Construction of hyperbranched imprinted nanomaterials for selective adsorption of cadmium (II).

A hyperbranched ion-imprinted polymer (IIP) material containing multiple selective adsorption sites was synthesized using halloysite nanotubes, methyl acrylate, and ethylenediamine in the presence of a template ion [i.e. Cd (II) heavy metal]. The successful preparation of the Cd-IIP composition was confirmed by FT-IR, XRD, TEM, TGA, and elemental analysis. The polymers exhibited good adsorption of Cd (II) with a maximum adsorption capacity of 64.37 mg·g-1. The imprinting factor (α) for Cd (II) was 2.62 and the selection factor (ß) was 1.78, indicating a specific adsorption of Cd (II) ion. The selection coefficients of Cd-IIP for Cd (II)/Pb (II), Cd (II)/Cu (II), Cd (II)/Ni (II), Cd (II)/Cr (III), and Cd (II)/Na (I) also indicated an excellent selectivity of the hyperbranched polymers for Cd (II) in the presence of competitive ions. The removal efficiency remained more than 75% after five cycles of desorption/adsorption. We envision that the HNTs based Cd-IIP has promising applications in the removal of Cd (II) from wastewater.

Ion-imprinted aminoguanidine-chitosan for selective recognition of lanthanum (III) from wastewater.

Developing a sorbent for the removal of La3+ ions from wastewater offers significant environmental and economic advantages. This study employed an ion-imprinting process to integrate La3+ ions into a newly developed derivative of aminoguanidine-chitosan (AGCS), synthesized via an innovative method. The process initiated with the modification of chitosan by attaching cyanoacetyl groups through amide bonds, yielding cyanoacetyl chitosan (CAC). This derivative underwent further modification with aminoguanidine to produce the chelating AGCS biopolymer. The binding of La3+ ions to AGCS occurred through imprinting and cross-linking with epichlorohydrin (ECH), followed by the extraction of La3+, resulting in the La3+ ion-imprinted sorbent (La-AGCS). Structural confirmation of these chitosan derivatives was established through elemental analysis, FTIR, and NMR. SEM analysis revealed that La-AGCS exhibited a more porous structure compared to the smoother non-imprinted polymer (NIP). La-AGCS demonstrated superior La3+ capture capability, with a maximum capacity of 286 ± 1 mg/g. The adsorption process, fitting the Langmuir and pseudo-second-order models, indicated a primary chemisorption mechanism. Moreover, La-AGCS displayed excellent selectivity for La3+, exhibiting selectivity coefficients ranging from 4 to 13 against other metals. This study underscores a strategic approach in designing advanced materials tailored for La3+ removal, capitalizing on specific chelator properties and ion-imprinting technology.

Progress and Prospect of Ion Imprinting Technology in Targeted Extraction of Lithium.

Ion Imprinting Technology (IIT) is an innovative technique that produces Ion-Imprinted polymers (IIPs) capable of selectively extracting ions. IIPs exhibit strong specificity, excellent stability, and high practicality. Due to their superior characteristics, the application of IIPs for lithium resource extraction has garnered significant attention. This paper discusses the following aspects based on existing conventional processes for lithium extraction and the latest research progress in lithium IIPs: (1) a detailed exposition of existing lithium extraction processes, including comparisons and summaries; (2) classification, comparison, and summarization of the latest lithium IIPs based on different material types and methods; (3) summarization of the applications of various lithium IIPs, along with a brief description of future directions in the development of lithium IIP applications. Finally, the prospects for targeted recovery of lithium resources using lithium IIPs are presented.

Iodide ion-imprinted chitosan beads for highly selective adsorption for nuclear wastewater treatment applications.

Iodide ions from radioactive iodine isotopes are common contaminants present in nuclear wastewater from nuclear power plants which are considered hazardous contaminants to be released in water sources even at low concentrations due to their association with metabolic disorders, therefore its removal from the nuclear wastewater effluents is necessary. Chitosan beads are natural and cost-efficient adsorbents that have been used for ion removal from wastewater. However, issues of poor selectivity persist in achieving high-efficiency iodide ion removal. In this study, ion-imprinted chitosan beads (IIC) have been synthesized using the phase-inversion method, IIC beads were modified by cross-linking with epichlorohydrin (IIC-EPI) and modified by cross-linking with epichlorohydrin and silicon dioxide nanoparticles (IIC-SiO2-EPI). Through 4 h of batch adsorption experiments, IIC beads achieved a maximum adsorption capacity (Qe) of 0.65 mmol g-1 and showed more preference for the iodide ions compared to the non-imprinted chitosan beads which achieved a maximum adsorption capacity of 0.27 mmol g-1 at pH 7. While the modified beads IIC-EPI and IIC-SiO2-EPI beads have boosted the adsorption capacities to 0.72 mmol g-1 and 0.91 mmol g-1. Scanning electron microscopic cross-sectional images have shown more pores and cavities than the surface images which agrees with the multilayer heterogeneous diffusion suggested by the Freundlich adsorption isotherm, that the experimental data has fitted. Adsorption kinetic data have fitted the Pseudo-second-order model as well as the Weber and Morris intraparticle model, which suggest an intraparticle pore diffusion adsorption mechanism, with the involvement of the physical electrostatic interactions with the cationic chitosan surface.

Ion imprinted differential modulation system based on enhanced optic-fiber evanescent wave for sensitive and label-free detection of trace nickel ions.

An optical system with low cost monitoring, high sensitivity, strong selectivity and much lower nickel ion (Ni2+) content in tap water than the World Health Organization (WHO) standard (1.19 µM) has been prepared by a simple strategy. This proposed ion-imprinted differential modulation system is based on the Bragg grating (FBG) and microfiber interferometer structure, and the interferometer sensing surface is coated with a polydopamine (PDA)/graphene oxide (GO) film to enhance its sensitivity. Combined with the ion imprinting technique, the microfiber interferometer sensor sensitivity can reach 0.32 nm/nM with the detection limit of 0.66 nM in the low concentration range (Ni2+ concentration range is 0 nM-100 nM). The experiment not only studies the principle of microfiber interferometer and FBG and their refractive index and temperature performance, but also shows that the FBG power change has a good fitting relationship with wavelength change. In addition, this system performance by the amount of power difference rather than the amount of wavelength shift, which significantly saves on the high cost weight, and size associated with the use of spectral analyzers in traditional inspection systems. This study provides a novel and easy method to develop new sensors with higher comprehensive performance.

Biomass chitosan/sodium alginate colorimetric imprinting hydrogels with integrated capture and visualization detection for cadmium(II).

Due to Cd(II) with highly toxic, persistent and bioaccumulative, the discharge of it into the environment brings serious pollution. Developing strategies that are efficient, low-cost, pollution-free and specific to removing Cd(II) from wastewater is therefore of great urgency and prime importance. A novel chitosan/sodium alginate ionic imprinting(IICA) hydrogels with specific adsorption capacity for Cd(II) was prepared through freeze-thaw and ion imprinting, and finally the colorimetric sensor (IICAS) was prepared via introducing Rhodamine B(RhB) and Victoria blue(VBB) by immersion to achieve visual detection of Cd(II). The IICA hydrogels with imprinted hole structure had higher adsorption capacity and better specific selectivity for Cd(II). As well as internal diffusion, coordination, ion exchange, and hydrogen bonding influenced the adsorption rate. Moreover, the IICAS exhibited good selective detection ability and linearity for Cd(II) with the fitted correlation coefficient (R2) = 0.98, limit of detection (LOD) = 35 nmol/L. Combined with the smartphone platform, portable and quantitative detection of Cd(II) can be achieved, Within the 0-100 mg/L range, R2 remained 0.94, and LOD was 75 nmol/L. This strategy of preparing a novel whole biomass IICAS integrating capture and visual detection provides a new insight into the construction of a promising candidate sensor for the removal and detection of Cd(II).

Diels-Alder clickable furan-thiosemicarbazide cellulose for selective ruthenium (III) imprinting.

Developing an efficient adsorbent for Ru3+ ions in wastewater is crucial for both environmental protection and resource recovery. This study introduces a novel approach using cellulose-based adsorbents, specifically modified with furan-thiosemicarbazide (FTC), to enhance their selectivity for Ru3+ ions. By cross-linking the Ru3+/FTC-modified cellulose (FTC-CE) complex with a bis(maleimido)ethane (BME) cross-linker, we created a Ru3+ ion-imprinted sorbent (Ru-II-CE) that exhibits a strong affinity and selectivity for Ru3+ ions. The synthesis process was thoroughly characterized using NMR and FTIR spectroscopy, while the surface morphology of the sorbent particles was examined with scanning electron microscopy. The Ru-II-CE sorbent demonstrated exceptional selectivity for Ru3+ among competing metal cations, achieving optimal adsorption at a pH of 5. Its adsorption capacity was notably high at 215 mg/g, fitting well with the Langmuir isotherm model, and it followed pseudo-second-order kinetics. This study highlights the potential of FTC-CE for targeted Ru3+ removal from wastewater, offering a promising solution for heavy metal decontamination.

Designing of a cellulose-based ion-imprinted biosorbent for selective removal of lead (II) from aqueous solutions.

Developing an effective adsorbent for Pb2+ removal from wastewater has huge economic and environmental implications. Adsorbents made from cellulosic materials that have been modified with certain chelators could be used to get rid of metal cations from aqueous solutions. However, their selectivity for specific metals remains very low. Here, we describe the synthesis of 4-(2-pyridyl)thiosemicarbazide (PTC) hydrazidine-functionalized cellulose (Pb-PTC-CE), a polymer imprinted with Pb2+ ions that may be used to remove Pb2+ ions from wastewater. Owing to its potent -NH2 functionalization, PTC hydrazidine not only served as an efficient chelator to effectively supply coordinating sites and construct hierarchical porous structures on Pb-PTC-CE, but it also made it possible for cross-linking to occur through the glyoxal cross-linker. The abundant chelators, along with the hierarchical porous construction of the developed Pb-PTC-CE with PTC functionality, result in a greater sorption capacity of 336 mg/g and a short sorption period of 40 min for Pb2+. Additionally, Pb-PTC-CE exhibits highly selective Pb2+ uptake compared to competing ions. This study proposes a feasible methodology for the development of high-quality materials for Pb2+ remediation by combining the advantages of active ligand functionality with ion-imprinting techniques in a straightforward way.

Development and assessment of isatin hydrazone-functionalized/ion-imprinted cellulose adsorbent for gadolinium (III) removal.

It is of tremendous economic and environmental significance to obtain a powerful adsorbent for the extraction of Gd3+ from wastewater. Adsorbents derived from cellulosic materials functionalized with specific chelators show great promise for the removal of heavy metal ions from wastewater. The selectivity of these sorbents for metal ions is, however, still rather poor. Here, we present a technique for trapping Gd3+ ions from wastewater by synthesizing Gd3+ ion-imprinted polymers based on isatinhydrazone-functionalized cellulose (Gd-ISH-CE). Not only did isatinhydrazone work as a tridentate ligand to directly provide ligand vacancies and build hierarchy pores on Gd-ISH-CE, but it also enabled cross-linking through the epichlorohydrine cross-linker thanks to its very effective NH2 functionalization. The as-prepared Gd-ISH-CE with ISH functionality shows a high adsorption capacity of 275 mg/g and a rapid equilibration time of 30 min for Gd3+ due to its plentiful binding sites and hierarchical pore structure. Furthermore, Gd-ISH-CE shows very selective capture of Gd3+ over competing ions. By integrating the benefits of ion-imprinting and chelator functionalization methodologies in an effortless manner, this study presents a practical approach to the development of superior materials for Gd3+ recovery.

Development and evaluation of thiosalicylic-modified/ion-imprinted chitosan for selective removal of cerium (III) ion.

Chitosan was used in this study as the bio-based product for the development of microparticles for the specifically targeted removal of cerium ions (Ce3+) by ion-imprinting technology. A thiosalicylic hydrazide-modified chitosan (TSCS) is produced via cyanoacetylation of chitosan, followed by hydrazidine derivatization to finally introduce the thiosalicylate chelating units. Ion-imprinted Ce-TSCS sorbent microparticles were prepared by combining the synthesized TSCS with Ce3+, crosslinking the polymeric Ce3+/TSCS complex with glutaraldehyde, and releasing the chelated Ce3+ using an eluent solution containing a mixture of EDTA and HNO3. Ce-TSCS had a capacity of 164 ± 1 mg/g and better removal selectivity for Ce3+ because it was smart enough to figure out which target ions would fit into the holes made by Ce3+ during the imprinting process. The kinetic data were well suited to a pseudo-second-order model, and the isotherms were well described by the Langmuir model, both of which pointed to chemisorption and adsorption through Ce3+ chelation. XPS and FTIR analyses demonstrate that the predominant adsorption mechanism is the coordination of Ce3+ with the -NH-, -NH2, and -SH chelating units of the thiosalicylic hydrazidine. These findings provide fresh direction for the development of sorbent materials that can effectively and selectively remove Ce3+ from aqueous effluents.

Selective adsorption of tetracycline and copper(II) on ion-imprinted porous alginate microspheres: performance and potential mechanisms.

A novel epichlorohydrin and thiourea grafted porous alginate adsorbent (UA-Ca/IIP) was synthesized using ion-imprinting and direct templating to remove copper ions (Cu(II)) and tetracycline (TC) in aqueous solution. UA-Ca/IIP demonstrated great selectivity for Cu(II) and TC among different coexisting anions (CO32-, PO43- and SO42-), cations (Ca2+, Mg2+ and NH4+), and antibiotics (oxytetracycline and sulfamethoxazole). The adsorption of TC and Cu(II) by UA-Ca/IIP was significantly affected by the pH of the solution, and the quantity of TC and Cu(II) adsorbed reached a maximum at pH 5. A pseudo-second-order model better fitted the kinetic data; the Langmuir model predicted the maximum adsorption quantities 3.527 mmol TC g-1 and 4.478 mmol Cu(II) g-1 at 298 K. Thermodynamic studies indicated that the TC and Cu(II) adsorption was more rapid at a higher temperature. Antagonistic and synergistic adsorption experiments showed that the adsorption capacity of TC would increase significantly with the increase of Cu(II) concentration. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy indicated that along with the influence of pH, electrostatic interaction and complexation were the main mechanisms of TC and Cu(II) adsorption. Regeneration experiments revealed that TC and Cu(II) were removed efficiently and that UA-Ca/IIP was recyclable over the long term. These results show that the modified porous alginate microsphere is a green and recyclable adsorbent, which has good selectivity and high adsorption performance for the removal of TC and Cu(II).

"One-pot" preparation and adsorption performance of chitosan-based La3+/Y3+ dual-ion-imprinted thermosensitive hydrogel.

Temperature-sensitive materials are increasingly of deep interest to researchers. Ion imprinting technology is widely used in the field of metal recovery. In order to solve the problem of rare earth metal recovery, we designed a temperature-sensitive dual-imprinted hydrogel adsorption product (CDIH) with chitosan as the matrix, N-isopropylacrylamide as a thermally responsive monomer, and La3+ and Y3+ as the co-templates. The reversible thermal sensitivity and ion-imprinted structure were determined by differential scanning calorimetry, Fourier transform infrared spectrometer, Raman spectra, Thermogravimetric analysis, X-ray photoelectron spectroscopy, Scanning electron microscopy and X-ray energy spectroscopy various characterizations and analyses. The simultaneous adsorption amount of CDIH for La3+ and Y3+ was 87.04 mg/g and 90.70 mg/g, respectively. The quasi-secondary kinetic model and Freundlich isotherms model well described the adsorption mechanism of CDIH. It's worthy to mention that CDIH could be well regenerated through washing with deionized water at 20 °C, with a desorption rate of 95.29 % for La3+ and 96.03 % for Y3+. And after 10 cycles of reuse, 70 % of the adsorption amount could be maintained, revealing excellent reusability. Furthermore, CDIH expressed better adsorption selectivity to La3+ and Y3+ than its non-imprinted counterparts in a solution containing six metal ions.

Design of ion-imprinted cellulose-based microspheres for selective recovery of uranyl ions.

Herein, cellulose was selected as the raw material for the production of sorbent microspheres for the selective separation of uranyl (UO22+) ions by ion-imprinting technique due to their low cost, biodegradability, and renewability. To begin, an amidoxime cellulosic derivative (AOCE) is synthesized by a Michael addition followed by an amidoximation reaction, both of which are homogeneous reactions. In the end, microspheres of ion-imprinted U-AOCE sorbent were made by mixing the developed AOCE derivative with UO22+, crosslinking the UO22+ polymer complex with glyoxal, and eluting the coordinated ions with H+/EDTA. U-AOCE smartly recognized the target ions for fitting the cavities generated during the UO22+-imprinting process, resulting in a much greater adsorption capacity of 382 ± 1 mg/g and enhanced adsorption selectivity for UO22+. A pseudo-second-order model fit the data well in terms of kinetics, while the Langmuir model adequately explained the isotherms, indicating chemisorption and adsorption via UO22+ chelation. The coordination between UO22+ and both the -NH2 and -OH groups of the amidoxime units is the primary adsorption process, as shown by NMR, XPS, and FTIR studies. For UO22+ biosorption from aqueous effluents, the results of this study deliver new guidance for the design of biosorbents with high removal capability and excellent selectivity.

Selective removal of uranyl ions using ion-imprinted amino-phenolic functionalized chitosan.

The recovery of uranium from aqueous effluents is very important for both the environment and the future of nuclear power. However, issues of sluggish rates and poor selectivity persist in achieving high-efficiency uranium extraction. In this study, uranyl (UO22+) ions were imprinted on an amino-phenolic chitosan derivative using an ion-imprinting method. First, 3-hydroxy-4-nitrobenzoic acid (HNB) units were joined to chitosan via amide bonding, followed by reducing the -NO2 residues into -NH2. The amino-phenolic chitosan polymer ligand (APCS) was coordinated with UO22+ ions, then cross-linked with epichlorohydrin (ECH), and finally the UO22+ ions were taken away. When compared to non-imprinted sorbent, the resulting UO22+ imprinted sorbent material (U-APCS) recognized the target ions preferentially, allowing for much higher adsorption capacities (qm = 309 ± 1 mg/g) and improved adsorption selectivity for UO22+. The FTIR and XPS analyses supported the pseudo-second-order model's suggestion that chemisorption or coordination is the primary adsorption mechanism by fitting the data well in terms of kinetics. Also, the Langmuir model adequately explained the isotherms, suggesting UO22+ adsorption in the form of monolayers. The pHZPC value was estimated at around 5.7; thus, the optimum uptake pH was achieved between pHs 5 and 6. The thermodynamic properties support the endothermic and spontaneous nature of UO22+ adsorption.

Construction of amino-thiol functionalized ion-imprinted chitosan for lead (II) ion removal.

Ion-imprinting technique was used to create a lead ion-imprinted sorbent from an amino-thiol chitosan derivative (Pb-ATCS). First, 3-Nitro-4-sulfanylbenzoic acid (NSB) unit's amidized the chitosan, and then the -NO2-residues were selectively reduced to -NH2. Imprinting was accomplished by cross-linking with epichlorohydrin and removing the Pb (II) ions from the across-linked polymeric complex formed from the amino-thiol chitosan polymer ligand (ATCS) and Pb (II) ions. The synthetic steps have been investigated by nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR), and the sorbent was tested for its ability to selectively bind Pb (II) ions. The produced Pb-ATCS sorbent had a maximum capacity of roughly 300 mg/g, and it showed a greater affinity for the Pb (II) ions than the control NI-ATCS sorbent particle. The pseudo-2nd-order equation was also consistent with the adsorption kinetics of the sorbent, which were quite rapid. This demonstrated that metal ions were chemo-adsorbed onto the Pb-ATCS and NI-ATCS solid surfaces via coordination with the introduced amino-thiol moieties.

Nanomaterials-Based Ion-Imprinted Electrochemical Sensors for Heavy Metal Ions Detection: A Review.

Heavy metal ions (HMIs) pose a serious threat to the environment and human body because they are toxic and non-biodegradable and widely exist in environmental ecosystems. It is necessary to develop a rapid, sensitive and convenient method for HMIs detection to provide a strong guarantee for ecology and human health. Ion-imprinted electrochemical sensors (IIECSs) based on nanomaterials have been regarded as an excellent technology because of the good selectivity, the advantages of fast detection speed, low cost, and portability. Electrode surfaces modified with nanomaterials can obtain excellent nano-effects, such as size effect, macroscopic quantum tunneling effect and surface effect, which greatly improve its surface area and conductivity, so as to improve the detection sensitivity and reduce the detection limit of the sensor. Hence, the present review focused on the fundamentals and the synthetic strategies of ion-imprinted polymers (IIPs) and IIECSs for HMIs detection, as well as the applications of various nanomaterials as modifiers and sensitizers in the construction of HMIIECSs and the influence on the sensing performance of the fabricated sensors. Finally, the potential challenges and outlook on the future development of the HMIIECSs technology were also highlighted. By means of the points presented in this review, we hope to provide some help in further developing the preparation methods of high-performance HMIIECSs and expanding their potential applications.

[Magnetic ion imprinting techniques for the separation and analysis of elemental speciation].

Metal and metalloid elements have various possible isotopic compositions and oxidation states and often form coordination or covalent compounds with inorganic and organic small molecules or biological macromolecules, resulting in complex elemental speciation. Different species of the same element often have different properties, which dictate their behavior. Thus, elemental speciation analysis is vital for comprehensively and accurately assessing an element's environmental and biological effects and the corresponding risks. Because elemental speciation determines the behavior of an element in different environmental and biological processes, the analysis of elemental species has, in recent years, been important in various subjects, including analytical chemistry, environmental chemistry, geochemistry, ecology, agronomy, and biomedicine. The complexity of environmental and biological sample matrices, as well as the multiformity, low levels, and lability of chemical forms pose severe challenges in elemental speciation analysis. Therefore, the highly selective identification and efficient separation of native species is necessary for conducting the identification, quantification, ecotoxicity evaluation, and physiological function study of elemental speciation. Sample pretreatment by solid-phase extraction is an effective solution to the aforementioned problems, but the existing methods do not meet the requirements of current research. The transition of the target species from pre-processing to the detection device includes both on- and off-line arrangements. Compared with the on-line approach, the off-line approach requires more manual participation, increasing the analysis workload. However, the off-line approach can improve the analysis efficiency through high-throughput pretreatment when large batches of samples are encountered, meaning the off-line approach is still an effective model. Ion imprinting technology has been developed based on existing molecular imprinting technology, with four main steps present in the synthesis of ion imprinted polymers. First, ion imprinting technology uses metal ions as templates. Then, these templates are combined with the functional monomers through coordination, electrostatic or hydrogen bonding. The functional monomers simultaneously surround and fix the templates, after which the cross-linkers and functional monomers polymerize to prepare ion-imprinted polymers with a specific structure and composition. Finally, the imprinted holes are created in the polymers by eluting the template ions. Therefore, the template molecules, functional monomers, and cross-linkers are three precursors necessary for synthesizing ion-imprinted polymers. These polymers can specifically bind to the imprinted metal ions with accuracy, sensitivity, and reliability. In recent years, they have been widely used in separating, enriching, analyzing, and detecting elemental species. During solid-phase extraction, the non-magnetic adsorbent materials dispersed in the sample solution need to be separated by centrifugation or filtration, which is time-consuming and laborious. Because an external magnetic field can be used for rapid magnetic solid-phase extraction, it has become a potential method for separating and enriching elemental species. This review systematically summarizes the latest progress in ion-imprinting technology, including its principle and the preparation methods of ion-imprinted polymers. The challenges faced by ion imprinting technology are analyzed in the context of the development of ion-imprinting magnetic solid-phase extraction in elemental speciation analysis. Finally, the direction of future development and the strategies of ion imprinting technology in elemental speciation analysis are proposed. It is important to exploit novel organic-inorganic hybrid polymerization-based multifunctional ion-imprinted magnetic nanocomposites for the magnetic solid-phase extraction and separation of elemental species. By establishing the pretreatment protocols with high recognition selectivity, strong separation ability, large adsorption capacity, and good speciation stability, we expect to achieve the research objectives of simultaneously separating and enriching the multiple-species of typical metal/metalloid elements in environmental and biological samples.

Cyclic enrichment of chromium based on valence state transformation in metal-free photocatalytic reductive imprinted composite hydrogel.

Cr (VI) exists in anion form and can be reduced to positive charged Cr (III) under certain conditions. Can positive charged Cr (III) be continually used for absorbing Cr (VI) to achieve cyclic accumulation of chromium? In this paper, an ion imprinting material for adsorption of Cr (VI) was prepared by dispersing polypyrrole (PPy) in a gelatin/chitosan (Gel/CS) hydrogel network, named Gel/CS/PPy. Based on the conversion of Cr (VI) to Cr (III), a cyclic enrichment process including adsorption-photoreduction-fixation-readsorption of Cr (VI) was established in Gel/CS/PPy hydrogel. The composition and structure of the Gel/CS/PPy were analyzed by scanning electron microscopy (SEM), Fourier transform-infrared spectroscopy (FT-IR), thermogravimetric (TGA), texture analyzer (Universal TA), zeta potential and ultraviolet-visible-near infrared spectra (UV-vis-NIR). The conversion of Cr (VI) and Cr (III) and its promoting effect on readsorption were verified by XPS. The results showed that Gel/CS/PPy has good adsorption capacity for Cr (VI) and excellent photocatalytic ability to reduce Cr (VI) to Cr (III). Cr (III)-loaded Gel/CS/PPy can be further used to adsorb Cr (VI) and showed good adsorption efficiency even after four cycles. The optimal operating condition for Cr (VI) adsorption is pH = 3; 2 g/L dose of Gel/CS/PPy; and the adsorption capacity of Cr (VI) was about 106.8 mg/g after six adsorption cycles. Since Gel/CS/PPy is composed of organic components, high purity chromium can be recovered by simple calcination method later. Therefore, the synthesized Gel/CS/PPy has great potential in the practical application of low concentration Cr (VI) treatment in water.

A Novel Electrochemical Sensor Modified with a Computer-Simulative Magnetic Ion-Imprinted Membrane for Identification of Uranyl Ion.

In this paper, a novel ion-imprinted electrochemical sensor modified with magnetic nanomaterial Fe3O4@SiO2 was established for the high sensitivity and selectivity determination of UO22+ in the environment. Density functional theory (DFT) was employed to investigate the interaction between templates and binding ligands to screen out suitable functional binding ligand for the reasonable design of the ion imprinted sensors. The MIIP/MCPE (magnetic ion imprinted membrane/magnetic carbon paste electrode) modified with Fe3O4@SiO2 exhibited a strong response current and high sensitivity toward uranyl ion comparison with the bare carbon paste electrodes. Meanwhile, the MCPE was fabricated simultaneously under the action of strong magnetic adsorption, and the ion imprinted membrane can be adsorbed stably on the electrode surface, handling the problem that the imprinted membrane was easy to fall off during the process of experimental determination and elution. Based on the uranyl ion imprinting network, differential pulse voltammetry (DPV) was adopted for the detection technology to realize the electrochemical reduction of uranyl ions, which improved the selectivity of the sensor. Thereafter, uranyl ions were detected in the linear concentration range of 1.0 × 10-9 mol L-1 to 2.0 × 10-7 mol L-1, with the detection and quantification limit of 1.08 × 10-9 and 3.23 × 10-10 mol L-1, respectively. In addition, the sensor was successfully demonstrated for the determination of uranyl ions in uranium tailings soil samples and water samples with a recovery of 95% to 104%.

Designing of modified ion-imprinted chitosan particles for selective removal of mercury (II) ions.

Ion-imprinting methodology was utilized in the fabrication of mercury ion-imprinted sorbent derived from modified chitosan derivatives. The Schiff base ligand was first derived from 4-amino-3-hydroxybenzoic acid and 2-pyridinecarboxaldehyde (HPB) and then incorporated with chitosan via amide bonds. The obtained modified chitosan polymeric ligand (PBCS) was combined with Hg(II) ions to produce the corresponding polymeric complex and the imprinting was then achieved upon the glutaraldehyde cross-linking and eliminating the incorporated Hg(II) ions to finally have the Hg(II) ion-imprinted sorbent material (Hg-PBCS). The materials have been investigated using various techniques such as NMR and FTIR and the obtained sorbent was examined to evaluate its selective affinity to capture the target Hg(II) ions. The developed Hg-PBCS sorbent exhibited a higher tendency toward the targeted Hg(II) ions compared to the control non-imprinted sorbent particle (NI-PBCS) with a maximum capacity of 315 mg/g. Also, the sorbent displayed relatively rapid adsorption kinetics that best correlated with the pseudo-second-order model.