Search Results (112)

Against the backdrop of global energy transition and strict environmental regulations, supercritical carbon dioxide (scCO₂) fracturing and oil displacement technologies have emerged as pivotal green approaches in shale gas exploitation, offering the dual advantages of zero water consumption and carbon sequestration. However, the inherent low viscosity of scCO₂ severely restricts its sand-carrying capacity, fracture propagation efficiency, and oil recovery rate, necessitating the urgent development of high-performance thickeners. The current research on scCO₂ thickeners faces a critical trade-off: traditional fluorinated polymers exhibit excellent philicity CO₂, but suffer from high costs and environmental hazards, while non-fluorinated systems often struggle to balance solubility and thickening performance. The development of new thickeners primarily involves two directions. On one hand, efforts focus on modifying non-fluorinated polymers, driven by environmental protection needs—traditional fluorinated thickeners may cause environmental pollution, and improving non-fluorinated polymers can maintain good thickening performance while reducing environmental impacts. On the other hand, there is a commitment to developing non-noble metal-catalyzed siloxane modification and synthesis processes, aiming to enhance the technical and economic feasibility of scCO₂ thickeners. Compared with noble metal catalysts like platinum, non-noble metal catalysts can reduce production costs, making the synthesis process more economically viable for large-scale industrial applications. These studies are crucial for promoting the practical application of scCO₂ technology in unconventional oil and gas development, including improving fracturing efficiency and oil displacement efficiency, and providing new technical support for the sustainable development of the energy industry. This study innovatively designed an amphiphilic modified amino silicone oil polymer (MA-co-MPEGA-AS) by combining maleic anhydride (MA), methoxy polyethylene glycol acrylate (MPEGA), and amino silicone oil (AS) through a molecular bridge strategy. The synthesis process involved three key steps: radical polymerization of MA and MPEGA, amidation with AS, and in situ network formation. Fourier transform infrared spectroscopy (FT-IR) confirmed the successful introduction of ether-based CO₂-philic groups. Rheological tests conducted under scCO₂ conditions demonstrated a 114-fold increase in viscosity for MA-co-MPEGA-AS. Mechanistic studies revealed that the ether oxygen atoms (Lewis base) in MPEGA formed dipole–quadrupole interactions with CO₂ (Lewis acid), enhancing solubility by 47%. Simultaneously, the self-assembly of siloxane chains into a three-dimensional network suppressed interlayer sliding in scCO₂ and maintained over 90% viscosity retention at 80 °C. This fluorine-free design eliminates the need for platinum-based catalysts and reduces production costs compared to fluorinated polymers. The hierarchical interactions (coordination bonds and hydrogen bonds) within the system provide a novel synthetic paradigm for scCO₂ thickeners. This research lays the foundation for green CO₂-based energy extraction technologies. Full article

The efficient simultaneous removal of NO_x and CO from sintering flue gas under low-temperature conditions (110–180 °C) in iron and steel enterprises remains a significant challenge in the field of environmental catalysis. In this study, we present an innovative strategy to enhance the performance of CuSmTi catalysts through silver modification, yielding a bifunctional system capable of oxygen structure regulation and demonstrating superior activity for the combined NH₃-SCR and CO oxidation reactions under low-temperature, oxygen-rich conditions. The modified AgCuSmTi catalyst achieves complete NO conversion at 150 °C, representing a 50 °C reduction compared to the unmodified CuSmTi catalyst (T_100% = 200 °C). Moreover, the catalyst exhibits over 90% N₂ selectivity across a broad temperature range of 150–300 °C, while achieving full CO oxidation at 175 °C. A series of characterization techniques, including XRD, Raman spectroscopy, N₂ adsorption, XPS, and O₂-TPD, were employed to elucidate the Ag-Cu interaction. These modifications effectively optimize the surface physical structure, modulate the distribution of acid sites, increase the proportion of Lewis acid sites, and enhance the activity of lattice oxygen species. As a result, they effectively promote the adsorption and activation of reactants, as well as electron transfer between active species, thereby significantly enhancing the low-temperature performance of the catalyst. Furthermore, in situ DRIFTS investigations reveal the reaction mechanisms involved in NH₃-SCR and CO oxidation over the Ag-modified CuSmTi catalyst. The NH₃-SCR process predominantly follows the L-H mechanism, with partial contribution from the E-R mechanism, whereas CO oxidation proceeds via the MvK mechanism. This work demonstrates that Ag modification is an effective approach for enhancing the low-temperature performance of CuSmTi-based catalysts, offering a promising technical solution for the simultaneous control of NO_x and CO emissions in industrial flue gases. Full article

Polymer electrolytes (PEs) provide enhanced safety for high–energy–density lithium metal batteries (LMBs), yet their practical application is hampered by intrinsically low ionic conductivity and insufficient electrochemical stability, primarily stemming from suboptimal Li⁺ solvation environments and transport pathways coupled with slow polymer dynamics. Herein, we demonstrate a molecular design strategy to overcome these limitations by regulating the Li⁺ solvation structure through the synergistic interplay of conventional Lewis acid–base coordination and engineered hydrogen bond (H–bond) networks, achieved by incorporating specific H–bond donor functionalities (N,N′–methylenebis(acrylamide), MBA) into the polymer architecture. Computational modeling confirms that the introduced H–bonds effectively modulate the Li⁺ coordination environment, promote salt dissociation, and create favorable pathways for faster ion transport decoupled from polymer chain motion. Experimentally, the resultant polymer electrolyte (MFE, based on MBA) enables exceptionally stable Li metal cycling in symmetric cells (>4000 h at 0.1 mA cm⁻²), endows LFP|MFE|Li cells with long–term stability, achieving 81.0% capacity retention after 1400 cycles, and confers NCM622|MFE|Li cells with cycling endurance, maintaining 81.0% capacity retention after 800 cycles under a high voltage of 4.3 V at room temperature. This study underscores a potent molecular engineering strategy, leveraging synergistic hydrogen bonding and Lewis acid–base interactions to rationally tailor the Li⁺ solvation structure and unlock efficient ion transport in polymer electrolytes, paving a promising path towards high–performance solid–state lithium metal batteries. Full article

In previous studies, a new methodology was developed to determine the free dispersive and polar energies, the surface energies, and Lewis acid–base parameters of a polystyrene–divinylbenzene (S-DVB) copolymer modified by melamine, 5-Hydroxy-6-methyluracil, and 5-fluouracil. In this paper, we were interested in the determination of the work of the adhesion of solvents on the modified copolymer as a function of temperature and for the different modifiers with the help of inverse gas chromatography at infinite dilution. The variations in the London dispersive and polar surface properties of copolymers against the temperature led to the determination of the different acid–base components of their surface energies. Using Fowkes’s equation, van Oss’s relation, and Owens’s concept, we obtained the variations in the dispersive and polar works of the adhesion of the different solid surfaces, and the corresponding forces of interaction between the organic solvents and the modified copolymer. It was shown that the work of adhesion is a function of two thermodynamic variables: the temperature and the modifier percentage. Full article

Nickel phosphides (Ni_xP_y) are recognized as promising alternatives to noble-metal catalysts for the oxygen evolution reaction (OER). NiP, consisting of the equal stoichiometric ratio of Ni and P, could help quantify the catalytic effect of P and Ni. In this work, density functional theory (DFT) is employed to investigate the OER mechanism on NiP surfaces. We found that P atoms help stabilize O* at the adsorption sites. The rich electron donation from the Ni atom can alter the local charge distribution and enhance the interaction between O* and P atoms. Both oxygen intermediate adsorption energy and OER overpotential exhibit linear correlations with the charge of adsorption sites. Electron loss at the site induces the overall system to exhibit Lewis acidic characteristics, facilitating the OER and leading to a substantial overpotential reduction of up to 0.61 V compared to Lewis basic structures. Leveraging electronic structure theory and Lewis acid–base theory, we offer a new insight into the OER mechanism on the NiP surface, demonstrating that the catalytic activity of bulk metallic surface materials like NiP can be optimized by tailoring the local surface chemical environment. Full article

The London dispersive and polar surface properties of solid materials are very important in many chemical processes, such as adsorption, coatings, catalysis, colloids, and mechanical engineering. One of the materials, a styrene–divinylbenzene copolymer modified with 5-hydroxy-6-methyluracil at different percentages, has not been deeply characterized in the literature, and it isparticularly crucial to determine its London dispersive and polar properties. Recent research in the inverse gas chromatography (IGC) technique allowed a full determination of the surface properties of a styrene–divinylbenzene copolymer modified with 5-hydroxy-6-methyluracil by using well-known polar and non-polar organic solvents and varying the temperature. Applying the IGC technique at infinite dilution resulted in the retention volume of adsorbed molecules on styrene–divinylbenzene copolymer modified with 5-hydroxy-6-methyluracil at different percentages, using the Hamieh thermal model and our recent results on the separation of the two polar and dispersive contributions to the free energy of interaction. The surface properties of these materials, such as the surface free energy of adsorption, the polar acid and base surface energy, and the Lewis acid–base parameters, were obtained as a function of temperature and for different percentages of 5-hydroxy-6-methyluracil. The obtained results proved that the polar free energy of adsorption on styrene–divinylbenzene copolymer increased when the percentage of 5-hydroxy-6-methyluracil (HMU) increased. However, a decrease in the London dispersive surface energy of the copolymer was observed for higher percentages of 5-hydroxy-6-methyluracil. A Lewis amphoteric character was shown for the copolymer with the highest acidity, while the basicity linearly increased when the percentage of HMU increased. Full article

The ozonation of norfloxacin (NOF), a widely used fluoroquinolone antibiotic, in the presence of Na⁺, Fe²⁺, Cu²⁺, Ni²⁺, and Co²⁺ cations and their montmorillonite-supported counterparts was investigated. The NOF degradation and the toxicity of the ozonized mixtures towards an aquatic organism (Lemna minor) were evaluated in terms of changes in its frond number, chlorophyll content, photosynthesis efficacy, and production of reactive oxygen species (ROS). The evolution over time of the NOF degradation grade and the toxicity were discussed in terms of i. the observed changes in the interactions of the cation and clay catalyst with NOF molecules; ii. the pH decay, during ozonation. Ion-exchange and Lewis acid–base interactions appear to govern NOF adsorption and clay catalyst dispersion in correlation with the progressive formation of acidic species in the aqueous media. These findings reveal promising prospects for tailoring optimum oxidative water treatments with minimum toxicity and for predicting their environmental impacts on aquatic media. Full article

Metal–organic frameworks (MOFs) have garnered significant attention for water purification in recent years. In particular, UiO-66 (a member of the UiO-MOF family, developed at the University of Oslo) has emerged as a promising water purification material. UiO-66 exhibits excellent adsorption through electrostatic interaction, π–π stacking and Lewis acid–base coordination mechanisms. The photocatalytic degradation property was enhanced through metal doping, composite with semiconductor materials, defect engineering, etc., and the removal efficiency of pollutants was significantly improved. This review systematically describes the structure of UiO-66 and the synthesis methods of UiO-66, including solvothermal, microwave-assisted, mechanized and electrochemical methods, as well as the application of UiO-66 in the adsorption and photocatalytic degradation of various pollutants. Full article

This study addresses the dual challenges of water pollution and waste management by exploring the valorization of chicken bone biomass in native (NBio) and calcined (CBio) forms as biosorbents for dye removal. Basic fuchsine (BF) and methylene blue (MB) were selected as model pollutants, and adsorption was assessed under varying operational conditions. Characterization using Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) showed that calcination improved crystallinity, eliminated organic impurities, and increased surface area (247 m²/g for NBio vs. 370 m²/g for CBio). Adsorption tests revealed higher performance for CBio, with maximum adsorption capacities of 100 mg/g (BF) and 142.85 mg/g (MB) based on the Langmuir isotherm, while NBio with maximum adsorption capacities of 111 mg/g (BF) and 111.11 mg/g (MB) followed the Freundlich model. Adsorption kinetics indicated pseudo-second-order behavior, suggesting chemisorption. The possible interactions between dyes and the biosorbent are hydrogen bonding, electrostatic interactions, and Lewis acid–base interactions. Thermodynamic analysis highlighted exothermic behavior for NBio and endothermic, entropy-driven adsorption for CBio, with both processes being spontaneous. A decision tree with Least Squares Boosting (DT_LSBOOST) provided accurate predictions (R² = 0.9999, RMSE < 0.003) by integrating key parameters. These findings promote chicken bone biomass as a cost-effective, sustainable biosorbent, offering promising potential in wastewater treatment and environmental remediation. Full article

III-nitrides are crucial materials for solar flow batteries due to their versatile properties. In contrast to the well-studied MOVPE reaction mechanism for AlN and GaN, few works report gas-phase mechanistic studies on the growth of InN. To better understand the reaction thermodynamics, this work revisited the gas-phase reactions involved in metal–organic vapor-phase epitaxy (abbreviated as MOVPE) growth of InN. Utilizing the M06-2X function in conjunction with Pople’s triple-ζ split-valence basis set with polarization functions, this work recharacterized all stationary points reported in previous literature and compared the differences between the structures and reaction energies. For the reaction pathways which do not include a transition state, rigorous constrained geometry optimizations were utilized to scan the PES connecting the reactants and products in adduct formation and XMIn (M, D, T) pyrolysis, confirming that there are no TSs in these pathways, which is in agreement with the previous findings. A comprehensive bonding analysis indicates that in TMIn:NH₃, the In-N demonstrates strong coordinate bond characteristics, whereas in DMIn:NH₃ and MMIn:NH₃, the interactions between the Lewis acid and base fragments lean toward electrostatic attraction. Additionally, the NBO computations show that the H radical can facilitate the migration of electrons that are originally distributed between the In-C bonds in XMIn. Based on this finding, novel reaction pathways were also investigated. When the H radical approaches MMInNH₂, MMIn:NH₃ rather than MMInHNH₂ will generate and this is followed by the elimination of CH₄ via two parallel paths. Considering the abundance of H₂ in the environment, this work also examines the reactions between H₂ and XMIn. The Mulliken charge distributions indicated that intermolecular electron transfer mainly occurs between the In atom and N atom whiling forming (DMInNH₂)₂, whereas it predominately occurs between the In atom and the N atom intramolecularly when generating (DMInNH₂)₃. Full article

The main categories of transition metal–mercury heterometallic compounds are briefly summarized. The attention is focused on complexes and clusters where the {Hg-Y} fragment, where Y represents a halide atom, interacts with transition metals. Most of the structurally characterized derivatives are organometallic compounds where the transition metals belong to the Groups 6, 8, 9 and 10. More than one {Hg-Y} group can be present in the same compound, interacting with the same or with different transition metals. The main synthetic strategies are discussed, and structural data of representative compounds are reported. According to the isolobality with hydrogen, {Hg-Y} can form from one to three M-{Hg-Y} bonds, but further interactions can be present, such as mercurophilic and Hg···halide contacts. The formal oxidation state of mercury is sometimes ambiguous and thus {Hg-Y} can be considered as a Lewis acid or base on varying the transition metal fragment. Density functional theory calculations on selected Group 6 and Group 9 model compounds are provided in order to shed light on this aspect. Full article

Chalcogen bonds (ChBs) involving selenium have attracted substantial scholarly interest in past years owing to their fundamental roles in various chemical and biological fields. However, the effect of the valency state of the electron-deficient selenium atom on the characteristics of such ChBs remains unexplored. Herein, we comparatively studied the σ-hole-type Se∙∙∙O ChBs between SeF₂/SeF₄ and a series of oxygen-bearing Lewis bases, including water, methanol, dimethyl ether, ethylene oxide, formaldehyde, acetaldehyde, acetone, and formic acid, using ab initio computations. The interaction energies of these chalcogen-bonded heterodimers vary from −5.25 to −11.16 kcal/mol. SeF₂ participates in a shorter and stronger ChB than SeF₄ for all the examined heterodimers. Such Se∙∙∙O ChBs are closed-shell interactions, exhibiting some covalent character for all the examined heterodimers, except for SeF₄∙∙∙water. Most of these chalcogen-bonded heterodimers are predominantly stabilized through orbital interactions between the lone pair of the O atom in Lewis bases and the σ*(Se–F) antibonding orbitals of Lewis acids. The back-transfer of charge from the lone pair of selenium into the σ* or π* antibonding orbitals of Lewis bases is also observed for all systems. Energy decomposition analysis reveals that the electrostatic component significantly stabilizes the targeted heterodimers, while the induction and dispersion contributions cannot be ignored. Full article

The dispersive and polar properties of materials, and especially of polymers and copolymers, play an important role in several engineering applications implying their surfaces and interfaces. The surface energetic properties of poly(styrene-co-butadiene) have never been studied. We proposed in this study an accurate determination of such properties by using inverse gas chromatography (IGC) at infinite dilution. Background: The IGC surface technique led to the dispersive and polar properties of poly(styrene-co-butadiene) rubber (SBR) by adsorption of organic solvents at various temperatures. Methods: Our new methodology, based on the thermal Hamieh model and the London dispersion interaction energy, was used to determine the London dispersion surface energy, the polar acid–base surface energy, and the Lewis acid–base properties of the copolymer. Results: The different surface energy parameters of the SBR were obtained as a function of temperature from the chromatographic measurements. Conclusions: The dispersive and polar free energies of adsorption of the various n-alkanes and polar molecules on poly(styrene-co-butadiene) were determined at different temperatures. A decrease in the London dispersive surface energy and the polar Lewis acid–base surface energies of SBR was highlighted when the temperature increased. It showed a Lewis amphoteric character of poly(styrene-co-butadiene) with a highest basic constant 10 times larger than its acidic constant. This new and original method can better characterize the surface thermodynamic properties of poly(styrene-co-butadiene). Full article

The linear diblock copolymer polystyrene-b-poly(4-vinylpyridine) (PS-P4VP) is an important copolymer recently used in many applications such as optoelectronics, sensors, catalysis, membranes, energy conversion, energy storage devices, photolithography, and biomedical applications. (1) Background: The surface thermodynamic properties of PS-P4VP copolymers are of great importance in many chemical and industrial processes. (2) Methods: The inverse gas chromatography (IGC) at infinite dilution was used for the experimental determination of the retention volumes of organic solvents adsorbed on copolymer surfaces as a function of temperature. This led to the variations in the free energy of interaction necessary to the evaluation of the London dispersive and polar acid–base surface energies, the polar enthalpy and entropy, the Lewis acid–base constants, and the transition temperatures of the PS-P4VP copolymer. (3) Results: The application of the thermal Hamieh model led to an accurate determination of the London dispersive surface energy of the copolymer that showed non-linear variations versus the temperature, highlighting the presence of two transition temperatures. It was observed that the Lewis acid–base parameters of the copolymer strongly depend on the temperature, and the Lewis base constant of the solid surface was shown to be higher than its acid constant. (4) Conclusions: An important effect of the temperature on the surface thermodynamic properties of PS-P4VP was proven and new surface correlations were determined. Full article

Using rapeseed straw as a raw material and potassium bicarbonate (KHCO₃) and urea (CO(NH₂)₂) as modification reagents, the pyrolysis raw materials were mixed in a certain proportion, and the unmodified biochar GBC800, KHCO₃-modified biochar KGBC800, and (KHCO₃)/(CO(NH₂)₂) co-modified biochar N-KGBC800 were, respectively, prepared using the one-pot method at 800 °C. The physicochemical properties, such as surface morphology, pore characteristics, functional group distribution, and elemental composition of the three biochars, were characterized, and the adsorption performance and mechanism of the typical antibiotic tetracycline (TC) in water were studied. The results showed that the surface of GBC800 was smooth and dense, with no obvious pore structure, and both the specific surface area and total pore volume were small; the surface of KGBC800 showed an obvious coral-like three-dimensional carbon skeleton, the number of micropores and the specific surface area were significantly improved, and the degree of carbonization and aromatization was enhanced; N-KGBC800 had a coral-like three-dimensional carbon skeleton similar to KGBC800, and there were also many clustered carbon groups. The carbon layer changed significantly with interlayer gaps, presenting a multi-level porous structure. After N doping, the content of N increased, and new nitrogen-containing functional groups were formed. When the initial TC concentration was 100 mg/L, pH ≈ 3.4, the temperature was 25 °C, and the dosage of the three biochars was 0.15 g/L, the adsorption equilibrium was reached before 720 min. The adsorption capacities of GBC800, KGBC800, and N-KGBC800 for TC were 16.97 mg/g, 294.86 mg/g, and 604.71 mg/g, respectively. Fitting the kinetic model to the experimental data, the adsorption of TC by the three biochars was more in line with the pseudo-second-order adsorption kinetic model, and the adsorption isotherm was more in line with the Langmuir model. This adsorption process was a spontaneous endothermic reaction, mainly chemical adsorption, specifically involving multiple adsorption mechanisms such as pore filling, electrostatic attraction, hydrogen bonds, n−π interaction, Lewis acid–base interaction, π−π stacking, or cation −π interaction between the aromatic ring structure of the carbon itself and TC. A biochar-adsorption column was built to investigate the dynamic adsorption process of tetracycline using the three biochars against the background of laboratory pure water and salt water. The adsorption results show that the Thomas model and the Yoon–Nelson model both provide better predictions for dynamic adsorption processes. The modified biochars KGBC800 and N-KGBC800 can be used as preferred materials for the efficient adsorption of TC in water. Full article