Adsorption Of Compounds Research Articles

Mechanism insights and experimental feasibility of using boron nitride nanocones for rapid adsorption and degradation of SF6 decomposition compounds

Gas-insulated switchgear (GIS) employs sulfur hexafluoride (SF6) as an insulating medium to shield electrical gadget. However, SF6 can decompose under sure situations, generating dangerous sulfur-based totally compounds which include SO2, SOF2, and SO2F2. These byproducts pose enormous dangers to both protection and environmental integrity. Efficiently adsorbing and disposing of those compounds is critical for ensuring operational reliability and reducing environmental dangers. This study investigates the adsorption and degradation mechanisms of SF₆ decomposition compounds (SO₂, SOF₂, and SO₂F₂) on boron nitride nanocones (BNNCs) using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. Our comprehensive analysis covers five distinct systems, exploring individual and combined adsorption scenarios. The findings reveal that the apex of BNNCs plays a crucial role in the adsorption process, showing high efficiency in adsorbing SO₂ (adsorption energy − 1.22 eV) and facilitating the catalytic breakdown of SOF₂ (adsorption energy − 1.57 eV). The positively charged potential at the nanocone’s apex significantly influences the dissociation and subsequent adsorption of fluorine atoms, with an energy barrier for F dissociation at the apex (1.8 kcal/mol) much lower than at the sidewall (5.3 kcal/mol). In gas mixtures, SO₂ preferentially binds to the apex region of BNNCs, with a bond length of approximately 1.38 Å. BNNCs demonstrate superior adsorption capabilities for SO₂ and SOF₂ compared to other boron nitride nanostructures, with adsorption energies up to 89% higher. The electron transfer analysis reveals that BNNC complexes act as potent electron donors, particularly in the case of BNNC@3SO₂F₂. Additionally, BNNCs show significant potential as sensors for detecting SO₂F₂, with a rapid recovery time of 4.67 ps and a notable decrease in the Fermi level energy to -4.97 eV upon adsorption. The study also provides insights into the angular distribution and charge density difference profiles, offering a detailed understanding of the adsorption mechanisms. These findings have important implications for improving the safety and efficiency of gas-insulated switchgear (GIS) and contribute to the development of more effective environmental protection solutions in electrical power systems.

Eco-friendly, stable, and high-performance biochar prepared by a twice-modification scheme: Saccharification of raw materials & thermal air oxidation of biochar

Organic pollutants, such as phenolic compounds, pose significant risks to both the environment and human health. While biochar is an effective adsorbent for removing these pollutants, its dissolved solid (DS) components can lead to the loss of functional groups, structural disintegration, unstable performance, and environmental issues. This study introduces a twice-modification scheme designed to produce a biochar (BC-M) that combines high stability with superior performance. The process begins with the preparation of a stable biochar from cellulase-treated lignocellulose. This precursor biochar is then subjected to thermal air oxidation to enhance its oxygen-containing functional groups, thereby improving its adsorption capabilities. A mathematical model was developed to explore the relationship between different thermal air oxidation conditions and the properties of BC-M, aiming to optimize both adsorption capacity and DS. The model's multi-objective optimization indicated the optimal modification conditions. Compared to unmodified biochar (BC-O), BC-M showed significant improvements: its specific surface area increased by 63.6%, pore volume by 139%, and functional groups by 50%–1271%. Notably, the DS of BC-M was reduced to just 1.08 mg/L, representing a 97.5% reduction from BC-O, with a minimal mass loss of only 0.78 ± 0.45% during modification. BC-M also demonstrated a remarkable enhancement in the adsorption of phenolic compounds, with a capacity 21%–2408% higher than BC-O. Furthermore, calculations indicated that BC-M could reduce carbon emissions by 0.70 t CO2/yr/t, outperforming activated carbon in this regard. This study offers valuable insights into biochar modification, providing a low-cost, high-stability, and high-efficiency alternative for environmental cleanup.

Towards the mechanical stability of biocrusts in drylands: Insights from inorganic ions and organic compounds and their interactions

Biocrusts are an important component of dryland ecosystems as they perform crucial ecological functions like stabilizing soils, mediating the hydrological cycle, and improving nutrient availability. The high mechanical stability of biocrusts is understood to be linked to exopolymeric substances (EPS), which in turn, are responsible for the adsorption of various ions and chemical compounds. This study aimed to investigate the chemical composition of biocrusts and assess potential correlations between their chemical composition and mechanical stability. Samples of three types of biocrusts (cyanobacteria, cyanobacteria and moss mixed, and moss crusts) and bare soil (as control) were collected from the northern Loess Plateau of China. The inorganic ions and organic compounds present in biocrusts were quantified using inductively coupled plasma-optic emission spectrometry, ion chromatography, and gas chromatography-mass spectrometry. Biocrust mechanical stability was assessed by penetration resistance (PR) and the mean weight diameter (MWD) of aggregates. Finally, the contribution of inorganic ions and organic compounds to the stability of the biocrusts was elucidated. The results indicated that all three types of biocrusts were more stable than bare soil, with moss crusts being the most stable. Chemical analyses revealed an enrichment of inorganic ions such as K+, Ca2+, Na+, Mg2+, SO42–, and halogen ions within the biocrusts, while they showed a depletion of Fe2+, Al3+, and NO3–. Ten types of organic compounds were identified in biocrusts and bare soil, with medium-chain alkanes and long-chain acids being the dominant compounds. In some cases, acids accounted for more than 40 % of the total organic compound content of the biocrusts. Redundancy analysis showed that the content of inorganic ions, such as Ca2+ and Mg2+, and organic compounds such as acids, amides, and alkenes, exhibited the closest association with the biocrust stability. Partial least squares path modeling indicated that both inorganic ions and organic compounds indirectly affected biocrust stability by influencing electric conductivity, bulk density, EPS, and fine particle (clay and silt) content. A strong association was found between the inorganic ions and PR or MWD (0.658 and 0.744, respectively), whilst the total effect of organic compounds on PR and MWD was 0.814 and 0.801, respectively. It is suggested that both the magnitude and types of chemicals associated with EPS indicate their capability to grant mechanical stability of the biocrusts, which in turn is conducive to maintaining the critical functions of biocrusts in global drylands.

DFT study of the structures and electronic properties of Au cluster– and Pt cluster–functionalized BC3 nanosheets and their effects on sensing and adsorption of volatile organic compounds

DFT study of the structures and electronic properties of Au cluster– and Pt cluster–functionalized BC3 nanosheets and their effects on sensing and adsorption of volatile organic compounds

Influence of Solvent Polarity on Crocin Content and Surface Properties of Saffron (Crocus sativus L.) Extracts.

The saffron composition is being widely studied for authenticity and traceability, but very few works have been carried out to investigate the relationship between the chemical and physico-chemical properties of saffron solutes and their technological functionality in colloidal systems. This study aims at evaluating the surface properties of saffron extracts obtained using solvents of different polarities to achieve extracts with different compositions in terms of the pattern and content of polar and medium polarity crocins. The air-water surface was evaluated alone and in the presence of Tween 20 at different surfactant-extract ratios. Saffron extracts were able to decrease the surface tension of the aqueous phase, indicating the presence of surface-active compounds. In the mixed saffron extract-Tween 20 systems, competitive adsorption at the air-water interface occurred when the surfactant was present at a low concentration, while at concentrations higher than the CMC, Tween 20 hindered the adsorption of the extract surface-active compounds. The results highlight the interesting technological functionality of saffron extracts for applications in colloidal systems. To better exploit their use in the design and development of formulated foods, nutraceutics and pharma products, further studies are needed to unravel the relationship between the composition of saffron extracts and corresponding surface activity.

Study on the Phosphate Compound Adsorption onto MgO-KOH/Biochar Adsorbent as Binding Agent in Diffusive Gradient in Thin Film (DGT) Technique for Bioavailable Phosphate Detection

Phosphate compounds, particularly bioavailable forms like PO₄³⁻, are critical contributors to eutrophication. In this study, MgO-KOH/biochar was used as a binding agent in the Diffusive Gradient in Thin Films (DGT) technique to enhance phosphate detection. The adsorbent was synthesized from biochar derived from palm oil waste, activated with KOH to increase surface area, and combined with MgO for enhanced adsorption efficiency. The adsorption process followed a pseudo-second-order kinetic model, indicating that chemical interactions dominated the adsorption mechanism. Under different pH levels and phosphate concentrations, the material showed a good selectivity for orthophosphate, achieving an adsorption capacity of approximately 100 mg/g. Characterization via FTIR, XRD, and SAA confirmed the successful synthesis of MgO-KOH/biochar and its structural properties, which contributed to its performance. Additionally, the MgO-KOH/biochar DGT device demonstrated better efficiency in adsorbing PO₄³⁻ compared to conventional ferrihydrite-based DGT systems, positioning it as a highly effective tool for monitoring bioavailable phosphates in aquatic environments. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Enhanced VOCs adsorption with UIO-66–porous carbon nanohybrid from mesquite grain: A combined experimental and computational study

In this study, adsorption of volatile organic compounds (VOCs) (here just gasoline vapor) by activated carbon- modified UIO-66 was investigated. First, activated carbon prepared from mesquite grain (ACPMG) and then UIO/ACPMG nanohybrid was synthesized by the solvothermal method. In following, the effect of main key parameters which effect on the surface and adsorption capacity such as the ratio of ACPMG to UIO-66 was studied. Physiochemical changes of as- synthesized samples were investigated by TGA, HR-TEM, PSD, SEM, EDX/MAP, BET, FT-IR, XRD, and XPS. It was found the UIO/ACPMG20% nanohybrid had the highest adsorption capacity (391.304 mg/g) for VOCs compared with the other samples, while the adsorption capacity of UIO-66, UIO/ACPMG10% nanohybrid, and UIO/ACPMG30% nanohybrid was 298.871, 309.523, and 320 mg/g respectively. UIO/ACPMG20% nanohybrid desorbed 285.71 mg/g of the adsorbed gasoline, which is an excellent result in desorption. So, the sample of UIO/ACPMG20% nanohybrid was selected as the optimum nano-adsorbent. In other hand, all the nano-adsorbent showed a rapid kinetic behavior for gasoline vapor adsorption and the maximum time for reaching a high adsorption capacity approximately was obtained in 20 min. Density functional theory calculations also performed to understand the adsorption characteristics of gasoline vapor on activated carbon-modified UIO-66.

Achieving Ultra-Low-Sulfur Model Diesel Through Defective Keggin-Type Heteropolyoxometalate Catalysts

Various Keggin-type heteropolyoxometalate catalysts with structural defects and surface acidity were synthesized by immobilizing 12-phosphotungstic acid (HPW) on mesoporous SBA−15, to produce near-zero-sulfur diesel fuel. As the calcination temperature increased, the W=O and the corner-shared W–O–W bonds in the Keggin unit partially broke, creating oxygen defects, as evidenced by the Rietveld refinement and in situ FTIR characterization. All the catalysts contained Lewis (L) and Brønsted (B) acid sites, with L acidity predominant. The relative intensity of the IR band (I980) of W=O bond inversely correlated with the number of L acid sites as the calcination temperature varied, suggesting that oxygen defects contributed to the Lewis acid sites formation. In the oxidation of dibenzothiophene (DBT) in a model diesel within a biphasic system, DBT conversion exceeded 99% under the optimal reaction conditions (reaction temperature 70 °C, reaction time 60 min, H2O2/sulfur molar ratio 8, H2O2/formic acid molar ratio 1.5, catalyst concentration 2 mg/mL). The influence of fuel composition and addition of indole and 4,6-DMDBT on DBT oxidation were also evaluated. Indole and cyclohexene negatively impacted the DBT oxidative removal. Oxygen defects served as active centers for competitive adsorption of sulfur compound and oxidant. Both L and B acid sites were involved in transferring O atom from peroxophosphotungstate complex to sulfur in DBT, resulting in DBTO2 sulfone, which was immediately extracted by polar acetonitrile. This study confirms that structural defects and surface acidity are crucial in the deep oxidative desulfurization (ODS) reaction, and in enabling the simultaneous oxidation and separation of refractory organosulfur compounds in a highly efficient model diesel.

Microplastics–biofilm in aquatic ecosystem: Formation, pollutants complexation, greenhouse gas emission and ecotoxicology

The omnipresent microplastics (MPs) have gradually become a significant environmental problem due to its adverse consequences for ecological systems. MPs serve as substrates for biofilms colonization, which enhances adsorption of harmful contaminants on MPs surface in the aquatic ecosystem. The present study provides a critical discussion on the mechanism involved in MPs–biofilm formation, microbial colonization and the robust factors influencing the process in the aquatic ecosystem. Subsequently, the impact of MPs–biofilm on adsorption of inorganic and organic contaminants is explored. The ecological significance of MPs–biofilm associated pollutant complex for promoting greenhouse gases (GHGs) emissions from aquatic ecosystem is extensively discussed for understanding the climatic risk. Furthermore, the discussion is extended over ecotoxicological impact of MPs–biofilm on aquatic biodiversity and humans. The protective extracellular polymeric substances secreted by colonised bacteria over MPs during biofilm formation creates sticky MPs surface for heteroaggregates formation with swift adsorption of chemical compounds and microorganisms. MPs with functional aromatic groups facilitate the bacterial adhesion on the surface, but affect formation of biofilm. Alternatively, MPs–biofilm promotes the Mn and Fe hydrous oxides formation that can co–precipitate with heavy metal ions and facilitate in remediation measures. However, MPs biodegradation generates GHGs emission per unit mass, comparably more from freshwater than marine ecosystem. Considering the toxicity, MPs–biofilm induces the oxidative response in fishes, causing painful death and thus, destroys aquatic biodiversity. This study will be useful to address MPs–biofilm associated pollution scenario via trace, test and treat strategy involving future engineering research framework for ecological restoration.

Research Progress on the Mechanism of the Impact of Myofibrillar Protein Oxidation on the Flavor of Meat Products.

Myofibrillar proteins primarily consist of myosin, actin, myogenin, and actomyosin. These proteins form complex networks within muscle fibers and are crucial to the physical and chemical properties of meat. Additionally, myofibrillar proteins serve as significant substrates for the adsorption of volatile flavor compounds, including aldehydes, alcohols, ketones, and sulfur and nitrogen compounds, which contribute to the overall flavor profile of meat products. A series of chemical reactions occur during the processing, storage, and transportation of meat products. Oxidation is one of the most significant reactions. Oxidative modification can alter the physical and chemical properties of proteins, ultimately impacting the sensory quality of meat products, including flavor, taste, and color. In recent years, considerable attention has been focused on the effects of protein oxidation on meat quality and its regulation. This study investigates the impact of myofibrillar protein oxidation on the sensory attributes of meat products by analyzing the oxidation processes and the factors that initiate myofibrillar protein oxidation. Additionally, it explores the control of myofibrillar protein oxidation and its implications on the sensory properties of meat products, providing theoretical insights relevant to meat processing methods and quality control procedures.

A theoretical insight into the adsorption behavior of organic molecules on MoS2 monolayer

AbstractThe adsorption stage is crucial in sensing performance and photoreaction on material surfaces. This study investigates volatile organic compounds (VOC) adsorption on MoS2 monolayer using first‐principle calculations. The adsorption configurations are stabilized by H···S hydrogen bonds and C/O···S intermolecular interactions. The process of molecules attached to MoS2 is evaluated as weak physical adsorption and decreases in ordering 1‐propanol > isopentane > acetone > propenal ≈ ethylamine. Besides, AIM analysis indicates that the H···S and C/O···S contacts are weak interactions and are non‐covalent in nature. The intermolecular hyper‐conjugation energy values resulting from the NBO approach determine the stronger hydrogen bonds of H···S in comparison to C/O···S interactions. Remarkably, the gas sensing response of the MoS2 monolayer for VOC molecules is observed theoretically. The sensing responses of gas molecules on the MoS2 monolayer are achieved considerably, up to 99.80% for ethylamine, 97.96% for acetone, and 18–32% for the remaining gases. The MoS2 monolayer is expected to be a suitable sensing material for VOC.

Adsorption of aqueous insensitive munitions compounds by graphene nanoplatelets

Mitigation strategies for potential environmental impacts of insensitive munition (IM) compounds, including 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), nitroguanidine (NQ), and methylnitroguanidine, (MeNQ) are being considered to enhance sustainability of current or potential IM formulations. Graphene nanoplatelets (GnPs) were investigated for adsorptive removal of each compound. GnPs were characterized to determine surface areas, along with particle size and zeta potential at different pH and ionic strength conditions. Adsorption kinetics and isotherm studies were conducted, comparing results against granular activated carbon (GAC). Ionic strength, pH, and temperature were adjusted to inform impacts on adsorptive behaviors and performance. The results indicated that GnPs adsorbed IM compounds more rapidly than GAC. Additionally, GnPs removed DNAN with greater capacity compared to GAC, likely due to π-π interactions. GnPs removed other compounds via van der Waals forces, while GAC exhibited greater adsorption capacities due to higher surface area. Although negative charges associated with GnPs and dissociated NTO species hindered adsorption, pH and ionic strength did not impact other compounds. Moreover, this study reports the first environmental treatment technique for MeNQ. Overall, these findings suggest that GnPs are a promising treatment technology for IM-laden waters, particularly those with compounds like DNAN where specific interactions enhance removal efficiency.

Construction of hydrophobic HKUST-1 in wood with selective adsorption performance for toluene and moisture blends

The effect of moisture on the volatile organic compound (VOC) adsorption on biomass-derived metal–organic framework composites is significant in practical applications. In this study, wood-based metal organic frameworks (MOF199-W) and hydrophobic MOF199-W (HMOF199-W) were developed using HKUST-1 (MOF199) and long alkyl chains to investigate the adsorption performance of toluene and enhance the selectivity of adsorption under high humidity conditions. The results demonstrated that HKUST-1 could be anchored onto the surface of wood vessels and fibers through coordination with Cu2+, resulting in an improved surface area in comparison to natural wood. The toluene adsorption capacity of MOF199-W with a 20 % loading was comparable to that of an equivalent amount of MOF199, with adsorption capacities of 323.5 mg/g and 369.9 mg/g, respectively. Further, the Yoon-Nelson model was found to adequately describe the dynamic adsorption process. Following the introduction of long alkyl chains, MOF199 and MOF199-W were endowed with strong hydrophobic character (water contact angle of 107.0◦, 104.0◦, and water uptake of 30.5 mL/g, 55.3 mL/g). With the increase in humidity, the adsorption performance of MOF199 and MOF199-W for toluene sharply decreased, but HMOF199 and HMOF199-W still maintained the adsorption capacities at 304.7 mg/g and 226.7 mg/g, even under 80 % RH conditions. Therefore, HMOF199-W has shown great potential in wooden building materials with the ability for toluene capture under humid conditions.

A study on the properties of chloroquine and hydroxychloroquine derivatives as biomass corrosion inhibitors

Since corrosion causes significant economic and environmental damage, sustainable corrosion inhibitors are essential. This work examined the corrosion prevention properties of a series of closely related compounds with names: Chloroquine (S1) Hydroxychloroquine (S2) Desethylchloroquine (S3) Desethylhydroxychloeoquine (S4) Bisdesethylchloroquine (S5). With applying DFT/B3LYP/6-31+G(d,p) foundation, also Monte Carlo simulations showed compound adsorption on Fe(1 1 0). The HOMO-LUMO, refractive index, dielectric constant, and electrical conductivity, the results for S1 and S2 indicate that all inhibitors were bound to Fe (1 1 0), as predicted by the Monte Carlo simulation.

Density Functional Theory analysis and molecular dynamic simulation to understand the mechanism of hazardous dyes adsorption onto cellulose in aqueous solution

This work examines the use of cellulose in the elimination of anionic dye, indigo carmine and methyl red, from aqueous media. Theoretical analyses revealed that the examined compounds had several reactive sites that encouraged dyes to adhere to the cellulose surface, and molecular dynamics simulations demonstrated that this adsorption occurred flat-lying on the cellulose (200) surface. However, it has been discovered that the reactivity of individual molecules is limited in its ability to foretell the effectiveness and characteristics of compound adsorption on cellulose. The capacity to model dye adsorption on polymeric surfaces in the presence of a simulated aqueous solution is one of the key benefits of molecular dynamics modeling, and it can reveal valuable information regarding the selected molecules' adsorption configuration and its competitiveness. Both dyes exhibit high adsorption on the cellulose adsorbent, indicating that chemical bonds play a major role in the adsorption capacity of the dyes. The order of adsorption energy indicates a clear selective adsorption tendency. The radial distribution function analysis shows that both dyes are chemisorbed at the cellulose surface. Quantum and dynamic descriptors have validated the experimental results in the literature. This offers valuable insights into the adsorption mechanism of anionic dyes on cellulose.

Adsorption of phenolic compounds on polymeric ionic liquids: Adsorption isotherms interpretation and thermodynamic study

This study describes the thermodynamic assessment and steric interpretation of the 4-nitrophenol (4-NP) and 4-chlorophenol (4-CP) adsorption on polymeric ionic liquids (PILs) using advanced statistical physics model. A monolayer model with a single energy level was employed to elucidate the adsorption mechanisms of these phenolic compounds. The results showed that the orientation of 4-NP and 4-CP on the surface of this adsorbent was a combination of parallel and non-parallel configurations at the tested adsorption temperatures. The values of the adsorption capacities at saturation were 484.7 and 406.7 mg/g for4-NP and 4-CP, respectively. The modelling results indicated that more active sites from PILs surface were involved in the removal of 4-nitrophenol than those required for the 4-chlorophenol adsorption. The calculation of adsorption energies confirmed that the adsorption of 4-NP and 4-CP on PILs was exothermic and driven by physical forces involving hydrogen bonds and van der Waals forces. Three thermodynamic functions were analyzed to complete the macroscopic analysis of the adsorption mechanism for these relevant phenolic contaminants.

Adsorption Desulfurization of Simulated Diesel Fuel Using Graphene Oxide

Graphene oxide (GO) was synthesized from graphite powder by the improved Hammers method and used for the adsorption of organosulfur compound (dibenzothiophene, DBT) from model diesel fuel. FT-IR spectroscopy, X-ray diffraction, SEM, EDX, and BET were used to characterize the GO. Several factors, such as solution pH, initial DBT concentration, adsorption contact time, adsorption temperature, and adsorbent dosage were used to test the DBT removal efficiency. The results show that the maximum removal was 96.4% at pH = 5, initial solution concentration of 200 ppm, adsorption time of 45 min, temperature of 45C and adsorbent dosage of 0.4 g/25 mL.

Development of a natural ingredient based on phenolic compounds from propolis extract and bentonite and its application in carrageenan hydrogels

Nowadays, there is an increasing consumer demand for more natural and environmentally friendly food additives. The current research aimed to produce and characterize a new additive based on bentonite and the phenolic compounds from green propolis extract, as well as to characterize the effect of this additive on the rheological properties of carrageenan hydrogels. The new additive (biohybrid) was obtained after the adsorption of phenolic compounds on the clay platelets. The adsorption mechanism was explained by Langmuir and Freundlich models, which suggested that adsorbed phenolic compounds form a monolayer and multilayers on the clay surface. Despite phenolic adsorption, the physico-chemical attributes of the bentonite remained unchanged. The incorporation of the biohybrid (BH) increased the sol-gel transition temperature of carrageenan hydrogels. This research reports for the first time the development and application of a new natural ingredient with potential food applications.

Molecular simulation on competitive adsorption of ethanol, acetaldehyde and acetic acid on zeolites in humid conditions

Adsorption is a key technique for purifying volatile organic compounds (VOCs) from indoor air. Due to the complexity of multi-component VOCs and humid environment, the competitive adsorption among VOCs under the influence of water vapor remains unclear, which limits adsorbent selection and performance prediction. In this work, adsorption characteristics of typical indoor VOCs (ethanol, acetaldehyde, and acetic acid) on commercial zeolites (BETA-25 and ZSM5-300) under varying humidity were studied through molecular simulation. The simulation based on charge-corrected molecular structures and force field was validated by experiments. The unary, binary and ternary adsorption isotherms of three VOCs were obtained. At both dry and wet conditions, the VOCs with higher polarity shows greater adsorption capacity: acetic acid > ethanol > acetaldehyde. BETA-25 exhibits stronger adsorption on all three gases under dry conditions, while under wet conditions ZSM5-300 shows greater adsorption capacity of ethanol and acetaldehyde with lower polarity as compared to BETA-25. Simulation of adsorption energy and adsorbate density distribution in ternary equilibrium demonstrates the presence of water vapor alters the sorbate-sorbent interaction, particularly for ethanol and acetaldehyde showing stronger adsorption on BETA-25 than on ZSM5-300 at dry conditions but reversely at wet conditions. The lower-silica zeolite favors the adsorption of highly-polar VOC regardless of water, and the higher-silica counterpart with greater hydrophobicity facilitates adsorption of less-polar compounds in competing with water. The findings in this work can provide methodological reference for adsorbent screening and data basis for real VOCs purification applications.

Layered Silicates Exhibiting MOF-Like Gate-Opening Behaviors in Liquid-Phase Adsorptions: Experimental and Theoretical Investigations.

Layered silicates, including clay minerals, can be used as liquid-phase adsorbents in many important applications. However, because their two-dimensional interlayer space is narrow and not entirely opened due to the presence of interlayer species, guest species are forced to penetrate while expanding the interlayer space, which limits their adsorption performances compared with microporous materials such as MOFs and zeolites. Herein, as reported for the adsorption of gaseous species on flexible MOFs, we report a layered silicate that exhibits gate-opening adsorption in liquid phases. This layered silicate, synthesized via dilute acid treatment of the parent sodium-type, exhibits an abrupt increase in the basal spacing (layer thickness + interlayer space) to reach a plateau even at an earlier stage of benzoic acid adsorption from acetonitrile, whereas a typical layered silicate, magadiite, exhibits a gradual increase in the basal spacing as adsorption progress under identical conditions. The layered silicate shows an excellent adsorption capacity and rate for benzoic acid uptake from acetonitrile, which is considerably higher than that of magadiite. With comprehensive adsorption tests using different adsorbates and solvents, we propose that the layered silicate has zeolite-like but distorted, flexible open microchannels within each layer, and the intralayer microchannels can effectively and rapidly accommodate the solvent (acetonitrile) molecules, which are capable of expanding the framework to initiate the adsorption of aromatic compounds. The density function theory calculation revealed the adsorption mechanism, where the layered silicate accommodates acetonitrile in the intralayer microchannel followed by the interlayer space, and the former selectively plays a role as the adsorption site of aromatic compounds via exchange with acetonitrile.