Recent Progress on the Adsorption of Heavy Metal Ions Pb(II) and Cu(II) from Wastewater.

With the processes of industrialization and urbanization, heavy metal ion pollution has become a thorny problem in water systems. Among the various technologies developed for the removal of heavy metal ions, the adsorption method is widely studied by researchers and various nanomaterials with good adsorption performances have been prepared during the past decades. In this paper, a variety of novel nanomaterials with excellent adsorption performances for Pb(II) and Cu(II) reported in recent years are reviewed, such as carbon-based materials, clay mineral materials, zero-valent iron and their derivatives, MOFs, nanocomposites, etc. The novel nanomaterials with extremely high adsorption capacity, selectivity and particular nanostructures are summarized and introduced, along with their advantages and disadvantages. And, some future research priorities for the treatment of wastewater are also prospected.

Intrinsically Decoupled Coordination Chemistries Enable Quasi-Eutectic Electrolytes with Fast Kinetics toward Enhanced Zinc-Ion Capacitors.

Eutectic electrolytes show potential beyond conventional low-concentration electrolytes (LCEs) in zinc (Zn)-ion capacitors (ZICs) yet suffer from high viscosity and sluggish kinetics. Herein, we originally develop an intrinsically decoupling strategy to address these issues, producing a novel electrolyte termed "quasi-eutectic" electrolyte (quasi-EE). Joint experimental and theoretical analyses confirm its unique solution coordination structure doped with near-LCE domains. This enables the quasi-EE well inherit the advanced properties at deep-eutectic states while provide facilitated kinetics as well as lower energy barriers via a vehicle/hopping-hybridized charge transfer mechanism. Consequently, a homogeneous electroplating pattern with much enhanced Sandꞌs time is achieved on the Zn surface, followed by a twofold prolonged service-life with drastically reduced concentration polarization. More encouragingly, the quasi-EE also delivers increased capacitance output in ZICs, which is elevated by 12.4%-144.6% compared to that before decoupling. Furthermore, the pouch cell with a cathodic mass loading of 36.6 mg cm-2 maintains competitive cycling performances over 600 cycles, far exceeding other Zn-based counterparts. This work offers fresh insights into eutectic decoupling and beyond.

Halloysite-derived mesoporous silica with high ionic conductivity improves Li-S battery performance.

The slow Li+ transport rate in the thick sulfur cathode of the Li-S battery affects its capacity and cycling performance. Herein, Fe-doped highly ordered mesoporous silica material (Fe-HSBA-15) as a sulfur carrier of the Li-S battery shows high ion conductivity (1.10 mS cm-1) and Li+ transference number (0.77). The Fe-HSBA-15/S cell has an initial capacity of up to 1216.7 mA h g-1 at 0.2C and good stability. Impressively, at a high sulfur load of 4.34 mg cm-2, the Fe-HSBA-15/S cell still maintains an area specific capacity of 4.47 mA h cm-2 after 100 cycles. This is because Fe-HSBA-15 improves the Li+ diffusion behavior through the ordered mesoporous structure. Theoretical calculations also confirmed that the doping of iron enhances the adsorption of polysulfides, reduces the band gap and makes the catalytic activity stronger.

Integrating Structural and Thermodynamic Mechanisms for Methanol Intercalated Kaolinite Nanoclay: Experiments and Density Functional Theory Simulation.

Methanol intercalated kaolinite (Kaol) plays an important role in the intercalation, exfoliation, and organic modification of kaolinite nanoclay. However, the evolution of the layer structure of Kaol and its thermodynamic stability during the methanol intercalation process have not been clarified at the atomic level. Here, by combination of density functional theory (DFT) calculation and experimental characterizations, the interlayer bonding, structure evolution, and energetics from dimethyl sulfoxide (DMSO) intercalated Kaol to methanol intercalated Kaol were investigated. Partial methanol molecules entered the interlayers of Kaol to form some intermediate structures with the same d-spacing as that of DMSO intercalated Kaol. Different numbers of grafted methoxy and water molecules coexist together in the interlayer to form the final structures of methanol intercalated kaolinite (MeOm/nH2O/Kaol). The whole intercalation process is energy-consuming, and the presence of DMSO would affect the intercalation of methanol. Meanwhile, the formation energy from intermediate structures to final structures was found reduced under the participation of water.

Nanoclay-Modulated Interfacial Chemical Bond and Internal Electric Field at the Co3 O4 /TiO2 p-n Junction for Efficient Charge Separation.

To achieve a high separation efficiency of photogenerated carriers in semiconductors, constructing high-quality heterogeneous interfaces as charge flow highways is critical and challenging. This study successfully demonstrates an interfacial chemical bond and internal electric field (IEF) simultaneously modulated 0D/0D/1D-Co3 O4 /TiO2 /sepiolite composite catalyst by exploiting sepiolite surface-interfacial interactions to adjust the Co2+ /Co3+ ratio at the Co3 O4 /TiO2 heterointerface. In situ irradiation X-ray photoelectron spectroscopy and density functional theory (DFT) calculations reveal that the interfacial Co2+ OTi bond (compared to the Co3+ OTi bond) plays a major role as an atomic-level charge transport channel at the p-n junction. Co2+ /Co3+ ratio increase also enhances the IEF intensity. Therefore, the enhanced IEF cooperates with the interfacial Co2+ OTi bond to enhance the photoelectron separation and migration efficiency. A coupled photocatalysis-peroxymonosulfate activation system is used to evaluate the catalytic activity of Co3 O4 /TiO2 /sepiolite. Furthermore, this work demonstrates how efficiently separated photoelectrons facilitate the synergy between photocatalysis and peroxymonosulfate activation to achieve deep pollutant degradation and reduce its ecotoxicity. This study presents a new strategy for constructing high-quality heterogeneous interfaces by consciously modulating interfacial chemical bonds and IEF, and the strategy is expected to extend to this class of spinel-structured semiconductors.

Interfacial Chemical Bond Modulation of Co3(PO4)2-MoO3-x Heterostructures for Alkaline Water/Seawater Splitting.

The development of a high current density with high energy conversion efficiency electrocatalyst is vital for large-scale industrial application of alkaline water splitting, particularly seawater splitting. Herein, we design a self-supporting Co3(PO4)2-MoO3-x/CoMoO4/NF superaerophobic electrode with a three-dimensional structure for high-performance hydrogen evolution reaction (HER) by a reasonable devise of possible "Co-O-Mo hybridization" on the interface. The "Co-O-Mo hybridization" interfaces induce charge transfer and generation of fresh oxygen vacancy active sites. Consequently, the unique heterostructures greatly facilitate the dissociation process of H2O molecules and enable efficient hydrogen spillover, leading to excellent HER performance with ultralow overpotentials (76 and 130 mV at 100 and 500 mA cm-2) and long-term durability of 100 h in an alkaline electrolyte. Theoretical calculations reveal that the Co3(PO4)2-MoO3-x/CoMoO4/NF promotes the adsorption/dissociation process of H2O molecules to play a crucial role in improving the stability and activity of HER. Our results exhibit that the HER activity of non-noble metal electrocatalysts can be greatly enhanced by rational interfacial chemical bonding to modulate the heterostructures.

Expression and Analyses of CXCL9/10/11 and CXCR3 in Ulcerative Cutaneous Tuberculosis.

We explored the biological functions, signaling pathways, potential inflammation, and immune biomarkers involved in ulcerative cutaneous tuberculosis (UCT). Mycobacterium tuberculosis-infected tissues from UCT patients and patients with noncutaneous tuberculous ulcers (NCTUs) were studied using transcriptomic analysis. Functional enrichment determined using the Gene Ontology database and enrichment of signaling pathways was ascertained using the Kyoto Encyclopedia of Genes and Genomes database. Protein-protein interaction (PPI) networks were analyzed to determine the hub genes. A total of 4,396 differentially expressed genes (DEGs) were identified. DEGs were enriched in CXCR3 chemokine receptor binding, chemokine activity, and cytokine-cytokine receptor interaction and other aspects. Analyses of PPI networks identified 15 hub genes. Expression of chemokine (C-X-C motif) ligand 9 (CXCL9)/10/11 messenger RNA (mRNA) and C-X-C motif chemokine receptor 3 (CXCR3) mRNA in the lesions of patients with UCT increased compared with that in NCTU cases. Expression of CXCL9 mRNA and CXCL10 mRNA in plasma also increased, which was consistent with other test results. We discovered a novel plasma CXC chemokine signature that could be used to differentiate UCT from NCTU. Our study (1) provides a reference for UCT diagnosis and selection of diagnostic markers and (2) lays the foundation for further elucidation of UCT pathogenesis.

Contrasting Photochemical Activity of Two Sub-layers for Natural 2D Nanoclay with an Asymmetric Layer Structure.

The two-dimensional (2D) materials with asymmetric sub-layers have recently attracted tremendous interest in many fields, and investigating the structure-performance relationship of different sub-layers is critical but challenging. Herein, we report that natural kaolinite (Kaol) nanosheets with an asymmetric layer structure possess a contrasting photocatalytic activity on its Al-O and Si-O sub-layers. The experimental and theoretical results reveal that the ion isovalent structure of Fe3+ and Al3+ not only results in a high iron doping concentration in the Al-O sub-layer but also causes superb intrinsic photochemical activity of the Al-O sub-layer compared with the Si-O sub-layer. Thus, the Al-O sub-layers of Kaol NSs have more excellent photogenerated charge generation and separation efficiency than Si-O sub-layers, resulting in about 1-2 orders of magnitude higher photocatalytic performance. This study not only unravels the structure-performance relationship of different sub-layers of 2D nanoclay but also sheds new light on the design of 2D materials with the asymmetric sub-layer.

Energetics, Interlayer Molecular Structures, and Hydration Mechanisms of Dimethyl Sulfoxide (DMSO)-Kaolinite Nanoclay Guest-Host Interactions.

Two-dimensional (2D) kaolinite nanoclay is an important natural mineral with promising application potential, especially tuned with organic intercalates. However, thus far, the organics-kaolinite guest-host interactions, the atomic scale structures of organic intercalates under confinement, and molecular level mechanisms of hydration are rarely systematically explored using both experimental and computational methodologies. We integrated density functional theory with dispersion scheme (DFT-D) with various experimental methods to investigate the intercalation of dimethyl sulfoxide (DMSO) in kaolinite with and without hydration. The kinetic, thermodynamic, and structural impacts of hydration were highlighted. In short, water molecules significantly promote intercalation of DMSO into kaolinite because of favorable intercalation energy, which is enabled by effective hydrogen bonding at the guest species (DMSO and water)-kaolinite interfaces.

Surface modified halloysite nanotubes with different lumen diameters as drug carriers for cancer therapy.

Paclitaxel (PTX) is successfully loaded by surface modification of distearoyl phosphoethanolamine (DSPE) on halloysite nanotubes (HNTs) with different inner lumen diameters. Drug loading of DSPE-HNTs-PTX attains 18.44% of DSPE content with a nearly complete release (near 100%) achieved. The anticancer efficacy (cell viability less than 52%) of DSPE-HNTs15-PTX increased and is attributed to the lower interfacial energy both inside and outside the tubes that improves tube loading.

Utilization of iron tailings to prepare high-surface area mesoporous silica materials.

Iron tailings are fine, stable and complex materials, which are mainly composed of minerals and metal oxides. Residual silicon in iron tailings can be used to prepare mesoporous silica materials applied to energy storage, environmental protection and other fields. This paper reported a novel synthesis strategy from iron tailings to high-surface area hexagonally ordered mesoporous silica materials in an innovative non-hydrothermal system at room temperature. A pretreatment process involving acid leaching and hydrothermal alkaline reaction was vital to the successful utilization of iron tailings. X-ray fluorescence (XRF) data suggested that about 95% of the silicon of iron tailings changed to the silicate as a silicon source. The samples were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), N2-adsorption-desorption isotherms, Fourier transform infrared (FTIR) spectroscopy, Thermogravimetry and differential scanning calorimetry (TG-DSC) and 29Si solid-state nuclear magnetic resonance (NMR) spectroscopy. The SAXRD patterns of mesoporous silica materials exhibited an intense (100) diffraction peak and two weak (110, 200) diffraction peaks, corresponding to characteristic of the ordered mesoporous lattice. TEM images further confirmed the hexagonally ordered porous structure of mesoporous silica materials. The WAXRD patterns and 29Si MAS NMR spectra of the samples indicated that mesoporous silica materials were composed of amorphous SiO2. The obtained mesoporous silica materials had a high surface area of 1915 m2/g and pore volume of 1.32 cm3/g. Furthermore, the evolution from iron tailings to mesoporous silica materials was elucidated and a proposed synthesis mechanism was discussed. Collectively, these results provided an insight into efficient recycling of iron tailings and the production of advanced functional materials from solid waste.

Energetic Cost for Being "Redox-Site-Rich" in Pseudocapacitive Energy Storage with Nickel-Aluminum Layered Double Hydroxide Materials.

Defining the energetic landscape of pseudocapacitive materials such as transition metal layered double hydroxides (LDHs) upon redox-site enrichment is essential to harnessing their power for effective energy storage. Here, coupling acid solution calorimetry, in situ XRD, and in situ DRIFTS, we demonstrate that as the Ni/Al ratio increases, both as-made (hydrated) and dehydrated NiAl-LDH samples are less stable as evidenced by their enthalpies of formation. Moreover, the higher specific capacity at an intermediate Ni/Al ratio of 3 is enabled by effective water-LDH interactions, which energetically stabilize the excessive near-surface Ni redox sites, solvate intercalated carbonate ions, and fill the expanded vdW gap, paying for the "energetic cost" of being "redox-site-rich". Thus, from a thermodynamic perspective, engineering molecule/solid-LDH interactions on the nanoscale with confined guest species other than water, which energetically impose stronger stabilization, may help us to achieve their specific capacitance potential.

Interfacial Chemical-Bond-Modulated Charge Transfer of Heterostructures for Improving Photocatalytic Performance.

Interface engineering of heterostructured photocatalysts plays a very important role in the transfer and separation process of interfacial charge carriers, but how to regulate the transfer and separation of photogenerated charge carriers still is a huge challenge at the nanometric interface of heterostructures (HCs). Herein, we demonstrate that interfacial chemical bonds can effectively modulate photogenerated charge transfer in nanoclay-based HCs constructed by natural Kaolinite (Kaol) nanosheets and P25-TiO2. Experimental results and density functional theory (DFT) calculations confirm that stable Al-O-Ti bonds form at the interfaces by interactions of the Al-OH groups of Kaol and (101) surfaces of anatase TiO2. The Al-O-Ti bond strengthens the energy band bending of the space charge region near the interfacial bond and thus provides a fast transfer channel for interfacial photogenerated charge, resulting in the boosted charge transfer and separation ability of Kaol/P25 HCs. The findings reported here provide a deeper insight into modulating interfacial charge transfer by chemical bonds and shed new light on interface engineering of efficient heterostructured photocatalysts for environmental applications.

Triptonide inhibits metastasis potential of thyroid cancer cells via astrocyte elevated gene-1.

BACKGROUND: Triptonide (TN) was recently proved to have anti-tumor effects. The current study explored whether TN inhibited thyroid cancer and the possible underlying mechanism. METHODS: MDA-T68 and BCPAP cells were treated by TN. Cell viability, migration and invasion rate were detected by MTT and Transwell. Protein expressions were determined by Western blot and mRNA expressions were detected by Real-time Quantitative PCR (qPCR). RESULTS: TN at the concentration higher than 50 nmol/L inhibited cell viability, migration and invasion of MDA-T68 and BCPAP cells, and astrocyte elevated gene (AEG-1) expression, was decreased by TN at the concentration higher than 50 nmol/L. Furthermore, AEG-1 overexpression inhibited cell viability, migration and invasion capacity of MDA-T68 and BCPAP cells, while TN reduced AEG-1 expression, and weaken the effect of AEG-1 overexpression on cell viability, migration and invasion capacities. Moreover, TN depressed the increase of matrix metalloproteinase (MMP) 2, MMP9 and N-cadherin expressions caused by AEG-1 overexpression. Meanwhile, E-cadherin expression reduced by AEG-1 overexpression was increased by TN. CONCLUSIONS: TN could inhibit the metastasis potential of thyroid cancer cells through inhibiting the expression of AEG-1. Our findings reveal the mechanism of TN in the treatment of thyroid cancer, which should be further explored in the study of thyroid cancer. KEYWORDS: Triptonide; metastasis; thyroid cancer; regulation; drug monomer.

Amino-functionalized hierarchical porous SiO2-AlOOH composite nanosheets with enhanced adsorption performance.

Hierarchical porous SiO2-AlOOH composite nanosheets (HPSA) with a three-dimensional (3D) structure were prepared from two-dimensional (2D) layered mineral kaolinite (A12Si2O5(OH)4) via a template-free structural reorganization method. The obtained material was subjected to homogeneous and effective amino-functionalization by grafting it with (3-aminopropyl) triethoxysilane. Owing to the enhanced 3D hierarchical meso-macroporous structure containing highly dispersed protonated amino groups (NH3+), the as-prepared amino-functionalized HPSA (NH2-HPSA) showed unique adsorption performance towards the congo red anionic dye. It provides feasibilities to fabricate other functional hierarchical porous materials from clay minerals, which can offer potential applications in adsorption, separation, catalysis and other environmental remediation fields.

Seeding Iron Trifluoride Nanoparticles on Reduced Graphite Oxide for Lithium-Ion Batteries with Enhanced Loading and Stability.

Development of electric vehicles and portable electronic devices during the past decade calls for lithium-ion batteries (LIBs) with enhanced energy density and higher stability. Integration of FeF3 phases and carbon structures leads to promising cathode materials for LIBs with high voltage, capacity, and power. In this study, FeF3·0.33H2O nanoparticles were synthesized on reduced graphite oxide (rGO) nanosheets using an in situ approach. By chemically tuning the interfacial bonding between FeF3·0.33H2O and rGO, we successfully achieved high particle loading and enhanced cycling stability. Specifically, a discharge capacity of ∼208.3 mAh g-1 was observed at a current density of 0.5 C. The FeF3·0.33H2O/rGO nanocomposites also demonstrate great cycle capability with a reversible discharge capacity of 133.1 mAh g-1 after 100 cycles at 100 mA g-1; the capacity retention is about 97%. This study provides an alternative strategy to further improve the stability and performance of iron fluoride/carbon nanocomposite materials for LIB applications.

A nanoclay-induced defective g-C3N4 photocatalyst for highly efficient catalytic reactions.

A nanoclay-induced defective graphitic carbon nitride (g-C3N4) catalyst was successfully synthesized through intercalation and in situ calcination. The degradation time for Orange II dye using the as-synthesized g-C3N4/kaolinite (g-C3N4/Kaol) catalyst was only 10 min under visible light irradiation, which could be attributed to their special structures and synergistic effects.

Substitutional Doping for Aluminosilicate Mineral and Superior Water Splitting Performance.

Substitutional doping is a strategy in which atomic impurities are optionally added to a host material to promote its properties, while the geometric and electronic structure evolution of natural nanoclay mineral upon substitutional metal doping is still ambiguous. This paper first designed an efficient lanthanum (La) doping strategy for nanotubular clay (halloysite nanotube, HNT) through the dynamic equilibrium of a substitutional atom in the presence of saturated AlCl3 solution, and systematic characterization of the samples was performed. Further density functional theory (DFT) calculations were carried out to reveal the geometric and electronic structure evolution upon metal doping, as well as to verify the atom-level effect of the La doping. The CdS loading and its corresponding water splitting performance could demonstrate the effect of La doping. CdS nanoparticles (11 wt.%) were uniformly deposited on the surface of La-doped halloysite nanotube (La-HNT) with the average size of 5 nm, and the notable photocatalytic hydrogen evolution rate of CdS/La-HNT reached up to 47.5 µmol/h. The results could provide a new strategy for metal ion doping and constructive insight into the substitutional doping mechanism.

Structure and Electronic Properties of Transition Metal Doped Kaolinite Nanoclay.

In this work, a series of transition metal (Cr, Mn, Fe, and Co) doped kaolinite nanoclays were investigated by density functional theory (DFT) calculations. The influence of metal doping on geometric structure and electronic structure of kaolinite was analyzed. The ferromagnetic (FM), antiferromagnetic (AFM), and nonmagnetic (NM) states of transition metal (TM) doped kaolinite structures were studied. The crystal volume, lattice parameters, bond length, charge, and spin were calculated by dispersion-corrected density functional theory (DFT-D2). The results indicated that Cr3+ and Fe3+ dopants showed more stable under AFM state, while Mn3+ preferred both AFM and FM states, and Co3+ dopant preferred NM state. Also, the transition metal doping could induce lattice volume expansion and some dopant states in the band gap.

Perovskite LaFeO3/montmorillonite nanocomposites: synthesis, interface characteristics and enhanced photocatalytic activity.

Perovskite LaFeO3/montmorillonite nanocomposites (LaFeO3/MMT) have been successfully prepared via assembling LaFeO3 nanoparticles on the surface of montmorillonite with citric acid assisted sol-gel method. The results indicated that the uniform LaFeO3 nanoparticles were densely deposited onto the surface of montmorillonite, mainly ranging in diameter from 10 nm to 15 nm. The photocatalytic activity of LaFeO3/MMT was evaluated by the degradation of Rhodamine B (RhB) under visible light irradiation, indicating that LaFeO3/MMT exhibited remarkable adsorption efficiency and excellent photocatalytic activity with the overall removal rate of RhB up to 99.34% after visible light irradiation lasting for 90 min. The interface characteristic and possible degradation mechanism were explored. The interface characterization of LaFeO3/MMT suggested that LaFeO3 nanoparticles could be immobilized on the surface of montmorillonite with the Si-O-Fe bonds. The abundant hydroxyl groups of montmorillonite, semiconductor photocatalysis of LaFeO3 and Fenton-like reaction could enhance the photocatalytic degradation through a synergistic effect. Therefore, the LaFeO3/MMT is a very promising photocatalyst in future industrial application to treat effectively wastewater of dyes.