Adsorption Properties Research Articles

Research Progress in Starch-based Dye Adsorbents

Abstract: Starch is a typical environment-friendly biomass material and there are considerable quantities of reactive hydroxyl groups in the starch molecule chain. Modifications could introduce a large number of functional groups, which can bind some dyeing contaminants, thereby removing the dyes. According to the different modification methods, starch-based adsorbents can be divided into three categories that are aminated-modified starch, ionic-modified starch, and composite-modified starch. The preparation method, structure properties, and adsorption capacity of modified starch dye adsorbents have been reviewed in this article. It can be concluded that the adsorption property of adsorbents depends on different adsorption conditions and modification methods. The adsorption properties of the adsorbents have been found to be influenced by temperature, initial concentration of dyes, and pH value of solution. Amination modification can introduce amino or amine groups into the starch skeleton to enhance the chelation or electrostatic effect of the adsorbents on dyes. Ion modification can improve the ion exchange and electrostatic interaction between the adsorbents and the dye. Composite modification can improve specific surface area, pore size, adsorption site, and structural stability of the adsorbents. Future studies are required to focus on producing dye adsorbents with high adsorption performance, stable structure, recyclability, and degradability.

Composite of Organo-LDH and biochar for diclofenac sodium removal from aqueous solutions

Classic layered double hydroxides (LDHs) and their composites with biochar are promising adsorbents for removing emerging contaminants like diclofenac sodium (DFS) from water. However, the use of organo-LDHs in these composites remains unexplored and could enhance their adsorption properties for organic molecules. This study investigates the synthesis, characterization, and application of an organo-LDH based on sodium dodecyl sulfate as intercalating agent (SDS-LDH) and its composite with tangerine peel biochar (SDS-LDH/BC) for the removal of DFS from water. The adsorption performance of these materials was compared with those of a composite of SDS-LDH and tangerine peel biomass (SDS-LDH/Bio) and the layered double oxides (LDOs) obtained from the pyrolysis of SDS-LDH and SDS-LDH/Bio, referred to as SDS-LDO and SDS-LDO/Bio, respectively. The materials were characterized by FTIR, XRD, SEM, TG, and pH point of zero charge analyses, and the adsorption of DFS was evaluated in aqueous medium under different conditions. XRD and FTIR demonstrated the successful incorporation of sodium dodecyl sulfate into the interlamellar space of the SDS-LDH, which was preserved in the SDS-LDH/BC and SDS-LDH/Bio composites. SEM analysis revealed that the SDS-LDH structures, with varied shapes and sizes, were dispersed on the matrix of the biochar, while TG analysis showed that the SDS-LDH/BC had similar thermal stability to SDS-LDH. SDS-LDH achieved 90 % DFS removal at pH 8.0 and 25 °C, while SDS-LDH/BC reached 81 % removal under the same conditions, with maximum DFS adsorption capacities of 247 and 169 mg g−1, respectively, outperforming pristine biochar (no removal). Under the same conditions, SDS-LDH/Bio, SDS-LDO/Bio, and SDS-LDO removed 55 %, 36 %, and 36 % of DFS, respectively. These results revealed the pivotal role of the interlamellar structure of SDS-LDH in DFS adsorption, as confirmed by XRD and FTIR, which indicated that DFS interacted with dodecyl sulfate anion in the SDS-LDH interlamellar space, specially through hydrophobic interaction. Kinetics studies revealed that DFS adsorption on SDS-LDH/BC followed the pseudo-first-order model, while adsorption on SDS-LDH followed the pseudo-second-order model, with equilibrium reached in approximately 30 min. The Redlich-Peterson model satisfactorily fitted the adsorption equilibrium isotherms for both SDS-LDH and SDS-LDH/BC. Although no synergistic effect was observed between biochar and SDS-LDH/BC regarding the adsorption capacity, the formation of the SDS-LDH/BC composite improved the preservation of the SDS-LDH structures, allowing for a lower loss of adsorption capacity upon reuse. These findings suggest that the study of such advanced material can contribute to the development of more effective biochar-LDH composite-based adsorbents, specifically for the removal of organic pollutants.

Green synthesis of magnetic graphene-like biochar with oxygen vacancies for efficient adsorption and degradation of emerging antivirals from water

In this research, a magnetic biochar derived from the Vicia ervilia plant and possessing graphene-like properties (BC-G/Fe3O4) was used along with the activator persulfate for the adsorption and degradation of emerging pollutants such as Remdesivir and Favipiravir. The morphology, specific surface area, graphitization degree, and surface chemistry properties of the composite were determined using various techniques. The results showed that the synthesized BC-G/Fe3O4 had a high SSA (506.556 m2/g), indicating its suitable adsorption properties for the removal of antiviral drugs. The impact of various factors on the adsorption-oxidation process, including pH, catalyst dosage, oxidant concentration, antiviral concentration, and temperature, was examined and optimized through the utilization of response surface methodology and central composite design. The highest removal percentage of Remdesivir (93 %) and Favipiravir (98 %) was achieved at an initial antiviral concentration of 125 mg/L, catalyst dosage of 7 mg for Remdesivir and 5 mg for Favipiravir, contact time of 120 min, and pH of 7. Through the implementation of radical scavenging experiments, a thorough understanding of the mechanisms involved in PMS activation and the degradation of Favipiravir and Remdesivir was attained. The findings of this study indicate that the BC-G/Fe3O4 catalyst possesses excellent biocompatibility, adsorption-degradation capabilities, and reusability. Consequently, it can be successfully employed to eliminate emerging pollutants from aquatic environments.

Enhanced cesium removal from wastewater using a potassium hexacyanoferrate/gelatin aerogel composite

In the wake of the 2011 Fukushima nuclear disaster, the presence of radioactive cesium (137Cs) in nuclear wastewater has posed a critical and enduring health risk. Addressing this challenge, we have synthesized a gelatin aerogel, denoted as KCuFC/GA, immobilized with potassium cupric ferrocyanide (KCuFC) through an in situ approach, aiming for the efficient extraction of 137Cs from aqueous environments. This novel aerogel's rich porous structure enhances the accessibility of adsorption sites, thereby significantly promoting the capture of Cs+. The adsorption of cesium onto KCuFC/GA was investigated under various experimental conditions, including initial solution pH, contact time, initial cesium concentration, and the presence of coexisting ions (K+, Na+, Ca2+, Mg2+, Sr2+). The results indicated that the adsorption performance was largely independent of pH, achieving a high cesium removal rate of 93.4 % within the first 5 minutes. The cesium adsorption data were well-described by the Langmuir adsorption model, indicating a maximum adsorption capacity of 222.22 mg·L−1. Furthermore, in the presence of various competing ions, KCuFC/GA has demonstrated unparalleled selectivity for Cs+, with a partition coefficient (Kd) of 2.49 × 105 mL·g−1, and has sustained its adsorptive properties across five cycles of use. Through systematic investigation, including X-ray photoelectron spectroscopy (XPS) analysis, we have elucidated the adsorption mechanism, highlighting the pivotal role of ion exchange between lattice K+ and Cs+. The straightforward fabrication process and the aerogel's robust cesium removal capabilities from complex solutions indicate that KCuFC/GA is a promising candidate for real-world applications in the treatment of radioactive wastewater.

Synthesis of Some Eco-Friendly Materials for Gold Recovery.

The aim of this study was to develop new materials with adsorbent properties that can be used for the adsorption recovery of Au(III) from aqueous solutions. To achieve this result, it is necessary to obtain inexpensive adsorbent materials in a granular form. Concomitantly, these materials must have a high adsorption capacity and selectivity. Other desired properties of these materials include a higher physical resistance, insolubility in water, and materials that can be regenerated or reused. Among the methods applied for the separation, purification, and preconcentration of platinum-group metal ions, adsorption is recognised as one of the most promising methods because of its simplicity, high efficiency, and wide availability. The studies were carried out using three supports: cellulose (CE), chitosan (Chi), and diatomea earth (Diat). These supports were functionalised by impregnation with extractants, using the ultrasound method. The extractants are environmentally friendly and relatively cheap amino acids, which contain in their structure pendant groups with nitrogen and sulphur heteroatoms (aspartic acid-Asp, l-glutamic acid-Glu, valine-Val, DL-cysteine-Cys, or serine-Ser). After preliminary testing from 75 synthesised materials, CE-Cys was chosen for the further recovery of Au(III) ions from aqueous solutions. To highlight the morphology and the functionalisation of the material, we physicochemically characterised the obtained material. Therefore, the analysis of the specific surface and porosity showed that the CE-Cys material has a specific surface of 4.6 m2/g, with a porosity of about 3 nm. The FT-IR analysis showed the presence, at a wavelength of 3340 cm-1, of the specific NH bond vibration for cysteine. At the same time, pHpZc was determined to be 2.8. The kinetic, thermodynamic, and equilibrium studies showed that the pseudo-second-order kinetic model best describes the adsorption process of Au(III) ions on the CE-Cys material. A maximum adsorption capacity of 12.18 mg per gram of the adsorbent material was achieved. It was established that the CE-Cys material can be reused five times with a good recovery degree.

Magnetic iron-based waterworks sludge modified by chitosan and FeS for aqueous Cr(vi) adsorption and reduction.

Heavy metals have been considered an evolving environmental concern due to their harmful and long-lasting impacts. We synthesized a composite of FeS/CS@MIBWS for aqueous Cr(vi) adsorption and reduction utilizing the iron-based waterworks sludge modified by chitosan and FeS. After determining the optimal conditions for the FeS/CS@MIBWS preparation, its Cr(vi) removal capability was evaluated using material characterisation and static Cr(vi) adsorption assays. Cr(vi) elimination by the composite was a pH-dependent process, with pH 2 being the optimum in the range of 2-10. The adsorption process was befitted a pseudo-second-order model, and the equilibrium results agreed well with the Langmuir model. The thermodynamics investigation showed that Cr(vi) removal by the composite has both spontaneous and endothermic nature. Considering the ionic effects, Cl-, SO4 2- and PO4 3- decreased Cr(vi) elimination in the sequence of Cl- < SO4 2- < PO4 3-. The key mechanisms for Cr(vi) elimination were physical and chemical adsorption, chelation, and Cr(vi) reduction into Cr(iii). Furthermore, FeS/CS@MIBWS demonstrated steady reusability (removal effectiveness of 70% after 5 cycles). FeS/CS@MIBWS's rapid, high-performance, reusable, and easily separable adsorption properties make it a promising choice for heavy metal environmental cleaning.

The potential of Gd doping as a promising approach for enhancing the adsorption properties of nickel-cobalt ferrites.

The study shows that the addition of gadolinium ions has a significant impact on the structure, morphology, and adsorption properties of Ni-Co spinel ferrite that was synthesized by the sol-gel auto-combustion method. The research also indicates that the higher the Gd content, the greater the increase in the lattice parameter, which suggests that Gd3+ ions uniformly replaced the octahedral Fe3+ ions. The morphology and chemical composition of Gd-doped Ni-Co ferrites have been studied using SEM and EDS. Gd adding to the NiCoFe matrix increases the BET surface area by 50% (from 48 to 72 m2/g) and promotes the formation of mesopores with an average radius from 3.9 to 4.9nm. The pHPZC values of Gd-doped ferrites are in the range of 7.22-7.39, which means that the ferrite surface will acquire a positive charge at natural pH, so this will promote the adsorption of Congo red anionic dye through electrostatic interaction forces. Langmuir, Freundlich, and Dubinin-Radushkevich models were used to explain the mechanism of CR adsorption on the Ni0.5Co0.5GdxFe2-xO4 adsorbent surface. The ionic-covalent parameter has been estimated to describe the surface acid-base properties. Overall, this study highlights the potential of Gd3+ doping as a promising approach for enhancing the adsorption properties of nickel-cobalt ferrites.

First-Principles Study on Bi2Te2S Monolayer for Adsorption Performance and Sensing Capability.

In this study, a comprehensive investigation into the gas sensing capabilities of the two-dimensional (2D) Bi2Te2S was conducted using first-principles calculations based on density functional theory. A wide array of gas molecules, including CH4, Cl2, CO, CO2, H2, H2O, H2S, N2, NH3, NO, NO2, O2, and SO2, was encompassed in this work. Through the strategic placement of these gas molecules at different locations on the Bi2Te2S monolayer and taking into account a range of configurations, the adsorption process was thoroughly investigated, with a particular emphasis on the structures that are most thermodynamically stable. It was revealed that Cl2, O2, NO, and NO2 molecules exhibit a pronounced affinity for the Bi2Te2S monolayer. Notably, it was found that the Cl2@Bi2Te2S, O2@Bi2Te2S, and NO2@Bi2Te2S systems' gas adsorption capabilities are greatly enhanced by the introduction of an external electric field. Moreover, the addition of horizontal biaxial strain significantly impacts the gas adsorption properties of the O2@Bi2Te2S system, underscoring the tunability of the Bi2Te2S monolayer's sensing capabilities. In light of these theoretical results, the Bi2Te2S monolayer is proposed to have great potential as an extremely sensitive and selective gas sensing material, especially for identifying Cl2, O2, NO, and NO2. This study clarifies the intrinsic gas sensing capabilities of the Bi2Te2S monolayer, while highlighting how its performance can be tailored in response to external stimuli, setting the stage for the advancement of more sophisticated gas sensing devices.

A machine-learning interatomic potential to study dry/wet oxidation process of silicon

We developed an accurate and efficient machine learning potential with DFT accuracy and applied it to the silicon dry/wet oxidation process to investigate the underlying physics of thermal oxidation of silicon (001) surfaces. The accuracy of the potential was verified by comparing the melting point and structural properties of silicon, the structural properties of a-SiO2, and the adsorption properties on the silicon surface with experiment and DFT data. In subsequent thermal oxidation simulations, we successfully reproduced the accelerated growth phenomenon of the wet oxidation in the experiment, discussed the oxide growth process in detail, and elucidated that the accelerated growth is due to hydrogen in the system that both enhances the adsorption of oxygen on the silicon surface and promotes the migration of oxygen atoms. Finally, we annealed the oxidized structure, counted the defect information in the structure before and after annealing, and analyzed the defect evolution behavior during the annealing process.

A novel hydrogel composite of chitosan-phytic acid complex with PAAm: Characterization and adsorptive properties for UO22+and methylene blue

The composite of a polyelectrolyte combination of chitosan and phytic acid (CsPa) and its entrapped form in polyacrylamide (PAAmCsPa) were synthesized. The composites were characterized by a number of methods including ATR-FTIR, SEM-EDX, XRD and XPS. The adsorptive properties of CsPa and PAAmCsPa were analyzed and modelled for UO22+ and methylene blue (MB+). The results showed that the composites exhibited physico-chemical properties that were both inherited from the components as well as unique to them. The isotherms of UO22+ and MB+ were L-type Giles isotherms. The adsorption kinetics followed the pseudo-second-order model, in contrast to the Langmuir model, which predicts first-order kinetics for both species. According to the Weber-Morris model, the nature of the adsorption process was ion exchange and/or complex formation for both composites and ions. The thermodynamics showed that the adsorption process was endothermic (ΔH > 0), with increasing entropy (ΔS > 0) and spontaneous (ΔG < 0). The reusability tests of the composites for UO22+ adsorption showed that the composites were substantially reusable for 6 cycles. The composites were selective for UO22+ over MB+ ions, and UO22+ adsorption increased significantly when MB+ adsorbed composites were used. Reproducible measurements demonstrating the storability of the composites were obtained over a period of approximately one year.

Enhanced removal of lead ions from wastewaters by electrochemical adsorption using nitrogen-doped Ti3C2Tx MXene

As a two-dimensional material containing transition metal carbides and nitrides, MXene is often used in capacitive deionization for its excellent hydrophilic and pseudocapacitive properties. Nitrogen doping is widely used to improve the adsorption properties of certain materials. However, the effect of nitrogen doping on the electrochemical adsorption properties of MXene remains unclear. In this work, nitrogen-doped Ti3C2Tx MXene was synthesized using a simple hydrothermal method to achieve highly selective and efficient removal of Pb(II) at a constant cell voltage. The concentration of Pb(II) decreased from 4.95 to 0.02 mg L−1 in a 100 mg L−1 NaCl supporting electrolyte after electrosorption. The removal efficiency of Pb(II) reached 99.5%, whereas it was only 15.2% for Na+. The introduction of nitrogen functional groups increased the electrical conductivity and layer spacing of MXene, thereby improving the pseudocapacitive adsorption performance in the presence of Pb(II). The complexation function of the Ti-OH group on nitrogen-doped Ti3C2Tx surface increased and contributed to the selective adsorption of Pb(II). The removal efficiency of Pb(II) increased with increasing solution pH and cell voltage, reaching the maximum value at pH 5.0 and 1.5 V, respectively. The effect of supporting electrolyte type on the removal of Pb(II) was negligible. In addition, the removal efficiency for mixed heavy metal ion solutions, including Cu(II), Ni(II), and Pb(II), exceeded 79.0%. It exhibited the highest removal efficiency for Pb(II) at 97.9%. After five cycles of electrochemical adsorption–desorption, the nitrogen-doped Ti3C2Tx maintained a stable Pb(II) removal efficiency of 97.0%. This work provides a promising material for the electrochemical removal of low-concentration heavy metal ions from wastewaters.

Cu promoted Ni-Ca dual functional materials for integrated CO2 capture and utilization in O2-containing flue gas: Eliminating the delay in the utilization stage

Integrating CO2 capture and utilization by dry reforming methane (ICCU-DRM) technology is promising in concentrating and utilizing diluted CO2 from flue gas, which depends on developing Dual Functional Materials (DFMs) with adsorption and catalytic sites. Ni-Ca materials are widely applied in ICCU-DRM due to their excellent catalytic and CO2 adsorption properties. Nevertheless, the challenge remains that oxygen in the actual flue gas would oxidize the active Ni, leading to a delay in the DRM stage. In this work, Cu-promoted, ZrO2-stabilized Ni-Ca based DFMs were developed, which suppressed the delay and enhanced the performance of the DRM reaction. Attribute to the excellent reducing properties, Cu could be rapidly reduced in the CH4 atmosphere and further promote the reduction of NiO to the catalytically active Ni monomers by activating methane to generate reactive hydrogen (H*). What’s more, attributed to the disappearance of delay times, it is accompanied by a satisfying yield distribution with a 0.11 decrease in H2/CO ratio and an improvement in conversion, especially CH4 conversion with an increase of more than 10%. In addition, the bifunctional material also exhibits favorable cycling stability due to the stabilizers.

A generalized adsorption model of CO2-CH4 in shale based on the improved Langmuir model

CO2 enhanced shale gas recovery (CO2-ESGR), as one of the most promising carbon capture, utilization and storage (CCUS) technologies, can both improve the shale gas production for clean energy supply and mitigate greenhouse gas emissions for the goal of carbon neutrality. The adsorption characteristics of CO2 and CH4 in shale play a key role in the reserve assessment of shale gas and the implementation of CO2-ESGR. The problem of accurate prediction of the adsorption and competitive adsorption characteristics of CO2 and CH4 in shale is still one of the main challenges for CO2-ESGR. To bridge the gap, this work developed a generalized prediction model for the adsorption properties of CH4, CO2, and their mixed gas in shale by improving the Langmuir model, covering a large range of temperature, pressure, and total organic carbon content (TOC). The mathematical models for the key parameters of the Langmuir model, the saturated adsorption capacity Q0 and Langmuir pressure PL, were built for the single-component gas based on their functional relationship with temperature and TOC, and for the mixed gas based on their relationship with Q0 and PL of the single-component gas and CO2 content. Then an improved Langmuir model for the adsorption properties of CO2-CH4 in shale was established. The accuracy of the improved model was verified with a relative deviation below 5 % in a large range of temperature (303–363 K), pressure (0–15 MPa) and TOC (1.06 %-3.83 %) by comparing the calculated adsorption with the experimental data. This generalized adsorption model not only ensures the prediction accuracy of CO2-CH4 adsorption characteristics in shale but also expands its application convenience in a large range of temperatures, pressures and TOC, providing a certain theoretical basis for CO2-ESGR technology.

Croconic Acid Integrated Zwitterionic Conjugated Porous Polymer for Effective Iodine Adsorption.

Given the rapid growth of the nuclear sector, effective treatment of radioactive iodine is critical. Herein, we report the synthesis and the iodine adsorption properties of croconic acid (CTPB) and squaric acid (STPB) containing π-conjugated novel zwitterionic conjugated porous polymers (CPPs). The CPPs have been synthesized through a condensation reaction of tris(4-aminophenyl)benzene with croconic acid or squaric acid in high yields (~95%). The ionic nature of the polymers promoted high iodine/polyiodide vapour adsorption capacity of up to 4.6 g/g for CTPB and 3.5 g/g for STPB under ambient pressure at 80 °C. The zwitterionic framework (croconic acid or squaric acid units) coupled with the aromatic units is expected to effectively capture molecular iodine (I2) and polyiodides (I3- and I5-). The iodine adsorption properties of the polymers have been studied using Fourier-Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Brauner-Emmett-Teller (BET) analysis, and Raman Spectroscopy. Besides this work, there are only three ionic units for effective iodine adsorption. This work demonstrates the importance of zwitterionic units in the porous network reported for iodine adsorption and separation.

Physical performance, durability, and carbon emissions of recycled cement concrete and fully recycled concrete

This study introduces innovative concepts for closed-loop recycling waste concrete to produce fully recycled concrete (FRC). Multiple test methods and characterization techniques were used to evaluate the physical properties and durability of four types of concrete (normal concrete, recycled aggregate concrete, recycled cement concrete and FRC). The fresh density, compressive strength, ultrasonic characteristics, chloride resistance, water adsorption properties, carbonation behaviors, and microstructure characteristics of these concretes were investigated. The water absorption behavior of FRC can be divided into three stages, with the initial stage having a water absorption rate three times that of ordinary concrete. It was found that carbonation depth varied among different concrete types, influenced by binder quality, which can affect the porosity and mechanical properties. Overall, recycled cement concrete and FRC demonstrate considerable potential for reducing carbon emissions, with total emissions of 59.152 kgCO2/m3, representing an 85 % reduction compared to ordinary concrete.

Atomic Phosphorus Sites for Anchoring Platinum–Tungsten Dimers to Facilitate Proton Transfer in All‐pH Hydrogen Evolution

AbstractBimetallic single‐atom‐dimer (SAD) with unique electronic structures and adsorption properties presents exceptional catalytic performance owing to atomic‐level synergistic effects from direct bonding between different metal atoms. However, inherent characteristics of substrate present great challenges in their synthesis and mechanism investigation. Herein, a unique phosphorus modified atomic layer deposition (P‐ALD) strategy is designed to synthesize P‐anchored Pt–W dimers, overcoming substrate limitation (Pt1W1–P/C). Motivated introduction of atomic P site via ALD can effectively anchor one‐to‐one AB bimetallic dimer structure on various substrates, confirmed by X‐ray absorption spectroscopy (XAS). Density functional theory reveals an interatomic synergistic adsorption mechanism, with W as primary hydrogen adsorption site extending to Pt, optimizing hydrogen coverage, leading to 60‐fold increase in mass activity compared to commercial Pt/C in both acidic and alkaline electrolytes. Anion exchange membrane water electrolyzer with ultra‐low loading Pt1W1–P/C (50 µgPt cm−2) catalyst operates durability at 1000 mA cm−2 for 550 h with ultra‐low degradation of 38 µV h−1. Operando XAS confirms hydrogen adsorption pathway between atoms and remarkable self‐healing ability of P–Pt–W–O sites under all‐pH conditions. These findings extend the application domain of SAD to catalytic manufacturing methods and aid in designing advanced materials with multi‐atomic active sites.

Effect of solvothermal reaction time on adsorption and photocatalytic activity of spinel ZnFe2O4 nanoparticles

The present investigation explored the impact of solvothermal reaction time on the adsorption properties of synthesized spinel ZnFe2O4 Nanoparticles (ZF NPs) and their photocatalytic activity for the degradation of congo red (CR) dye. The structure, morphology and chemical composition is identified for the synthesized ZF NPs. The reaction times for the solvothermal synthesis of ZF NPs were investigated at time intervals of 6 hrs and 18 hrs which are denoted as ZF-6 h and ZF-18 h respectively. The XRD confirms the formation of spinel-type ZF-6 h and ZF-18 h with crystallite size of 5.50 nm and 8.36 nm for ZF-6 h and ZF-18 h respectively. The FESEM image of ZF-6 h exhibits microspheres, whereas in ZF-18 h NPs, the microspheres undergoes deformation. TEM analysis of ZF-6 h revealed that the microspheres were consists of 8–10 nm size ZF-NPs. Raman spectroscopy and XPS studies indicates, the reaction time influence the occupancy with 64 % and 32 % of inversion of Zn2+ cations from tetrahedral to octahedral sites in ZF-6 h and ZF-18 h, respectively. The surface area of mesoporous ZF-6 h and ZF-18 h are 138.29 m2/g and 128.41 m2/g respectively as confirmed using BET and BJH techniques. The CR dye adsorption capacity of 123.73 mg/g for ZF-6 h is higher compared to ZF-18 h (99.93 mg/g). The maximum dye removal efficiency evaluated for ZF-6 h NPs and ZF-18 h NPs was 87.33 % and 73.09 % respectively upon exposure of natural sunlight. The recyclability study identifies that ZF-6 h NPs remain stable for three degradation cycles. These results indicate that reaction time in solvothermal synthesis is sensitive to the morphology and physicochemical properties of ZF NPs. The enhanced performance of such ZF NPs is attributed to the synergistic effect of adsorption followed by photocatalytic (photo-Fenton) degradation of dyes.

Dissolution Mechanisms and Surface Charge of Clay Mineral Nanoparticles: Insights from Kinetic Monte Carlo Simulations

The widespread use of clay minerals and clays in environmental engineering, industry, medicine, and cosmetics largely stems from their adsorption properties and surface charge, as well as their ability to react with water. The dissolution and growth of minerals as a function of pH are closely related to acid–base reactions at their surface sites and their surface charge. The vivid tapestry of different types of surface sites across different types of clay minerals generates difficulties in experimental studies of structure–property relationships. The aim of this paper is to demonstrate how a mesoscale stochastic kinetic Monte Carlo (kMC) approach altogether with atomistic acid-base models and empirical data can be used for understanding the mechanisms of dissolution and surface charge behavior of clay minerals. The surface charge is modeled based on equilibrium equations for de/protonated site populations, which are defined by the pH and site-specific acidity constants (pKas). Lowered activation energy barriers for these sites in de/protonated states introduce pH-dependent effects into the dissolution kinetics. The V-shaped curve observed in laboratory experiments is reproduced with the new kMC model. A generic rate law for clay mineral dissolution as a function of pH is derived from this study. Thus, the kMC approach can be used as a hypothesis-testing tool for the verification of acid–base models for clay and other minerals and their influence on the kinetics of mineral dissolution and growth.

Enhancing Fenton-like reaction mediating performance of covalent organic frameworks through porosity modification

Covalent organic framework (COF) catalytic photocatalysts mediating Fenton-like reactions have been applied to the treatment of organic dyes in printing and dyeing wastewater. However, the photocatalytic performance of original COF is often unsatisfactory. This study investigated the impact of porosity modification strategies on the performance of COF photocatalysts in mediating the removal of organic dyes via Fenton-like reaction. Porosity modification was achieved by increasing the concentration of acetic acid (HAc) catalyst during COF preparation. The modified TAPB-DMTA COF (12M COF) exhibited excellent adsorption and photocatalytic properties. The Fenton-like reaction mediated by 12M COF photocatalysis removed nearly 96% of malachite green (MG) within 20 min, with a rate constant of 0.091 min−1, which was 2.9 and 6.5 times higher than that of g-C3N4 and original COF under the same reaction conditions, respectively. Additionally, the modulation mechanism of porosity modification on COF photocatalysis was explored. The conduction band (CB) of COF was reduced from −0.14 eV to −0.38 eV after porosity modification, facilitating the generation of longer-lived O2•- in the reaction system, which was conducive to efficient MG removal. Anti-interference experiments showed that the photocatalytic Fenton-like reaction system based on 12 M COF was less affected by common anions, cations and dissolved organics, while maintaining a high MG removal rate in tap water, mid-water, secondary clarifier effluent and river water. In summary, porosity modification was an effective strategy to improve the catalytic performance of original COFs. This study presented an efficient metal-free photocatalyst modification strategy for the Fenton-like reaction while avoiding the production of toxic by-products during dye degradation.

Synthesis of a new oil-absorbing PVC oil boom and its application to maritime oil spills

This paper aims to address the issue of environmental pollution resulting from marine oil spills by evaluating the oil adsorption performance of commonly used fence materials. Conventional oil adsorption materials exhibit limited rates and capacities for oil adsorption. Existing methods have proven insufficient in meeting the requirements for efficient and rapid oil–water separation. A new oil-absorbing barrier was developed by utilizing high oil adsorption resin as the primary material and hydroxypropyl methyl cellulose (HPMC) as the binder, leveraging the exceptional oil adsorption and hydrophobic properties of P(BMA-SMA-St)/MIL-101(Fe) resin. The oil-absorbing fence was characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The oil adsorption rates of carbon tetrachloride, toluene, diesel and gasoline by the oil adsorption fence with 25 g/L resin content were 101.26 g/m2, 68.12 g/m2, 35.19 g/m2, and 46.69 g/m2, respectively. After 120 h of UV irradiation, the coating’s oil absorption capacity remained nearly unchanged, and it demonstrated outstanding mechanical, chemical, and wear resistance. As a result, the oil adsorption fence possesses the capability to rapidly absorb oil from the water’s surface during the process of containing oil pollution, leading to positive social and economic impacts.