Anthropogenic discharges of radionuclides and heavy metal ions have exacerbated global water pollution and posed severe ecological risks, stimulating the development of selective removal and resource recovery strategy. So far, electrode materials for electrosorption (Capacitive Deionization, CDI) have expanded to carbon composite systems, MXenes, transition metal oxides/sulfides, metal-organic frameworks and covalent organic frameworks. Conventional flow-between CDI reactors have been innovatively optimized into advanced architectures including membrane capacitive deionization, flow-electrode capacitive deionization and hybrid capacitive deionization. Combining bibliometric mapping and network analysis, this paper delineates the evolution of electrosorption research, elucidates its fundamental mechanisms, and identifies electrode performance as the decisive factor governing treatment efficiency. This review systematically evaluates recent advances in carbon-based, Faradaic, and novel composite electrodes, verifying their exceptional selectivity and adsorption capacity toward radionuclides, and summarizes cutting-edge technological trends in this field and thoroughly analyzes the long-standing core bottlenecks that hinder the practical deployment of electrosorption technology. This work offers theoretical references for research hotspots in this field and facilitates the innovative development of advanced electrosorption technologies for sustainable water purification.
Lead (Pb) contamination in soils is a critical environmental issue requiring urgent attention, yet traditional phosphate stabilization is limited by poor long-term stability, slow reaction kinetics, and the risk of phosphorus leaching. To address these limitations, this work combined the high efficiency of thermal treatment with phosphate stabilization to elucidate the structural incorporation and immobilization mechanism of Pb in soil. The thermal-enhanced phosphate strategy proved to be highly effective for the long-term stabilization of high-Pb contaminated soils. Investigations into the impacts of amendment type, dosage, and temperature revealed that potassium-based phosphate exhibits improved phosphorus (P) retention at elevated temperatures in addition to Pb stabilization; however, excessive phosphate addition can compromise performance by inducing structural reorganization and elevating P mobility. In multi-metal co-contaminated systems, thermally enhanced phosphate treatment exhibited significantly higher stabilization efficacy for Pb than for Zn and Cd, attributed to the exceptionally high affinity of phosphate for Pb ions during the thermal process. Speciation analysis revealed a significant transformation of all three metals (Pb, Zn and Cd) from labile acid-soluble and reducible fractions to the stable residual fraction following treatment. Structural and surface analyses reveal that the thermal reconstruction of the soil matrix induces divergent distribution behaviors for the metals. Pb and Cd are prone to incorporation via phosphate-mediated co-precipitation, whereas Zn preferentially binds to silicate matrices. These findings offer a scientific foundation for establishing high-efficiency strategies utilizing thermally enhanced phosphate stabilization for both the remediation and safe reuse of Pb-contaminated soils.
Efficient capture of radioactive iodine isotopes from nuclear waste is crucial for environmental protection and human health. In this study, a high-entropy strategy was introduced into the zeolitic imidazolate framework-8 (ZIF-8) system to overcome the inherent limitations of conventional monometallic ZIF-8 and to elucidate entropy-regulated iodine capture behavior. Using a solvothermal method assisted by triethylamine (TEA), a series of ZIF-8 derivatives with entropy levels ranging from low to high were successfully synthesized to explore the relationship between entropy level and iodine adsorption performance. Furthermore, given that Cd incorporation has been reported to enhance the structural flexibility of ZIF-8, the influence of different Zn/Cd ratios was investigated. Characterization results showed that although TEA enhanced the doping efficiency of poorly coordinating metal ions, it simultaneously reduced crystallinity and BET surface area, leading to pore blockage and a substantial decline in iodine adsorption performance. Iodine adsorption did not show a positive correlation with increasing compositional complexity. The synergistic effects of multimetal nodes did not improve the iodine uptake capacity of ZIF-8, and the high-entropy ZnCdCoMgNi-ZIF-8 exhibited the lowest iodine uptake capacity (1.10 g⋅g-1). In contrast, Cd doping increased the iodine uptake capacity to 2.80 g g-1 in phase-pure Cd-ZIF-8, corresponding to a 2.2-fold enhancement over conventional ZIF-8. Moreover, a structural phase transition was induced during iodine adsorption in Cd-rich systems. This work provides important insights into the design of high-performance iodine capture materials and highlights the potential of cadmium-modified ZIF-8 derivatives as promising adsorbents.
Radioactive cesium released from nuclear activities poses persistent threats to ecosystems and human health, necessitating low cost and highly efficient remediation techniques such as adsorption process. Machine learning has been considered to be a powerful tool to guide the design of novel adsorbents. This study developed a robust predictive framework by optimizing XGBoost, LightGBM, CatBoost, and Random Forest using Bayesian optimization and five-fold cross-validation. In addition, two Stacking ensemble strategies with Ridge and ElasticNet were developed to be meta-learners to compensate for the prediction errors of individual base models. It was found that the Stacking ensemble could substantially enhance the predictive performance, with the Ridge meta-model achieving the best outcomes, yielding a coefficient of determination (R2) of 0.9761 and a root-mean-square error (RMSE) of 10.9208, outperforming all base learners. SHAP analysis reveals that Stacking leverages the complementary strengths of individual base learners. This study implements a Stacking-based transfer learning strategy that addresses the prediction accuracy bottleneck for novel adsorbent systems under limited data, offering predictive support for the rational design of advanced cesium adsorbents with both scientific and practical value.
As human society enters the era of information explosion, the demand for brain-like energy-efficient parallel operation systems has bolstered the development of hardware devices with functionally integrated capabilities. In this work, we present a Mo/Ga2O3 (oxygen-rich)/Ga2O3 (oxygen-deficient)/W device with integrated rectifying, memory, and biomimicry functions. The as-fabricated device shows a good rectifying characteristic with a rectification ratio of 108, which is attributed to the synergistic effects of the Mo/Ga2O3 Schottky barrier and the interfacial barrier formed within the Ga2O3 homojunction. After being electrically triggered by a reverse voltage, the device spontaneously switches from the rectifying mode to the resistive switching characteristics, which can emulate multiple synaptic functions such as potentiation and depression processes of synaptic weights. Moreover, the memristive device is capable of displaying nociceptor-like responses, and typical sensitization behaviors of nociceptors are vividly reproduced. This work offers an alternative solution for functionally versatile devices based on an ultrawide bandgap semiconductor for next-generation integrated intelligence applications.
Perovskites CaMnO3-delta with defects have been extensively investigated as thermochemical energy storage (TCES) materials. However, their high temperature stability is limited by decomposition into CaMn2O4, a predominant oxide found in the Ca-Mn-O phase diagram. To expand the scopes of TCES materials, we aim to explore whether CaMn2O4 exhibits similar structural defects and whether these defects can enhance TCES performance. The findings revealed that Ca(1-x)Mn2O4-delta exhibits a degree of solid solubility, forming a single-phase region within x = 0-0.15 and resulting in a decrease in lattice parameters. Structural characterization techniques, including XRD, Raman and XANES, further examine the cation defects and oxygen vacancies in the lattice structure and the corresponding local structural variations. The variations in local environments led to varying redox reaction properties. These findings highlight the potential of defects-bearing Ca0.95Mn2O4-delta as a thermally stable material for thermal energy storage applications.
Radioactive strontium (Sr2+) and cobalt (Co2+) in nuclear wastewater pose significant environmental risks, leading the need of developing effective remediation strategies. In this study, a poly (triazine imide) (PTI) composite intercalated with bromide (Br-), referred to as PTI/LiBr, synthesized via a molten salt method, is introduced as a novel adsorbent for the removals of Sr2+ and Co2+. PTI/LiBr composite exhibited rapid adsorption and high efficiency for both radionuclides, driven by electrostatic interactions and partial exchange of Li+ ions. The removal efficiency for Sr2+ and Co2+ exceeded 95 % within 30 min. Adsorption kinetics followed a pseudo-second-order model, while isotherm analysis indicated that Sr2+ adsorption aligned with the Freundlich model and Co2+ adsorption followed the Langmuir model. The adsorption process was confirmed to be spontaneous and endothermic. The gamma-radiation tolerance tests verified the structural stability and high adsorption efficiency of the material under ionizing radiation conditions. Additionally, DFT-based wave function and charge density analyses showed a stronger and more stable interaction between PTI/LiBr and Co2+ compared to Sr2+, which might be driven by favorable magnetic interactions and significant charge transfer. This study highlights the potential of PTI/LiBr as a robust and efficient adsorbent for mitigating radioactive pollutants in complex aqueous environments.
The efficacy of VIR-7831, a class 3 anti-SARS-CoV-2 monoclonal antibody (mAb), was demonstrated repeatedly in clinical trials; yet, reduced neutralization against Omicron variants in cell-line-based neutralization assays led to its withdrawal from clinical use. We developed organoid-based neutralization assays to measure mAb potency. We found that most class 3 mAbs, especially those not blocking receptor-binding domain-ACE2 binding, including VIR-7831, were substantially underestimated in cell-line-based assays. Nasal organoids adequately recapitulated the real-world effectiveness of VIR-7831 because of biologically relevant low ACE2 expression, and exclusively reproduced the in vivo protection of S2 mAbs due to the high TMPRSS2 expression, reminiscent of native human respiratory epithelial cells. Collectively, the robust organoid culture system and biologically relevant expression profiles of ACE2 and TMPRSS2 make nasal organoids present a correlate of in vivo protection of neutralizing mAbs exclusively. The organoid-based neutralization assays, superior to conventional cell-line-based assays, can recapitulate and predict the real-world efficacy of mAbs.
In recent years, increasing evidence has shown that metals play important roles in both innate and adaptive immunity. An emerging concept of metalloimmunotherapy has been proposed, which may accelerate the development of immunotherapy for cancers. Here, we discuss how metals affect T cell function through different signaling pathways. Metals impact the fate of T cells, including their activation, proliferation, cytotoxicity, and differentiation. Most importantly, metals also participate in mitochondrial operation by regulating energy production and reactive oxygen species homeostasis in T cells. We also identified the metal-based mutual effects between tumor cells and T cells in the tumor microenvironment. Overall, the antitumor effect of T cells can be improved by targeting metal metabolism and metalloimmunotherapy, which will be a step forward in the treatment of cancers.
The extraction of uranium (U) from wastewater is of vital importance for ensuring the sustainable and safe development of nuclear energy, as it addresses both environmental protection and resource recycling. Vanadium (V) and its compounds are extensively employed in iron and steel manufacturing, and their utility in pollutant remediation further promotes the circular use of V-bearing materials. However, studies on utilizing inexpensive and readily available vanadium oxides (e.g., V2O5) for the treatment of highly acidic uranium-containing wastewater remain scarce. This study investigated the effectiveness of V2O5 in removing U(VI) and immobilizing it into crystalline uranyl vanadates, providing the first confirmation of the feasibility of using V2O5 for uranium elimination and capture. The results indicate that V2O5 exhibits excellent extraction capacity and selectivity for uranyl ions in contaminated solutions, achieving a U(VI) extraction efficiency exceeding 97 % even under highly acidic conditions (e.g., pH = 2.0). Adsorption equilibrium was attained within 240 min, and kinetic studies combined with model fitting indicated that the process was governed by both intra-particle diffusion and chemical adsorption mechanisms. It was discovered that the captured U(VI) was ultimately incorporated into a stable crystalline phase, identified as uvanite (U2V6O21·15H2O), through a coprecipitation pathway, revealing a novel crystallization mechanism. The overall immobilization process was attributed to the synergistic effects of chemical adsorption and coprecipitation. These findings support the development of vanadium oxide-based technologies for U(VI) purification and recovery from complex wastewater.
Polluted environments often contain large amounts of toxic metals, such as cadmium, which pose a major threat to ecosystems and public health. Contamination by cadmium and its compounds is often observed in areas surrounding zinc mining sites and electroplating factories, and the control of cadmium pollution is essential for environmental safety and health. In this study, a highly efficient and straightforward separation strategy for K 4 Fe (CN) 6 @Fe 3 O 4 nanocomposites is successfully developed to capture the Cd ions in the water environment. Batch adsorption experiments revealed that K 4 Fe(CN) 6 @Fe 3 O 4 exhibited a high cadmium removal rate (greater than 98 %) at a pH level of 6.0 and solid-liquid ratio of 1.0 g/L at room temperature (298 K). Kinetic analysis revealed that the adsorption process followed a pseudo-second-order model and cadmium was rapidly removed in the first 10 min, with chemisorption dominating the capture of Cd 2+ by K 4 Fe(CN) 6 @Fe 3 O 4 . Adsorption isotherms revealed a heterogeneous adsorption behavior, with a maximum adsorption capacity of 40.78 mg/g. The intrinsic adsorption of Cd 2+ by K 4 Fe(CN) 6 @Fe 3 O 4 occurring primarily through electrostatic interaction and ion exchange. In addition, K 4 Fe(CN) 6 @Fe 3 O 4 exhibited an excellent regeneration capacity. Therefore, integrating Fe 3 O 4 into the metal cyanide not only provided the composite material with excellent chemical stability and selective adsorption sites for Cd 2+ , but also facilitated subsequent sorbent collection and recovery. Overall, this study presents a simple and feasible approach for integrating Fe 3 O 4 into potassium ferrocyanide frameworks for efficient cadmium removal from contaminated water.
The growing demand for upgraded electronic products has resulted in a significant amount of waste batteries. In this paper, we propose a low-carbon, scalable mechanochemical waste-to-value strategy to convert spent ZnO from alkaline batteries into Zn-MOF-74, a functional metal-organic framework (MOF), for CO2 capture. The conversion pathway of ZnO-to-MOF-74 was investigated via structural characterization techniques. Compared with commercial ZnO with a hexagonal prism-like morphology, spent ZnO, exhibiting a rod-shaped morphology, demonstrated greater readiness in transforming into Zn-MOF-74, completing the transformation in nearly 5 h via ball milling and reducing energy consumption by around 50%. Moreover, the CO2 adsorption capacity of ZnMOF-74 synthesized using spent ZnO, which is 2.07 mmol/g (at 273 K), is nearly triple that synthesized from commercial ZnO that has a hexagonal prism-shaped morphology. Overall, this study highlights the potential of repurposing spent ZnO in waste valorization, thereby significantly contributing to the advancement of a circular economy.
Zeolitic imidazolate framework-8 (ZIF-8) exhibits excellent performance in capturing iodine. However, the solvent-based procedures and raw materials for ZIF-8 synthesis often lead to secondary pollution. We developed a solvent-minimizing method for preparing ZIF-8 via ball milling of raw material obtained from spent alkaline batteries, and studied its iodine-capture performance and structural changes. Exposure of the ZIF-8 to iodine vapor for 60 min demonstrated that it exhibited industrially competitive iodine-capture performance (the adsorbed amount reaches to 1123 mg g-1 within 60 min). Spectroscopic studies showed that ZIF-8 underwent a structural transformation upon iodine loading. Iodine molecules were adsorbed onto the surface of ZIF-8 and also formed C-I bond with the methyl groups on the imidazole rings, reducing iodine release. This work represents a comprehensive revelation of long-range order and short-range order evolution of ZIF-8 during iodine vapor adsorption over time. Moreover, this green synthesis of ZIF-8 is of lower cost and generates fewer harmful byproducts than existing methods, and the produced ZIF-8 effectively entraps toxic iodine vapor. Thus, this synthesis enables a sustainable and circular material flow for beneficial utilization of waste materials.
The COVID-19 pandemic caused by SARS-CoV-2 resulted in a global public health crisis. In addition to vaccines, the development of effective therapy is highly desirable. Targeting a protein that plays a critical role in virus replication may allow pan-spectrum antiviral drugs to be developed. Among SARS-CoV-2 proteins, helicase (i.e., non-structural protein 13) is considered as a promising antiviral drug target due to its highly conserved sequence, unique structure and function. Herein, we demonstrate SARS-CoV-2 helicase as a target of bismuth-based antivirals in virus-infected mammalian cells by a metal-tagged antibody approach. To search for more potent bismuth-based antivirals, we further screened a panel of bismuth compounds towards inhibition of ATPase and DNA unwinding activity of nsp13 and identified a highly potent bismuth compound Bi(5-aminotropolonate)3, namely Bi(Tro-NH2)3 with an IC50 of 30 nM for ATPase. We show that bismuth-based compounds inhibited nsp13 unwinding activity via disrupting the binding of ATP and the DNA substrate to viral helicase. Binding of Bi(iii) to nsp13 also abolished the interaction between nsp12 and nsp13 as evidenced by immunofluorescence and co-immunoprecipitation assays. Finally, we validate our in vitro data in SARS-CoV-2 infected mammalian cells. Notably, Bi(6-TG)3 exhibited an EC50 of 1.18 ± 0.09 μM with a selective index of 847 in VeroE6-TMPRSS2 infected cells. This study highlights the important role of helicase for the development of more effective antiviral drugs to combat SARS-CoV-2 infection.
Metals are essential for human health and play a crucial role in numerous biological processes and pathways. Gaining a deeper insight into these biological events will facilitate novel strategies for disease prevention, early detection, and personalized treatment. In recent years, there has been significant progress in the development of metal-detection based techniques from single cell metallome and proteome profiling to multiplex imaging, which greatly enhance our comprehension of the intricate roles played by metals in complex biological systems. This perspective summarizes the recent progress in advanced metal-detection based techniques and highlights successful applications in elucidating the roles of metals in biology and medicine. Technologies including machine learning that couple with single-cell analysis such as mass cytometry and their application in metallobiology, cancer biology and immunology are also emphasized. Finally, we provide insights into future prospects and challenges involved in metal-detection based techniques, with the aim of inspiring further methodological advancements and applications that are accessible to chemists, biologists, and clinicians.
The rapid pace of technology advancement has quickly depleted valuable rare earth elements (REEs), which are critical for the function and performance of electric and electronic components, and there is thus a need for REE extraction from secondary sources rather than from virgin mines. This study presents an approach involving the ball-milling-induced construction of zeolitic imidazolate framework-8 (ZIF-8) that integrates REE extraction and recovery processes. ZIF-8 demonstrates remarkable extraction capacities for various REEs, and notably promotes nanoscaled CeO2 formation. Ball-milling-prepared ZIF-8 (ZIF-8-BM) effectively concentrates cerium (III) ions (CeIII), and a purity of 99.34% is achieved by controlling the processing parameters, offering a comprehensive solution for efficient Ce retrieval from water. The superior Ce extraction performance is attributed to the greater numbers of structural defects and surface hydroxyl (-OH) groups and the enhanced phase transformation efficiency. Moreover, Ce extraction by ZIF-8-BM is found to be efficient in both low and high Ce concentration ranges. ZIF-8-BM nanoparticles spontaneously oxidize Ce III in solution to insoluble CeO2, thereby facilitating the efficient extraction and subsequent recovery of cerium from complex matrices. The findings of this study provide an environmentally benign approach for the safe and efficient recovery of REEs from waste streams, supported by a scientifically sound and economically feasible processing strategy.
Stabilizing heavy metals (HMs) in sewage sludge is urgently needed to facilitate its recycling and reuse. Pyrolysis stands out as a promising method for not only stabilizing these metals but also producing biochar. Our research delves into the migration and transformation of specific HMs (Cr, Mn, Ni, Cu, Zn, As, and Pb) during co-pyrolysis under various conditions, including the presence and absence of microplastics (PVC and PET). We examined different concentrations of these plastics (1 %, 5 %, 10 %, and 15 %) and temperatures (300 °C, 500 °C, and 700 °C). Findings reveal that microplastics, particularly PVC, enhance the migration of Zn and Mn, leading to significant volatilization of Zn and Pb at higher temperatures, peaking at 700 °C. The increase in temperature also markedly influences HM migration, with As showcasing notable loss rates that climbed by 18.0 % and 16.3 % in systems with PET and PVC, respectively, as temperatures soared from 300 °C to 700 °C. Moreover, our speciation analysis indicates that microplastics aid in transforming certain HMs from unstable to more stable forms, suggesting their beneficial role in HM stabilization during pyrolysis. This study significantly enriches our understanding of microplastics’ impact on HM behavior in sewage sludge pyrolysis, offering new avenues for pollution control and environmental management strategies.
Arsenic (As) contamination in water remains a formidable concern due to its high toxicity and detrimental impacts on human health and the environment. Selective adsorption utilizing solid adsorbents has emerged as a promising method for the removal of arsenate (As(V)) from drinking water. However, current adsorbents encounter limitations in effectively reducing relatively low-concentration As(V) from water. Here, we designed a Fe-Ti heteroatom-based metal-organic framework (MOF) MIL-125(Ti,Fe) with vantage defects for efficient As(V) removal. In the batch adsorption experiments, MIL-125(Ti,Fe) exhibited an exceptional removal efficiency of 99.3 % from the 10 ppm As(V)-containing water, which clearly overperformed counterpart MOF adsorbents of MIL-125(Ti) and MIL-101(Fe). Kinetic analysis indicated that the adsorption behavior of all three adsorbents followed pseudo-second-order kinetics. Importantly, dynamic breakthrough experiments demonstrated that MIL125(Ti,Fe) could effectively reduce the As(V) concentration from 1 ppm to 3 ppb, well below the safety limit of 10 ppb set by WHO. Mechanistic analysis revealed that the arsenic adsorption mechanism of MIL-125(Ti,Fe) involved chemical adsorption between As(V) and the incorporated Fe as well as formed oxygen vacancies in MIL-125(Ti,Fe), which acted as essential adsorption sites and interacted with As(V) through the formation of FeO-As groups. The novel MIL-125(Ti,Fe) adsorbent demonstrated its great potential for arsenic removal, particularly in treating relatively low-concentration As-contaminated water.
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