Metal Research Articles

Composition and Structure of the solid electrolyte interphase on Na-Ion Anodes Revealed by Exo- and Endogenous Dynamic Nuclear Polarization─NMR Spectroscopy.

Sodium ion batteries (SIB) are among the most promising devices for large scale energy storage. Their stable and long-term performance depends on the formation of the solid electrolyte interphase (SEI), a nanosized, heterogeneous and disordered layer, formed due to degradation of the electrolyte at the anode surface. The chemical and structural properties of the SEI control the charge transfer process at the electrode-electrolyte interface, thus, there is great interest in determining these properties for understanding, and ultimately controlling, SEI functionality. However, the study of the SEI is notoriously challenging due to its heterogeneous nature and minute quantity. In this work, we present a powerful approach for probing the SEI based on solid state NMR spectroscopy with increased sensitivity from dynamic nuclear polarization (DNP). Utilizing exogenous (organic radicals) and endogenous (paramagnetic metal ion dopants) DNP sources, we obtain not only a detailed compositional map of the SEI but also, for the first time for the native SEI, determine the spatial distribution of its constituent phases. Using this approach, we perform a thorough investigation of the SEI formed on Li4Ti5O12 used as a SIB anode. We identify a compositional gradient, from organic phases at the electrolyte interface to inorganic phases toward the anode surface. We find that the use of fluoroethylene carbonate as an electrolyte additive leads to performance degradation which can be attributed to formation of a thicker SEI, rich in NaF and carbonates. We expect that this methodology can be extended to examine other titanate anodes and new electrolyte compositions, offering a unique tool for SEI investigations to enable the development of effective and long-lasting SIBs.

Heterologous expression of GH11 xylanase from Myceliophthora heterothallica F.2.1.4 in Pichiapastoris

This research is centered on improving a xylanase enzyme derived from Myceliophthora heterothallica by expressing it in Pichia pastoris to enhance biomass hydrolysis. Lignocellulosic biomass holds significant potential for renewable applications in biofuels, chemicals, and pharmaceuticals. The study explores the impact of the choice of expression host on enzyme properties, specifically addressing challenges in thermostability by utilizing P. pastoris and leveraging its glycosylation capabilities. Previously expressed in Escherichia coli, the xylanase exhibited in this work cooperative kinetics, pH stability, and resistance to phenolic compounds. Gene integration and expression in P. pastoris were verified through PCR and activity assays. After 120 h of induction, an enzymatic activity of 48.8 U mL−1 was obtained. Subsequent characterization revealed improved specific activity, substrate affinity, and optimal temperature compared to the enzyme expressed in E. coli. The enzyme exhibited excellent pH and temperature stability for industrial applications, maintaining over 90% of its activity within a pH range of 5.0–10.0 and remaining stable even after 90 min of incubation at 55 °C. It also demonstrated resistance to metal ions and responsiveness to phenolic compounds. These findings underscore the versatility of the recombinant xylanase from M. heterothallica expressed in P. pastoris, highlighting its potential as a valuable resource for biomass conversion. The study emphasizes the pivotal role of host choice in optimizing enzyme characteristics for industrial applications, underscoring the importance of employing heterologous expression systems, as demonstrated in this investigation.

Proton‐Enriched Alginate–Graphene Hydrogel Microreactor for Enhanced Hydrogen Peroxide Photosynthesis

AbstractEfficient synthesis of H2O2 via photocatalytic oxygen reduction without sacrificial agents is challenging due to inadequate proton supply from water and difficulty in maintaining O−O bond during O2 activation. Herein, we developed a straightforward strategy involving a proton‐rich hydrogel cross‐linked by metal ions [M(n)], which is designed to facilitate the selective production of H2O2 through proton relay and metal ion‐assisted detachment of crucial intermediates. The hydrogel comprises CdS/graphene and alginate cross‐linked by metal ions via O=C−O−M(n) bonds. Efficient O2 reduction and hydrogenation occurred, benefitting from the collaboration between proton‐rich alginate and the photocatalytically active CdS/graphene. Meanwhile, the O=C−O−M(n) bonds enhance the electron density of α‐carbon sites on graphene, crucial for O2 activation and *OOH intermediate detachment, preventing deeper O−O bond cleavage. The role of metal ions in promoting *OOH desorption was demonstrated through Lewis acidity‐dependent activity, with Y(III) having the highest activity, followed by Lu(III), La(III), and Ca(II).

Multifunctional Bionic Periosteum with Ion Sustained-Release for Bone Regeneration.

In this study, a novel bionic periosteum (BP)-bioactive glass fiber membrane (BGFM) is designed. The introduction of magnesium ion (Mg2+) and zinc ion (Zn2+) change the phase separation during the electrospinning (ES) jet stretching process. The fiber's pore structure transitions from connected to closed pores, resulting in a decrease in the rapid release of metal ions while also improving degradation via reducing filling quality. Additionally, the introduction of magnesium (Mg) and zinc (Zn) lead to the formation of negative charged tetrahedral units (MgO4 2- and ZnO4 2-) in the glass network. These units effectively trap positive charged metal ions, further inhibiting ion release. In vitro experiments reveal that the deigned bionic periosteum regulates the polarization of macrophages toward M2 type, thereby establishing a conducive immune environment for osteogenic differentiation. Bioinformatics analysis indicate that BP enhanced bone repair via the JAK-STAT signaling pathway. The slow release of metal ions from the bionic periosteum can directly enhance osteogenic differentiation and vascularization, thereby accelerating bone regeneration. Finally, the bionic periosteum exhibits remarkable capabilities in angiogenesis and osteogenesis, demonstrating its potential for bone repair in a rat calvarial defect model.

Aggregation-induced electrochemiluminescence of an indium-based metal–organic framework and resonance energy transfer strategy for the sensitive detection of β2-microglobulin

This study aimed to construct a novel aggregation-induced electrochemiluminescence (AIECL) system with an indium-based metal–organic framework (In-MOF) as a new luminophore and K2S2O8 as a co-reactant. In the constructed electrochemiluminescence (ECL) system, In-MOF served not only as a novel luminophore but also as a co-reaction accelerator. The In-MOF produced strong cathodic ECL emission over the wavelength range of 425–600 nm. The aggregation-caused quenching effect was overcome by altering the π-π stacking structure of 9,10-di(p-carboxyphenyl)anthracene (DPA) aggregates through coordination with metal ions. The In-MOF exhibited efficient ECL performance and better stability than the DPA ligand. Then, a novel quenched sensor based on the quenching effect of CeO2@PDA on the In-MOF ECL emission was fabricated for detecting β2-microglobulin (β2M). The immunosensor demonstrated an excellent linear relationship with a wide linear range (10 fg/mL – 200 ng/mL) and a low detection limit (2.9 fg/mL, S/N = 3) under optimized experimental conditions. The proposed biosensor had high sensitivity, reasonable specificity, high stability, and reproducibility, thus positively affecting the clinical application of sensing analysis.

Self-expanding cellulose sponge with enhanced hemostatic ability by tannic acid/metal ion composite coating for highly effective hemostasis of difficult-to-control bleeding wounds

Refractory bleeding presents a critical, life-threatening challenge, and the goal of medical professionals and researchers has always been to achieve safe and effective hemostasis for bleeding wounds. In this study, we utilized the benefits of a self-expanding cellulose sponge to control incompressible bleeding, which is achieved this by creating a tannic acid/metal ion coating on the surface and within the pores of the sponge to improve its hemostatic effectiveness. The effects of various types and concentrations of metal ions (calcium, magnesium, iron, and zinc) on hemostatic efficiency and biosafety is systematically investigated. The results from bacteriostasis and in vitro coagulation experiments identified 0.3 wt% Fe3+ as the optimal metal ion coating. Scanning electron microscope energy spectrum analysis confirmed the uniform distribution of Fe3+ within the cellulose sponge. Furthermore, the in vivo and in vitro results demonstrated that the prepared tannic acid/Fe3+ coated composite hemostatic sponge exhibits excellent coagulation ability and biocompatibility. Both the bleeding time and theblood loss in two bleeding models are significantly reduced, showing promising potential for treating extensive surface bleeding and deep penetrating wounds. Furthermore, the straightforward preparation method for this composite hemostatic sponge facilitates additional research towards market application.

Heterocyclic Hemipiperazines: Multistimuli-Responsive Switches and Sensors for Zinc or Cadmium Ions.

Advance in the design of molecular photoswitches - adapters that convert light into changes at molecular level - opens up exciting possibilities in preparing smart polymers, drugs photoactivated inside humans, or light-fueled nanomachines that might in the future operate in our bloodstream. Hemipiperazines are recently reported biocompatible molecular photoswitches based on cyclic dipeptides. Here we report a multistimuli-responsive hemipiperazine-based switch that reacts on light, solvents, acidity, or metal ions. Its photoequilibration is controlled by the intramolecular hydrogen bonding pattern. The compound can be used as a mid-nanomolar photoswitchable fluorescent sensor for zinc and cadmium ions, applicable to monitor environmental pollution in real time.

Enhancing Wound Healing With Sprayable Hydrogel Releasing Multi Metallic Ions: Inspired by the Body's Endogenous Healing Mechanism.

In the pursuit of new wound care products, researchers are exploring methods to improve wound healing through exogenous wound healing products. However, diverging from this conventional approach, this work has developed an endogenous support system for wound healing, drawing inspiration from the body's innate healing mechanisms governed by the sequential release of metal ions by body at wound site to promote different stages of wound healing. This work engineers a multi-ion-releasing sprayable hydrogel system, to mimic this intricate process, representing the next evolutionary step in wound care products. It comprises Alginate (Alg) and Fibrin (Fib) hydrogel infused with Polylactic acid (PLA) polymeric microcarriers encapsulating multi (calcium, copper, and zinc) nanoparticles (Alg-Fib-PLA-nCMB). Developed sprayable Alg-Fib-PLA-nCMB hydrogel show sustained release of beneficial multi metallic ions at wound site, offering a range of advantages including enhanced cellular function, antibacterial properties, and promotion of crucial wound healing processes like cell migration, ROS mitigation, macrophage polarization, collagen deposition, and vascular regeneration. In a comparative study with a commercial product (Midstress spray), developed Alg-Fib-PLA-nCMB hydrogel demonstrates superior wound healing outcomes in a rat model, indicating its potential for next generation wound care product, addressing critical challenges and offering a promising avenue for future advancements in the wound management.

Synthesis of Novel 2-Amino Thiazole Derivatives and Salicyaldehyde based Ligand to have Biological Activity

In inorganic chemistry, Schiff bases and complexes come in a variety of forms. Therefore, the discovery of new organic and inorganic compounds with remarkable anti-fungal, anti-bacterial, and anticancer characteristics represents a major advancement in biochemistry, pharmacy, and medicine. All of the chemicals that were employed in this study were A.R. grade. The following materials provided by SD's fine chemical Ltd. and Merck chemicals, Mumbai were utilised impurification: methanol, calcium hydroxide, sodium acetate, thiourea, ethylacetoacetate, benzoyl chloride, acetyl chloride, 1,4-dioxane, and sulfuric acid. Additionally, this Schiff base may combine with the ions of several transition metals, such as Ni(II), Cu(II), Co(II), and Cd(II), to create complexes. In addition to chemical analysis, conductivity, and magnetic tests, we further characterized the complexes using electronic and infrared spectroscopy in order to examine their structures. Every compound's antibacterial activity was evaluated. In the agar cup test method, all of the Schiff base metal complexes had a moderate level of antibacterial activity. Spectroscopic data suggests that these complexes are all of type ML2.(H2O)2 (M=Mn, Fe, Co, Ni, and Cu).

Fe3C/Fe implanted hierarchical porous carbon as efficient electromagnetic wave absorber

The rapid development of communication technology has led to severe microwave pollution, which presents a challenge for microwave-absorbing composites. Current research suggests achieving superior microwave absorption requires the use of multi-component operation and ingenious structural design. Consequently, the present study has prepared continuous porous carbon (CPC) materials doped with large amounts of Fe3C/Fe nanoparticles (Fe@CPC) using carbonization and acid etching. By balancing the advantages of the above strategies, it is possible to address issues such as poor impedance match, single loss capacity, easy oxidation of magnetic metals/alloys, and the limited absorption bandwidth of conventional absorbing materials at the same time. The material exhibits a minimum reflection loss of −23.2 dB with an efficient absorption range of 5.3 GHz at 1.9 mm at a filler content of just 10 wt% in the paraffin matrix. In this paper, the samples with a continuous porous structure were prepared by a simple method, and the properties were excellent due to the appropriate preparation method and the synergistic effect of the multi-component composite. The porous structure facilitates the presence of a considerable number of active sites, which enables the loading of a substantial quantity of metal ions. Furthermore, nanoparticles are capable of aggregating and dispersing on the surface. This paper presents a theoretical framework for understanding the synergistic effect of microwave radiation through interfacial polarization and micro-scale magnetic interaction. Nevertheless, there are still obstacles to overcome in terms of achieving precise control over the structural design and ensuring the compatible integration of metal components.

Novel coumarin-Schiff base derived electronically distinct fluorescent probes: Synthesis and comparative investigations of their unique selective sensing properties with Cu2+ and Cu+ ions

The present work describes the synthesis and comparative investigations of Cu2+ and Cu+ ions sensing properties of two novel π-extended coumarin-Schiff base-derived electronically distinct fluorescent probes (4 and 5). Due to the additional electron donating group substituent (-NEt2) close proximate to the binding site of Schiff base in probe 5, it exhibits distinct electronic properties compared to probe 4. Our studies indicate that probe 5 displays efficient and highly selective fluorescence quenching behaviors with Cu2+ and Cu+ ions compared to other competitive metal ions (Ca2+, Mg2+, Al3+, Hg2+, Pb2+, Cd2+, Mn2+, Co2+, Ni2+, Fe2+, Fe3+, Cr3+ and Zn2+). In our studies, Job's plot experiments revealed that the binding stoichiometry of the ligand-Cu2+ was 1:1 for both probes. The limit of detection (LOD) of 2.35 × 10–5 M and 1.56 × 10–5 M were obtained for the probes 4 and 5, respectively. Further, the Stren-Volmer equation has been used to calculate the binding abilities of probes with Cu2+ ions; it reveals the binding constant of 6.70 × 104 M-1 and 22.0 × 104 M-1 for probes 4 and 5, respectively. Also, in the present studies, our DFT computed results were comparatively presented to understand the electronic parameters (HOMO-LUMO energy band gaps, ESP and Mulliken atomic charge distribution) of compound 1, probes 4 and 5. We anticipate that the developed probes can be used to analyze Cu2+ and Cu+ ions in environmental and biological samples.

2D Covalent Organic Framework Covalently Anchored with Carbon Nanotube as High-Performance Cathodes for Lithium and Sodium-Ion Batteries.

Covalent organic frameworks (COFs), featuring structural diversity, permanent porosity, and functional versatility, have emerged as promising electrode materials for rechargeable batteries. To date, amorphous polymer, COF, or their composites are mostly explored in lithium-ion batteries (LIBs), while their research in other alkali metal ion batteries is still in infancy. This can be due to the challenges that arise from large volume changes, slow diffusion kinetics, and inefficient active site utilization by the large Na+ or K+ ion. Herein, microwave-assisted imide-based 2D COF, TAPB-NDA covalently connected with amine-functionalized carbon nanotubes (TAPB-NDA@CNT) targeting the application in both Li-/Na-ion batteries, is synthesized. As-synthesized, TAPB-NDA@CNT50 displays the good performance as LIB cathode with a specific capacity of ≈138mAhg-1 at 25mAg-1, long cycling stability (81.2% retention after 2000 cycles at 300mAg-1), with excellent reversible capacity retention of ≈79.6%. Similarly, TAPB-NDA@CNT50, when employed in sodium-ion battery (SIB), exhibited 136.7mAhg-1 specific capacity at 25mAg-1, retained ≈80% of the reversible capacity after 1000 cycles at 300mAg-1 and showing excellent rate performance. The structural advantage of TAPB-NDA@CNT will encourage researchers to design COF-based cathodes for the alkali ion batteries.

Revealing the effect regularity of cations on electron storage capacity of poly(heptazine imide) in “dark photocatalysis”

As a crystalline carbon nitride material, poly(heptazine imide) (abbreviated as PHI) exhibits higher photoinduced charge separation performance than traditional melon-based carbon nitride. The excellent charge separation is mainly attributed to the fact that the photoinduced electrons can be captured by cations (such as K+ and H+) and further stored in the PHI framework with the presence of sacrificial agents (such as methanol). Due to this special property, the stored electrons can be used for delayed H2O2 or H2 production in the “dark photocatalysis” field. Nevertheless, the effect regularity of cations on the electron storage capacity of PHI is still not clear. In this work, this problem has been preliminarily revealed. The electron storage capacity of a series of PHI materials has been quantified by the H2O2 production test in dark conditions. The result indicates that the electron storage capacity of PHI samples shows a volcano curve with the alkali metal ion content. Based on experimental tests and theoretical simulations, it is concluded that the electron storage capacity of PHI is related to the conductivity of the cation and its binding force for photogenerated electrons.

Atomistic Simulations Reveal Crucial Role of Metal Ions for Ligand Binding in Guanidine-I Riboswitch.

Riboswitches are structured ribonucleic acid (RNA)segments that act as specific sensors for small molecules in bacterial metabolism. Due to the flexible nature of these highly charged macromolecules, molecular dynamics simulations are instrumental to investigating the mechanistic details of their regulatory function. In the present study, the guanidine-I riboswitch serves as an example of how atomistic simulations can shed light on the effect of ions on the structure and dynamics of RNA and on ligand binding. Relying on two orthologous crystal structures from different bacterial species, it is demonstrated how the ion setup crucially determines whether the simulation yields meaningful insights into the conformational stability of the RNA, functionally relevant residues and RNA-ligand interactions. The ion setup in this context includes diffuse ions in solution and bound ions associated directly with the RNA, in particular a triad of 2 Mg2+ ions and a K+ ion in close proximity to the guanidinium binding site. A detailed investigation of the binding pocket reveals that the K+ from the ion triad plays a decisive role in stabilizing the ligand binding by stabilizing important localized interactions, which in turn contribute to the overall shape of the folded state of the RNA.

Ultrahigh Pyridinic/Pyrrolic N Enabling N/S Co-Doped Holey Graphene with Accelerated Kinetics for Alkali-Ion Batteries.

Carbonaceous materials hold great promise for K-ion batteries due to their low cost, adjustable interlayer spacing, and high electronic conductivity. Nevertheless, the narrow interlayer spacing significantly restricts their potassium storage ability. Herein, hierarchical N, S co-doped exfoliated holey graphene (NSEHG) with ultrahigh pyridinic/pyrrolic N (90.6at.%) and large interlayer spacing (0.423nm) is prepared through micro-explosion assisted thermal exfoliation of graphene oxide (GO). The underlying mechanism of the micro-explosive exfoliation of GO is revealed. The NSEHG electrode delivers a remarkable reversible capacity (621 mAhg-1 at 0.05 Ag-1), outstanding rate capability (155 mAhg-1 at 10 Ag-1), and robust cyclic stability (0.005% decay per cycle after 4400 cycles at 5 Ag-1), exceeding most of the previously reported graphene anodes in K-ion batteries. In addition, the NSEHG electrode exhibits encouraging performances as anodes for Li-/Na-ion batteries. Furthermore, the assembled activated carbon||NSEHG potassium-ion hybrid capacitor can deliver an impressive energy density of 141 Whkg-1 and stable cycling performance with 96.1% capacitance retention after 4000 cycles at 1 Ag-1. This work can offer helpful fundamental insights into design and scalable fabrication of high-performance graphene anodes for alkali metal ion batteries.

TESMIN is a Prognostic Biomarker Associated with Immunosuppression and Activated Cell Cycle in Lung Adenocarcinoma.

The Testis Expressed Metallothionein Like Protein (TESMIN) gene encodes highly conserved, cysteine-rich, low-molecular proteins that are activated by and have an affinity for heavy metal ions. Previous literature has shown its association with cancer. Nevertheless, no thorough bioinformatics analysis of TESMIN has been done yet in lung adenocarcinoma (LUAD). Differential expression of TESMIN between cancer and normal tissues was confirmed by analyzing databases and immunohistochemistry staining. Enrichment analysis was adopted to explore biological functions. The relationship of TESMIN with immune infiltration was evaluated by ssGSVA, with immunotherapy response predicted by TCIA and TIDE tools, with mutational traits analyzed by R software. Drug sensitivity analysis was implemented via GSCA tool, pRRophetic algorithms, and CellMiner database. The results demonstrated that TESMIN expression was upregulated in tumor tissue and related to Ki67. TESMIN was associated with poor survival and significantly related to age, gender, N stage, M stage, pathological stage, and survival status. TESMIN- related genes (TRGs) were primarily involved in cell division and cancer-related enrichment pathways. TESMIN was associated with high frequencies of somatic mutations and an immunosuppressive tumor microenvironment. Interestingly, patients with elevated levels of TESMIN expression benefited more from commonly used chemotherapy drugs such as cisplatin, paclitaxel, vinorelbine, and docetaxel, whereas those with low levels of TESMIN expression showed favorable clinical responses to immunotherapy. As a prognostic biomarker associated with the cell cycle and immune infiltration, TESMIN may serve as an effective target for predicting the sensitivity to immunotherapy and chemotherapy.

Design of Point Charge Models for Divalent Metal Cations Targeting Quantum Mechanical Ion–Water Dimer Interactions

Divalent metal cations are of vital importance in biochemistry and materials science, and their structural and thermodynamic properties in aqueous solution have often been used as targets for the development of ion models. This study presented a strategy for designing nonbonded point charge models of divalent metal cations (Mg2+ and Ca2+) and Cl− by targeting quantum mechanics (QM)-based ion–water dimer interactions. The designed models offered an accurate representation of ion–water interactions in the gas phase and showed reasonable performance for non-targeted properties in aqueous solutions, such as the ion–water oxygen distance (IOD), coordination number (CN), and density and viscosity of MgCl2 and CaCl2 solutions at low concentrations. Our metal cation models yielded considerable overestimates of the hydration free energies (HFEs) of the ions, whereas the Cl− model displayed good performance. Together with the overestimated density and viscosity of the salt solutions, these results indicated the necessity of re-optimizing ion–ion interactions and/or including polarization effects in the design of ion models. The designed Mg2+ model was capable of maintaining the crystal metal-binding networks during MD simulation of a metalloprotein, indicating great potential for biomolecular simulations. This work highlighted the potential of QM-based ion models to advance the study of metal ion interactions in biological and material systems.

Multi-ligand strategy for enhanced removal of heavy metal ions by thiol-functionalized defective Zr-MOFs

Given the significant global concern about heavy metal pollution, the development of effective adsorbents to capture pollutants has become an urgent issue. In this work, thiol-functionalized defective Zr-MSA-DMSA was designed by mixing 2,3-dimercaptosuccinic acid and mercaptosuccinic acid, which was applied for the rapid and efficient removal of M(II) (i.e., Pb(II), Hg(II), Cd(II)) from wastewater. Zr-MSA-DMSA exhibited excellent adsorption performance, and the maximum adsorption capacities for Pb(II), Hg(II), and Cd(II) were 715.2 mg g−1, 862.7 mg g−1, and 450.5 mg g−1. In actual wastewater, Zr-DMSA-MSA exhibited up to 97 % M(II) removal efficiency and excellent anti-interference ability. It also maintained good structural stability after five adsorption/regeneration cycles. Thus, the abundant oxygen vacancies and unsaturated adsorption sites on Zr-MSA-DMSA significantly improved the adsorption performance of M(II). Spectral analysis and DFT calculations confirmed that Zr-MSA-DMSA mainly relied on the coordination of sulfur and oxygen atoms, electrostatic attraction and a large number of defective sites to achieve the adsorption of M(II). Fixed bed experiments showed that Zr-MSA-DMSA exhibited a depletion time of 10500 min and a volume of 7.0 L. In summary, Zr-MSA-DMSA holds significant potential for treating heavy metal wastewater and provides potential applications for defect engineering.

Ultra-hydrophilic MOF-303 on electrospun nanofibers with Burr Puzzles structure for the purification of oily wastewater containing heavy metal ions

The current oil-water separation field is extremely complex and the material system is variable. Therefore, the full process applicability of membrane technology is extremely demanding, both in terms of high oil-water separation efficiency and the treatment of soluble substances in wastewater, such as heavy metal ions. The high demand for membrane performance is accompanied by the complexity of the membrane manufacturing process, resulting in the development of membrane technology being hindered. If we can purify heavy metal ions from wastewater while meeting the conditions of oil-water treatment, and simplify the process flow, it is an innovation that we are happy to see. Herein, the use of a seed pre-embedded growth strategy is taking polyacrylamide (PEI) as a breakthrough point, we take advantage of blending to introduce embedding sites in polyacrylonitrile (PAN) membranes. Uniform growth of MOF-303 with Burr Puzzle structure on membrane surface using in situ hydrothermal growth method. The Burr Puzzles structure on the membrane surface is not only able to effectively deal with nanoscale stabilized oil-water mixture and effectively adsorb heavy metal ions, but also enables the MOF-303 crystals to grow more firmly on the membrane surface, so that the modified membrane still maintains good performance in harsh environments. The separation fluxes of the oil-in-water emulsions were all higher than 6987 L m−2 h−1 for oil-in-water emulsion with a separation efficiency of 98.4 %, and the adsorption efficiency of heavy metal ions was also as high as 98.3 %. After 20 cycles, the membrane maintains its promising performance. Due to its simple preparation process and excellent efficiency of emulsions separation and heavy metal ions separation, simplifies complex membrane processes while meeting the rigors of wastewater treatment. it has great prospects for development in the current complex wastewater treatment process.

Cu(Ⅱ)-EDTA degradation and copper recovery from wastewater in wide pH ranges by an electrooxidation-capacitive deionization system

The treatment and recovery of metal resources from complex industrial wastewater has posed significant challenges due to the presence of multiple heavy metal ions, heavy metal complexes, and acidic conditions. In this study, a novel electrooxidation-capacitive deionization (EO-CDI) system was proposed, which ingeniously harnessed the unheeded Faraday side reaction in capacitive deionization for simultaneous degradation and recovery of copper complexes from wastewater through two electrode integration. Specially, the cathode CuS0.78Se0.22 synthesized through the anionic Se-substitution strategy exhibited a remarkable adsorption capacity up to 672.02 mg/g for Cu ions, outstanding selectivity and stability, particularly in acidic environments. The water oxidation process occurring at the activated carbon anode played a crucial role by generating active species that contribute to the degradation of Cu(Ⅱ)-EDTA, which leaded to the release of copper ions, facilitating their subsequent recovery. Cyclic experiments further confirmed the excellent cyclic stability of the hybrid EO-CDI system, along with its impressive performance in copper extraction when applied to real industrial wastewater. This innovative approach offered promising prospects for addressing the challenges associated with the treatment of complex industrial wastewater and the recovery of valuable metal resources.