Adsorption Interaction Research Articles

Investigation of the effect and mechanism on the flotation performance of alkylglycine-based collectors by acyl group

The structure difference of the flotation reagent has a significant influence on its flotation performance. In this work, sodium N-lauroyl glycinate (SNG) was synthesized by introducing an acyl group into sodium N-dodecylglycinate (SN), and was using the collector in the oxide ores flotation. Properties of these two collectors were compared, and the effects behavior and mechanism of introducing the acyl group on the flotation performance of alkylglycine-based collectors to the zinc oxide minerals were systematically investigated. Flotation results proved that the introduction of C = O group into SN barely affected the floatability of smithsonite, hemimorphite and calcite, while the floatability of quartz was greatly reduced. Contact angle tests, surface tension tests, and froth collapse measurements indicated that the introduction of the acyl group into SN could selectively weaken its ability to improve the hydrophobicity of mineral surfaces, reduce its surface tension, adsorption capacity and intensity on the mineral surface, and the froth stability, thereby enhancing its selectivity, consistent with the flotation results. Fourier transform infrared spectroscopy (FTIR) analyses and density functional theory (DFT) calculations revealed that the introduction of the acyl group could increase the cross-sectional area and reduce the charge of the SNG polar groups to selectively weaken the adsorption interaction, particularly by significantly reducing the electrostatic adsorption between SNS and quartz surfaces. These also confirm that SNG is a promising highly selective collector for the flotation separation of zinc oxide minerals.

Quantum Chemical Model Calculations of Adhesion and Dissociation between Epoxy Resin and Si-Containing Molecules

There is no doubt that when solid surfaces are modified, the functional groups and atoms directly bonded to solid atoms play a major role in adsorption interactions with molecules or resins. In this study, the adhesion and dissociation between epoxy resin and molecules containing Si atoms were analyzed. The analysis, conducted in contact with the solid surface of silicon, utilized quantum chemical calculations based on a molecular model. We compared some Si-containing molecular models to test quantum chemical calculations that contribute to the study of adhesion and dissociation between epoxy resins and solid surfaces somehow other than simple potential energy curve calculations. The AFIR (artificial force induced reaction) method, implemented in the GRRM (global reaction route mapping) program, was employed to separate an epoxy resin model molecule and three types of silicon compounds (Si(CH3)2(OH)2, Si(CH3)4, and (CH3)2SiF2) in three directions, determining their minimum dissociation energy when changing the applied energy by 2.5 kJ/mol. In systems with weak hydrogen bonds, such as Si(CH3)4 or (CH3)2SiF2, the energy required for dissociation was not large; however, in systems with strong hydrogen bonds, such as Si(CH3)2(OH)2, dissociation was more difficult in the vertical direction. Although anisotropy due to hydroxyl groups was calculated in the horizontal direction, dissociation remained relatively easy.

Electrocatalysts for Urea Synthesis from CO2 and Nitrogenous Species: From CO2 and N2/NOx Reduction to urea synthesis.

The traditional industrial synthesis of urea relies on the energy-intensive and polluting process, namely the Haber-Bosch method for ammonia production, followed by the Bosch-Meiser process for urea synthesis. In contrast, electrocatalytic C-N coupling from carbon dioxide (CO2) and nitrogenous species presents a promising alternative for direct urea synthesis under ambient conditions, bypassing the need for ammonia production. This review provides an overview of recent progress in the electrocatalytic coupling of CO2 and nitrogen sources for urea synthesis. It focuses on the role of intermediate species and active site structures in promoting urea synthesis, drawing from insights into reactants' adsorption behavior and interactions with catalysts tailored for CO2 reduction, nitrogen reduction, and nitrate reduction. Advanced electrocatalyst design strategies for urea synthesis from CO2 and nitrogenous species under ambient conditions are explored, providing insights for efficient catalyst design. Key challenges and prospective directions are presented in the conclusion. Mechanistic studies elucidating the C-N coupling reaction and future development directions are discussed. The review aims to inspire further research and development in electrocatalysts for electrochemical urea synthesis.

Removal mechanism and effects of aqueous chemistry on rapid adsorption of perfluorooctanoic and perfluorooctanesulfonic acids by microscale zero valent magnesium

Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) as the two most typical perfluorinated compounds, their effective and rapid removal are still facing enormous challenges. In this study, the adsorption performance and mechanism of PFOA and PFOS by ball milled micrometer zero valent magnesium (mZVMg) were revealed firstly through the adsorption kinetics and isothermal, ions coexisting competitive adsorption and extraction experiments. Rapid adsorption equilibrium within 0.5 h was observed in the mZVMg system, and the higher adsorption affinities at 1.9 and 6.5 L/mg for PFOA and PFOS respectively were approximately 4.4–110 times higher than those of the carbon materials, layered double hydroxide and magnetite reported in the literature. Correspondingly, high removal efficiencies for PFOS were observed even under a wide pH ranging from 3.0 to 11.0. In the meantime, negligible influences on the PFOS adsorption were identified from the coexisting PFOA, perfluorobutanoic acid (PFBA), perfluorobutanoic sulfonic acid (PFBS), anions of Cl−, NO3− and SO42−. Reversely, the PFOA adsorption was adversely influenced by enhanced electrostatic repulsion under the increased pH and the presence of the abovementioned anions. Additionally, the original removal efficiency of 67.18 % for PFOA in the absence of any cations and anions was decreased to 7.98 %, 31.08 % and 39.65 % respectively in the presence of humic acid, HCO3− and CO32−. Similarly, the removal efficiency of 94.41 % for PFOS was declined to 40.01 %, 70.04 % and 80.58 % respectively when humic acid, HCO3− and CO32− were added to the solution. However, in the presence of respective Mg2+ and Ca2+, the original removal efficiencies were increased from 67.18 % to 75.78 % and 74.68 % for PFOA, and from 84.99 % to 93.23 % and 92.49 % for PFOS, likely due to the cation’s bridge effect. Consequently, the hydrophobic adsorption and electrostatic interaction accounted for 71.3 % and 19.75 % for PFOA, while 86.26 % and 5.85 % for PFOS removal, respectively through the solvent extraction and long-term effective removal experiments. Overall, this study provided an alternative, promising and environmental-friendly mZVMg for rapid adsorption of PFOA and PFOS.

A Grafting Hydrogen‐bonded Organic Framework for Benchmark Selectivity of C2H2/CO2 Separation under Ambient Conditions

Reticular chemistry and pore engineering have garnered significant advancements in metal‐organic frameworks and covalent organic frameworks, leveraging robust metal‐coordination and covalent bonds. However, these achievements remain elusive in hydrogen‐bonded organic frameworks, hindered by their inherent weakness in hydrogen bonding. Herein, we strategically manipulate the porosity of hydrogen‐bonded frameworks through a grafting approach, culminating in the synthesis of two isomorphic HOFs, HOF‐FJU‐99 and HOF‐FJU‐100, with distinct pore environments. Remarkably, HOF‐FJU‐100, with its microporous architecture, not only showcases exceptional stability but also achieves unparalleled separation efficiency and ultrahigh selectivity for C2H2/CO2 mixtures (50/50, v/v) under ambient conditions. Its IAST selectivity value of 201 stands as a benchmark, towering over all previously reported HOFs. The pore of HOF‐FJU‐100 boasts an electrostatic potential highly favourable for C2H2 adsorption, as evidenced by single crystal X‐ray diffraction analysis revealing multiple hydrogen bonding interactions between C2H2 molecules and the framework. In situ gas‐carrier powder X‐ray diffraction analysis underscores the adaptability of pore structure, dynamically adjusting its orientation in response to C2H2, thereby enabling a highly efficient and specific separation of C2H2/CO2 mixtures through specific adsorptive interactions.

A Grafting Hydrogen-bonded Organic Framework for Benchmark Selectivity of C2H2/CO2 Separation under Ambient Conditions.

Reticular chemistry and pore engineering have garnered significant advancements in metal-organic frameworks and covalent organic frameworks, leveraging robust metal-coordination and covalent bonds. However, these achievements remain elusive in hydrogen-bonded organic frameworks, hindered by their inherent weakness in hydrogen bonding. Herein, we strategically manipulate the porosity of hydrogen-bonded frameworks through a grafting approach, culminating in the synthesis of two isomorphic HOFs, HOF-FJU-99 and HOF-FJU-100, with distinct pore environments. Remarkably, HOF-FJU-100, with its microporous architecture, not only showcases exceptional stability but also achieves unparalleled separation efficiency and ultrahigh selectivity for C2H2/CO2 mixtures (50/50, v/v) under ambient conditions. Its IAST selectivity value of 201 stands as a benchmark, towering over all previously reported HOFs. The pore of HOF-FJU-100 boasts an electrostatic potential highly favourable for C2H2 adsorption, as evidenced by single crystal X-ray diffraction analysis revealing multiple hydrogen bonding interactions between C2H2 molecules and the framework. In situ gas-carrier powder X-ray diffraction analysis underscores the adaptability of pore structure, dynamically adjusting its orientation in response to C2H2, thereby enabling a highly efficient and specific separation of C2H2/CO2 mixtures through specific adsorptive interactions.

Impact of Surface Enhanced Raman Spectroscopy in Catalysis.

Catalysis stands as an indispensable cornerstone of modern society, underpinning the production of over 80% of manufactured goods and driving over 90% of industrial chemical processes. As the demand for more efficient and sustainable processes grows, better catalysts are needed. Understanding the working principles of catalysts is key, and over the last 50 years, surface-enhanced Raman Spectroscopy (SERS) has become essential. Discovered in 1974, SERS has evolved into a mature and powerful analytical tool, transforming the way in which we detect molecules across disciplines. In catalysis, SERS has enabled insights into dynamic surface phenomena, facilitating the monitoring of the catalyst structure, adsorbate interactions, and reaction kinetics at very high spatial and temporal resolutions. This review explores the achievements as well as the future potential of SERS in the field of catalysis and energy conversion, thereby highlighting its role in advancing these critical areas of research.

Multilayer Adsorption Characteristics of CO2 in Organic Nanopores with Different Pore Sizes: Molecular Simulation and Ono-Kondo Lattice Model.

Shale contains numerous organic micropores with significant potential for CO2 storage. To precisely evaluate the CO2 storage potential of shale reservoirs, it is essential to accurately quantify the adsorption of CO2 within these pores. This study used Grand Canonical Monte Carlo (GCMC) molecular simulations to analyze the CO2 adsorption behavior in organic micropores of varying sizes. The study clarified the number and width of the CO2 adsorption layers in micropores of various sizes and proposed a method for segmenting the multilayer adsorption structure. Additionally, the classic Ono-Kondo lattice (OK) model was extended to characterize pore-filling adsorption, incorporating solid-gas and gas-gas interactions. Accurate characterization of CO2 multilayer adsorption and precise calculation of CO2 absolute adsorption in micropores were achieved. Results indicate that CO2 exhibits pore-filling adsorption behavior in organic micropores, forming a multilayer adsorption structure governed by the pore size. Following symmetry principles, the adsorption layer structure in organic micropores can be simplified to a maximum of three layers. When only one adsorption layer forms, its width equals the gas-accessible pore size. For two or more layers, the width of the original layer stabilizes as additional layers form. The stable adsorption layer widths, from nearest to farthest from the pore wall, are 0.33, 0.45, and 0.39 nm. The improved OK model accurately describes CO2 excess and absolute adsorption isotherms across different pore sizes and calculates the CO2 density in each adsorption layer, showing high consistency with GCMC simulation results. These findings highlight the importance of understanding the CO2 multilayer adsorption structure for accurately estimating CO2 adsorption in organic micropores.

Adsorption sites and interactions of pigments in molasses-based distillery effluent on starch-based composites: Ternary competitive adsorption and theoretical calculations

The pigment present in molasses-based distillery effluent constitutes a primary factor influencing its degradation. Adsorption is an effective approach to eliminate pigment from wastewater. In this study, a cationic cassava starch (CCS) magnetic composite (CCS@Fe3O4) was prepared and used as adsorbents for the removal of undesirable pigments. The adsorption behaviors of caffeic acid (CA), gallic acid (GA), and melanoidin (ME) on CCS@Fe3O4 in the wastewater were investigated using single and ternary competitive adsorption systems. The equilibrium adsorption capacities of CA, GA, and ME on CCS@Fe3O4 were 197.04, 195.55, and 623.97 mg/g at the optimized conditions (0.3 mg/mL CCS@Fe3O4 dosage, temperature of 38 °C, and pH of 7). The adsorption kinetic model showed that chemisorption accounted for most of the adsorption of CA, GA, and ME on CCS@Fe3O4. The adsorption mechanisms of pigments on CCS@Fe3O4 were explored at the molecular level through quantum chemical calculations. The electrostatic potentials (ESP), average local ionisation energy (ALIE), and Fukui indices calculation indicated that the quaternary ammonium group in CCS@Fe3O4 was more susceptible to electrophilic reactions. The CC and benzene rings in CA and GA, and the COO- in ME, represent sites of attack for quaternary ammonium during adsorption. Furthermore, the competitive adsorption results, adsorption energy, and electron transfer data demonstrated that the adsorption capacity of CCS@Fe3O4 for pigments followed the order ME>GA>CA. Overall, the competitive adsorption mechanisms of CA, GA, and ME on CCS@Fe3O4 were unveiled, with quantum chemical calculations offering crucial insights into the adsorption process.

Garlic Peel-Based Biochar Prepared under Weak Carbonation Conditions for Efficient Removal of Methylene Blue from Wastewater

Background: Due to it containing cellulose, hemicellulose, and lignin with abundant specific functional groups which could interact with organic dyes, garlic peel (GP) might be used as an efficient biosorbent. The aim of this study is to evaluate the adsorption performances of GP-based bio-adsorbents and obtain optimum preparation conditions. Methods: GP-based bio-adsorbents were prepared by thermal pyrolysis under different temperatures (150–400 °C). The morphologies, chemical states, and surface functional groups of the adsorbents were analyzed by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). Batch experiments were conducted to investigate the adsorption of methylene blue (MB) under various conditions, including contact time, contact temperature, initial dye concentration, and initial pH value. The equilibrium adsorption data were fitted to different kinetic and isothermal models, and the adsorption thermodynamics were also calculated. Significant Findings: The physicochemical properties of the GP-based bio-adsorbents were primarily dominated by the pyrolysis temperature, because their morphologies and surface functional groups of GP-based bio-adsorbents significantly varied with the changes in pyrolysis temperature. The adsorption capacity of GP materials for MB decreased as the pyrolysis temperature increased. At an initial concentration of 50.00 mg L−1, GP150 possessed a higher adsorption capacity of 167.74 mg g−1 toward MB. The possible adsorbate–adsorbent interactions, including electrostatic attraction, hydrogen bonding, and π-π stacking, were recognized. After 10 consecutive adsorption–desorption cycles, GP150 maintained a high removal rate (88%) for MB, demonstrating its excellent adsorption performance, good reusability, and potential application in the treatment of MB-contaminated water.

Enhancing CO2 photoreduction efficiency with MXene-modified ZnO@Co3O4 double heterojunction

The photocatalytic reduction of CO2 into energy carriers holds significant industrial appeal, but achieving this process kinetically remains challenging due to the lack of well-designed catalysts. This study presents a novel 2D/3D nanostructured photocatalyst, developed by attaching a few-layer Ti3C2 MXene to polyethylenimine (PEI)-modified ZnO@CO3O4 nanocages, which are derived from a bimetallic zinc-cobalt ZIF. The resulting Mx-PEI-ZnO@Co3O4 catalyst achieved impressive yields of CO and CH4 at 594.37 and 42.67μmol g−1h−1, respectively, without the need for sacrificial agents and photosensitizers, and maintained remarkable stability across multiple cycles. These yields represent the highest performance for ZnO-based catalysts to date, with quantum efficiency at 380 nm reached up to 25.06 %. The unique S-scheme and Mott-Schottky junctions, along with enhanced CO2 adsorption and hydrogen-bond interactions facilitated by the conductive PEI within the Ti3C2/ZnO/Co3O4 double heterojunctions, effectively inhibit electron-hole recombination and significantly enhance CO2 photoreduction performance. This study underscores the combined benefits of double heterojunction engineering, PEI-functionalized CO2 uptake, and MXene co-catalyst integration within a single system, proposing a new approach for designing highly efficient photocatalysts for solar-driven CO2 reduction in energy-efficient fuel production.

Sctudies on adsorption of Brilliant Green from aqueous solution onto nutraceutical industrial pepper seed spent

The study proposed the removal of Brilliant Green, a cationic dye, by adsorption process from wastewater solution utilizing a low-cost adsorbent such as Nutraceutical Industrial Pepper Seed Spent (NIPSS). The study comprises an investigation of the parametric influence on the adsorption process. The parameters identified are pH, dye concentration, process temperature, quantity of the adsorbent, and particle size. The study of statistics found from experiments was carried out by incorporating Freundlich, Brouers-Sotolongo, Langmuir, Toth, Sips, Jovanovic, and Redlich-Peterson isotherm models. The adsorption kinetics were determined by implementing pseudo-first-order and second-order models, diffusion film models, and Dumwald-Wagner and Weber-Morris models. The experimental adsorption capacity qe was found to be about 130 mg/g. This value was closest to the maximum adsorption of 144.6mg/g predicted by the Brouers-Sotolongo isotherm which had a correlation coefficient (R2) of 0.998. The adsorption kinetics data was confirmed to be a pseudo-second-order model. The change in free energy, enthalpy change, and entropy change were vital thermodynamic factors in concluding that adsorption is almost spontaneous and endothermic process. Change in enthalpy (ΔH°) reduced value indicates the physical nature of the process. The adsorption of BG dye on the adsorbent surface was authenticated by FTIR spectroscopy and SEM imaging. A Central Composite Design (CCD) Quadratic model under Response Surface Methodology (RSM) was implemented for statistical optimization of adsorption capacity for the five parameters studied, namely, time, temperature, concentration of the dye, weight of the adsorbent, and pH. Software Design Expert 7.0 was used to evaluate 3D contour plots. The process of optimization yielded a value of 350 mg/g. Thus, incrementing the adsorption process by 84.2 %. The study provides insights on various dye and adsorbent interaction possibilities and derives that NIPSS is an efficient adsorbent to extract BG dye from wastewater solutions.

Feasibility of carbon dioxide geological storage in abandoned coal mine: A fully coupled model with validated multi-physical interactions

It has gained wide attention that Carbon dioxide (CO2) is to be injected into abandoned coal mines for geological storage of CO2-enhanced coalbed methane recovery. Although abundantly evidences in literature indicate that the injection of CO2 will cause lots of interactions among the mechanical characteristics of coal and the properties of CO2 flow, further studies on these multi-physical interactions are still necessary. In this work, a series of laboratory experiments to elucidate the multi-physical interactions of CO2 adsorption, softening effect of coal and the non-Darcy gas flow were conducted. Based on the experimental results, theoretical and empirical models to describe these coal-CO2 interactions were meticulously proposed and validated, the results turned out to be satisfactory. Consequently, the compressive strength and elasticity modulus of coal decrease exponentially with the increased injection CO2 pressure. The gas flow in coal obeys the Izbash non-Darcy model, and coal permeability can be well modified by the volumetric stress. By taking these coal-CO2 interactions into account, this study established of a fully coupled model for coal deformation and CO2 conservation. The model was then implemented into the numerical simulations of CO2 storage in abandoned coal mine by using the finite element method. A series of scenario-based numerical simulations was conducted to investigate the feasibility and limitation of CO2 storage in abandoned coal mine. The conducted experiments, models and numerical simulation will offer implications on the multi-physical interactions between coal and gas especially in CO2 storage in abandoned coal mines.

Enhanced Adsorption of Cadmium by a Covalent Organic Framework-Modified Biochar in Aqueous Solution.

In the environmental field, the advancement of new high-efficiency heavy metal adsorption materials remains a continuous research focus. A novel composite, covalent organic framework-modified biochar (RH-COF), was fabricated via an in-situ polymerization approach in this study. The COF-modified biochar was characterized by elemental analysis, BET analysis, SEM, FT-IR, and XPS. The nitrogen and oxygen content in the modified material increased significantly from 0.96% and 15.50% to 5.40% and 24.08%, respectively, indicating the addition of a substantial number of nitrogen- and oxygen-containing functional groups to the RH-COF surface, thereby enhancing its adsorption capacity for Cd from 4.20 mg g-1 to 58.62 mg g-1, representing an approximately fourteen-fold increase. Both the pseudo-second-order model and the Langmuir model were suitable for describing the kinetics and isotherms of Cd2+ adsorption onto RH-COF. The adsorption performance of Cd2+ by RH-COF showed minimal sensitivity to pH values between 4.0 and 8.0, but could be slightly influenced by ionic strength. Mechanistic analysis showed that the Cd2+ adsorption on RH-COF was dominated by surface complexation and chelation, alongside electrostatic adsorption, surface precipitation, and Cπ-cation interactions. Overall, these findings suggest that the synthesis of COF-biochar composite may serve as a promising remediation strategy while providing scientific support for applying COF in environmental materials.

Luminescent Metal-Organic Framework-Based Fluorescent Sensor Array for Screening and Discrimination of Bisphenols.

Extensive applications of bisphenols in industrial products have led to their release into aquatic environments, causing a great threat to human health due to their endocrine-disrupting effects, whereas existing methods are difficult to implement the rapid and high-throughput detection of multiple bisphenols. To circumvent this issue, we constructed a sensor array using two luminescent metal-organic frameworks (LMOFs) (Zr-BUT-12 and Ga-MIL-61) for the rapid discrimination of six bisphenol contaminants (BPA, BPS, BPB, BPF, BPAF, and TBBPA). Wherein, Zr-BUT-12 and Ga-MIL-61 exhibited different fluorescence-emission properties and good luminescent stability. Interestingly, bisphenols with different structures had diverse quenching effects on the fluorescence intensity of Zr-BUT-12 and Ga-MIL-61 via the adsorptive interaction, resulting in unique fluorescent fingerprints. Based on pattern recognition methods, different bisphenols were successfully identified, with the limit of detection in the range of 1.59-16.7 ng/mL for six bisphenols. More importantly, the developed sensor array could be effectively utilized for distinguishing different ratios of mixed bisphenols, which was further applied for bisphenol discrimination in real water samples. Consequently, our finding provides a promising strategy for the simultaneous recognition of multiple bisphenols, which encourages the development of a sensor array for the detection of multiple contaminants in environmental monitoring and food safety.

Physicochemical study of the adsorption of chlorophenols on activated carbon using an advanced double layer model

An advanced theoretical analysis was performed to elucidate the adsorption of 2,4-dichlorophenol and 4-chlorophenol on an activated carbon obtained from pine sawdust. In particular, a double layer adsorption model was used to estimate the number of chlorophenols molecules adsorbed per activated carbon functional group, the concentration of active sites from activated carbon surface involved in the adsorption mechanism, the saturation adsorption capacities and interaction energies to form the adsorbate layers on activated carbon. This theoretical investigation showed that the saturation adsorption capacities for the removal of 2,4-dichlorophenol and 4-chlorophenol were 167 and 130 mg/g, respectively. The adsorption of 2,4-dichlorophenol on activated carbon outperformed the 4-chlorophenol adsorption under tested experimental conditions. The adsorption of these compounds was endothermic and governed mainly by van der Waals interactions and hydrogen bonding. The adsorption of 2,4-dichlorophenol on activated carbon was a multimolecular process with the presence of an aggregation process in the aqueous solution, while a multi-docking adsorption mechanism occurred for the removal of 4-chlorophenol. Overall, this study contributes with theoretical insights on the removal of two emerging water pollutants by using activated carbon.

Investigating Molecular Adsorption on Graphene-Supported Platinum Subnanoclusters: Insights from DFT + D3 Calculations.

Platinum (Pt) subnanoclusters have become pivotal in nanocatalysis, yet their molecular adsorption mechanisms, particularly on supported versus unsupported systems, remain poorly understood. Our study employs detailed density functional theory (DFT) calculations with D3 corrections to investigate molecular adsorption on Pt subnanoclusters, focusing on CO, NO, N2, and O2 species. Gas-phase and graphene-supported scenarios are systematically characterized to elucidate adsorption mechanisms and catalytic potential. Gas-phase Pt n clusters are first analyzed to identify stable configurations and assess size-dependent reactivity. Transitioning to graphene-supported Pt n clusters, both periodic and nonperiodic models are employed to study interactions with graphene substrates. Strong adsorbate interactions predominantly occur at single top sites, revealing distinct adsorption geometries and stabilization effects for specific molecules on Pt6 clusters. Energy decomposition analysis highlights the paramount role of graphene substrates in enhancing stability and modulating cluster-adsorbate interactions. The interaction energy emerges as a critical criterion within the Sabatier principle, crucial for distinguishing between physisorption and chemisorption. Hybridization indices and charge density flow tendencies establish direct relationships with stabilization processes, underscoring graphene's influence in stabilizing highly reactive subnanoclusters. This comprehensive investigation provides critical insights into molecular adsorption mechanisms and the catalytic potential of graphene-supported Pt nanoclusters. Our findings contribute to a deeper understanding of nanocatalysis, emphasizing the essential role of substrates in optimizing catalytic performance for industrial applications.

Kinetic, equilibrium, and thermodynamic studies of adsorptive interactions of eosin-B on chemically treated orange peels

The present study investigated the adsorption of eosin B on the surface of powdered and chemically treated orange peels, along with this process’s condition optimizations, kinetics, and thermodynamics. The adsorbent dose (0.1–0.5 g), temperature (298, 303, 308, and 313 K), contact time (15–120 min), initial pH value (2–11) of the solution, and interfering salts (0.01 and 0.1 mol L−1) were all taken into consideration during the experiments. At all investigated temperatures and pH of 2, adsorption was more favourable. Although the Langmuir model might also represent the adsorption data, the Freundlich and Dubinin–Radushkevich (D–R) models provided a good description. The pseudo-second order kinetic model was followed during the adsorption process. The mechanics of the rate-controlling step were examined by applying the intra-particle diffusion-based mass transfer model to the experimental data. It was discovered that the only process that controlled the rate was intra-particle diffusion. The adsorption process appears to be spontaneous, and endothermic and involves van der Waals forces based on thermodynamic data.

Enhanced adsorption of radioactive cesium from nuclear wastewater using ZIF-67 laminated 2D MXene Ti3C2

Development of nuclear industry has caused severe water pollution. Adsorptive removal of radionuclides from wastewater has been regarded as effective solution for environment. However, developing adsorbents with high adsorption capacity and selectivity for removal of radionuclides (such as 137Cs) is still a challenge. Herein, we adopted an in situ assemble strategy to construct a novel composite, in which zeolitic imidazolate framework (ZIF-67) was grafted into two-dimension (2D) layers of transition metal carbides/nitrides (MXenes) Ti3C2, and used it in adsorptive removal of Cs+ from wastewater. Laminated and pillaring effect of ZIF-67 increased interlayer spacing and specific surface area of Ti3C2, significantly enhancing Cs+ adsorption. MXenes matrix provided the main adsorptive sites and interaction to stabilize Cs+, while the hybrid ZIF-67 assisted adsorption. The adsorbent achieved 96.2 % removal for 5 mg·L-1 of Cs+ within 6 h, and 50.0 mg·g−1 of maximum adsorption capacity, with good recyclability for 4 times. Ion competition, kinetics and thermodynamics were studied in detail to obtain the behavior of Cs+ adsorption. Finally, adsorption mechanism was proposed that [Ti − O] − H+ and [Ti − O] groups of 2D Ti3C2 were main adsorptive sites to participate in ion exchange and complexation with Cs+, respectively, while 2-methylimidazole (2-MI) ligands in ZIF-67 were synergetic adsorption sites.

Insights into the factors influencing the oxidation of antibiotic pollutants in nitrogen-doped biochar/PMS system: The roles of physicochemical properties and reaction pathways

The advanced oxidation of persulfate catalyzed by nitrogen-doped biochar (NBC) has emerged as a significant area of research, owing to its remarkable efficacy in selectively removing antibiotic organic pollutants from aquatic environments. Despite exhibiting promising results, the comprehension of the selective oxidation mechanisms of NBC remains inadequate, primarily stemming from the intricate complexity of organic pollutants and the vast variety of free radical active species involved. This study aims to elucidate the underlying mechanisms that drive the different oxidation processes promoted by NBC, with a focus on understanding the interactions between the physicochemical properties of various antibiotic contaminants and the resulting oxidation pathways. Regression analysis reveals the significance of adsorption interactions in constructing reaction interfaces, where the molecular polarity, complexity, topological polarity surface area, and molecular weight of pollutants play pivotal roles. However, these parameters do not singularly dictate the oxidation process. Instead, the electrochemical properties of organic pollutants (open-circuit potential, half-wave potential, and molecular orbital energy) primarily determine the selective oxidation. Furthermore, the research highlights that free radicals contribute to the oxidation of pollutants with relatively weak electrochemical properties, such as norfloxacin, but are insufficient to drive the entire oxidation process. Conversely, for pollutants with strong electrochemical properties, such as ofloxacin and oxytetracycline, the influence of free radicals is negligible. Overall, the study seeks to provide insights into the roles of adsorption interactions, electrochemical properties, and free radical dynamics, thereby advancing the development of efficient and targeted strategies for environmental remediation.