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Developing facile methods to modulate the structure and performance of photocatalysts plays a pivotal role in the potential large-scale application of photocatalytic hydrogen production. Herein, a series of uniformly sized and highly dispersed copper-doped cadmium sulfide (CdS) nanoparticles (NPs) were successfully synthesized through a facile cation exchange strategy. The resulting Cu-doped CdS samples exhibited a remarkable photocatalytic hydrogen production rate of 2459.3 μ mol·h−1g−1, nearly 11 times that of pure CdS. The introduction of Cu+ ions effectively reduced the band gap, leading to enhanced light absorption, as well as improved charge carrier separation and transfer efficiency. Meanwhile, the theoretical investigation further confirmed that Cu+ doping substantially decreased the free energy of hydrogen adsorption and provided more suitable active sites, thereby promoting the photocatalytic hydrogen production activity on CdS NPs. This work provides compelling evidence for the exploration of novel transition metal-doped photocatalysts for hydrogen production using the cation exchange method. [Display omitted] • Controllable Cu-doped CdS was prepared via cation-exchange approach. • Cu doping induced extended light absorption and accelerated charge separation. • HER was promoted by reduced free energy of hydrogen adsorption via Cu doping. • Photocatalytic hydrogen production of CdS was enhanced by 11 times. [ABSTRACT FROM AUTHOR]

Therapeutic antibodies play an important role in the public healthcare system to treat patients with a variety of diseases. Protein characterization using an array of analytical tools provides in-depth information for drug quality, safety, efficacy, and the further understanding of the molecule. A therapeutic antibody candidate MAB1 exhibits unique binding properties to both cation and anion exchange columns at neutral pH. This uniqueness disrupts standard purification processes and necessitates adjustments in manufacturing. This study identifies that the charge heterogeneity of MAB1 is primarily due to the N-terminal cyclization of glutamine to pyroglutamine and, to a lesser extent, succinimide intermediate, deamidation, and C-terminal lysine. Using three approaches, i.e., deferential chemical labeling, H/D exchange, and molecular modeling, the binding to anion exchange resins is attributed to negatively charged patches on the antibody's surface, involving specific carboxylic acid residues. The methodologies shown here can be extended to study protein binding orientation in column chromatography. [ABSTRACT FROM AUTHOR]

Lead halide perovskites have been explored ardently in the past decade owing to their excellent photophysical properties. High‐temperature cation exchange reactions have been employed to improve the stability and performance in perovskite lattice, but lacks control over size, shape, and stoichiometry. Herein, the solution phase interaction of cesium lead bromide (CsPbBr3) nanocrystals with monovalent and bivalent copper ions, under ambient conditions is systematically investigated. The introduction of Cu1+ explicitly initiates a one‐dimensional growth with a distinct phase transition, that is from cubic to orthorhombic, while Cu2+ induces a partial exchange with Pb2+ with no phase change. DFT calculations suggest that Cu1+ induces structural distortion via Cs1+ substitution, altering the Goldschmidt tolerance factor and perovskite octahedral tilting, leading to the phase transition. Additionally, the oleic acid/amine ligands used to stabilize the nanocrystals, are preferentially etched away to form complexes with Cu1+, initializing an oriented growth of the nanocubes to nanorods. A mechanistic investigation of the evolution of the nanorods gave insights on tuning the tolerance factor via room temperature modifications and cation exchanges in perovskites for anisotropy and morphology tuning. This effortlessly obtained perovskite nanorods with Cu1+ could find effective applications in optoelectronics, and as novel photocatalysts. [ABSTRACT FROM AUTHOR]

Phase control over cation exchange (CE) reactions has emerged as an important approach for the synthesis of nanomaterials (NMs), enabling precise determination of their reactivity and properties. Although factors such as crystal structure and morphology have been studied for the phase engineering of CE reactions in NMs, there remains a lack of systematic investigation to reveal the impact for the factors in heterogeneous materials. Herein, we report a molybdenum disulfide induced phase control method for synthesizing multidimensional Co3S4‐MoS2 heteronanostructures (HNs) via cation exchange. MoS2 in parent Cu1.94S‐MoS2 HNs are proved to affect the thermodynamics and kinetics of CE reactions, and facilitate the formation of Co3S4‐MoS2 HNs with controlled phase. This MoS2 induced phase control method can be extended to other parent HNs with multiple dimensions, which shows its diversity. Further, theoretical calculations demonstrate that Co3S4 (111)/MoS2 (001) exhibits a higher adhesion work, providing further evidence that MoS2 enables phase control in the HNs CE reactions, inducing the generation of novel Co3S4‐MoS2 HNs. As a proof‐of‐concept application for crystal phase‐ and dimensionality‐dependent of cobalt sulfide based HNs, the obtained Co3S4‐MoS2 heteronanoplates (HNPls) show remarkable performance in hydrogen evolution reactions (HER) under alkaline media. This synthetic methodology provides a unique design strategy to control the crystal structure and fills the gap in the study of heterogeneous materials on CE reaction over phase engineering that are otherwise inaccessible. [ABSTRACT FROM AUTHOR]

Precise control over the composition of heterostructure nanocrystals and their self-assembly is an emerging research interest. Superstructures of this type are typically enhanced in terms of their collective functionalities. Herein, we developed a practical yet simple approach to synthesize and self-assemble Cu2–xS/CuYS (Y = In, Sb, and Sn) heterostructured nanorods (NRs) into their vertically standing up assemblies. First NRs come together via depletion–attraction forces, and then partial cation exchange between Cu31S16 NRs and the injected cationic precursor taken in stoichiometric amounts dissolved in trioctylphosphine and oleylamine (Olam) results in heterostructured NRs possessing compositions of Cu2–xS/CuYS (Y = In, Sb, and Sn). The chemical composition changes lead to surface chemistry modifications as the injected guest cationic part of the NR is either naked or covered with Olam which is quite easy to strip-off from the NC surface at high temperature, resulting in a 2D sheetlike structure of heterostructured vertically oriented NRs in solution. The route to obtaining long-range heterostructured assembled NRs is studied and characterized systematically. This work presents a detailed mechanistic insight into the cation exchange-induced self-assembly of heterostructured NRs, where the particles are coupled, which is of growing importance as a synthesis tool. The complex nanostructures synthesized in the present work may benefit solution-processed optoelectronic applications. [ABSTRACT FROM AUTHOR]

Metal chalcogenide nanocrystals with variable composition and shape can conveniently be produced using cation exchange synthesis; however, the presence of cation‐containing ligands inherited from the starting material often results in contamination of the final product. To address this issue, a two‐step ligand replacement strategy is developed to fabricate CuInSe2/CuInS2 nanorods from CdSe/CdS nanorods via removal of Cd‐phosphonates from an intermediate Cu2‐xSe/Cu2‐xS phase used in the cation exchange conversion. This synthetic approach furnishes CuInSe2/CuInS2 nanorods with cadmium content below 1 at.%, and high photoluminescence quantum yields reaching 40% in the near‐infrared spectral range. Transient absorption studies reveal that the band alignment in the CuInSe2/CuInS2 heterostructure features a quasi‐type II character, with an electron localized in the core and a hole wavefunction spread over the entire nanorod. The efficient passivation of the core and the reduced Cd content leads to excitonic emission with full width at half maximum down to 110 meV, superimposed with a broad emission band from copper‐induced defects. Field‐effect transistors based on cadmium‐free CuInSe2/CuInS2 nanorods show two orders of magnitude lower noise current density compared with the cadmium‐rich devices. The responsivity and specific detectivity of these devices reach 230 mA W−1 and 108 Jones, respectively, under near‐infrared excitation at room temperature. [ABSTRACT FROM AUTHOR]

In this study, sugarcane bagasse (SB), which was preliminarily treated with H3PO4, was utilized to produce biochar (SB-BC). The SB-BC was subsequently modified with KOH to enrich oxygen-containing functional groups (OCFGs) for the enhanced adsorption of NH4+ from wastewater. Batch tests revealed that KOH-modified SB-BC (SB-MBC) increased the maximum Langmuir adsorption capacity of NH4+ by approximately twofold, from 27.1 mg/g for SB-BC to 53.1 mg/g for SB-MBC. The optimal operational conditions for NH4+ adsorption onto SB-MBC were pH of 7.0 and a biochar dose of 3.0 g/L for the removal of 50 mg/L NH4+ at room temperature (25 ± 2 °C) over 180 min of contact. The enhanced adsorption capacity of NH4+ onto SB-MBC was due to the important contribution of the OCFGs enriched on the surface of biochar, which was increased by about fourfold, after being modified by KOH. The NH4+ adsorption dynamics were better fitted by the Elovich and the NH4+ adsorption isotherms were better described by Langmuir and Sips models, showing that the adsorption process was dominated by monolayer chemisorption. The properties of the adsorption materials before and after adsorption of NH4+ confirmed that cation exchange, electrostatic attraction and surface complexation were the main mechanisms controlling the adsorption process. The desorption and reusability tests of NH4+-saturated SB-MBC revealed that NH4+ adsorption slightly decreased after three successive sorption‒desorption cycles. The findings suggested that SB-MBC is a promising and feasible adsorbent for the effective treatment of NH4+-contaminated water sources. Future work should conduct tests for treatment of NH4+-rich real wastewater and utilize NH4+-saturated SB-MBC as slow releasing fertilizer for plants growth. [ABSTRACT FROM AUTHOR]

Considering groundwater from the aquifers overlying the bedrock is an important water source for drinking purposes. As such, the investigation of its property is essential. Based on the spatial structure of aquifers in the study area, the aquifers in the Cenozoic strata are divided into three groups. The multivariate statistical approaches are employed to identify the hydrogeochemical processes and hydro-chemical types, and hydrogeochemical inverse modeling is applied to further validate and elucidate the hydrogeochemical process and water–rock interaction. The results are as follows: (1) The hydro-chemical type of the upper aquifer is dominated by the K + Na-HCO3 type, while others have similar water quality types, which are dominated by the K + Na-Cl type and the K + Na-SO4 type. (2) The saturation index of anhydrite, gypsum, halite, and CO2(g) is below zero in three aquifers, indicating that they are unsaturated. While aragonite, calcite, and dolomite in the middle aquifer remain in the unsaturated–saturated state. (3) The cation exchange process accelerating the reduction of Ca2+ concentration and the increase of SO42− concentration occurs in three aquifers, and the dissolution of calcite and dolomite minerals occurs in most cases. This study supports the fundamental evidence for the hydrogeochemical processes and water resource utilization and has a certain practical significance. HIGHLIGHTS Hydrogeochemical characteristics of the Cenozoic aquifers are investigated.; Relationship between ions reveals the hydrogeochemical processes and water–rock interaction.; Cation exchange process accelerates the reduction of Ca2+ concentration and the increase of SO42+ concentration.; A hydro-chemical boundary is identified.; Reverse simulation and cluster analysis further validate the water–rock interaction processes.;

The synthesis of the accurate composition and morphological/structural design of multielement semiconductor materials is considered an effective strategy for obtaining high-performance hybrid photocatalysts. Herein, sulfur vacancy (Vs)-bearing In2S3/CuInS2 microflower heterojunctions (denoted Vs-In2S3/CuInS2) were formed in situ using In2S3 microsphere template-directed synthesis and a metal ion exchange-mediated growth strategy. Photocatalysts with flower-like microspheres can be obtained using hydrothermally synthesized In2S3 microspheres as a template, followed by Ostwald ripening growth during the metal cation exchange of Cu+ and In3+. The optimal heterostructured Vs-In2S3/CuInS2 microflowers exhibited CO and CH4 evolution rates of 80.3 and 11.8 μmol g−1 h−1, respectively, under visible-light irradiation; these values are approximately 4 and 6.8 times higher than those reported for pristine In2S3, respectively. The enhanced photocatalytic performance of the Vs-In2S3/CuInS2 catalysts could be attributed to the synergistic effects of the following factors: (i) the constructed heterojunctions accelerate charge-carrier separation; (ii) the flower-like microspheres exhibit highly uniform morphologies and compositions, which enhance electron transport and light harvesting; and (iii) the vs. may trap excited electrons and, thus, inhibit charge-carrier recombination. This study not only confirms the feasibility of the design of heterostructures on demand, but also presents a simple and efficient strategy to engineer metal sulfide photocatalysts with enhanced photocatalytic performance. [ABSTRACT FROM AUTHOR]

Lepidocrocite-type layered sodium titanate (NaxH2−xTi2O5) is widely used in environmental remediation because of its large specific surface area, formed by anisotropic crystal growth, and its ability to store and exchange cations between layers. Additionally, peroxo-titanate nanotubes (PTNTs), which are tubular titanates with peroxy groups, exhibit visible-light absorption capabilities, rendering them suitable for photocatalytic applications under visible light irradiation. However, because of cation exchange reactions, the Na+ concentration and pH of the solution can fluctuate under aqueous conditions, affecting the photocatalytic performance of the PTNTs. Herein, we evaluated the impact of cation exchange reactions on the photocatalytic degradation of Rhodamine B (Rh B) by PTNTs at controlled Na+ ratios. The observed pH of Rh B solutions increases due to the cation exchange reaction with Na+ and H3O+, leading to the formation of zwitter-ionic Rh B molecules, eventually weakening their adsorption and photodegradation performance. Moreover, the results indicate that inhibiting the pH increase of the Rh B solution can prevent the weakening of both the adsorption and photodegradation performance of PTNTs. This study highlights the significance of regulating the sodium ion content in layered titanate materials, emphasizing their importance in optimizing these materials' photocatalytic efficacy for environmental purification applications. [ABSTRACT FROM AUTHOR]

The concentration of heavy metals in soil layers has increased due to the rapid development of the industry. Lead and zinc are two frequent heavy metal contaminants in soil. This paper aims to study the effect of these types of contaminants on different fines, including kaolinite, bentonite, and zeolite mixed with sand. First, mixtures of sand and kaolinite, bentonite, and zeolite were prepared, then they were contaminated by two contaminants of lead and zinc nitrates, separately. Consolidated undrained triaxial tests, Soil Conservation Service (SCS) double hydrometer tests, scanning electron microscope (SEM), Atterberg limits, and pH determination tests were conducted on the soil samples to investigate the changes in the strength and microstructure in the presence of heavy metals. In general, triaxial test results showed that various parameters influence the strength results of these heavy metal-contaminated sandy soil samples such as type, percentage, and structure of the fine portion, type, and concentration of contaminants, bonding mechanism of fine grains, and ion exchange capacity. For instance, in the presence of kaolinite (and kaolinite-zeolite mixtures), contamination with lead decreased the strength of soil samples, but in the soil mixtures containing bentonite (and bentonite-kaolinite mixtures), an opposite trend was seen. The plasticity index of mixtures containing kaolinite and zeolite increased in the presence of heavy metal contaminants, but it decreased when the fine portion of the soil was bentonite. Heavy metal contaminants decreased the pH of all soil mixtures and made them to be acidic. The results of the SCS double hydrometer test and SEM indicated that contaminated kaolinite and zeolite soil mixtures have a dispersed structure, while bentonite soil mixtures are not dispersive. [ABSTRACT FROM AUTHOR]

A comprehensive understanding of the hydrochemical evolution and spatial patterns of shallow groundwater systems is essential for water resource management and wetland ecological restoration. The Baiyangdian Wetland is one of the most concerning areas because of the development of the Xiong'an New Area. The spatial characteristics of groundwater hydrochemistry and potential controlling factors associated with hydrochemical evolution remain unclear. In this study, hydrogeochemistry together with the hierarchical cluster analysis were used to elucidate the hydrochemical processes and hydrological zoning patterns of shallow groundwater systems in the Baiyangdian Wetland, North China Plain. The results showed that hydrochemical compositions of shallow groundwater had considerable spatial variations, which was closely related to the inflow rivers hydrochemistry and the dynamics of groundwater–surface water interactions. A significant increase in SO42− concentration occurring at the cone of the depression was related to extensive pumping caused by anthropogenic activities. Anthropogenic activities were also a major factor controlling the spatial distribution patterns of shallow groundwater hydrochemistry. Ca2+, Mg2+, and SO42− in the wetland and shallow groundwater were primarily derived from carbonate and gypsum dissolution, while Na+ and Cl− originated from halite and silicate dissolution. Rock weathering predominated the geochemical evolution of shallow groundwater in conjunction with carbonate precipitation and cation exchange. The hydrochemistry of the shallow groundwater system presented distinct spatial zonation patterns that were classified into four clusters corresponding to seven subzones. In Zones I–IV, water‐rock interaction was the dominant factor controlling shallow groundwater chemistry, which was driven by the positive groundwater–surface water exchange. The coupled effects of anthropogenic activities and river infiltration and mixing caused the high levels of dissolved components in Zones V–VII. This study contributes to have a better understanding of the water cycle and hydraulic connections among different bodies, and will benefit the rational evaluation of hydrochemical evolution and wetland ecological restoration in the Baiyangdian Wetland. [ABSTRACT FROM AUTHOR]

The amendment of agricultural soils by crushed silicate minerals has been proposed to enhance weathering rates and facilitate carbon dioxide (CO2) removal from the atmosphere. Laboratory dissolution experiments typically provide weathering rates that are significantly higher than those observed under natural conditions, while field studies are limited in the nature of data they can collect. This study uses an experimental setup that aims to emulate natural field conditions in a controlled setting using soil cores retrieved from UK cropland amended with crushed olivine at 32°C. Results are compared to enhanced weathering experiments run at 4°C and 19°C under otherwise identical conditions. The data reveal temperature-dependent variations in the behaviour of different elements, most importantly Mg and Si, with silicon being retained at moderate temperatures and magnesium being retained at higher temperatures. These patterns are most likely due to different retention mechanisms, notably Si reprecipitation (e.g. as cation-depleted Si-enriched mineral surface coatings) and cation exchange (affecting Mg, but to a lesser degree Si), such that the influence of cation exchange should be accounted for when interpreting enhanced weathering field data. We therefore recommend that estimates of carbon sequestration should not be based on the behaviour of individual elements. A temperature effect on the weathering rate of olivine added to soil columns is observed with the weathering rate being higher at 32°C than at 19°C and 4°C, and significantly lower than laboratory experiment-derived weathering rates. This further emphasises the need for enhanced weathering field trials, as simple laboratory-derived rates cannot be used to assess the feasibility of enhanced weathering measures. The carbon dioxide capture potential at 32°C is conservatively estimated at ~115 t CO2 km-2 yr-1 assuming an olivine amendment rate of 12.7 kg m-2. Our data suggests that soil accumulation of heavy metals like Cu and Cr at high temperatures (hence high weathering rates) is nondangerous, however, Ni concentrations in the effluent solution are close to EU guidelines while Cr and Cu are considerably lower than guidelines. All of these conclusions have implications for the application of enhanced weathering for carbon dioxide removal from the atmosphere. [ABSTRACT FROM AUTHOR]

A geosynthetic clay liner (GCL) was exhumed from a composite liner (geomembrane over GCL containing granular sodium bentonite) in the base of a landfill cell after 12 years of atmospheric exposure. The GCL was altered appreciably during exposure, despite being overlain by a geomembrane. Water content, hydration, and bentonite erosion varied considerably along the slope. GCL samples from the top of the slope were dry, with visible bentonite granules comparable to those in a virgin GCL as if the bentonite had not hydrated. No substantial change in exchange complex or swell index (SI) occurred in samples from the top of the slope, and hydraulic conductivity of these samples to water was low (≈10−11 m/s). GCL samples from the toe of the slope varied considerably, from moist and soft to dry and cracked, but all had undergone hydration, and had low SI, a small mole fraction of monovalent cations in the exchange complex, and high hydraulic conductivity (10−8 m/s or higher). Bentonite in GCL samples from midslope had a cracked structure commonly observed in GCLs that have undergone wet–dry cycling. Midslope GCLs typically had hydraulic conductivity greater than 10−7 m/s. A sample from the top of the slope from a location near a GCL panel separation was comparable to other samples from the top of the slope. GCL samples from the anchor trench differed considerably, being very permeable or having low hydraulic conductivity. Hydraulic conductivity was strongly correlated with SI; GCL samples with SI<15 mL/2 g were highly permeable, and those with SI>15 mL/2 g were comparable to a virgin GCL. The variation in SI was related directly to replacement of sodium by calcium in the exchange complex of the bentonite. Hydraulic conductivity also was affected by the thinning of the GCL. [ABSTRACT FROM AUTHOR]

This work found that rectorite (REC) has a good adsorption effect on cationic pollutants such as ciprofloxacin (CIP), with a maximum adsorption capacity of 79.73 mg/g for CIP. The zeta potential analysis showed that the electronegativity of the REC surface would be weakened after CIP adsorption under acidic conditions. Through adsorption kinetics, isotherm study, XRD, FTIR, and other characterizations, the phenomenon of reduced negative charge on the surface of REC adsorbed with CIP under acidic conditions was explained. Based on the Langmuir and Temkin models, the adsorption process of CIP on REC is a spontaneous endothermic adsorption process. The adsorption kinetics can be better described using a pseudo-second-order model, indicating that the adsorption rate is mainly controlled by chemical adsorption. The characterization further proved that REC adsorbed ciprofloxacin mainly through hydrogen bonding, cation exchange, and electrostatic gravitational interaction. CIP, as an emerging contaminant discharged into the water environment, will be harmful to the ecological environment and human health. Therefore, the utilization of REC for the removal of CIP from an aqueous solution has potential prospects. [ABSTRACT FROM AUTHOR]

Salt stress seriously hinders the normal growth of plant seedling roots. Magnesium, as one of the essential medium elements for plant growth, can effectively alleviate the damage of salt stress to plant roots, but the key genes involved and their mechanism are still unclear. The purpose of this study was to explore the related molecular mechanism of exogenous magnesium regulating cation homeostasis in peanut seedlings under salt stress. Firstly, according to plant physiology experiments, it was found that exogenous magnesium treatment significantly improved the tolerance of peanut seedlings to salt stress. After that, the transcriptome data were integrated, and further gene expression analysis showed that the expression of genes such as CNGC1, NCLs, and NHX7 was regulated under exogenous magnesium treatment, which effectively reduced the accumulation of sodium ions in cells. At the same time, exogenous magnesium also regulates the expression of genes such as ACAs and POTs and maintains the homeostasis of calcium and potassium ions in cells. These results reveal the molecular mechanism of exogenous magnesium regulating the cation homeostasis of peanut seedlings under salt stress, which provides an important reference for further revealing the key genes of salt tolerance in plants. [ABSTRACT FROM AUTHOR]

Interactions at the oil/brine/rock interfaces play a pivotal role in the mobility of crude oil within reservoir matrices. Unraveling the microscopic mechanisms of these interactions is crucial for ion-engineered water flooding in secondary and tertiary oil recovery. In this study, the occurrence and transport behavior of crude oil in kaolinite nanopores covered with thin brine films was investigated by molecular dynamics simulation. There is an apparent interface layered phenomenon for the liquid molecules in slit pores and the polar oil components primarily concentrate at the oil/brine interfacial region and form various binding connections with ions. The interfacial interactions between the polar oil components and brine ions exhibit an inhibitory effect on the transport of crude oil through nanopores. The interaction mechanism between acetic acid molecules and hydrated ions was elucidated by interaction modes and interaction intensity, which was proved to illustrate the flow difference in different brine film systems. Moreover, a strategy of exchanging the binding sites of divalent cations with acetic acid molecules by monovalent cations with a higher concentration was proposed. The cation exchange scheme was further validated, demonstrating an enhancement in the oil mobility within nanopores. These findings deepen our understanding of oil/brine/rock interfacial interactions and provide a significant molecular perspective on ion-engineered water flooding for enhanced oil recovery. [ABSTRACT FROM AUTHOR]

Montmorillonite (Mt) is a ubiquitous swelling clay mineral and major component of soft rocks, sediments, and soils with an inherent capability to sorb metal cations. This unique feature renders Mt important for the enrichment and mobilization of environmentally important metal cations, retardation of heavy metals and radionuclide ions, the evolution of clay mineral itself, soils and sediments, and other geological processes. Understanding the interfacial interactions of Mt with metal cations at the molecular level is of fundamental importance in all these processes, but still remains elusive, due to the chemical and structural complexity of Mt surfaces and the diverse chemistries of metal cations. In this Review, we aim to provide the reader with a comprehensive overview of the adsorption modes of metal cations on basal and edge surfaces of Mt, local chemical environments of the cation binding sites, the driving forces for metal sorption, and factors influencing the dynamics of cation uptake onto Mt surfaces. Various surface complexation models [i.e., nonelectrostatic model (NEM), constant capacitance model (CCM), diffuse layer model (DLM), and triple-layer model (TLM)], advanced spectroscopic techniques (i.e., NEM, CCM, DLM, and TLM), and atomistic simulation methods (i.e., MD, DFT, and FPMD) have been used in conjunction with macroscopic adsorption experiments to gain detailed insights into the interfacial interactions of metal cations on Mt. Mt adsorbs metal cations via three independent pathways: (1) cation exchange; (2) surface complexation; and (3) nucleation and surface precipitation. The principal driving force for cation exchange is electrostatic interaction, while chemical bonding governs the two other mechanisms that depend on the basal and edge surface properties of Mt. The siloxane cavities on the tetrahedral basal plane exhibit the strongest adsorption sites for cation exchange and are greatly affected by the the degree of Al3+/Si4+ tetrahedral substitutions. At the amphoteric edge surfaces bearing hydroxyl groups, metal cations could form mono/multidentate surface complexes on Mt [010] and [110] edges. Ionic strength, pH, the presence of competing cations, temperature, and layer charge have been shown to affect the adsorption mechanisms and quantity of adsorbed cations. The updated information on the interfacial interactions of metal cations with Mt basal and edge surfaces presented in this review provides an improved understanding of the enrichment of metals, formation of metal ores, and natural biogeochemical cycles, as well as may promote technological and engineering applications of this important clay mineral in environmental remediation, geological repository, petroleum exploration and extraction, and extraterrestrial research. [ABSTRACT FROM AUTHOR]

It is investigated to identify the controlling processes for chemical compositions of unconfined groundwater along mainly eastward flowpaths on Musashino Uplands, located in Tokyo Metropolitan. Along the flowpaths, Ca2+ concentrations decreased, while Mg2+ and Na+ concentrations increased. Considering the facts that the observed changes along the paths occurred without a remarkable increase of TDS (total dissolved solid) values and that saturation index for calcite (SIc) of the groundwater samples indicated they were mostly under unsaturated conditions, the changes would be attributed to cation exchange reactions. This idea is concordant well with two previsous reports; one is for exchangeable cation compositions extracted from Kanto Loam and the other is for long-term monitoring of groundwater chemical compositions. Moreover, decrease of NO3- concentrations and increase of SO42- concentrations occured in special wards, the eastern part of Tokyo, These occurences can be caused by denitrification under anoxic conditions associated with higher covering area and by oxidation of sulfide involved in marine clays. Such an oxidation is likely induced by local percolation of precipitation and/or leakage from water supply pipes accompanied with dissolved O2. By using previous reports for the unconfined groundwater sources and aquifer parameters in Musashino Uplands, it is evaluated that percentage of the both of leakage and precipitation components is approximately 16% and the remaining is for groundwater advection component from upstream of special wards. In this evaluation, such a low percentage of oxic water components is accordant with regards to the occurrence capability for anoxic conditions in special wards. [ABSTRACT FROM AUTHOR]

To trace Critical Zone processes and to quantify Li fluxes from one Critical Zone compartment into another, we investigated the Li concentration and isotopic composition (δ7Li) of time-series water samples (including subsurface flow, groundwater and creek water), vegetation, bedrock (including separated minerals from bedrock), and regolith (including exchangeable fraction and clay-sized fraction of regolith) in a temperate forested headwater catchment in the Black Forest, Conventwald, Germany. Our estimation of the Li budget shows that atmospheric deposition and biological processes played minor roles in the Li cycle relative to chemical weathering. All water samples (δ 7Li value of 6.5 to 20.4 ‰) were enriched in 7Li compared to bedrock (-1.3 ‰) and regolith (∼-1.7 ‰), but δ7Li differed between water pathways: δ7Li variations in subsurface flow, creek water and groundwater were controlled by conservative mixing, exchangeable pool buffering and Li incorporation/adsorption, respectively. Fractionated heavy Li isotopes in water samples resulted from the formation of secondary solids which preferentially incorporated 6Li, with the separated clay-sized fraction of the regolith exhibiting more negative δ7Li values (-5.4 to −3.5 ‰) than the bulk regolith (∼-1.7 ‰). However, Li in secondary solids only accounted for 8 ± 6 % of the total Li hosted in bulk regolith, and consequently δ7Li in soil did not differ significantly from δ 7Li in bedrock. This is unexpected considering water is continuously removing 7Li in preference over 6Li from regolith. Mass balance calculations applied at the catchment scale point to an irreconcilable imbalance with our data. On one hand, the regolith's δ7Li values are not negative enough to balance the 7Li export by river water, and on the other hand Li in the riverine dissolved load only accounts for ∼ 30 % of the Li solubilized from regolith. Therefore, we suggest that there might be a "hidden export pathway" for Li at our site, possibly subsurface removal of fine particles enriched in 6Li. In light of increasingly frequent observations of such isotopic imbalances in the Critical Zone this phenomenon deserves increased attention. [ABSTRACT FROM AUTHOR]

Ningnanmycin is a widely used antibiotic in agricultural production that effectively controls fungal and viral diseases in tea trees and chrysanthemums. The polarity characteristic of ningnanmycin has posed limitations on the development of robust detection methods, thereby hindering effective monitoring and control measures. By combining cation exchange solid phase extraction (SPE) with hydrophilic interaction chromatography tandem mass spectrometry (HILIC-MS/MS), we have effectively tackled the issue pertaining to the separation and retention of ningnanmycin. The average recoveries of ningnanmycin in green tea, black tea, and chrysanthemum were 77.3–82.0%, 80.1–81.5%, and 74.0–80.0%, respectively. The intraday and interday relative standard deviations (RSDs) were below and equal to 7.7%. Good linearity was observed in the concentration range of 1–1000 μg/L (R2 > 0.998). The limits of detection (LODs) ranged from 1.1 μg/kg to 7.1 μg/kg, and the limits of quantification (LOQs) ranged from 3.6 μg/kg to 23.7 μg/kg for ningnanmycin. These results indicate the good accuracy, repeatability, reproducibility, and sensitivity of the method. It is suitable for detecting ningnanmycin in tea and chrysanthemum. [ABSTRACT FROM AUTHOR]

Bicarbonate ions (HCO3−) are abundant in karst water with poor lead (Pb) utilization and biodegradation. This study aimed to investigate the mechanism of HCO3− on the Pb removal efficiency and uptake ability of Pontederia crassipes (a widespread hydrophyte in the karst area) from karst water. The Pb concentration, Pontederia crassipes morphology, and functional group were detected. As the HCO3− molarity in karst water increased (3, 4, and 5 mmol/L), the removal of Pb increased (85.31%, 93.28%, and 95.16%), whereas the bioconcentration amount of Pb decreased (573, 501, and 301 mg/kg), mainly due to the insoluble PbCO3 and Pb (OH)2. The Pb bioconcentration factor was the highest (15,564) at 4 mmol/L HCO3− due to the maximum strength of cation exchange and cell wall protein C=O. High HCO3− molarities changed the variety of positive ions of cation exchange (HCO3− ≤ 4 mmol/L: Na, K, and Mg; HCO3− > 4 mmol/L: Mg and K), and relieved the breaking of roots, stomatal closure, and vascular system shrinking. Moreover, high HCO3− molarities diminished the C≡C oxidation, enlarged the displacement of SO42− and C-O, and stimulated the methyl transfer reaction and the bonding between -CH3 and Pb. [ABSTRACT FROM AUTHOR]

Owing to the absence of organic cations, all‐inorganic perovskite exhibits superior thermal and irradiation stability compared to organic‐inorganic perovskite. However, it is difficult for the traditional solution method to produce pinhole‐free and phase‐pure all‐inorganic perovskite films, which hinders its application. Here, a method of in situ A‐site cation exchange to synthesize CsPbBr3 films is introduced. The MAPbBr3 films are treated with CsAc solution to initiate cation exchange, where the intermediate product MAAc plays a crucial role in guiding grain growth during evaporation, resulting in the production of pinhole‐free and phase‐pure CsPbBr3 films. The self‐powered photodetector, based on compact and pinhole‐free CsPbBr3 film, exhibits excellent performance with an LDR of 126.7 dB, a detectivity of 1.1 × 1013 Jones, and a rise/decay time of 2.9/25.1 µs. Furthermore, the photodetector maintains over 90% of its original performance after a 2500 s irradiation test and a 30‐day air exposure test. Benefiting from the exceptional device performance and stability, the photodetector proves to be a valuable component in the laser eavesdropping system. [ABSTRACT FROM AUTHOR]

Thick‐shell colloidal quantum dots (QDs) are promising building blocks for solar technologies due to their size/composition/shape‐tunable properties. However, most well‐performed thick‐shell QDs suffer from frequent use of toxic metal elements including Pb and Cd, and inadequate light absorption in the visible and near‐infrared (NIR) region due to the wide bandgap of the shell. In this work, eco‐friendly AgInSe2/AgInS2 core/shell QDs, which are optically active in the NIR region and are suitable candidates to fabricate devices for solar energy conversion, are developed. Direct synthesis suffers from simultaneously controlling the reactivity of multiple precursors, instead, a template‐assisted cation exchange method is used. By modulating the monolayer growth of template QDs, gradient AgInSeS shell layers are incorporated into AgInSe2/AgInS2 QDs. The resulting AgInSe2/AgInSeS/AgInS2 exhibits better charge transfer than AgInSe2/AgInS2 due to their favorable electronic band alignment, as predicted by first‐principle calculations and confirmed by transient fluorescence spectroscopy. The photoelectrochemical cells fabricated with AgInSe2/AgInSeS/AgInS2 QDs present ≈1.5‐fold higher current density and better stability compared to AgInSe2/AgInS2. The findings define a promising approach toward multinary QDs and pave the way for engineering the QDs' electronic band structures for solar‐energy conversion. [ABSTRACT FROM AUTHOR]

The western U.S. is experiencing shifts in recharge due to climate change, and it is currently unclear how hydrologic shifts will impact geochemical weathering and stream concentration–discharge (C–Q) patterns. Hydrologists often use C–Q analyses to assess feedbacks between stream discharge and geochemistry, given abundant stream discharge and chemistry data. Chemostasis is commonly observed, indicating that geochemical controls, rather than changes in discharge, are shaping stream C–Q patterns. However, few C–Q studies investigate how geochemical reactions evolve along groundwater flowpaths before groundwater contributes to streamflow, resulting in potential omission of important C–Q controls such as coupled mineral dissolution and clay precipitation and subsequent cation exchange. Here, we use field observations—including groundwater age, stream discharge, and stream and groundwater chemistry—to analyse C–Q relations in the Manitou Experimental Forest in the Colorado Front Range, USA, a site where chemostasis is observed. We combine field data with laboratory analyses of whole rock and clay x‐ray diffraction and soil cation‐extraction experiments to investigate the role that clays play in influencing stream chemistry. We use Geochemist's Workbench to identify geochemical reactions driving stream chemistry and subsequently suggest how climate change will impact stream C–Q trends. We show that as groundwater age increases, C–Q slope and stream solute response are not impacted. Instead, primary mineral dissolution and subsequent clay precipitation drive strong chemostasis for silica and aluminium and enable cation exchange that buffers calcium and magnesium concentrations, leading to weak chemostatic behaviour for divalent cations. The influence of clays on stream C–Q highlights the importance of delineating geochemical controls along flowpaths, as upgradient mineral dissolution and clay precipitation enable downgradient cation exchange. Our results suggest that geochemical reactions will not be impacted by future decreasing flows, and thus where chemostasis currently exists, it will continue to persist despite changes in recharge. [ABSTRACT FROM AUTHOR]

Mullite-type AMn2O5 materials represent a group of promising candidates to substitute noble metal catalysts for the catalytic removal of volatile organic compounds (VOCs). When applied to catalytic oxidation of aromatic hydrocarbons such as toluene, AMn2O5 exhibits undesirable performance due to its poor intrinsic activity of oxygen species, leading to a light-off temperature above 250 °C. In this work, we have developed a synthesis route combining a two-step calcination and cation-exchange process to prepare a nanoporous CeO2-decorated Cu-SmMn2O5 composite mullite oxide catalyst applied in toluene oxidation. The best performing sample reached 90% toluene conversion at 190 °C, surpassing other transition metal oxide catalysts. Comprehensive characterizations reveal that Cu ion doping into the crystal lattice of the mullite phase is achieved via the cation-exchange process. In this catalyst design, surface CeO2 decoration and Cu doping promote the reduction ability and improve oxygen species activity to accelerate toluene oxidation. Overall, this work provides a strategy to prepare composite mullite oxide catalysts with high performance in the removal of VOCs, broadening the industrial application prospects of mullite-type materials. [ABSTRACT FROM AUTHOR]

Carbonate weathering plays a significant role in regulating global carbon budget at short time scales, and thus needs to be better constrained in the context of global warming. Riverine magnesium isotopes (δ26Mg) have the potential to trace carbonate weathering intensity (CWI) but require further testing under various climatic and geological settings. Cation exchange is an important mechanism buffering river water chemistry, especially in catchments characterized by high erosion. However, field evidence on the influence of cation exchange on riverine δ26Mg is rare. In this study, spatial riverine δ26Mg variation within the Three Rivers (i.e., the Jinsha Jiang, the Lancang Jiang, and the Nu Jiang), three extremely-high-erosion catchments in the southeastern Tibetan Plateau, was investigated to address this issue. The results showed that riverine δ26Mg values present a wide range from –1.11 ‰ to –0.59 ‰ in the Jinsha Jiang, from –1.39 ‰ to –0.65 ‰ in the Lancang Jiang, and from –1.19 ‰ to –0.50 ‰ in the Nu Jiang. An inversion model was used to partition riverine Mg2+ sources and confirmed that the riverine Mg2+ budget was dominated by carbonate weathering, followed by evaporite dissolution. However, conservative mixing could not explain riverine δ26Mg variation within the Three Rivers catchments, because measured δ26Mg values (δ26Mg measured) systematically deviated from the modeled ones (δ26Mg modeled), with Δ26Mg measured–modeled (δ26Mg measured – δ26Mg modeled) up to 0.79 ‰. The positive correlations between Δ26Mg measured–modeled and suspended particulate matter (SPM) concentrations indicate Mg isotopic fractionation was related to high suspended loads owing to extremely-high erosion rates. Given the significant cation exchange capacity of SPM, Mg2+-Na+ exchange is proposed for the first time as an explanation for the observed δ26Mg variations in the rivers draining the Tibetan Plateau, although the role of carbonate precipitation could not be excluded. The strong positive correlations between riverine δ26Mg and exchangeable Mg/Na ratios in the Three Rivers further support that light Mg isotopes may be preferentially retained in the riverine exchange pool during Mg2+-Na+ exchange, driving riverine δ26Mg towards higher values. Expanding our finding to global rivers, the negative correlation between riverine δ26Mg and CWI can be interpreted by a competition between the fast dissolution of carbonates leading to the enrichment of 24Mg in waters and Mg isotope fractionation induced by cation exchange leading to the depletion of 24Mg in the residual waters. This study provides new insight into cation exchange as a regulator of riverine δ26Mg and Mg cycling, highlighting the robustness of riverine δ26Mg in tracing CWI and constraining the carbon cycle. [ABSTRACT FROM AUTHOR]

Clinoptilolite (CLN) from Bigadiç and that of calcined forms after NH4NO3 modification were investigated to demonstrate their possible usability in industrial applications. -modified forms were prepared using 0.2, 1.0, and 2.0 M NH4NO3 solutions at 90°C for 3 and 6 h, and then all samples were calcined at 400°C for 13 h. All samples were characterized using XRD, XRF, SEM and nitrogen adsorption methods. BET specific surface areas (17.8–272.9 m2 g–1) and total pore volumes (0.055–0.197 cm3 g–1) of the clinoptilolites were calculated from nitrogen adsorption isotherms obtained at 77 K by 3Flex (Micromeritics) equipment volumetrically. After increasing the molarity and processing time of the ammonium nitrate solutions, the calcination of the samples significantly affected both morphological and textural features. Compared to starting material, XRD peaks of the samples calcined at 400°C broadened and agglomeration of clinoptilolite crystals decreased. In addition, calcined clinoptilolite samples showed different ammonia adsorption capacities (4.853–5.388 mmol g–1). [ABSTRACT FROM AUTHOR]

Lead chalcogenide nanoplatelets (NPLs) have emerged as a promising material for devices operating in the near IR and IR spectrum region. Here, we first apply the cation exchange method to PbSe/PbS core/shell NPL synthesis. The shell growth enhances NPL colloidal and environmental stability, and passivates surface trap states, preserving the main core physical properties. To prove the great potential for optoelectrical applications, we fabricate a photoconductor using PbSe/PbS NPLs. The device demonstrates enhanced conductivity and responsivity with fast rise and fall times, resulting in a 13 kHz bandwidth. The carrier transport was investigated with the field effect transistor method, showing p-type conductivity with charge mobility of 1.26 × 10−2 cm2·V−1·s−1. [ABSTRACT FROM AUTHOR]

This study focuses on assessing hydrochemical characteristics and non-carcinogenic health risks associated with fluoride contamination in groundwater within the Palacode and Pennagaram taluks of Dharmapuri district. The presence of fluoride in drinking water is a significant concern due to its potential health impacts on both adults and children. We collected a total of 158 groundwater samples during both the summer (SUM) and monsoon (MON) seasons in 2021 to evaluate the suitability of water for drinking purposes in this region. During the SUM season, groundwater exhibits alkaline characteristics with a pH range of 6.70 to 8.73 and a mean value of 7.43, while the MON season falls within the neutral pH range with values ranging from 6.60 to 7.60 and a mean of 7.00. Hydrogeochemical analysis reveals that fluoride concentrations during the SUM season range from 0.13 to 2.7 mg/L, with a mean of 0.82 mg/L, whereas the MON season exhibits concentrations ranging from 0.08 to 1.6 mg/L, with a mean of 0.5 mg/L. Spatial distribution analysis indicates a gradual increase in fluoride concentrations from the northeast to the central and southern parts of the study area during both seasons. Residents in these areas have been exposed to high fluoride levels for an extended period, leading to health issues related to fluorosis. Our hydrogeochemical analysis attributes fluoride dominance to the Cl--SO42- water type in both seasons. Furthermore, the relationship between fluoride and pH, HCO3-, Ca2+, and Na+ suggests the influence of geological factors in fluoride dissolution under alkaline conditions, while a reverse cation exchange process and increasing calcium concentration inhibit fluoride concentration. Saturation indices indicate that the unsaturated state of gypsum dissolution contributes to elevated fluoride levels in groundwater. Additionally, Gibbs plots highlight rock-water interactions as a significant factor influencing groundwater chemistry in the study area. Based on our hazard quotient (HQ) investigation, children are at a higher risk during both seasons compared to adults, with the central and northern regions showing alarming HQ values. These findings underscore the urgent need for enhanced groundwater quality monitoring and a comprehensive assessment of health risks, providing valuable insights for groundwater safety management in vulnerable areas of this region. [ABSTRACT FROM AUTHOR]

In order to reduce the degree of efflorescence in alkali-activated metakaolin geopolymers, a modified 5A zeolite with cation-exchange properties was used to reduce the content of free alkali metal cations in the geopolymer. This work aims to investigate the effect of different dosages of modified 5A zeolite on the microstructure and properties of geopolymer by using compressive strength testing, pore structure analysis (BET), and SEM-EDS. The cation content in the leachate was evaluated using inductively coupled plasma atomic emission spectrometry (ICP-OES). The efflorescence area of the geopolymer was calculated using Image Pro Plus (IPP) software to evaluate the effect of modified 5A zeolite on the degree of efflorescence of the geopolymer and to reveal the effect of modified 5A zeolite on the migration patterns of Na+ and Ca2+ in the geopolymer. The results showed that modified 5A zeolite with a 4 wt.% content could optimize the pore structure and enhance the mechanical properties of MK geopolymer through internal curing and micro-aggregate effects, which could also exchange cations with the pore solution to form (N, C)-A-S-H gels. The Na+ leaching was reduced by 19.4%, and the efflorescence area of the MK geopolymer was reduced by 57.3%. [ABSTRACT FROM AUTHOR]

[Display omitted] Construction of semiconductor heterojunctions which promote the separation and transport of photogenerated carriers is an effective strategy for improving photocatalytic reaction efficiency. Based on the anisotropic electrical conductivity of layered ZnIn 2 S 4 (ZIS) photocatalyst, an efficient heterojunction should be constructed along the layer plane of ZIS, that is, a J type heterojunction. However, achieving controllable synthesis of the oriented heterojunction of ZIS faces challenges. Herein, we develop a facile, cost-effective and spatially-selective cation exchange synthesis approach to construct J type ZnIn 2 S 4 @CdIn 2 S 4 (J-ZIS@CIS) heterojunction using a flower-like hexagonal ZIS as the parent material. The developed synthesis approach can also control crystal structure of the heterojunction component CIS. This work presents a facile and controllable synthesis strategy to construct oriented anisotropic heterojunctions that are otherwise inaccessible. The as-prepared J-ZIS@CIS heterojunction displays a greatly enhanced photocatalytic hydrogen evolution activity with a rate of 183 μmol h−1, 2.77 times higher than that of pristine ZIS. Furthermore, the possible photocatalytic reaction mechanism is presented for the heterojunction. [ABSTRACT FROM AUTHOR]

The inferior electrical conductivity of conventional electrodes and their slow charge transport impose limitations on the electrochemical performance of supercapacitors (SCs) using those electrodes, necessitating strategies to overcome the limitations. An in situ Ag ion‐incorporated cation‐exchanged bimetallic sulfide/metal oxide heterostructure (Ag‐Co9‐xFexS8@α‐FexOy) is synthesized using a two‐step hydrothermal method. The coordination bond formation and Ag nanoparticle (NP) incorporation improve the electrical conductivity and adhesion of the heterostructure and reduce its interface resistance and volume expansion throughout the charge/discharge cycles. Density functional theory investigations indicate that the remarkable interlayer and interparticle conductivities of the heterostructure resulting from Ag doping have changed its electronic states, leading to an enhanced electrical conductivity. The optimized electrode has an excellent specific capacity (213.6 mA h g−1 at 1 A g−1) and can maintain 93.2% capacity retention with excellent Coulombic efficiency over 20 000 charge/discharge cycles. A flexible solid‐state extrinsic pseudocapacitor (EPSC) is fabricated using Ag‐Co9‐xFexS8@α‐FexOy and Ti3C2TX electrodes. The EPSC has specific and volumetric capacitances of 259 F g−1 and 2.7 F cm−3 at 0.7 A g−1, respectively, an energy density of 80.9 Wh kg−1 at 525 W kg−1, and a capacity retention of 92.8% over 5000 charge/discharge cycles. [ABSTRACT FROM AUTHOR]

With the aim of better directing the polycondensation of oligomers during the synthesis of amorphous aluminosilicate xerogels by the sol-gel process using Na2SiO3, we reinforced the sols with K+ counterion and studied its effect on the physicochemical and structural properties of the xerogels using XRD, FTIR, N2 physisorption, SEM, EDX, and TGA techniques as well as quantitative analysis of the acid sites by N-butylamine adsorption followed by potentiometric titration. Based on the results, the introduction of K+ generated xerogels with good porosity and conferred resistance to matrix cracking. The amorphous character of the xerogels did not change after adding K+. FTIR spectra showed that the composition of the xerogels was improved after the addition of K+. Cation exchange and sulfur removal were much more efficient in the presence of K+ which improved the acidity of the xerogels. The best percentages of Si and Al were observed at the Na+/K+ ratios of 4 and 1.The enhanced xerogel prepared with Na+/K+ ratio of 1 gave a biodiesel yield of 80.44% at the optimum parameters and was used for three reaction cycles without significant loss of biodiesel yield. [ABSTRACT FROM AUTHOR]

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The synthesis of the accurate composition and morphological/structural design of multielement semiconductor materials is considered an effective strategy for obtaining high-performance hybrid photocatalysts. Herein, sulfur vacancy (Vs)-bearing In2S3/CuInS2 microflower heterojunctions (denoted Vs-In2S3/CuInS2) were formed in situ using In2S3 microsphere template-directed synthesis and a metal ion exchange-mediated growth strategy. Photocatalysts with flower-like microspheres can be obtained using hydrothermally synthesized In2S3 microspheres as a template, followed by Ostwald ripening growth during the metal cation exchange of Cu+ and In3+. The optimal heterostructured Vs-In2S3/CuInS2 microflowers exhibited CO and CH4 evolution rates of 80.3 and 11.8 μmol g−1 h−1, respectively, under visible-light irradiation; these values are approximately 4 and 6.8 times higher than those reported for pristine In2S3, respectively. The enhanced photocatalytic performance of the Vs-In2S3/CuInS2 catalysts could be attributed to the synergistic effects of the following factors: (i) the constructed heterojunctions accelerate charge-carrier separation; (ii) the flower-like microspheres exhibit highly uniform morphologies and compositions, which enhance electron transport and light harvesting; and (iii) the vs. may trap excited electrons and, thus, inhibit charge-carrier recombination. This study not only confirms the feasibility of the design of heterostructures on demand, but also presents a simple and efficient strategy to engineer metal sulfide photocatalysts with enhanced photocatalytic performance.

Lepidocrocite-type layered sodium titanate (NaxH2−xTi2O5) is widely used in environmental remediation because of its large specific surface area, formed by anisotropic crystal growth, and its ability to store and exchange cations between layers. Additionally, peroxo-titanate nanotubes (PTNTs), which are tubular titanates with peroxy groups, exhibit visible-light absorption capabilities, rendering them suitable for photocatalytic applications under visible light irradiation. However, because of cation exchange reactions, the Na+ concentration and pH of the solution can fluctuate under aqueous conditions, affecting the photocatalytic performance of the PTNTs. Herein, we evaluated the impact of cation exchange reactions on the photocatalytic degradation of Rhodamine B (Rh B) by PTNTs at controlled Na+ ratios. The observed pH of Rh B solutions increases due to the cation exchange reaction with Na+ and H3O+, leading to the formation of zwitter-ionic Rh B molecules, eventually weakening their adsorption and photodegradation performance. Moreover, the results indicate that inhibiting the pH increase of the Rh B solution can prevent the weakening of both the adsorption and photodegradation performance of PTNTs. This study highlights the significance of regulating the sodium ion content in layered titanate materials, emphasizing their importance in optimizing these materials’ photocatalytic efficacy for environmental purification applications.

Therapeutic antibodies play an important role in the public healthcare system to treat patients with a variety of diseases. Protein characterization using an array of analytical tools provides in-depth information for drug quality, safety, efficacy, and the further understanding of the molecule. A therapeutic antibody candidate MAB1 exhibits unique binding properties to both cation and anion exchange columns at neutral pH. This uniqueness disrupts standard purification processes and necessitates adjustments in manufacturing. This study identifies that the charge heterogeneity of MAB1 is primarily due to the N-terminal cyclization of glutamine to pyroglutamine and, to a lesser extent, succinimide intermediate, deamidation, and C-terminal lysine. Using three approaches, i.e., deferential chemical labeling, H/D exchange, and molecular modeling, the binding to anion exchange resins is attributed to negatively charged patches on the antibody’s surface, involving specific carboxylic acid residues. The methodologies shown here can be extended to study protein binding orientation in column chromatography.

In this paper, the coal pillar dam body of the underground reservoir in Daliuta coal mine, along with the residual coal and the mine water present in the goaf, were taken as research subjects, and a dynamic simulation experiment device was constructed to simulate the actual process of a coal mine underground reservoir (CMUR). The composition and structure of middling coal during the experiment were determined by X-ray diffraction analysis (XRD) and X-ray fluorescence spectrometry (XRF), while changes in ion content in the mine water were assessed through ion chromatography (IC) and inductively coupled plasma emission spectrometry (ICP-OES). Based on both the composition and structure of coal as well as variations in ion concentrations in water, the interaction mechanism between coal and mine water was explored. The results showed that the water–coal interaction primarily arose from the dissolution of minerals, such as rock salt and gypsum, within coal. Additionally, coal samples in mine water exhibited adsorption and precipitation of metal ions, along with cation exchange reaction. Na+ in mine water predominantly originated from the dissolution of rock salt (sodium chloride) in coal, while Ca2+ and SO 4 2 − were released through the dissolution of gypsum and other minerals in coal. In the process of the water–coal interaction, Ca2+ in the water body was adsorbed and immobilized by the coal sample, leading to the formation and deposition of CaCO3 on the surface of the coal, thereby increasing the calcite content. These processes collectively contributed to a decrease in the concentration of Ca2+ in the water body. Moreover, the cation exchange reaction occurred between Ca2+ and Mg2+ in mine water and Na+ in the coal sample. The presence of Ca2+ and Mg2+ resulted in their displacement of Na+ within the coal matrix, consequently elevating Na+ concentration in the mine water while reducing both the Ca2+ and Mg2+ concentrations. On this basis, combined with insights from the water–rock interaction, it can be inferred that the adsorption mechanisms involving rocks played a dominant role in the decrease of Ca2+ concentration during the water–rock interactions. Meanwhile, the dissolution processes of minerals both in the water–rock and water–coal interactions predominantly contributed to the increase of Na+ and Cl− concentrations. [ABSTRACT FROM AUTHOR]

Chemical weathering is one of the most important processes on the Earth's surface, and lithium isotopes have been used as a promising tracer of silicate weathering, as the secondary clay minerals precipitated during silicate weathering are thought to preferentially incorporate the lighter 6Li isotope. However, to utilize lithium isotopes as a geochemical tracer, it is essential to quantitatively understand the partitioning of Li in clay minerals, including structurally bound Li and exchangeable interlayer ions, as well as the associated isotope fractionation. With classical molecular dynamic simulations and thermodynamic calculations, the cation exchange between Na-/K-montmorillonite and solvated Li in environmental solution are disclosed under different aqueous activity conditions. The Li+ ion, whose hydration ability is stronger than Na+ and K+ ions, is easier to swell the montmorillonite and shows less affinity for the clay. And the calculated cationic selectivity coefficients between Na+/K+ and Li+ ions are K c (Li → Na) = 2.0, K c (Li → K) = 10.0 for Arizona-type montmorillonite and K c (Li → Na) = 1.0, K c (Li → K) = 4.0 for Wyoming-type montmorillonite, which are comparable to reported experiments. The cationic partition of Li in the clay interlayer decreases when the hydration states of montmorillonite transform from triple-layer to bilayer and then to monolayer. Based on the density functional theory, the Li isotope fractionations for Li in clay interlayer sites and structural octahedral sites are further derived by thermodynamic calculations with path integral molecular dynamic simulation, which deals with the quantum anharmonicity. The behaviors of Li isotope in the bilayer hydration state closely resembles that in the aqueous solution, and only a slight Li isotope fractionation is found between the monolayer hydrated octahedral-substituted clay and solution phase (Δ7Li monolayer-aq = −2.0‰). While Li isotope fractionation between aqueous solution and mica structural sites is significant (Δ7Li structural-aq = −10.4‰) and shows an obvious quantum anharmonicity, which indicates the importance of the anharmonic treatment for Li isotope fractionation calculations. The newly calculated Li equilibrium isotope fractionation between clay and aqueous solution deviates from the experimentally determined fractionation factor, which can be attributed to the kinetic effects. Moreover, on the basis of the surface kinetic reaction model, the Li isotope fractionation becomes more pronounced with higher clay growth rate. By integrating the cationic selectivity coefficient and Li isotope fractionation, it is possible to constrain the fluid composition during Li-clay deposit and diagenesis, and to evaluate the intensity of chemical weathering processes as well as the related carbon cycle. [ABSTRACT FROM AUTHOR]

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Cation exchange (CE) has been emerged as a promising post-synthesis strategy of colloidal nanocrystals. However, it is unclear how the cation precursor affects the CE process and the final colloidal nanocrystals. Herein, we utilized two Zn-B Lewis acid-base adduct complexes (B = oleylamine (OAM) and methanol (MeOH)) as Zn precursors for CE with Ag2S quantum dots (QDs). Our study revealed that the steric hindrance and complexing capabilities of Zn precursor significantly affect the CE kinetics. As a result, the Zn-doped Ag2S (Zn:Ag2S) and Ag2S@ZnS core–shell QDs were successfully obtained with enormous enhancement of their photoluminescence (PL) intensities. Theoretical simulation showed that the Zn-OAM with higher desolvation energy and spatial hindrance tended to form doped Zn:Ag2S QDs due to the inefficient cation exchange. Whereas the Zn-MeOH with lower exchange barrier promoted the conversion of Ag-S to Zn-S, thus forming Ag2S@ZnS core–shell QDs. We anticipate that this finding will enrich the regulatory approaches of post-synthesis of colloidal nanocrystals with desirable properties. [ABSTRACT FROM AUTHOR]

This work reports the use of smectite clays (raw and modified samples) as adsorbents in the adsorption process for removing benzene, toluene, and metal ions present in wastewater generated in the petrochemical industries. Smectite clay was used in the adsorption of organic compounds and in the cation exchange process for the removal of heavy metal ions Cu(II) and Pb(II) as a post-treatment process for refinery effluents. From the chemical treatment of raw smectite clay with sodium carbonate (Na-modified smectite clay, Na-MSC) it has been achieved a good exchange of Ca(II) and Mg(II) ions for Na(I). Moreover, characterization analysis evidenced that the raw smectite and Na-MSC had mesoporous structure. The number of exchangeable ions increased from 81.34 to 89.39 meq 100 g−1 after Na-addition. The adsorption and cation exchange experiments were conducted in batch mode using the sodium clays as adsorbents in the kinetic and equilibrium study. The isotherm of Langmuir–Freundlich was the most representative, and the adsorption capacity monolayer for benzene and toluene were 7.28 and 7.39 mg g−1. The ionic exchange model was applied to represent the removal of Cu(II) and Pb(II), which indicated a capacity of 0.99 mg g−1 and 1.10 mg g−1 respectively. Kinetic constants obtained for benzene and toluene were 0.0016 L mg−1 min−1 and 0.019 L mg−1 min−1. Finally, Na-MSC obtained kinetic constants 0.049 L mg−1 min−1 and 0.063 L mg−1 min−1 for Cu(II) and Pb(II) respectively. The results acquired in batch experiments evidence the high efficiency of Na-MSC to remove BTEX and heavy metals from wastewater. [ABSTRACT FROM AUTHOR]

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Cesium methylammonium lead iodide (CsxMA1−xPbI3) nanocrystals were obtained with a wide range of A‐site Cs‐MA compositions by post‐synthetic, room temperature cation exchange between CsPbI3 nanocrystals and MAPbI3 nanocrystals. The alloyed CsxMA1−xPbI3 nanocrystals retain their photoactive perovskite phase with incorporated Cs content, x, as high as 0.74 and the expected composition‐tunable photoluminescence (PL). Excess methylammonium oleate from the reaction mixture in the MAPbI3 nanocrystal dispersions was necessary to obtain fast Cs‐MA cation exchange. The phase transformation and degradation kinetics of films of CsxMA1−xPbI3 nanocrystals were measured and modeled using an Avrami expression. The transformation kinetics were significantly slower than those of the parent CsPbI3 and MAPbI3 nanocrystals, with Avrami rate constants, k, at least an order of magnitude smaller. These results affirm that A‐site cation alloying is a promising strategy for stabilizing iodide‐based perovskites. [ABSTRACT FROM AUTHOR]