Adsorption Behavior Research Articles

Understanding the adsorption performance of hetero-nanocages (C12-B6N6, C12-Al6N6, and B6N6-Al6N6) towards hydroxyurea anticancer drug: a comprehensive study using DFT.

Cancer is a paramount health challenge to global health, which forms tumors that can invade nearby tissues and spread to neighboring cells. Recently, nanotechnology has been used to control the growth of cancer, in which anticancer drugs are delivered to cancerous cells via nanoparticles without damaging healthy tissues. In this study, DFT investigations were carried out to examine the adsorption behavior of C24, B12N12, and Al12N12 nanocages as well as their heterostructures C12-B6N6, C12-Al6N6, and B6N6-Al6N6 towards the hydroxyurea (HU) anticancer drug. In this regard, adsorption energy, interaction distance between the drug and nanocages, charge transfer, energy gap, dipole moment, quantum molecular descriptors, work function, and COSMO surface analysis were analyzed to understand their adsorption performance. Findings demonstrate that the adsorption energies of two hetero-nanocages on their hexagonal (SH) and tetragonal (ST) sites are favorable for the drug delivery process. The computed adsorption energy of B6N6-Al6N6 of the ST/AlN site is 183.59 kJ mol-1, which is higher than that of the C12-Al6N6 nanocage, including minimum adsorption distances. Negative adsorption energy with low adsorption distances implies an attractive interaction between the drug and nanocages. During the interaction, a significant amount of charge is transferred between the drug and nanocages. Furthermore, for both complexes, larger dipole moments were observed in water media compared to gas media. From DOS spectra, prominent peaks were found in the Fermi level after adsorption of HU on the nanocages, implying the reduction of the energy gap. Noticeable overlaps between the PDOS spectra of the nanocages and HU's close contact atom demonstrate the formation of chemical bonds between two specific atoms. Therefore, it can be concluded that among the nanocages, C12-Al6N6 and B6N6-Al6N6 may be suitable carriers for HU drug.

Layered double hydroxides/biochar composites for adsorptive removal of tetracycline and ciprofloxacin

Modification of biochar (BC) using layered double hydroxides (LDHs) is an anticipated strategy to strengthen the adsorption performance of BC. In this work, sawdust was used to prepare pristine BC to act as a matrix, and the MgFe-LDHs were selected as typical LDHs to prepare BC-LDHs composites via a coprecipitation technique, and the adsorption mechanisms toward tetracycline (TC) and ciprofloxacin (CIP) were evaluated. The effect of LDHs amount on the characteristics of BC-LDHs composites and the adsorption behavior and mechanisms of TC and CIP were also studied. Results showed that the loading of LDHs reduced the specific surface area and total pore volume of BC but developed more mesoporous structure in composites, created metal oxygen-containing functional groups (Mg–OH, Mg–O, Fe–O), and introduced a typical mineral (Mg6Fe2(OH)16CO3·4H2O) on the surface of the BC. The BC-1/3LDHs obtained by loading LDHs on 3 g BC exhibited the maximum adsorption capacity toward TC and CIP, and reached 77.04 mg∙g−1 and 66.74 mg∙g−1, respectively. The introduction of MgFe-LDHs greatly intensified the complexation interaction and hydrogen bonding of the composites. The Freundlich and pseudo-second-order models well-described the adsorption process of TC and CIP on BC-1/3LDHs. In addition, BC-1/3LDHs could adsorb TC and CIP in a wide range of pH values despite the interference of coexisting ions and also presented a good recycle utilization potential. Furthermore, the introduction of LDHs, especially BC-1/3LDHs, shifted the adsorption thermodynamic properties of BC. Overall, the prepared BC-1/3LDHs could be used as a promising adsorbent for the removal of TC and CIP from water environments.

Tuning of Particle Size of Zeolitic Imidazolate Framework-7 via Rapid Synthesis Duration for CH4 Adsorption

In this work, zeolite imidazolate framework-7 (ZIF-7) nanoparticles are synthesized via a solvothermal method and rapid synthesis durations of 1 h and 3 h. The effect of the synthesis duration on the structural properties of ZIF-7 was characterized by XRD and FESEM analyses. Subsequently, CH4 single gas adsorption over ZIF-7 nanoparticles was examined using the volumetric method at room temperature and pressure ranging from 2 to 9 bar. The results showed that the synthesized ZIF-7 adsorbents were highly crystalline with a well-defined and homogeneous particle size distribution of 50–60 nm. It was found that increasing the synthesis duration from 1 h to 3 h did not amend the structure and morphology of the resultant samples significantly, mainly due to the short synthesis duration. Meanwhile, the CH4 adsorbed by ZIF-7 nanoparticles increased with rising pressure for both samples, and the ZIF-7 nanoparticles synthesized at 3 h showed a greater adsorption capacity than that of 1 h, mainly due to its higher crystallinity and well-developed pore structure. The ZIF-7 synthesized at 3 h demonstrated an adsorption capacity up to 2.2 mol/kg, which was higher than those values reported in the literature for micron-sized ZIF-7 samples. The CH4 gas adsorption behavior of ZIF-7 nanoparticles synthesized at 1 h and 3 h were well predicted by the Langmuir isotherm model, with coefficients of determination, R2, of 0.9994 and 0.9982, respectively.

Adsorption of eco-friendly insulating gas C4F7N on PdSe2 monolayer surface: A first-principles study

Heptafluoro-isobutyronitrile (C4F7N) is a novel environmentally friendly insulating and arc extinguishing gas utilized as a replacement for SF6 in gas insulated equipment (GIE). Nevertheless, the potentially hazardous decomposition byproducts of C4F7N resulting from sudden equipment failure may jeopardize the normal operation of GIE and the physical well-being of the operator. In this paper, using the first principles study the adsorption behavior of four common C4F7N decomposition gases (CF4, COF2, CF3CN, C2F5CN) on PdSe2 monolayer, and explore the adsorption mechanism of PdSe2 monolayer on C4F7N decomposition gas. The results show that the PdSe2 monolayer interacts with the four decomposition gases by physical adsorption mechanism, in which the PdSe2 monolayer causes the largest change in electronic properties and maximum work function (0.15 eV) near the Fermi level before and after adsorption of C2F5CN, indicating a strong interaction between C2F5CN and PdSe2 monolayer. The sensitivity of PdSe2 monolayer to C2F5CN was up to 68.61 %. Therefore, PdSe2 monolayer has the potential of selective detection of C2F5CN gas sensing materials, and the findings in this paper provide theoretical guidance for the development of PdSe2 monolayer gas sensing sensors for monitoring C4F7N insulation equipment.

Innovative strategies for time-release PCE design and cement paste flowability control

Extending the retention time of cement paste flowability with the addition of admixtures containing slow-release components is standard practice for ensuring the continued building quality of cement-based materials. This study aims to control the release rate of PCE and enhance its time-varying dispersion effect in fresh cement paste by utilizing Time-dependent Release PCEs (TRPCEs) with varying side-chain structures. The structural characterization of the synthesized TRPCEs was investigated using GPC (Gel Permeation Chromatography), FTIR (Fourier Transform Infrared Spectroscopy), and 1H NMR (Proton Nuclear Magnetic Resonance) techniques. Furthermore, experiments were carried out on time-varying flowability with different dosages of TRPCEs to investigate the flowability changes under the time-varying release effect. The influence of TRPCEs on cement hydration was examined using isothermal calorimetry by measuring the early hydration heat of cement paste. The time-dependent adsorption behaviors of TRPCEs were also examined using a TOC (Total Organic Carbon) analyzer. The findings show that TRPCEs have a minor effect on the cement hydration process's rapid reaction period but little effect on its induction and acceleration periods because of variations in the initial dispersion effect. Additionally, the adsorption behaviors of TRPCEs on cement particles vary significantly due to the hydrolysis of slow-release groups. The varying adsorption and consumption of TRPCEs on cement particles and hydration products in different hydration phases are key controlling factors for the time-varying flowability changes in cement paste. Finally, this innovative approach offers a novel perspective for designing and preparing new types of PCEs with a strong capability for time-varying flowability retention.

The adsorption mechanism and optimal dosage of walnut shell biochar for chloramphenicol

Biochar derived from biomass pyrolysis has proven to be an excellent material for pesticide adsorption and can be used as soil amendment for pesticide non-point pollution. However, the adsorption and desorption mechanisms for certain biochar and pesticide are still unclear. In this study, we investigated the properties of biochar derived from walnut (Juglans regia L.) shell (WSB), and used batch equilibrium method to investigate the adsorption and desorption behavior for chlorantraniliprole (CAP). The physical-chemical analysis showed that there were mainly lignin charcoal of alkyl carbon, methoxyl carbon, aromatic carbon, and carboayl carbon as the primary carbon compounds of WSB. The π - π electron donor acceptor interaction, electrostatic interaction, and hydrogen bond were the primary adsorption mechanisms of the WSB adsorption. Batch equilibrium study under 298 K showed that WSB application in the soil significantly improved the adsorption ability for CAP, and the adsorption behavior was a mono-layer adsorption process as Langmuir model fitted the adsorption isotherm data better than the Freundlich model. While Freundlich model analysis showed that WSB addition to the soil changed the isothermal adsorption line from the S style to the L style. The spontaneous degree reaction of sorbents from strong to weak was in the following order: 5%-WSB >7%-WSB >10%-WSB >1%-WSB >3%-WSB > soil > WSB, and the maximum application effect was achieved at 5 % (m/m) WSB dosage mixed with the soil. Therefore, we considered that WSB addition in soil increased its CAP adsorption capacity, and 5 % (m/m) WSB application was the best choice for CAP pollution control. These data will contribute to the adsorption mechanism and the optimal use dosage of WSB for CAP pollution control.

Adsorption behaviors and mechanisms of gold recovery from thiosulfate solution by ion exchange resin

The adsorption behaviors and mechanisms of gold from thiosulfate solution on strong-base anion exchange resin were systematically investigated. The comparison experiment of adsorption ability and selectivity for gold showed that gel Amberlite IRA-400 resin with Type I quaternary ammonium functional group had better adsorption performance. The increases of resin dosage, ammonia concentration and solution pH were favorable to gold adsorption, whereas the rises of cupric and thiosulfate concentrations were disadvantageous to gold loading. Microscopic characterization results indicated that gold was adsorbed in the form of [Au(S2O3)2]3– complex anion by exchanging with the counter ion Cl– in the functional group of the resin. Density functional theory calculation result manifested that gold adsorption was mainly depended on the hydrogen bond and van der Waals force generated between O atom in [Au(S2O3)2]3– and H atom in the quaternary ammonium functional group of the resin.

Molecular dynamics of CH4 adsorption and diffusion characteristics through different geometric shale kerogen nanopores

In shale, pore structure plays an extremely significant effect on CH4 storage and transportation in a reservoir, especially for the reservoir involving large amounts of extremely tiny nanopore and variance of microstructure. In this study, three molecular dynamics models for different types of kerogen nanopores such as serration type, arc type and great-wall type are established, validated and implemented to assess the impact of pore structure on CH4 adsorption and diffusion behaviors in kerogen matrix and nanopore at temperature 320 ∼ 380 K, pressure 5 ∼ 20 MPa and pore size 3 ∼ 5 nm. The simulation results demonstrate that the CH4 density in the bulk of serration-type, arc-type and great-wall-type pores is 1.6, 1.3 and 1.9 higher than that inside kerogen molecules. Increasing temperature can weaken the adsorption capacity of kerogen, but the serration-type pore is the most sensitive to temperature. Regardless of the pore type, increasing pressure can significantly enhance the adsorption capacity of kerogen which is almost unaffected by pore size, whereas the CH4 diffusion coefficient increases with pore size. Furthermore, the great-wall-type pore can adsorb more CH4 molecules due to its smooth surface, followed by change in the arc-type and serration-type pores in turn. Among these types of pores, the CH4 diffusion coefficient is the most insensitive to the size of arc-type pore. Hence, the influences of kerogen pore structure under different conditions of temperature, pressure and pore size are quantified in this work to improve a comprehensive understanding of CH4 adsorption and diffusion behaviors in shale, thereby contributing to high-efficient and sustainable development of shale gas reservoirs.

Cell Mediated Reactions Create TGF-β Delivery Limitations in Engineered Cartilage

During native cartilage development, endogenous TGF-β activity is tightly regulated by cell-mediated chemical reactions in the extracellular milieu (e.g., matrix and receptor binding), providing spatiotemporal control in a manner that is localized and short acting. These regulatory paradigms appear to be at odds with TGF-β delivery needs in tissue engineering (TE) where administered TGF-β is required to transport long distances or reside in tissues for extended durations. In this study, we perform a novel examination of the influence of cell-mediated reactions on the spatiotemporal distribution of administered TGF-β in cartilage TE applications. Reaction rates of TGF-β binding to cell-deposited ECM and TGF-β internalization by cell receptors are experimentally characterized in bovine chondrocyte-seeded tissue constructs. TGF-β binding to the construct ECM exhibits non-linear Brunauer–Emmett–Teller (BET) adsorption behavior, indicating that as many as seven TGF-β molecules can aggregate at a binding site. Cell-mediated TGF-β internalization rates exhibit a biphasic trend, following a Michaelis-Menten relation (Vmax=2.4 molecules cell-1 s-1, Km=1.7 ng mL-1) at low ligand doses (≤130ng/mL), but exhibit an unanticipated non-saturating power trend at higher doses (≥130ng/mL). Computational models are developed to illustrate the influence of these reactions on TGF-β spatiotemporal delivery profiles for conventional TGF-β administration platforms. For TGF-β delivery via supplementation in culture medium, these reactions give rise to pronounced steady state TGF-β spatial gradients; TGF-β concentration decays by ∼90% at a depth of only 500 μm from the media-exposed surface. For TGF-β delivery via heparin-conjugated affinity scaffolds, cell mediated internalization reactions significantly reduce the TGF-β scaffold retention time (160 to 360-fold reduction) relative to acellular heparin scaffolds. This work establishes the significant limitations that cell-mediated chemical reactions engender for TGF-β delivery and highlights the need for novel delivery platforms that account for these reactions to achieve optimal TGF-β exposure profiles. Statement of SignificanceDuring native cartilage development, endogenous TGF-β activity is tightly regulated by cell-mediated chemical reactions in the extracellular milieu (e.g., matrix and receptor binding), providing spatiotemporal control in a manner that is localized and short acting. However, the effect of these reactions on the delivery of exogenous TGF-β to engineered cartilage tissues remains not well understood. In this study, we demonstrate that cell-mediated reactions significantly restrict the delivery of TGF-β to cells in engineered cartilage tissue constructs. For delivery via media supplementation, reactions significantly limit TGF-β penetration into constructs. For delivery via scaffold loading, reactions significantly limit TGF-β residence time in constructs. Overall, these results illustrate the impact of cell-mediated chemical reaction on TGF-β delivery profiles and support the importance of accounting for these reactions when designing TGF-β delivery platforms for promoting cartilage regeneration.

Protein-metal interactions due to fretting corrosion at the taper junction of hip implants: An in vitro investigation using Raman spectroscopy

Modular hip implants are a clinically successful and widely used treatment for patients with arthritis. Despite ongoing retrieval studies the understanding of the fundamental physico-chemical mechanisms of friction and wear within the head-taper interface is still limited. Here, we Raman-spectroscopically analyze structural features of the biotribological material which is formed within the taper joint between Ti6Al4V and low-carbon cobalt alloy or high-nitrogen steel surfaces in in vitro gross-slip fretting corrosion tests with bovine calf serum. As a function of the fretting duration, we investigate short and long aliphatic chains and their adsorption behavior on the cobalt- and steel-type surfaces. Using the intensity and frequency shifts of the amide I and III Raman bands, we furthermore identify progressive protein folding and unfolding including the secondary structures of α-helix, β-sheet, and random-coil configuration as well as the formation of proteinaceous clusters depending on the hydrophilicity of the metallic surfaces. We additionally find a mixture of chromates and iron oxides with tryptophan and tyrosine at the worn cobalt alloy and high-nitrogen steel surfaces, respectively. Also, for long fretting duration, sp2 hybridized amorphous carbon is formed due to fretting-induced cleavage of proteins. Statement of significanceDespite efforts enhancing the biomedical tribology of hip implants, the impact of the organic environment on friction and wear at the femoral head-stem taper interface is limitedly understood. Using Raman spectroscopy we resolve structural changes within the biotribological material agglomerated at biomedical-grade metal alloys due to metal-organic interactions during in vitro fretting corrosion tests. Adsorption of short and long aliphatic chains, progressive protein (un)folding and proteinaceous cluster formation depend to a distinguishable extent on the fretting duration and type of alloy. Chromates and iron oxides are mixed with tryptophan and tyrosine, and amorphous carbon is formed resulting from a fretting-induced cleavage of serum proteins. Such information spectroscopically gleaned from biotribological material are vital to improve the design and performance of taper junctions.

Roles of Nitrogen- and Sulphur-Containing Groups in Copper Ion Adsorption by a Modified Chitosan Carboxymethyl Starch Polymer

Owing to the toxicity and widespread use of copper, the pollution caused by copper ions has become a long-standing environmental and industrial challenge. In this study, a new adsorbent was developed to dispose of and remove copper ions from water. The modified chitosan–carboxymethyl starch (MCTS-CMS) polymer was characterised, and FTIR and SEM-EDS confirmed the successful graft modification of the receptor. The adsorption behaviour was investigated through various parameters, and the results showed that the optimal parameters were pH > 4.0, an adsorption time of 30 min, a reaction temperature of 293 K, and an initial concentration of 100–120 mg/L. The experimental data exhibited a good fit with pseudo-second-order models, and the Langmuir isotherm revealed that the polymer was found to be highly suitable for adsorption, with a maximum adsorption capacity of 321.16 mg/g. Thermodynamic analysis revealed that the adsorption process was exothermic and spontaneous. XRD and XPS confirmed the generation of posnjakite after the adsorption and the predominant roles of nitrogen- and sulphur-containing groups in the adsorption. Further analysis confirmed the existence of chemisorption and physical adsorption, with chemisorption mainly facilitating the Cu(II) absorption of the polymer. MCTS-CMS showed an excellent removal efficiency of 98% in acidic solutions. On the basis of these findings, the MCTS-CMS polymer demonstrates excellent performance and high selectivity in the removal of copper ions from industrial wastewater or polluted water bodies. This work recommends expanding the polymer’s practical applications to contribute to water purification efforts.

Performance study of phenol sequestration from agricultural wastewater by chemical activated Montmorillonite

Agricultural by-products possess potential as cost-effective adsorbents for the remediation of phenolic contaminants in environmentally treated wastewater. This research focuses on the utilization of Algerian montmorillonite clay, specifically modified montmorillonite (Mo-5N), treated with 5N hydrochloric acid (HCl), compared to its untreated form (Mo-0N), for phenol sequestration from pesticide-laden waters. We employed various analytical techniques, such as chemical analysis, X-ray diffraction (XRD), and Fourier Transform Infrared (FTIR) spectroscopy, to characterize these adsorbents. The adsorption behavior was scrutinized under varying conditions, including pH, contact time, phenol concentration, and temperature. The maximum adsorption capacities achieved were 119.12 mg/g for Mo-5N and 100.89 mg/g for Mo-0N under optimal conditions of pH 5.72, a contact time of 120 minutes, and a temperature of 40°C. The kinetics of adsorption were best described by the pseudo-second-order and Elovich models, while the Freundlich isotherm model aptly described the equilibrium data. Thermodynamic analyses revealed that the phenol removal process using both forms of montmorillonite is spontaneous and endothermic. This study demonstrates the efficacy of Algerian montmorillonite clay in the removal of phenolic pesticides from agricultural wastewater.

Adsorption behavior and surface complexation models of plumbum and cadmium in basalt yellow soil

Adsorption behavior and surface complexation models of plumbum and cadmium in basalt yellow soil

An innovative guanidinium-based ionic covalent organic frameworks with abundant aromatic rings for high-efficiency naproxen removal: Adsorption behavior, mechanisms, and density functional theory calculations

In recent years, naproxen (NPX) has raised significant environmental concerns requiring urgent attention. This study presents an innovative guanidinium-based ionic covalent organic framework (TFPB-TgCl), containing abundant aromatic rings, which was successfully synthesized via Schiff base reaction for the efficient and selective removal of NPX. Remarkably, TFPB-TgCl manifested a maximal NPX adsorption capacity of 308 mg/g at pH = 5. The adsorption on the active site (AOAS) model highlighted the simultaneous occurrence of both physical and chemical adsorption during the NPX uptake. The coefficients of the physical adsorption rates (5.6479, 1.9224, and 1.9224 min−1 for NPX concentrations of 20, 50, and 100 mg/L, respectively) were significantly higher than those of the chemical adsorption rates (0.1759, 0.0681, and 0.0567 g·mg−1·min−1 for the same concentrations), indicating the predominance of physical adsorption. Furthermore, the multilayer adsorption (MLA) model suggested that an adsorption site can interact with more NPX molecules, benefiting from various electrostatic and π-π interactions. The negative values of enthalpy change (ΔH° = −11.956 kJ/mol) and Gibbs free energy (ΔG < 0) confirmed the exothermic and spontaneous nature of the adsorption process. Additionally, in the optimal adsorption configuration (−131.57 kcal/mol), the Independent Gradient Model based on Hirshfeld partition (IGMH) was utilized to identify interaction sites between the guanidinium group of TFPB-TgCl and the carboxyl group of NPX, with subsequent electrostatic potential (ESP) analysis emphasizing their crucial role in electrostatic adsorption. Overall, the adsorption mechanism of electrostatic and π-π interactions in TFPB-TgCl highlights the significant contribution of its guanidinium and aromatic rings in facilitating NPX adsorption.

Mesoporous TiO2@nitrogen-doped carbon nanosheets implanted in flexible and robust chitosan membrane with dual-function for efficient adsorption of iodide and methyl orange from aqueous solution

Radioactive iodide (I−) and methyl orange (MO) are two leading pollutants in wastewater, posing significant health risks. Crosslinked chitosan membranes (CCM) combined with TiO2@nitrogen-doped carbon nanosheets (CCM/TiO2@NC) were prepared as efficient I− and MO adsorbents in wastewater. These membranes leverage multiple interactions between I−/MO and functional groups (−NH2, nitrogen-doped carbon, and TiO2) within the membrane. As expected, CCM/TiO2@NC exhibited high I− removal efficiencies of nearly 82 % across a wide pH range (pH 3 − 11) and an exceptional MO removal efficiency of 96.1 % at a neutral condition. The adsorption behaviors followed the Langmuir isotherm and pseudo-second order kinetic model for both species, achieving maximum adsorption capacities of 1.383 mmol/g (175.6 mg/g) for I− and 661.4 mg/g for MO, respectively. Additionally, CCM/TiO2@NC maintained a high absorption efficiency for both I− and MO through five regeneration cycles. The I− adsorption mechanism of CCM/TiO2@NC involves electrostatic attraction, anion-π interaction, and hydrogen bonding, while MO adsorption involves electrostatic attraction, n/π-π interactions, and hydrogen bonding. This study offers feasible guidance on developing chitosan/nanomaterial composites as promising adsorbents for removing I− and MO from wastewater.

Effects of cyanotoxins on nitrogen transformation in aquaculture systems with microplastics coexposure: Adsorption behavior, bacterial communities and functional genes

Microcystin-LR (MC-LR) and microplastics (MPs) have attracted increasing attention as important new pollutants in freshwater fishery environments. However, there are few reports on the effects of long-term combined MC-LR and MPs pollution on nitrogen transformation and microbial communities in aquaculture ponds, and the resulting risks have yet to be determined. Therefore, in this study, traditional refractory MPs (polystyrene, PS), biodegradable MPs (polylactic acid, PLA) and MC-LR, which are common in freshwater fishery environments in China, were selected as pollutants to construct a microcosm that simulates freshwater aquaculture ponds. MC-LR coexposure to PS and PLA was tested to reveal the effects of these pollutants on nitrogen transformation and microbial communities in aquaculture ponds, as well as to elucidate the potential risks posed by traditional refractory MPs and biodegradable MPs to freshwater aquaculture ecosystems. The results revealed that the MPs had a relatively high adsorption rate for MC-LR and that PS presented a relatively high adsorption capacity, whereas PLA presented a relatively high desorption capacity. Single or combined MPs and MC-LR pollution disrupted the normal nitrogen cycle in the aquaculture system, causing an overall loss of nitrogen in the water, and denitrification and nitrogen fixation in the water were inhibited to a certain extent through the inhibition of nitrogen cycle-related functional genes, with the PS + MC-LR group having the greatest inhibitory effect. In addition, compared with single-pollutant exposure, combined exposure to MC-LR and MPs had a greater effect on the microbial community composition. Analysis of the integrated biomarker response (IBR) index revealed that the risk of combined exposure to MC-LR and PS was greater than that of single exposure, so this phenomenon merits further attention.

Exploring the adsorption characteristics of quinoline derivatives on iron via ab initio DFT simulations and COSMO-RS profiles

Quinoline derivatives have been the subject of extensive research due to their excellent electronic properties and wide range of applications. This study conducts a comprehensive computational examination of the adsorption properties of substituted quinoline derivatives on Fe(110) surfaces. Four specific compounds, namely 2-amino-7-hydroxy-4-phenyl-1,4-dihydroquinoline-3-carbonitrile (QN1), 2-amino-7-hydroxy-4-(p-tolyl)-1,4-dihydroquinoline-3-carbonitrile (QN2), 2-amino-7-hydroxy-4-(4-methoxyphenyl)-1,4-dihydroquinoline-3-carbonitrile (QN3), and 2-amino-4-(4-(dimethylamino)phenyl)-7-hydroxy-1,4-dihydroquinoline-3-carbonitrile (QN4) were investigated using first-principles density functional theory (DFT) calculations along with COSMO-RS analysis for solvation properties. Our results revealed that the presence of functional groups significantly influence the adsorption strength on Fe(110) surfaces. Quinoline molecules have adsorbed on the iron surface through complex mechanisms involving physical interactions and charge transfer. Specifically, QN1 and QN4 showed strong physical interactions with iron atoms while QN2 and QN3 exhibited high affinity to coordinate with Fe atoms. The stability of coordinated quinolines was enhanced by a notable charge redistribution and bond formation as observed via projected density of states (PDOS). On the other hand, electron density difference (EDD) and electron localization function (ELF) iso-surfaces highlighted the critical role of van der Waals interactions, predominantly influenced by nitrogen atoms, in stabilizing the adsorbed molecules. The COSMO-RS analysis elucidated the solvation characteristics, emphasizing the importance of hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) in the interaction of quinolines with water molecules. Overall, this study provides crucial insights into the molecular mechanisms underlying the corrosion inhibition properties of quinoline derivatives, emphasizing the influence of functional groups and solvation effects on adsorption behavior and stability.

A DFT study of SF6 decomposition products (H2S, SO2, and CS2) adsorption and detection on Pd-ZnO/SnS2 ternary composites

Real-time and accurate detection of SF6 decomposition products is a crucial approach to diagnosing internal faults of gas-insulated switchgear (GIS). However, the limited sensitivity and selectivity of SnS2 gas sensors have hindered their further development and application. This study employs density functional theory to design the optimal Pd-ZnO/SnS2 monolayer structure and investigate its adsorption behavior toward H2S, SO2, and CS2. The findings indicate that Pd atom doping and ZnO nanoparticle incorporation significantly enhance the conductivity of the SnS2 monolayer, reducing the band gap to 0.54 eV and lowering the work function by 5.019 eV. Regarding gas adsorption and sensing, the Pd-ZnO/SnS2 monolayer outperforms intrinsic SnS2 and ZnO/SnS2, showing the order in which SF6 decomposition products are selected is: CS2 > SO2 > H2S. Additionally, the sensitivity and recovery time of Pd-ZnO/SnS2 as a gas sensor were evaluated, confirming its excellent sensing performance for SO2 and CS2 detection. This study provides theoretical insights to advance the application of gas sensors in online insulation equipment monitoring.

Study on the preparation of a novel acrylic modified magnetic chitosan adsorbent and the adsorption behavior on Ga (III)

In the current study, a novel acrylic modified magnetic chitosan adsorbent (M- AA −CTS) was prepared, and then characterized using SEM, FTIR, and XPS. The preparation conditions, adsorption conditions, adsorption kinetics and thermodynamics were also studied. FTIR results indicate that acrylic acid is grafted onto the amino groups of chitosan in the form of poly acrylic acid and the amino groups are also crosslinked with glutaraldehyde. For the preparation process, the removal efficiency of Ga (III) ions is higher when the amount of acrylic acid is 3 mL, the reaction temperature is 308 K, the crosslinking time is 80 min, and the amount of glutaraldehyde is 0.6 mL. During the adsorption process, the higher adsorption capacity of Ga (III) ions can be achieved under the condition of the initial concentration of Ga (III) ions 50 mg/L, the adsorbent dose 0.05 g, the oscillation temperature 308 K and pH 3. The study on the adsorption kinetic indicates that the adsorption follows the pseudo-second-order kinetic model. The study on isotherm adsorption and thermodynamic indicates that the adsorption isotherm fits the Langmuir isotherm model better and the saturated adsorption capacity of Ga (III) ions on M−CTS−AA can reach 183.09 mg/g. Study on desorption and regeneration shows that after four cycles of desorption and reuse, the regeneration rate decreased from the initial 91.47 % to 73.3 %.

Synergistic effects of multi-walled carbon nanotubes and Mn0.4Cu0.6Fe2O4 on mercury removal with high efficiency and sulfur resistance

Although ferrite-based adsorbents are the potential mercury removal materials for the high thermal stability, they usually suffer from a low efficiency in flue gas environment, especially under SO2 condition. In the present paper, the multi-walled carbon nanotubes (MWCNTs) are utilized to improve the adsorption capacity of the Mn0.4Cu0.6Fe2O4 adsorbents as well as inhibit the influence of flue gas composition. The influences of temperature, adsorbent type and the flue gas composition on Hg0 removal efficiency are evaluated by experiments. The physical adsorption property of MWCNTs provides a platform for Hg0 oxidation by Mn0.4Cu0.6Fe2O4. The synergistic effect between MWCNTs and Mn0.4Cu0.6Fe2O4 enhances the mercury removal efficiency as well we the sulfur resistance. The results find that the adsorbent of Mn0.4Cu0.6Fe2O4 containing 14 % MWCNTs has a high mercury removal efficiency of 95.6 % at 120 °C even under 1000 ppm SO2 concentration. The kinetic behaviors of adsorbent adsorption are analyzed by theoretical models. The mechanisms of porous carbon-containing modifier to improve the mercury removal performance of Mn0.4Cu0.6Fe2O4 are explored carefully. The present ferrite-based adsorbent exhibits promising prospects for the practical industrial applications of the low temperature mercury removal from coal-fired flue gas.