; 0.2–1 GPa) with the aim of forming reaction coronas on corundum. Results showed that metastable corundum + quartz assemblages form persistently in pure ASH, even in Al2SiO5 seeded experiments, despite the presence of catalyzing fluid and evidence of fast reaction kinetics. Coronas on corundum spontaneously formed when additional components (Na, K, N, and Mg) were added to the experiment. In a similar experiment with baddeleyite (ZrO2) instead of corundum in silica saturated water, a zircon corona formed readily. This implies that nucleation and growth of Al2SiO5 is obstructed under conditions of Al and Si saturation in aqueous fluid, while both corundum and quartz saturated aqueous fluid are willing participants in other reactions towards stable corona formation. Instead of Al2SiO5 precipitation, an unexpected fluid-aided silica diffusion process into corundum was documented. The latter included the formation of nanometer wide hydrous silicate layers along the basal plane of the corundum host, which enhanced the silica diffusion rate drastically, leading to silica supersaturation in the host mineral, and ultimately to precipitation of quartz inside corundum. We conclude that the natural metastable assemblage of quartz and corundum is not necessarily the result of dry or fluid absent conditions, given that the aqueous fluid in experiments does not promote Al2SiO5 formation, but rather seems to support the formation and preservation of a metastable assemblage.

Effects of adding methane on the growth and electrical properties of GaN in oxide vapor phase epitaxy

GaN grown via oxide vapor phase epitaxy (OVPE-GaN) can produce free-standing substrates with ultra-low resistivity because of the high doping concentration of oxygen. The bulk growth of OVPE-GaN is hindered by polycrystals generated during long-term growth. We have previously reported that thicker films can be grown by reducing the partial pressure of water vapor in the growth atmosphere with CH4. However, as CH4 is a dopant of carbon, a compensating acceptor, its addition may increase electrical resistance. In this study, we further investigated the effect of reducing water vapor partial pressure on polycrystals by combining Ga2O production (reaction of Ga and water vapor: a Ga–H2O system), which can reduce water vapor, with CH4 addition. However, CH4 addition to the Ga–H2O system increased polycrystal generation, possibly owing to the thermal decomposition of excess CH4. The properties of OVPE-GaN with CH4 addition were also evaluated. Although the CH4 addition resulted in high carbon doping, the carbon-doped OVPE-GaN maintained low resistivity. This is because the OVPE method involves three-dimensional growth with growth pits, and the growth pits leave behind low-resistivity high-oxygen-concentration regions. As the resistivity remains low even when CH4 is added in the OVPE method, both polycrystallization suppression and low resistivity can be achieved by selecting an appropriate CH4 flow rate.

Construction of Ni−Re Supported on Hydrotalcite‐Derived MgAl Catalysts for Promoting the Ring Hydrogenation of Furfural into Tetrahydrofurfuryl Alcohol in Water

AbstractBiomass‐derived feedstocks play a vital role in sustainable economies for renewable energy, waste management, energy security, and commercial prospects. This study focused on promoting the ring hydrogenation of furfural (FAL) into tetrahydrofurfuryl alcohol (THFA) in an aqueous solution using a potential Ni−Re‐supported hydrotalcite‐derived MgAl catalyst at different Ni : Re molar ratios. Structural analyses, such as an in situ time‐resolved X‐ray absorption near edge structure, under H2 reduction elucidated the simultaneous transformation of Re6+ and Re7+ to Re0 with the remaining highly stable Ni2+. The construction of Ni−Re on hydrotalcite‐derived MgAl catalyst resulted in the alleviated H2 reduction behavior, facilitated H2 adsorption and desorption processes, and suitable catalyst acidity detected by H2 temperature‐programmed reduction, and H2 and NH3 temperature‐programmed desorption experiments, respectively. Under optimized conditions, a maximum THFA yield of 78 % with a complete FAL conversion was attained using Ni1Re0.16/MgO−Al2O3 catalyst at a reaction temperature of 140 °C, H2 pressure of 20 bar, catalyst loading of 20 %, and reaction time of 2 h in a H2O system. Isotopic deuterium (D2O) labeling revealed that D substitution was notably pronounced through isotopic exchange between the D atom from D2O and H atom in FAL during its hydrogenation to THFA.

Solubility in the MgSO4–NaCl–H2O System and Its Polythermal Diagram

Solubility in the MgSO4–NaCl–H2O System and Its Polythermal Diagram

Impact of Fe doping on the reactivity of γ-dicalcium silicate: Insights from DFT calculations

This study investigates the impact of Fe doping on the reactivity of γ-dicalcium silicate (γ-C2S) using density functional theory (DFT) calculations. We examined isolated point defects and defect complexes in various charge states to assess substitution tendencies. The results reveal that substituting Si with Fe is energetically more favorable than substituting Ca, due to smaller distortions and minimal impact on Fe-O bonds compared to Ca-O bonds. We systematically analyzed the impact of Fe impurities on γ-C2S reactivity through atomic charges, chemical bonds, and ab initio molecular dynamics (AIMD) simulations. On the one hand, Fe strengthens nearby Ca-O bonds, reducing the effective charge of oxygen atoms and inhibiting reactivity. On the other hand, hydroxylation of Fe-O groups, followed by dehydroxylation, decreases the coordination number of certain surface Ca ions, enhancing reactivity. The overall reactivity of Fe-doped γ-C2S balances inhibition and enhancement, depending on the reacting molecules. In pure H2O systems, the inhibitory effect prevails, while in the presence of H2CO3, the enhancement effect dominates. Experimental observations corroborate these findings. This study provides insights into impurity doping mechanisms in calcium silicate minerals.