Search Results (183)

Lanthanide rare earth elements possess significant promise for material applications owing to their distinctive optical and magnetic characteristics, as well as their versatile coordination capabilities. This study introduced a lanthanide-functionalized magnetic nanocellulose composite (NNC@Fe₃O₄@La(OH)₃) for effective phosphorus/nitrogen (P/N) ligand separation. The hybrid material employs the adaptable coordination geometry and strong affinity for oxygen of La³⁺ ions to show enhanced DNA-binding capacity via multi-site coordination with phosphate backbones and bases. This study utilized cellulose as a carrier, which was modified through carboxylation and amination processes employing deep eutectic solvents (DES) and polyethyleneimine. Magnetic nanoparticles and La(OH)₃ were subsequently incorporated into the cellulose via in situ growth. NNC@Fe₃O₄@La(OH)₃ showed a specific surface area of 36.2 m²·g⁻¹ and a magnetic saturation intensity of 37 emu/g, facilitating the formation of ligands with accessible La³⁺ active sites, hence creating mesoporous interfaces that allow for fast separation. NNC@Fe₃O₄@La(OH)₃ showed a significant affinity for DNA, with adsorption capacities reaching 243 mg/g, mostly due to the multistage coordination binding of La³⁺ to the phosphate groups and bases of DNA. Simultaneously, kinetic experiments indicated that the binding process adhered to a pseudo-secondary kinetic model, predominantly dependent on chemisorption. This study developed a unique rare-earth coordination-driven functional hybrid material, which is highly significant for constructing selective separation platforms for P/N-containing ligands. Full article

Marine–continental transitional shale is a promising unconventional gas reservoir, playing an increasingly important role in China’s energy portfolio. However, compared to marine shale, research on marine–continental transitional shale’s fractal characteristics of pore structure and complete pore size distribution remains limited. In this work, high-pressure mercury intrusion, N₂ adsorption, and CO₂ adsorption techniques, combined with fractal geometry modeling, were employed to characterize the pore structure of the Shanxi Formation marine–continental transitional shale. The shale exhibits generally high TOC content and abundant clay minerals, indicating strong hydrocarbon-generation potential. The pore size distribution is multi-modal: micropores and mesopores dominate, contributing the majority of the specific surface area and pore volume, whereas macropores display a single-peak distribution. Fractal analysis reveals that micropores have high fractal dimensions and structural regularity, mesopores exhibit dual-fractal characteristics, and macropores show large variations in fractal dimension. Characteristics of pore structure is primarily controlled by TOC content and mineral composition. These findings provide a quantitative basis for evaluating shale reservoir quality, understanding gas storage mechanisms, and optimizing strategies for sustainable of oil and gas development in marine–continental transitional shales. Full article

The development of high-performance adsorbent materials is crucial for any sorption-based energy conversion process. In such a context, composite sorbent materials, although promising in terms of performance and stability, are often challenging to shape into complex geometries. Additive manufacturing, also known as 3D printing, has emerged as a powerful technique for fabricating intricate structures with tailored properties. In this paper, an innovative three-dimensional structure, constituted by zeolite as filler and sulfonated polyether ether ketone as matrix, was obtained using additive manufacturing technology, which is mainly suitable for sorption-based energy conversion processes. The lattice structure was tailored in order to optimize the synthesis procedure and material stability. The complex three-dimensional lattice structure was obtained without a metal or plastic reinforcement support. The composite structure was evaluated to assess its structural integrity using morphological analysis. Furthermore, the adsorption/desorption capacity was evaluated using water-vapor adsorption isobars at 11 mbar at equilibrium in the temperature range 30–120 °C, confirming good adsorption/desorption capacity. Full article

Glancing Angle Deposition (GLAD) has emerged as a versatile and powerful nanofabrication technique for developing next-generation gas sensors by enabling precise control over nanostructure geometry, porosity, and material composition. Through dynamic substrate tilting and rotation, GLAD facilitates the fabrication of highly porous, anisotropic nanostructures, such as aligned, tilted, zigzag, helical, and multilayered nanorods, with tunable surface area and diffusion pathways optimized for gas detection. This review provides a comprehensive synthesis of recent advances in GLAD-based gas sensor design, focusing on how structural engineering and material integration converge to enhance sensor performance. Key materials strategies include the construction of heterojunctions and core–shell architectures, controlled doping, and nanoparticle decoration using noble metals or metal oxides to amplify charge transfer, catalytic activity, and redox responsiveness. GLAD-fabricated nanostructures have been effectively deployed across multiple gas sensing modalities, including resistive, capacitive, piezoelectric, and optical platforms, where their high aspect ratios, tailored porosity, and defect-rich surfaces facilitate enhanced gas adsorption kinetics and efficient signal transduction. These devices exhibit high sensitivity and selectivity toward a range of analytes, including NO₂, CO, H₂S, and volatile organic compounds (VOCs), with detection limits often reaching the parts-per-billion level. Emerging innovations, such as photo-assisted sensing and integration with artificial intelligence for data analysis and pattern recognition, further extend the capabilities of GLAD-based systems for multifunctional, real-time, and adaptive sensing. Finally, current challenges and future research directions are discussed, emphasizing the promise of GLAD as a scalable platform for next-generation gas sensing technologies. Full article

This study theoretically investigates the potential of a polyacrylamide copolymerized with amylose, a primary component of starch, to evaluate its efficiency in removing heavy metals from industrial wastewater. This material concept seeks to combine the high adsorption capacity of polyacrylamide with the low cost and biodegradability of starch, ultimately aiming to offer an economical, efficient, and sustainable alternative for wastewater treatment. To this end, a computational model based on density functional theory (DFT) was developed, utilizing the B3LYP functional with the 6-311++G(d,p) basis set, a widely recognized combination that strikes a balance between accuracy and computational cost. The interactions between an acrylamide-amylose (AM/Amy) polymer matrix, as well as the individual polymers (AM and Amy), and the metal ions Pb, Hg, and Cd in their hexahydrated form (M·6H₂O) were analyzed. This modeling approach, where M represents any of these metals, simulates a realistic aqueous environment around the metal ion. Molecular geometries were optimized, and key parameters such as total energy, dipole moment, frontier molecular orbital (HOMO-LUMO) energy levels, and Density of States (DOS) graphs were calculated to characterize the stability and electronic reactivity of the molecules. The results indicate that this proposed copolymer, through its favorable electronic properties, exhibits a high adsorption capacity for metal ions such as Pb and Cd, positioning it as a promising material for environmental applications. Full article

The adsorption performance of maize seeds in air-suction seed metering devices directly affects the operational quality of maize seeders. The suction holes on the seed metering disc play a crucial role in determining the device’s ability to adsorb maize seeds and serve as a key design parameter for air-suction seed metering systems. Existing research has primarily focused on seed posture control and suction force models for standard particles, while experimental studies on the actual adsorption performance of maize seeds remain scarce. To further investigate the adsorption characteristics of maize seeds under different suction hole geometries, this study employed a self-developed adsorption force measurement platform to conduct experiments on maize seeds in various adsorption postures. The resulting force–displacement curves reveal the variation of adsorption force as seeds detach from the suction holes. To assess the applicability of conventional suction force calculation models, computational fluid dynamics (CFD) simulations were performed to analyze the adsorption mechanism of standard particles. The simulation results indicate significant limitations in commonly used suction force estimation methods. For instance, in experiments evaluating the effect of equivalent adsorption area, the relative error between the suction force estimated by the traditional pressure-based method for triangular holes and the actual measured force reached 40.82%. Similarly, the relative error between the force estimated by the airflow drag method for square suction holes and the actual measured force under the same conditions was 17.14%. Therefore, when evaluating actual seed adsorption, it is essential to comprehensively consider factors such as suction hole geometry, blocked suction area, seed shape, vacuum pressure, and the overlap depth between the seed boundary and the suction hole, all of which significantly influence the adsorption effect. Full article

Silicon–lithium clusters are promising candidates for hydrogen storage due to their lightweight composition, high gravimetric capacities, and favorable non-covalent binding characteristics. In this study, we employ density functional theory (DFT), global optimization (AUTOMATON and Kick–MEP), and Born–Oppenheimer molecular dynamics (BOMD) simulations to evaluate the structural stability and hydrogen storage performance of key Li–Si systems. The exploration of their potential energy surface (PES) reveals that the true global minima of Li₆Si₆ and Li₁₀Si₁₀ differ markedly from those of the earlier Si–Li structures proposed as structural analogs of aromatic hydrocarbons such as benzene and naphthalene. Instead, these clusters adopt compact geometries composed of one or two Si₄ (T_d) units and a Si₂ dimer, all stabilized by surrounding Li atoms. Motivated by the recurrence of the Si₄–T_d motif, we explore oligomers of Li₄Si₄, which can be viewed as electronically transmuted analogues of P₄, confirming the additive H₂ uptake across dimer, trimer, and tetramer assemblies. Within the series of Si–Li clusters evaluated, the Li₁₂Si₅ sandwich complex, featuring a σ-aromatic Si₅¹⁰⁻ ring encapsulated by two Li₆⁵⁺ moieties, achieves the highest hydrogen capacity, adsorbing 34 H₂ molecules with a gravimetric density of 23.45 wt%. Its enhanced performance arises from the high density of accessible Li⁺ adsorption sites and the electronic stabilization afforded by delocalized σ-bonding. BOMD simulations at 300 and 400 K confirm their dynamic stability and reversible storage behavior, while analysis of the interaction regions confirms that hydrogen adsorption proceeds via weak, dispersion-driven physisorption. These findings clarify the structure–property relationships in Si–Li clusters and provide a basis for designing modular, lightweight, and thermally stable hydrogen storage materials. Full article

The main goal of the present study was to verify in detail whether the use of a cluster model for Stone–Wales (SW) defect-containing graphene (SWG) to study the adsorption of Ln atoms yields results similar to those previously obtained by employing a periodic model. We addressed this question by analyzing the optimized geometries of SWG + Ln complexes, their formation energies, and selected electronic parameters (in particular, the frontier orbital energies and atomic charges and spins). Within the frame of density functional theory, we used the computational methodology of the PBE-D2/DNP theoretical level using ECP pseudopotentials. The most important conclusion is that the use of a cluster model gives qualitatively similar results to those of the periodic model. While the corresponding plots of the dihedral angles θ versus the Ln atoms differ considerably, the two models have many common features in the trends of the bonding strength despite the use of two very different theoretical tools, namely periodic (plane waves) versus cluster calculations (localized basis sets). In comparing the results for SW defect-free and SW defect-containing cluster models, it is evident that SW defects serve as much more preferential adsorption sites compared to the conditions in the defect-free graphene model. Full article

The COVID-19 pandemic highlighted the urgent need for sustainable and scalable air disinfection technologies in HVAC systems, addressing the limitations of energy-intensive and chemically intensive conventional methods. This study developed and evaluated a pilot experimental installation integrating plasma chemistry and photocatalysis for airborne pathogen and pollutant mitigation. The installation, designed with a modular architecture to simulate real-world HVAC dynamics, employed a bipolar plasma ioniser, a TiO₂ photocatalytic module, and an adsorption-catalytic module for ozone abatement. Characterization techniques, including SEM and BET analysis, were used to evaluate the morphology and surface properties of the catalytic materials. Field tests in a production room demonstrated a 60% reduction in airborne microflora in three days, along with effective decomposition of ozone. The research also determined the optimal electrode geometry and interelectrode distance for stable corona discharge, which is essential for efficient plasma generation. Energy-efficient design considerations, which incorporate heat recovery and heat pump integration, achieved a 7–8-fold reduction in air heating energy consumption. These results demonstrate the potential of integrated plasma photocatalysis as a sustainable and scalable approach to enhance indoor air quality in centralised HVAC systems, contributing to both public health and energy efficiency. Full article

The pore–fracture structure of ultra-deep coal is critical for evaluating resource potential and guiding the exploration and development of deep coalbed methane (CBM). In this study, a coal sample was obtained from the Gaogu-4 well at a depth of 4369.4 m in the Shengli Oilfield of Shandong, China. A comprehensive suite of characterization techniques, including Field Emission Scanning Electron Microscopy (FE-SEM), X-ray diffraction (XRD), Mercury Intrusion Porosimetry (MIP), Low-temperature Nitrogen Adsorption (LT-N₂GA), and Low-pressure CO₂ Adsorption (LP-CO₂GA), were employed to investigate the surface morphology, mineral composition, and multi-scale pore–fracture characteristics of the ultra-deep coal. Based on fractal geometry theory, four fractal dimension models were established, and the pore structure parameters were then used to calculate the fractal dimensions of the coal sample. The results show that the ultra-deep coal surface is relatively rough, with prominent fractures and limited pore presence as observed under FE-SEM. Energy Dispersive Spectrometer (EDS) analysis identified the elements such as C, O, Al, Si, S, and Fe, thus suggesting that the coal sample contains silicate and iron sulfide minerals. XRD analysis shows that the coal sample contains kaolinite, marcasite, and clinochlore. The multi-scale pore–fracture structure characteristics indicate that the ultra-deep coal is predominantly composed of micropores, followed by mesopores. Macropores are the least abundant, yet they contribute the most to pore volume (PV), accounting for 70.9%. The specific surface area (SSA) of micropores occupies an absolute advantage, accounting for up to 97.46%. Based on the fractal model, the fractal dimension of the coal surface is 1.4372, while the fractal dimensions of the micropores, mesopores, and macropores are 2.5424, 2.5917, and 2.5038, respectively. These results indicate that the surface morphology and pore–fracture distribution of the ultra-deep coal are non-uniform and exhibit statistical fractal characteristics. The pore–fracture structure dominated by micropores in ultra-deep coal seams provides numerous adsorption sites for CBM, thereby controlling the adsorption capacity and development potential of deep CBM. Full article

Atmospheric water harvesting (AWH) is a promising alternative to address immediate water needs. Desiccant-based AWH could compete effectively with other commercially available AWH technologies. One of the primary challenges facing desiccant-based AWH is the energy required to desorb the captured water vapor from the desiccant. This work presents a multi-faceted approach targeted explicitly at low-humidity and arid regions, aiming to overcome the limitations of the refrigerant-based AWH system. It includes assessing common desiccants (zeolite, activated alumina, and silica gel) and their forms (beads, powdered, or coated on a substrate). A bench-scale test rig was designed to evaluate different types and forms of desiccants for adsorption and desorption cycles and overall adsorption capacity (g/g), kinetic profiles, and rates. Experimental results indicate that beaded desiccants possess the highest adsorption capacity compared to powdered or coated forms. Furthermore, coated desiccants double the water uptake (1.12 vs. 0.56 g water/g desiccant) and improve adsorption/desorption cycling by 52% compared to beaded forms under the same conditions. Additionally, Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), and dynamic vapor sorption (DVS) analysis show the pore geometry, morphology, and sorption capacity. The goal is to integrate these performance improvements and propose a more effective, energy-efficient desiccant-based AWH system. Full article

The rapid growth of industrial activities has increased environmental pollution, and solar-driven heterogeneous photocatalysis using TiO₂ has emerged as a promising solution. However, its wide band gap limits its efficiency, prompting research into various optimization strategies. One of these approaches is surface functionalization. Thus, this study investigates the adsorption of CuSO₄ on the anatase TiO₂ (101) surface using density functional theory calculations. The adsorption process induced a magnetic moment of 0.97 µ_B and a slight reduction in overall bandwidth. A preferential adsorption geometry pattern with an energy of −4.31 eV was identified. Charge transfer analysis revealed a net transfer from the TiO₂ surface to the CuSO₄ molecule, with increased net atomic charges for atoms involved in new chemical bond formation, indicating a chemisorption process. These electronic structure modifications are expected to influence the electronic and catalytic properties of the material. The findings provide insights into the CuSO₄ adsorption mechanism on an anatase TiO₂ (101) surface and its impact on the properties of the material, contributing to a deeper understanding of this system. Full article

The Mn-Mn dimer has been found to be catalytically active in various manganese oxides for NO oxidation. However, to date, it remains unclear how the dimer determines catalytic performance. Herein, we employed a combination of DFT theoretical calculations and an experimental approach to investigate the O₂ dissociation capability and NO oxidation activity of single Mn sites and Mn-Mn dimer sites with varying bond lengths. Our results indicate that Mn-Mn dimer sites outperform single Mn active sites in both O₂ activation and NO oxidation. This enhancement is primarily attributed to the short-range ordered geometry of the Mn-Mn dimers, which suppresses the formation of NO₃* intermediates and promotes NO₂* desorption. Among the three types of Mn-Mn dimers examined, the Mn-Mn dimer in BaMnO₃, with the shortest Mn-Mn bond length, aligns most favorably with O-O, supporting the most efficient O₂ activation. Conversely, MnO₂, characterized by the longest Mn-Mn bond length, exhibits greater charge transfer and synergistic effects at the local active site, achieving the highest NO catalytic activity. Furthermore, we found that dual-site exposure of Mn-Mn dimers is more effective for catalytic reactions than single-site exposure. This study provides important insights into the structure–activity relationship between the geometric structure of catalytic active sites and the adsorption of intermediates. Full article

Zeolites are amongst the most extensively explored crystalline microporous materials because of their variable chemical composition, framework geometry, pore dimensions, and tunability. Due to their high surface area, adsorption selectivity, mechanical, biological, chemical, and thermal stability, these molecular sieves are widely used in adsorption, catalysis, ion exchange, and separation technologies. This short review highlights the notable progress achieved in leveraging the properties of zeolite materials for multiple applications, including gas separation and storage, adsorption, catalysis, chemical sensing, and biomedical applications. The aim is to emphasize their capabilities by showcasing important achievements that have driven research in this field toward new and unforeseen areas of material chemistry. Full article

Many properties of 2,4-dichlorophenoxyacetic acid (2,4-D) depend on its molecular environment, such as whether it is an isolated molecule, a dimer, or in a crystalline state. The molecular geometry, conformational analysis, and vibrational spectrum of 2,4-D were theoretically calculated using Density Functional Theory (DFT) methods. A new slightly more stable conformer was found, which is different to those previously reported. The most stable conformer shows a dimer by means of hydrogen bonds between the carboxylic groups of both molecules, which agrees with the experimental results. The crystal structure of 2,4-D was also calculated with 3D periodical boundary conditions at the DFT level. From the theoretical IR spectra, a vibrational analysis of this molecular species was accomplished, and the bands were reassigned. ¹H and ¹³C NMR in the dissolution and solid states, respectively, showed intramolecular hydrogen bonds between carboxylic acid groups. The dimer is more stable than the isolated molecule. All these results indicated that the dimer can also exist in the solid state, which could explain the low solubility of this compound. In addition, the intercalation of 2,4-D into the confined interlayer space of montmorillonite was also calculated, and it was found that the adsorption is energetically favourable. This result was experimentally confirmed. These findings predicted that these natural clay minerals, which are found in the environment, can be excellent adsorbents for the 2,4-D pollutant. Full article