Selective Adsorption Research Articles

Size-Dependent Electrostatic Adsorption of Polymer-Grafted Gold Nanoparticles on Polyelectrolyte Brushes.

Designing a functional surface that selectively adsorbs nanoparticles based on their size and shape is essential for developing an advanced adsorption-based, postsynthesis nanoparticle separation device. We demonstrate selective adsorption of larger nanoparticles from solution onto a polyelectrolyte brush by tuning the salt concentration. Specifically, a positively charged polyelectrolyte brush is created by converting pyridine groups of poly(2-vinylpyridine) to n-methylpyridinium groups using methyl iodide. The adsorption kinetics and thermodynamics of poly(ethylene glycol)-grafted, negatively charged gold nanoparticles (diameters of 12 and 20 nm) were monitored as a function of salt concentration. In a salt-free solution, the polyelectrolyte brush adsorbs gold nanoparticles of both sizes. As the salinity increases, the areal number density of adsorbed nanoparticles monotonically decreases and becomes negligible at high salinity. Interestingly, there is an intermediate range of salt concentrations (i.e., 15-20 mM of NaCl) where the decrease in nanoparticle adsorption is more pronounced for smaller particles, leading to size-selective adsorption of the larger nanoparticles. As a further demonstration of selectivity, the polyelectrolyte brush is immersed in a binary mixture of 12 and 20 nm nanoparticles and found to selectively capture larger particles with ∼90% selectivity. In addition, the size distribution of as-synthesized gold nanoparticles, with an average diameter of 12 nm, was reduced by selectively removing larger particles by exposing the solution to polyelectrolyte brush surfaces. This study demonstrates the potential of a polyelectrolyte brush separation device to remove larger nanoparticles by controlling electrostatic interactions between polymer brushes and particles.

Preparation of Zeolite A from Ion-Adsorbing Rare Earth Tailings for Selective Adsorption of Pb2+: An Innovative Approach to Waste Valorization

Ion-adsorbing rare earth tailings (IRETs) contain a large amount of clay minerals, which are a potential source of silicon and aluminum for the preparation of zeolite materials. The complexity of the tailings’ composition and the impurity composition are the main difficulties in the controllable preparation of zeolite. Herein, IRETs were treated by classification activation technology for the preparation of IRET-ZEO, which was used for the removal of heavy metal Pb2+ in water. A new method of resource utilization of ion-type rare earth tailings is realized by “treating waste with waste”. The results showed that the IRETs were classified and then thermally activated, and the optimal activation parameter was calcination at 850 °C for 1 h. The optimal NaOH concentration used in the crystallization process was 5 mol/L, with a crystallization time of 3 h and a crystallization temperature of 85 °C, and the crystallization product was zeolite A. The removal rate of the Pb2+ solution with an initial concentration of 100 mg/L was as high as 96.7% in an acidic solution with a pH value from 2 to 5.5. In particular, when the solution pH was higher than 4.2, the adsorption rate of Pb2+ was close to 100%. The IRET-ZEO showed a fast adsorption rate (5 min to reach adsorption equilibrium), a large adsorption capacity (378.35 mg/g), excellent acid resistance, and selectivity and regenerability for Pb2+. This work provides a new strategy for the green resource utilization of IRETs and the treatment of lead-containing wastewater.

High-selective platinum and palladium capture using polyamide 6: A potent material for platinum group metals’ recovery from spent car catalytic converter

Platinum (Pt) and palladium (Pd) are commonly integrated into automotive catalytic converters to convert harmful emissions into relatively safer substances. Their scarcity has resulted in the rapid development of an industry focused on their recovery. Polyamide 6 (PA6), a microplastic pollutant, is a common industrial material. Proper recycling of PA6 can mitigate the environmental impact caused by its microplastic pollution. This work revealed the capability of PA6 in recovering Pt and Pd from solution. Experimental data demonstrated that PA6 recovered about 90% of Pt and 70% of Pd. Importantly, PA6, without any functionalization or modification, adsorbed Pt and Pd without adsorbing present competing metals, exhibiting notably greater recovery selectivity towards Pt and Pd than materials discussed in other works. Furthermore, approximately 81% of Pt and 83% of Pd could be desorbed from PA6 as noted by the desorption studies. After obtaining fitted results using empirical equations and surface group identification, chelation and electrostatic interaction were discerned to be the key pathways for Pt and Pd recovery. This study represents a novel investigation into PA6's adsorption selectivity for Pt and Pd, through which experimental results confirm PA6's potential as a practical, environmentally-friendly alternative for Pt and Pd recovery, distinguishing it from its conventional counterparts.

Boronate affinity metal–organic frameworks molecularly imprinted membranes with hierarchical porous channels for the selective separation of naringin

Naringin (NRG), known as an important natural flavoniod compounds, exhibits excellent phamaceutical value and clinical application prospect. However, the main obstacle to the isolation and purification of NRG is the low concentration and complexity of the extraction system. Herein, a new kind of hierarchical porous metal–organic frameworks (MOFs) based molecularly imprinted membranes (PBMMA-MIMs) for the specific separation of NRG. The prepared PBMMA-MIMs showed the fast adsorption kinetics (within 120 min). Moreover, the abundant boronic acid imprinted recognition sits and hydrophilic hierarchical porous MOFs improved the adsorption capacity (the maximum adsorption amounts 57.39 μmol/g) and exhibited selective NRG adsorption (imprinting factor 2.31) with efficiency over 91.69 % after seven adsorption–desorption cycles. In addition, the coarse NRG could be effectively extracted to a promising purity of 93.13 % via PBMMA-MIMs. This study provides new insights into the design molecularly imprinted membranes via environmentally friendly synthesis route for the preparation for enriching high-value flavoniods, achieving efficient purification rate of agricultural wastes for pollution control, and promoting the sustainable reuse in complex agricultural wastewater.

Beta-Cyclodextrin-Modified Covalent Organic Framework Nanochannel for Electrochemical Chiral Recognition of Amino Acids.

The chiral recognition and separation of enantiomers are of great importance for biological research and the pharmaceutical industry. Preparing homochiral materials with adjustable size and chiral binding sites is beneficial for achieving an efficient chiral recognition performance. Here, a homochiral covalent organic framework membrane modified with β-cyclodextrin (CD-COF) was constructed, which was subsequently utilized as an electrochemical sensor for the enantioselective sensing of tryptophan (Trp) molecules. The preferential adsorption of l-Trp over d-Trp at the β-CD sites can enhance the surface charge density and hydrophilicity of the CD-COF membrane, resulting in an increased transmembrane ionic current. Trp enantiomers with concentrations down to 0.28 nM can be effectively discriminated. The l-/d-Trp recognition selectivity increases with the Trp concentration and reaches a value of 19.2 at 1 mM. The selective adsorption of l-Trp to the CD-COF membrane will also hinder its transport, resulting in a l-/d-Trp permeation selectivity of 15.3. This study offers a new strategy to construct homochiral porous membranes and achieve efficient chiral sensing and separation.

Kinetics and Mechanism Study of Different Types of Surface‐Imprinted Polymers for CO2 Adsorption

ABSTRACTThe increased level of CO2 in the atmosphere has led to global warming and climate change. To mitigate these problems, solid adsorbents have become attractive materials for capturing excess CO2 in the post‐combustion method. Molecularly imprinted polymer (MIP) can be applied to prepare highly selective adsorbents that could capture CO2 molecules. The MIP was prepared using the surface imprinted polymer technique in this preliminary work. Only two types of support materials were used (graphite and silica gel) to screen the best support material that could enhance the CO2 adsorption capacity of the resulting adsorbent, which was analyzed using a fixed‐bed column reactor. Graphite‐imprinted polymer (GMIP) was found to be a good potential for CO2 adsorption. The Avrami model best described the adsorption system, while the fixed‐bed curve data fit the Yoon–Nelson model well. The semi‐empirical method was used to assess the interaction mechanism of the molecularly imprinted polymer with CO2 during adsorption. This investigation involved testing four different ratios of the template complex to functional monomers. The ratio of 1:4 (CO2:Allylthiourea) demonstrated the highest binding energy, with a higher formation of hydrogen bonds. Film diffusion and intraparticle diffusion were the main rate‐limiting steps that played vital roles at different stages of CO2 adsorption. This preliminary work has enhanced the development of MIP for CO2 adsorption and showcased the integration of computational approaches in tailoring specific MIPs.

Construction of a Fluorinated-Anion Pillared Metal-Organic Framework Exhibiting Dual-Pore Architecture for Simultaneous Enhancement of C2H2 Adsorption Capacity and Selectivity.

Physisorption-based separation processes represents a promising alternative to the conventional thermally driven methods, such as cryogenic separation. However, a significant challenge lies in balancing the trade-off between adsorption capacity and selectivity of adsorbents. In this study, we introduce a novel fluorinated-anion pillared metal-organic frameworks (APMOFs) featuring a dual-pore architecture, constructed using a pyridine-oxazole bifunctional ligand. The inherent low symmetry of the ligand leads to significant distortion of the fluorinated-anion pillars, resulting in a distinctive type of APMOFs characterized by dual-pore architecture. On pore structure with constrict pore width is enriched with a high density of anion fluorinated pillars, offering numerous active sites advantageous for enhancing separation selectivity. Concurrently, the other pore structure exhibits larger dimensions, facilitating increased gas molecule accommodation and thereby augmenting adsorption capacity. Gas sorption studies reveal a substantial C2H2 adsorption capacity and a high C2H2/CO2 separation selectivity. Breakthrough experiments confirm its exceptional separation performance, while theoretical investigations elucidate a sequential adsorption process within these APMOFs, underscoring the efficacy of this strategy in overcoming trade-off limits in adsorbents.

Recent Developments in the Adsorption of Heavy Metal Ions from Aqueous Solutions Using Various Nanomaterials

Water pollution is caused by heavy metals, minerals, and dyes. It has become a global environmental problem. There are numerous methods for removing different types of pollutants from wastewater. Adsorption is viewed as the most promising and financially viable option. Nanostructured materials are used as effective materials for adsorption techniques to extract metal ions from wastewater. Many types of nanomaterials, such as zero-valent metals, metal oxides, carbon nanomaterials, and magnetic nanocomposites, are used as adsorbents. Magnetic nanocomposites as adsorbents have magnetic properties and abundant active functional groups, and unique nanomaterials endow them with better properties than nonmagnetic materials (classic adsorbents). Nonmagnetic materials (classic adsorbents) typically have limitations such as limited adsorption capacity, adsorbent recovery, poor selective adsorption, and secondary treatment. Magnetic nanocomposites are easy to recover, have strong selectivity and high adsorption capacity, are safe and economical, and have always been a hotspot for research. A large amount of data has been collected in this review, which is based on an extensive study of the synthesis, characterization, and adsorption capacity for the elimination of ions from wastewater and their separation from water. The effects of several experimental parameters on metal ion removal, including contact duration, temperature, adsorbent dose, pH, starting ion concentration, and ionic strength, have also been investigated. In addition, a variety of illustrations are used to describe the various adsorption kinetics and adsorption isotherm models, providing insight into the adsorption process.

Conversion of waste polystyrene into porous adsorbents for efficient removal of hazardous pollutants: Adsorption properties and adsorption mechanism

Herein, the porous adsorbent material (PS-SAS) was prepared by introducing a large number of carboxyl groups on the benzene ring of waste polystyrene (WPS) by Friedel-Crafts acylation reaction using succinic anhydride as the modifying group, followed by further alkaline modification, and was used for the removal of hazardous dye and heavy metal ion. The chemical structure and surface morphology of the prepared adsorbent were assessed via Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), optical microscope (OM), Brunauer–Emmett–Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The prepared adsorbent gave highly efficient separation performance towards malachite green (MG) and Cu2+ with corresponding maximum sorption capacities of 2231 mg/g and 156 mg/g at 298 K. The experimental data indicated that the sorption process followed the Langmuir adsorption isotherm and the pseudo-second-order kinetic model. Moreover, thermodynamic studies also demonstrated that the sorption process occurred spontaneously. The adsorption mechanisms of the adsorbent for MG include hydrogen bonding, electrostatic attraction, n-π interactions, and π-π interactions, while for Cu2+ via electrostatic attraction, ion exchange, and complexation. Furthermore, the selective adsorption, regeneration, dynamic sorption, and simulated wastewater experiment demonstrated that the adsorbent is a promising adsorbent. And phytotoxicity test proved that the prepared adsorbent can effectively reduce the toxicity of dye and metal ions. In summary, the transformation of waste polystyrene into an adsorbent represents a promising solution for water purification.

Innovative eco-friendly methyl orange removal: Mechanism, kinetic, and thermodynamic study using starch cryogel-integrated mesoporous silica nanoparticles

This study introduces a novel, eco−friendly composite, uncalcined mesoporous silica nanoparticles incorporated into a starch cryogel (MSNs-Cry), designed for the effective removal of methyl orange (MO) from water. MSNs−Cry integrates uncalcined mesoporous silica nanoparticles (MSNs) within a starch cryogel network, leveraging the high adsorption capacity of MSNs. The composite achieved a maximum adsorption capacity of 18.98 mg g⁻1 and demonstrated high removal efficiencies of 99.00 % ± 0.21 % in synthetic water (10 mg L−1 MO) and 92.77 % ± 1.76 % in real wastewater containing 0.43 mg L−1 MO. The Langmuir isotherm model provided a superior fit (R2 = 0.9930) compared to the Freundlich model (R2 = 0.9180), and the adsorption kinetics followed a pseudo−second−order model (R2 = 0.9917). The primary adsorption mechanisms included electrostatic attraction, hydrophobic interactions, and hydrogen bonding. The process was endothermic (ΔH° = 31.3 kJ mol−1), spontaneous, and more favorable at higher temperatures (ΔG° = −34.2 to −38.6 kJ mol−1 at 298–318 K). In the presence of sodium silicate at 13.1 times the MO concentration, removal efficiency drops by 35.77 %, and with sodium sulfate and urea at 100 times the MO concentration, it decreases by 8.65 %. Despite these challenges, MSNs−Cry effectively removes MO in the presence of the anionic dye Congo Red and metal ions, demonstrating its selective adsorption capabilities. The tablet form of MSNs−Cry prevents the loss of uncalcined MSNs, mitigating potential environmental and operational impacts. Additionally, the composite's effectiveness at a natural pH of 6.65 eliminates the need for pH adjustment, offering a cost−effective solution for real−world applications. This study establishes MSNs−Cry as a promising material for sustainable water purification.

Molecular simulations of increased thermal energy storage in metal–organic heat carriers with R1234ze(E)/R32 mixtures combined with IRMOF-1

Metal-organic heat carrier (MOHC) nanofluids offer a promising solution to enhance the efficiency of Organic Rankine Cycle systems. In this study, we developed a computational model to assess the thermal energy storage capacity of MOHC nanofluids using a base fluid mixture of R1234ze(E) and R32 refrigerants. Through Grand Canonical Monte Carlo and molecular dynamics simulations, we examined the adsorption characteristics, desorption heat, and thermodynamic properties of MOHCs. Our findings reveal that R32 molecules are preferentially adsorbed in IRMOF-1 compared to R1234ze(E), with adsorption selectivity of R32 over R1234ze(E) increasing under higher adsorption pressures. When the temperature during the endothermic process surpasses the phase transition point of the base fluid, the latent heat of phase transition can be fully exploited to enhance energy storage. Moreover, the inclusion of IRMOF-1 nanoparticles significantly improves the energy storage properties of both R32 and R1234ze(E), as well as their mixtures. The energy storage enhancement provided by IRMOF-1 is particularly pronounced under high working pressures and low temperature differences. These insights offer valuable guidance for selecting appropriate base fluids in MOHC systems, thereby optimizing the utilization of low-grade energy sources.

Improvement of tetracycline removal using amino acid ionic liquid modified magnetic biochar based on theoretical design

In current research, biochar is widely used to remove antibiotic contamination from the environment. However, original biochar produced through direct pyrolysis has significant limitations in removing antibiotics. In this paper, response surface methodology provided the laudable choice for magnetic poplar biochar (MPBC) considering the synergistic effect of multi-factors as well as the restrictions abundance experiments during the preparation of MPBC. Amino acid ionic liquids (AAILs) are a class of ionic liquids in which amino acids act as the anionic component, combining the tunable properties of ionic liquids with the biocompatibility and functionality of amino acids. To ameliorate adsorption capacity of MPBC, tetra-ethylammonium glycinate ([TEA][Gly]) with the best affinity for tetracycline (TC) were screened from 600 AAILs based on theoretical predictions using the conductor-like screening model for real solvents (COSMO-RS) without extensive experimental. Furthermore, AAILs-modified magnetic biochar (MPBC-AAIL) was synthesized chemically for the first time. Adsorption kinetics, isotherms, and thermodynamic analyses revealed that TC adsorption by both MPBC and MPBC-AAIL is a monolayer, spontaneous, and exothermic chemical process. Moreover, MPBC-AAIL exhibited a maximum adsorption capacity of 305.9 mg·g−1. Meanwhile, MPBC-AAIL maintains superior adsorption performance for TC in different impurity solutions as well as in real water samples. The excellent reusability and selective adsorption capacity of the material demonstrate the superiority of the theoretical based design. The characterization reveals that the adsorption mechanisms include pore filling, π-π interactions, surface complexation, hydrogen bonding, and electrostatic interactions. In addition, theoretical calculations showed that ionic liquid modification altered the adsorption sites between TC and MPBC-AAIL, leading to enhanced adsorption. This comprehensive study introduces an innovative modification of biochar, providing a novel approach to designing biochar composites and promoting their application in the remediation of complex environmental pollution.

Energy-Efficient Separation of Xylene Isomers through Stacked 1-Aminopyrene Polymer Composite.

Developing high-performance adsorbents for energy-efficient separation of xylene isomers has important research and application value. Identification and separation of xylene isomers (PX, MX, and OX) at room temperature based on the different relative positions of two methyl groups on the benzene ring is an unprecedented attempt. Herein, 1-aminopyrene polymer (PAP) is designed and electro-synthesized composited with a supporting electrolyte as an adsorbent for the separation of xylene isomers using a multi-stage dispersed liquid-solid adsorption process at room temperature. Each -NH-pyrene-NH- unit can form a force field to identify and discriminate xylene isomer through π-π interaction combined with -CH3···-NH- interactions of different strength, thereby achieving separation of PX, MX, and OX isomers by amplifying the slight differences in the adsorption capacity and diffusion rates. The density functional theory (DFT) simulations provide a more quantitative analysis of the adsorbate-adsorbent interactions to illustrate PX > MX > OX order of adsorption selectivity. This study may offer an alternative strategy for the precise designing of energy-efficient and adsorption-based separation materials.

Precise Construction of the Triple-Phase Boundary and Its Antiphosphate Poisoning Effect in the Confined Region.

As a critical component for the oxygen reduction reaction (ORR), platinum (Pt) catalysts exhibit promising catalytic performance in High-temperature-proton exchange membrane fuel cells (HT-PEMFCs). Despite their success, HT-PEMFCs primarily utilize phosphoric acid-doped polybenzimidazole (PA-PBI) as the proton exchange membrane, and the phosphoric acid within the PBI matrix tends to leach onto the Pt-based layers, easily causing toxicity. Herein, we first propose UiO-66@Pt3Co1-T composites with precisely engineered interfacial structures. The UiO-66@Pt3Co1-T exhibits an octahedral porous framework with uniform structural dimensions and even distribution of surface nanoparticles, which demonstrate superior ORR performance compared to commercial Pt/C. The unique structure and morphology of the composites also exhibit a favorable half-wave potential in different concentrations of phosphoric acid electrolyte, regulated by the phosphoric acid adsorption site and intensity.This finding suggests that the incorporation of Co could effectively modulate the Pt d-band center, thereby enhancing the ORR performance. Furthermore, the selective adsorption of phosphoric acid by ZrO2 enables precise control over the phosphoric acid distribution. Notably, the retention of the octahedral framework post high-temperature treatment facilitates the establishment of dual transport pathways for gases and protons, leading to a stable and efficient triple-phase boundary.

A Hollow Hemispherical Mixed Matrix Lithium Adsorbent with High Interfacial Interaction for Lithium Recovery from Brine

Mixed matrix lithium adsorbents have attracted much interest for lithium recovery from brine. However, the absence of an interfacial interaction between the inorganic lithium-ion sieves (LISs) and the organic polymer matrix resulted in the poor structural stability and attenuated lithium adsorption efficiency. Here, a novel hollow hemispherical mixed matrix lithium adsorbent (H-LIS) with high interfacial compatibility was constructed based on mussel-bioinspired surface chemistry using a solvent evaporation induced phase transition method. The effects of types of functional modifiers, LIS loading amount, adsorption temperature and pH on their structural stability and lithium adsorption performance were systematically investigated. The optimized H-LIS adsorbent with the LIS loading amount of 50 wt.% possessed the structural merit that the LIS functionally modified by dopamine exposed on both the inner and outer surfaces of the hollow hemispheres. At the best adsorption pH of 12.0, it showed a comparable lithium adsorption capacity of 25.68 mg·g−1 to the powdery LIS within 4 h, favorable adsorption selectivity of Mg/Li and good reusability that could maintain over 90% of lithium adsorption capacity after the LiCl adsorption—0.25 M HCl pickling-DI water cleaning cycling processes for three times. The interfacial interaction mechanism of H-LIS for lithium adsorption was innovatively explored via advanced microcalorimetry technology. It suggested the nature of the Li+ adsorption process was exothermic and dopamine modification could reduce the activation energy for lithium adsorption from 15.68 kJ·mol−1 to 13.83 kJ·mol−1 and trigger a faster response to Li+ by strengthening the Li+-H+ exchange rate, which established the thermodynamic relationship between the structure and Li+ adsorption performance of H-LIS. This work will provide a technical support for the structural regulation of functional materials for lithium extraction from brine.

Separation of molybdenum and tungsten using selective adsorption with zirconium based metal organic framework

BackgroundThe separation of tungsten and molybdenum has always been a significant challenge. Metal organic frameworks (MOFs) has potential to solve the problem. In this study, the adsorption and separation performance of UiO-66 for tungsten and molybdenum and adsorption mechanism were investigated. MethodsUiO-66 was synthesized by solvothermal method. The physical and chemical properties of UiO-66 and adsorption mechanism were characterized and analyzed by XRD, SEM-EDS, FT-IR, Zeta-potential, XPS and thermodynamic analysis, the adsorption and separation performance of Mo/W using UiO-66 were evaluated by ICP-OES. Significant findingsUiO-66 with uniform pore size could be obtained under the conditions of crystallization for 24 h at 180 °C. This study revealed superior Mo/W separation performance under acidic conditions, where the adsorption capacity for Mo (QMo) of UiO-66 was 219.4 mg⋅g−1 and the highest separation factor (βMo/W) was 52.3. It was found that the mechanism involved the effect of pore size, electrostatic attraction and the metal point Zr had stronger affinity for Mo. This material was expected to serve as an eco-friendly and reusable adsorbent for separation of tungsten and molybdenum in resource recovery, aiming for high-quality regeneration of both metals.

An environmentally friendly depressant for magnesite and calcite flotation separation: Selective depression and adsorption mechanism

The similar crystal structures and chemical properties of magnesite and calcite make their effective separation through flotation challenging. This study explores the use of Glutamic acid diacetic acid tetrasodium salt (GLDA), a novel environmentally friendly chelating reagent, to enhance the flotation separation of magnesite and calcite. Flotation test results indicate that in a sodium oleate (NaOL) system, GLDA selectively inhibits the flotation of calcite. Under optimal conditions (slurry pH=9.20, GLDA 15 mg/L, and NaOL 140 mg/L), a flotation concentrate with an MgO grade of 46.21 %, CaO grade of 1.39 %, and an MgO recovery rate of 73.17 % was achieved. GLDA minimally affects the hydrophobicity of magnesite but significantly reduces the hydrophobicity of calcite. The selective inhibition mechanism of GLDA was investigated using zeta potential measurements, FTIR, and XPS analyses. Results show that GLDA selectively reacts with Ca sites on the calcite surface, adsorbing and covering it, thereby preventing NaOL from adsorbing on the calcite. Conversely, GLDA has a minor impact on the Mg sites on the magnesite surface, resulting in a negligible effect on NaOL adsorption by magnesite. Consequently, GLDA enhances the flotation separation efficiency of magnesite and calcite. The research results have potential for application in the purification of low-grade magnesite ore.

Beryllium adsorption from beryllium mining wastewater with novel porous lotus leaf biochar modified with PO43−/NH4+ multifunctional groups (MLLB)

Wastewater produced in beryllium mining seriously affects ecological balance and causes great environmental pressure. We designed a novel porous lotus leaf biochar modified with PO43−/NH4+ multifunctional groups (MLLB) and used it for beryllium(Be) removal from beryllium mining wastewater. Kinetic and thermodynamic experiments showed that the adsorption capacity (Qe) of Be with MLLB from the simulated beryllium mining wastewater could reach 40.38 g kg−1 (35 °C, pH = 5.5), and the adsorption process was spontaneous and endothermic. The dispersion coefficient Kd of Be with MLLB was 2.6 × 104 mL g−1, which proved that MLLB had strong selective adsorption capacity for Be. Phosphoric acid, ammonia, and hydroxyl groups on the MLLB surface would complex with Be to form Be(OH)2 and Be(NH4)PO4 complexation products, which implied that surface complexation and precipitation reactions might co-existed in the adsorption process. The above results showed that MLLB could effectively adsorb Be and prevent beryllium exposure in a beryllium mining process.Graphical

Zwitterionic covalent organic nanosheets for selective analysis of domoic acid in marine environment

BackgroundDomoic acid (DA) is a neurotoxic compound causing amnesic shellfish poisoning, secreted by red algae and diatoms. As a glutamate analogue, DA accumulates in filter-feeding marine organisms, posing significant health risks to humans upon consumption. Detecting DA in marine environments remains challenging due to its low concentration and interference from complex matrices. Effective detection and removal require materials with high efficiency and selectivity, which traditional inorganic ionic materials lack due to their limited adsorption capacity and selectivity. Ionic covalent organic frameworks (iCOFs) expected to become highly efficient DA adsorbents due to tunable ionic sites. ResultsThus, a zwitterionic covalent organic nanosheet (TGDB-iCONs) was synthesized to selectively capture DA. TGDB-iCONs was prepared by one-step Schiff-base reaction of the charged monomer triaminoguanidine hydrochloride. It uniformly distributed positively charged guanidinium and negatively charged chloride ions on the surface, forming zwitterionic binding sites. The self-peeling of TGDB-iCONs facilitated the exposure of active sites and improved the adsorption efficiency. Several binding forces were generated between TGDB-iCONs and DA, including complementary electrostatic hydrophilic interactions, which were verified by density functional theory (DFT) calculation. TGDB-iCONs exhibited ultra-fast adsorption kinetics (7 min) and relatively high adsorption capacity (66.48 mg/g) for DA. Furthermore, TGDB-iCONs exhibit strong salt resistance, which is attributed to the charge “shielding” effect of the zwitterionic ions present in TGDB-iCONs. TGDB-iCONs could highly selectively enrich DA and detect trace DA from marine environment including seawater, algae and marine organisms and the limit of detection as low as 0.3 ng/kg. Significance and noveltyThis comprehensive study not only sheds light on the vast potential of ionic covalent organic frameworks nanosheets (iCONs) in supporting early warning, control, and traceability of DA, but also lays a solid foundation for future research endeavors aimed at designing and harnessing the unique properties of iCONs.

Oxyanions Enhancing Crystallinity of Reconstructed Phase for Oxygen Evolution Reaction.

The catalysts were always undergoing continuous amorphization and dissolution of active structure in operating condition, hindering the compatibility between stability and activity for oxygen evolution reaction (OER). Herein, we propose the selective adsorption of leached NO3- to strengthen the crystallinity and activity of surface reconstructed layer with amorphous and crystalline (a-c) heterojunction. Taking a-c Ni doped Fe2O(OH)3NO3·H2O (Ni-FeNH) as a model precatalyst, we uncover that the leached NO3- are readily adsorbs on the crystalline phase in the formed a-c Fe(Ni)OOH during OER, lowering the disorder degree and further activating Ni and Fe ion of the crystalline Fe(Ni)OOH on a-c heterojunctions. Accordingly, Ni-FeNH deliver a low overpotential of 303 mV and high durability of 500 hours at 500 mA cm-2 for OER. Particularly, constructing industrial water electrolysis equipment exhibits high stability of 100 hours under a high operating current of 8000 mA.