Search Results (107)

A comprehensive thermodynamic and molecular-level investigation of adsorption on MgY and NH₄Y zeolites is presented using inverse gas chromatography at infinite dilution (IGC-ID), combined with a Hamaker-based formalism and an extended five-parameter Lewis acid–base model. The study introduces a unified framework that integrates dispersive, polar, and donor–acceptor interactions while explicitly accounting for temperature-dependent intermolecular geometry. The results demonstrate that the London dispersive free energy exhibits a highly linear temperature dependence (R² > 0.999), while the corresponding surface energy decreases linearly with temperature (e.g., ${\gamma }_s^d\left(T\right)=-0.297T+189.48$ mJ·m⁻² for MgY), reflecting the progressive weakening of dispersion forces. Simultaneously, the intermolecular separation distance follows a linear relation $r\left(T\right)=r_0+{\alpha }_{\mathrm{eff}}T$, with ${\alpha }_{\mathrm{eff}}$ values on the order of (2–3) × 10⁻³ Å·K⁻¹ for MgY, enabling the determination of intrinsic contact distances $r_0$ at 0 K, varying between 4.00 Å and 6.60 Å. A major finding is that the molecular surface area of adsorbed probes is not constant but follows a quadratic temperature dependence with excellent accuracy (R² > 0.999), establishing adsorption cross-section as a thermodynamic variable. The comparison between MgY and NH₄Y reveals two distinct adsorption regimes: MgY exhibits a structured and strongly dispersive interaction field associated with Mg²⁺ cations, whereas NH₄Y displays enhanced polarity, stronger specific interactions, and greater molecular flexibility driven by hydrogen bonding and protonic effects. Thermodynamic analysis of Lewis acid–base interactions shows that classical linear models are insufficient. Statistical evaluation (R² ≈ 0.986, minimum AIC/BIC, lowest RMSE) demonstrates that the five-parameter Hamieh model provides the most accurate and physically meaningful description, capturing nonlinear donor–acceptor interactions and amphoteric coupling effects. Overall, this work establishes a novel thermodynamic methodology that quantitatively links macroscopic surface energetics to microscopic interaction parameters, providing new insight into adsorption mechanisms and a robust framework for the rational design of porous materials in catalysis, separation, and energy applications. Full article

CO₂ adsorption on subnanometric metal clusters is highly sensitive to the computational protocol used to describe the potential energy surface, particularly when several low-lying geometries and spin states are accessible. In this work, CO₂ adsorption on Cu₄ and Sc₄ clusters was investigated using density functional theory (DFT) to evaluate how the choice of functional/basis-set protocol, spin multiplicity, initial geometry, and vibrational stability affects the predicted adsorption behavior. Four representative computational protocols (TPSSh, r²SCAN-3c, PBE-D4/def2-TZVP, and PBE0-SDD) were assessed for isolated clusters and cluster–CO₂ complexes. The lowest harmonic vibrational frequency, ω_min, was used as a diagnostic criterion to distinguish true minima from unstable or weakly defined stationary points. Selected cases were also cross-checked using the ORCA and Gaussian quantum-chemistry packages to assess whether comparable computational settings yielded consistent stationary-point character. The results show that Cu₄ generally exhibits weak CO₂ binding, whereas Sc₄ displays stronger but more protocol-dependent adsorption, consistent with its higher structural flexibility and more pronounced Lewis-acid character. Low-frequency and imaginary modes were found in several optimized structures, indicating that adsorption energies should not be interpreted without prior vibrational validation. The comparison also shows that variations in functional/basis-set treatment and spin multiplicity can alter both the optimized geometry and the predicted adsorption strength. Therefore, CO₂ adsorption on small metal clusters should be discussed using combined structural, vibrational, and energetic criteria rather than electronic adsorption energies alone. Overall, this study provides a protocol-oriented framework for evaluating the reliability of DFT predictions in CO₂ adsorption on Cu₄ and Sc₄ clusters. Full article

Here, we report a highly efficient and stable catalytic system based on monometallic oxides supported on HY zeolites for the catalytic oxidation of chlorobenzene (CB). Among the transition and rare-earth metal oxides screened, the 30Cu/HY catalyst demonstrates exceptional performance, achieving near 100% CB conversion at 300 °C (500 ppm CB, 10,000 h⁻¹) alongside outstanding 24 h continuous stability without deactivation. Quantitative Py-IR analysis reveals that this superior activity is fundamentally driven by extensive solid-state ion exchange, forming robust Lewis acid centers (Cu-Y structures) that synergize with zeolitic Brønsted acid sites to efficiently polarize and cleave C-Cl bonds. Through an integrated approach combining in situ DRIFTS, real-time mass spectrometry, TGA, and NLDFT pore size analysis, we elucidate that the exceptional deep-oxidation capability of Cu/HY continuously mineralizes carbonaceous intermediates. This property minimizes coke deposition (2.91 wt%) and preserves the hierarchical pore architecture, preventing the coverage of active sites and severe pore blockage by partially oxidized intermediates (such as phenolic, aldehydic, and quinonic species) and stable carbonate species responsible for the deactivation of other metal oxides. These insights provide a mechanistic framework for the rational design of robust, chlorine-resistant catalysts for the sustainable abatement of persistent organic pollutants. Full article

Ammonia decomposition represents a promising route for carbon-free hydrogen production, provided that efficient and cost-effective catalysts are developed. In this study, lanthanum-based mixed oxide catalysts (LaNi, LaCo, and LaCe) were synthesized via a controlled co-precipitation method and systematically evaluated for catalytic ammonia decomposition under atmospheric pressure in the temperature range of 350–500 °C. Comprehensive characterization combining N₂ physisorption, XRD, SEM–EDX, TGA–DTG, XPS, and FTIR-pyridine adsorption revealed pronounced structure–property relationships. LaNi exhibited the highest surface area (31.11 m²·g⁻¹), well-developed mesoporosity, and a balanced Lewis/Brønsted acidity (C_L/C_B ≈ 0.82), leading to superior catalytic performance with NH₃ conversion reaching ~48% at 500 °C (GHSV = 50 h⁻¹). LaCo showed intermediate activity (~30% conversion), while LaCe displayed limited performance (<13%), most likely due to its dense morphology and low surface accessibility. Increasing gas hourly space velocity resulted in decreased ammonia conversion for all catalysts, highlighting the critical role of residence time. These findings demonstrate that the catalytic efficiency of lanthanum-based systems is governed by the synergistic interplay between surface area, mesoporous architecture, and acidity distribution, with LaNi emerging as the most promising catalyst among the investigated materials. Full article

The rapid growth of polyethylene terephthalate (PET) waste and the limitations of conventional recycling methods for mixed waste streams emphasize the need for chemical recycling routes that deliver high-value monomers in a sustainable, resource-efficient manner. This work explores N-heterocyclic carbenes (NHCs) as organocatalysts for the glycolysis of PET with ethylene glycol to bis(hydroxyethyl)terephthalate (BHET), aiming for milder conditions and higher activity. A systematic catalyst screening links steric and electronic properties (percent buried volume, Tolman electronic parameter) of the NHCs to performance in the glycolysis process, resulting in a catalyst system with high PET conversion (up to 97%) and BHET yield (up to 65%). Mechanistic investigations (experimental and computational) support an anionic activation pathway for glycolysis. To lower the reaction temperature, selective cosolvent systems were explored, albeit with some loss of catalytic activity. Cooperative catalysis combining NHCs with Lewis acids enhances activity, leading to a high conversion (up to 90%) while maintaining lower temperatures than state-of-the-art glycolysis methods. The process was successfully transferred to post-consumer waste streams to validate the practicality. Full article

The increasing energy demand and global dependence on conventional fuels have resulted in severe greenhouse gas (GHG) emissions, necessitating the development of sustainable bioenergy alternatives. Algal is recognized as a promising feedstock for the production of fourth-generation biofuels. This study optimizes catalytic pyrolysis of Arthrospira platensis for bio-oil production via a dual-bed catalyst system of iron-impregnated dolomite (Fe/DM) and a copper-impregnated spent fluid catalytic cracking catalyst (Cu/sFCC). A face-central composite design (FCCD) and response surface methodology (RSM) were used for the delineation of optimal conditions, ensuring that all experimental tests remained within feasible operating conditions of 500–600 °C, a reaction time of 45–75 min, a N₂ flow rate of 50–200 mL/min, and a catalyst loading of 5–20 wt%. The bio-oil yield was maximized at 39.73 ± 2.86 wt% at 500 °C for 45 min, a N₂ flow of 50 mL/min, and 5 wt% catalyst loading to feedstock with a 0.4:0.6 mass ratio of Fe/DM: Cu/sFCC. The dual-catalysts combined Brønsted and Lewis acid sites enhanced the catalytic activity, which promotes the cleavage of carbon–carbon and carbon–hydrogen bonds, including the mechanism of catalytic pathways such as dehydration, decarboxylation, oligomerization, aromatization, and further cracking reactions, and was successful in converting high-molecular-weight molecules into lighter hydrocarbons and significantly improving product selectivity, demonstrating a highly effective pathway for producing high-quality sustainable biofuel. Full article

The escalation of thermal runaway in lithium-ion batteries presents severe safety hazards that necessitate advanced monitoring protocols to ensure early warning of potential failures. Carbon dioxide (CO₂) is released during preliminary decomposition well before catastrophic failure occurs, thereby providing a strategic advantage for early-stage warning. Consequently, identifying materials with high-selective CO₂ recognition is an essential prerequisite for developing reliable sensing platforms. This study integrates Grand Canonical Monte Carlo simulations with Random Forest (RF) models to systematically screen 1470 MOFs from the CoRE-MOF 2019 database. The screening process evaluates selective CO₂ recognition under multicomponent competitive adsorption conditions involving CO₂, C₂H₄, and O₂. The performance evaluation is based on working capacity, selectivity, and the trade-off between working capacity and selectivity (TSN). The RF model achieves high predictive accuracy, with tested R² exceeding 0.92 on the test samples. Shapley Additive Explanations (SHAP) interpretability analysis identifies Q⁰_st(CO₂), Q⁰_st(C₂H₄), WEPA, K_H(C₂H₄), and ETR as key performance drivers. The results indicate that CO₂ selectivity is constrained by the binding strength of competing C₂H₄. Optimal materials tend to have hard Lewis acid centers and polar inorganic clusters to minimize non-specific π-interactions with interfering species. Top-performing MOFs require balanced structural features, concentrating in moderate surface areas (965–1975 m²/g), narrow pore windows (PLD ≈ 4–7 Å, LCD ≈ 5.5–9.6 Å), high void fractions above 0.6, and low densities below 1.3 g/cm³. AJOTEY emerges as the optimal candidate with a TSN of 6.43 mol/kg, combining substantial working capacity (4.57 mol/kg) with strong selectivity (25.52). These results will accelerate the discovery of sensing materials and provide a practical pathway for MOF-based CO₂ sensor development to enhance lithium-ion battery safety. Full article

To address the challenges of zwitterionic dissociation and steric hindrance in the esterification of α-aromatic amino acids, this study prepared the solid superacid catalyst SO₄²⁻/TiO₂/HZSM-5 (STH) and its plasma-modified derivative SO₄²⁻/TiO₂/HZSM-5 (STH-RF) via an aging-impregnation method. Systematic characterization revealed that plasma modification optimizes the crystal morphology and particle dispersion of the catalyst, while also achieving pore clearance and an increase in the specific surface area. Furthermore, it gradationally enhances acidic properties by increasing the abundance of strong acid and Lewis acid sites, and promotes uniform loading and stable bonding of the SO₄²⁻ active component. Performance evaluation using the synthesis of L-phenylalanine methyl ester as a model reaction demonstrated that STH-RF exhibits optimal catalytic activity, affording a product yield of 85.7%, which is significantly higher than that of unmodified STH (19%) and the homogeneous catalyst H₂SO₄ (63%). This superior performance originates from a “structure–acidity” synergistic effect, combining the thermodynamic advantage of a lower energy barrier for the rate-determining step (12.6 Kcal·mol⁻¹) with efficient kinetics under optimal process conditions (1.0 MPa, 2000 rpm, 170 °C). Moreover, STH-RF maintained a yield above 80% after four consecutive reaction cycles, indicating excellent stability. This work provides a novel catalytic system for the green and efficient synthesis of highly hindered α-amino acid derivatives, holding significant theoretical and practical implications. Full article

This study developed a two-step conversion strategy for the efficient conversion of bamboo waste into 5-hydroxymethylfurfural (HMF). First, ultrasonic-assisted formic acid pretreatment was used at 80 °C for 3 h, removing approximately 83.7% of hemicellulose and 76.5% of lignin from the biomass, with a cellulose recovery of 93.5%. The ultrasonic step significantly enhanced the chemical action of formic acid through cavitation, allowing formic acid to penetrate deeper into the biomass, thereby more effectively removing hemicellulose and lignin. Subsequently, glucose was obtained through an enzymatic hydrolysis. In the second step of HMF preparation, citric acid in the hydrolysate was combined with ChCl to form an acidic deep eutectic solvent (DES), and metal chlorides were added as Lewis acid catalysts. Experiments results showed that when the ChCl–citric acid ratio was 2:1, and the Ca²⁺ concentration was 100 mM, an HMF yield of 51.9% was obtained at 220 °C for 1.5 h. This study provides an efficient, mild, and environmentally friendly method for the high-value valorization of waste bamboo. Full article

Aiming to obtain chemicals from renewable sources to mitigate global warming, the catalytic pyrolysis of tamarind pulp, obtained from juice industries, was studied. Catalysts based on HZSM-5 zeolite prepared from rice husk ash using ultrasound, microwaves, and a combination of both were used. The catalysts were characterized by elemental analysis, X-ray diffraction, specific surface area and porosity measurements, scanning electron microscopy, and acidity measurements. The specific surface areas and the micropore volumes were slightly affected by the treatments, with microwave alone or combined with ultrasound having the strongest effect. The number of acid sites increased, and the relative number of strong sites decreased with the treatments. The relative amount of Bronsted to Lewis sites was increased by ultrasound and decreased by microwave, alone or combined. These catalysts decreased oxygenated products and increased BTEX production during tamarind pulp pyrolysis. Product distribution was similar for all cases, meaning that HZSM-5 with the following characteristics is a selective catalyst for BTEX in tamarind pulp pyrolysis: specific surface area = 310–347 m²/g; micropore volume = 0.099–0.105 cm³ g⁻¹; acidity = 327 to 571 µmol NH₃ g_cat⁻¹; and ratio of Bronsted to Lewis acid sites = 0.034 to 0.044. Full article

In this work, the one-pot catalytic reductive fractionation of C-lignin in castor shell powders to efficiently provide catechyl monomers was achieved by tandem metal triflate and Pd/C catalysis. The optimized Pd/C + In(OTf)₃ combination performed best and provided a 66.9 mg·g⁻¹ yield of corresponding aromatic monomers with the catechol selectivity as high as 95.4%. For the promotion effect of the Lewis acid species, the mechanism studied indicated that the introduction of In³⁺ could significantly promote the C–O bond cleavage in the LCC to release the C-lignin fragments from the solid lignocellulose and simultaneously accelerate the cleavage of the critical C_α/β–OAr linkage bond in C-lignin to release catechol monomers. In addition, performance differences highlight the cooperation and function-matching effect between the hydrogenation metals and the Lewis ion species, which can promote the high-value utilization of forestry and agricultural residues in chemical synthesis. Full article

ZSM-5 zeolites with varying aluminum content were subjected to steam treatments of different severities by adjusting the temperature, duration, and water vapor pressure. The steamed samples were characterized using a range of analytical techniques. A quantitative assessment of the aluminum species—namely, tetrahedrally coordinated framework Al, dislodged framework Al, non-framework pentacoordinated Al, and non-framework hexacoordinated Al—was achieved through a combination of EDX analysis on Cs-exchanged materials and quantitative ²⁷Al MAS NMR spectroscopy, including spectral simulation. Contrary to previous reports, the catalytic activity per framework Al site in unsteamed ZSM-5 increases with aluminum content at low Si/Al ratios, aligning with recently proposed medium effects. Notably, at the point of maximum activity enhancement due to steaming, equivalent amounts (1:1) of framework and dislodged framework Al—both in tetrahedral coordination—are observed. The maximum enhancement factor per framework Al site, for a given material and reaction, remains independent of the specific steaming conditions (temperature, time, and pressure). However, the degree of activity enhancement varies with the type of reaction: it is more pronounced for n-hexane cracking (α-test) than for m-xylene isomerization. This suggests that both catalyst modification and reaction characteristics contribute to the observed steam-induced activity enhancement. A synergistic interaction between Brønsted and Lewis acid sites appears to underpin these effects. One plausible mechanism involves the strengthening of Brønsted acidity in the presence of adjacent Lewis acid sites. This enhancement is expected to be more significant for n-hexane cracking, which demands higher acid strength compared to m-xylene isomerization. In cases of n-hexane cracking, the increased acid strength and the formation of olefins via reactions on Lewis acid sites may act cooperatively. Importantly, the dislodged framework Al species—tetrahedrally coordinated in the hydrated catalyst at ambient temperature and functioning as Lewis acid sites in the dehydrated zeolite under reaction conditions—are directly responsible for the observed enhancement in acid activity. The transformation of framework Al into dislodged framework Al species is reversible, as demonstrated by hydrothermal treatment of the steamed samples at 150–200 °C. Nonetheless, reinsertion of Al into the framework is not fully quantitative: a portion of the dislodged framework Al is irreversibly converted into non-framework penta- and hexacoordinated species during the hydrothermal process. Among these, non-framework pentacoordinate Al species may serve as counterions to balance the lattice charges associated with framework Al. Full article

This study presents a sustainable and efficient strategy for removing contaminants of emerging concern (CECs) from wastewater using non-metal-doped pyrochar catalysts synthesized via a green, one-step pyrolytic process from pinewood sawdust, urea, and boric acid. The resulting N- and B-doped pyrochars were evaluated for their ability to activate peroxydisulfate (PDS) and degrade a mixture of 25 CECs (15 pesticides and 10 pharmaceuticals). B-doped pyrochar exhibited superior bifunctional performance, combining high adsorption capacity with efficient catalytic PDS activation. Structural characterization confirmed the incorporation of boron into the carbon matrix, generating electron-deficient Lewis acid sites and enhancing the affinity toward PDS and CECs. Quenching and adsorption–degradation analyses revealed a synergistic combination of radical and non-radical pathways, supported by π–π interactions, hydrogen bonding, and Lewis acid–base interactions. Reusability tests confirmed long-term stability and high degradation efficiency over four cycles. These findings demonstrate the potential of B-doped pyrochar as a cost-effective, stable, and environmentally friendly catalyst for practical wastewater treatment. Full article

Boron-containing compounds have made a significant impact on the field of medicinal chemistry since the discovery of Bortezomib (Velcade^®), a dipeptide boronic acid approved by the FDA in 2003 for the treatment of multiple myeloma. Since then, over the last two decades, four more boron-containing drugs have been approved by the FDA: Tavaborole (Kerydin^®), Ixazomib (Ninlaro^®), Crisaborole (Eucrisa^®), and Vaborbactam (in Vabomere^®). These compounds are approved for treating conditions such as onychomycosis, multiple myeloma, and atopic dermatitis, as well as an Aβ-lactamase inhibitor approved in combination with meropenem for treating infections. Further, many organic molecules containing boron are in clinical trials. Additionally, boron-containing compounds play a crucial role in various biological processes. Boron’s Lewis acidity has been utilized for diverse applications, from targeting biological molecules to the synthesis of organic compounds and in advanced drug delivery systems. Recent progress in the advancement of boron-containing compounds has not stopped, and the further use of Boron is emerging day-by-day with the discovery of multifaceted applications. This review aims to highlight the recent advances made in the last decade in the drug design of boron-containing compounds and their therapeutic applications. Here, in this work, we have focused on the recent diversification and progress of boron-containing compounds in medicinal chemistry applications. Full article

In this work, a novel solid polymer electrolyte with a disordered structure has been designed, combining polyethylene glycol (PEG) as the flexible segments and hexamethylene diisocyanate (HDI) as the rigid segments. The synthesis was realized by alternating flexible PEG with rigid HDI through a peptide bond (–CO–NH–), which disrupts the ordered structures of PEG, generating electron-deficient Lewis acid groups. The pathbreaking introduction of HDI blocks not only bridges links between the PEG molecules but also generates electron-deficient Lewis acid groups. Therefore, the original ordered structures of PEG are disrupted by both the alternating chains between PEG and HDI and the Lewis acid groups. As a result, the PEG_H/L4000 electrolytes (PEG molecular weight of 4000) exhibit a strong anion-capture ability that decreases the crystallinity of polymers, which further achieves a high ionic conductivity close to 10⁻³ S·cm⁻¹ with the lithium-ion transference numbers up to 0.88. The symmetric Li|PEG_H/L4000|Li cells maintain a low and stable voltage polarization for more than 800 h at 0.1 mA·cm⁻². Furthermore, the LiFePO₄|PEG_H/L4000|Li all-solid-state cells perform well both in cycling and rate performances. The design of polymer disordered structures for polymer electrolytes provides a new thought for manufacturing all-solid-state lithium-ion batteries with high safety as well as long life. Full article