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Due to its high efficiency, Fe(II)-based catalytic oxidation has been one of the most popular types of technology for treating growing organic pollutants. A lot of chemical Fe sludge along with various refractory pollutants was concomitantly produced, which may cause secondary environmental problems without proper disposal. We here innovatively proposed an effective method of achieving zero Fe sludge, reusing Fe resources (Fe recovery = 100%) and advancing organics removal (final TOC removal > 70%) simultaneously, based on the in situ formation of magnetic Ca-Fe layered double hydroxide (Fe3O4@CaFe-LDH) nano-material. Cations (Ca2+ and Fe3+) concentration (≥ 30 mmol/L) and their molar ratio (Ca:Fe ≥ 1.75) were crucial to the success of the method. Extrinsic nano Fe3O4 was designed to be involved in the Fe(II)-catalytic wastewater treatment process, and was modified by oxidation intermediates/products (especially those with COO- structure), which promoted the co-precipitation of Ca2+ (originated from Ca(OH)2 added after oxidation process) and by-produced Fe3+ cations on its surface to in situ generate core-shell Fe3O4@CaFe-LDH. The oxidation products were further removed during Fe3O4@CaFe-LDH material formation via intercalation and adsorption. This method was applicable to many kinds of organic wastewater, such as bisphenol A, methyl orange, humics, and biogas slurry. The prepared magnetic and hierarchical CaFe-LDH nanocomposite material showed comparable application performance to the recently reported CaFe-LDHs. This work provides a new strategy for efficiently enhancing the efficiency and economy of Fe(II)-catalyzed oxidative wastewater treatment by producing high value-added LDHs materials.

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Manganese oxides with porous structure and abundant active sites show potential in degrading sulfur mustard (HD). However, there is an interface effect between the oily liquid HD and nano oxides, and the powder is prone to agglomeration, which leads to incomplete contact and limited degradation ability. Here, we demonstrate a simple hydrothermal method for preparing MnO2/Ti3C2 composites to address this problem. The influence of morphology and crystal structure on performance are examined. Herein, flower-like MnO2 is loaded onto the surface or interlayer of Ti3C2-MXene nanosheets during in situ formation, significantly expanding the specific surface area. It also provides abundant acid-base sites and oxygen vacancies for the degradation of simulants 2-chloro-ethyl-ethyl thioether (2-CEES) without external energy, resulting in a reaction half-life as fast as 12.5 min. The relationship between structure and performance is clearly elaborated through temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure (XAFS) analyses. Based on in situ attenuated total reflection-Fourier transform infrared (ATR-FTIR) analysis, gas chromatography-mass spectrometry (GC-MS) analysis, and density functional theory (DFT) calculation, the proposed degradation pathway of the 2-CEES molecule is a synergistic effect of hydrolysis, elimination, and oxidation. Furthermore, the products are nontoxic or low toxic. Metal oxide/MXene composites are first illustrated for their potential use in degrading sulfur mustard, suggesting new insights into these materials as novel decontamination for decomposing chemical warfare agents.

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Acid mine drainage (AMD) contains high concentrations of heavy metals, causing serious environmental pollution. Current neutralization techniques fail to recover and utilize valuable heavy metals, and generate large quantities of hazardous sludge. Manganese (Mn) is generally present at high levels in AMD. Therefore, this paper proposed a technology to recover Mn from AMD, by adding KMnO4 to converting Mn into ε-MnO2. Ultra-Violet C (UVC) was used to photolyze the residual KMnO4. The study then evaluated the processes and mechanisms involved in the technology. The photolysis of KMnO4 in strong acidic conditions was determined, and new mechanisms were proposed. MnO2 produced by the photolysis process was formed through the reaction between Mn(III) and KMnO4. In the absence of KMnO4, Mn(III) underwent further photolysis and was reduced to Mn2+. The maximum adsorption capacities of in-situ formed ε-MnO2 for Pb2+, Cd2+, and Fe3+ were 449.80, 122.05, and 779.88 mg/g, respectively. Higher Mn-OH levels and MnO2 regeneration were crucial in improving adsorption performance. Proton exchange and inner-circle complexation were the main pathways for Pb2+ and Cd2+ adsorption by in-situ formed ε-MnO2. A phase transformation occurred when a substantial amount of Fe3+ was adsorbed, leading to the gradual transformation to MnFe binary oxides. When applying in-situ formed ε-MnO2 technology for actual AMD treatment, 98.62 % of Mn in AMD was recovered within 24 h in the presence of ε-MnO2 for possible further reuse in industries, with a final recovery of 0.76 kg/m3. Further, this technique removed other heavy metals and reduced the sludge volume by 20.99 % when used as a pre-treatment step for neutralization. These results demonstrated the broad potential of this treatment technology.

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BACKGROUND: Herein, a new extraction procedure based on in-situ formation of carbon dioxide-incorporated solid sorbent was introduced for dispersive solid phase extraction of phenolic compounds from aqueous samples. In this study, incorporation of carbon dioxide into the structure of a diamine led to the formation of a solid compound in the sample solution that adsorbed the analytes. RESULTS: The sample solution was mixed with isophorone diamine and placed under carbon dioxide stream. By doing so, isophorone diamine reacted with carbon dioxide and produced a carbamic acid analogue. It was dispersed into the sample solution as tiny particles that adsorbed the analytes. The adsorbed analytes were eluted by a volatile organic solvent and concentrated more by the vaporization of the eluate. The extraction procedure was done at low temperature to limit the releasing carbon dioxide from the produced compound. To obtain the reliable results, the method was validated and the obtained limits of detection and quantification were in the ranges of 0.29-41 and 0.96-1.3 ng/mL, respectively. Acceptable relative standard deviation (≤7.3%) and coefficient of determination (≥0.994) values confirmed the method repeatability and linearity. High enrichment factors (410-435) and extraction recoveries (82-87%) were attained with the introduced method. SIGNIFICANCE AND NOVELTY: In this work, a chemical reaction was done between isophorone diamine and carbon dioxide in solution. The produced product (sorbent) was insoluble in solution and dispersed in whole parts of the solution as tiny particles. A high contact area between the sorbent and analytes provided high extraction efficiency for the analytes. The method was successful utilized in determining target analytes in real samples and the matrix effect of the samples had no important effect on the obtained results.

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We report the feasibility of using gelatin hydrogel networks as the host for the in situ, environmentally friendly formation of well-dispersed zinc oxide nanoparticles (ZnONPs) and the evaluation of the antibacterial activity of the as-prepared composite hydrogels. The resulting composite hydrogels displayed remarkable biocompatibility and antibacterial activity as compared to those in previous studies, primarily attributed to the uniform distribution of the ZnONPs with sizes smaller than 15 nm within the hydrogel network. In addition, the composite hydrogels exhibited better thermal stability and mechanical properties as well as lower swelling ratios compared to the unloaded counterpart, which could be attributed to the non-covalent interactions between the in situ formed ZnONPs and polypeptide chains. The presence of ZnONPs contributed to the disruption of bacterial cell membranes, the alteration of DNA molecules, and the subsequent release of reactive oxygen species within the bacterial cells. This chain of events culminated in bacterial cell lysis and DNA fragmentation. This research underscores the potential benefits of incorporating antibacterial agents into hydrogels and highlights the significance of preparing antimicrobial agents within gel networks.

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Developing long-cycle stable Zn-ion batteries encounters significant challenges associated with Zn anodes. To address these issues, we propose an interface engineering strategy using an artificial protective layer called zinc hyaluronate (ZH) on the Zn anode surface. The ZH film acts as a barrier, preventing direct contact between Zn anode and electrolyte, reducing hydrogen evolution and corrosion. Its carboxyl and hydroxyl groups create uniform and plentiful nucleophilic sites for Zn2+ ions, promoting uniform Zn deposition and suppressing dendrite growth. Remarkably, a Zn//Zn symmetric cell assembled with ZH-decorated Zn foil (Zn@ZH) exhibits outstanding cycle life, lasting 3600 h at a current density of 5 mA cm-2 and a capacity density of 5 mAh cm-2, much better than cells with pristine Zn anode. Even under extremely tough conditions of 10 mA cm-2 and 10 mAh cm-2, the battery life exceeds 1300 h. Furthermore, the Zn@ZH//V2O5 full cell demonstrates superior capacity retention compared to the Zn//V2O5 cell after 1000 cycles at a current density of 10 A g-1. These results highlight the benefits of the artificial protective layer strategy for advanced Zn anodes, providing insights into the underlying mechanism and promoting the development of high-performance aqueous zinc ion batteries.

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In this research, a dispersive solid phase extraction procedure based on changing the solubility of octadecylamine with pH was proposed to determine Ag+ ions in different water samples. For this purpose, first, the pH of sample solution containing the analyte was adjusted to 10.5. Then desired volume of the octadecylamine dissolved in acidic solution was injected into the solution. Because of the low solubility of octadecylamine in alkaline solution, a cloudy state was formed. The produced octadecylamine particles acted as a complexing agent for Ag+ ions and adsorbent for the formed complex. The obtained cloudy solution was centrifuged and the sedimented particles were removed and dissolved in a diluted nitric acid solution. It was injected into a flame atomic absorption spectrometry to determine the extracted amounts of the analyte. The effect of important parameters such as the amount of octadecylamine, volume of nitric acid, and centrifugation and vortexing conditions on the extraction efficiency of the procedure was studied and optimized. In optimal conditions, the developed method showed a linear range of 0.50-200 µg L-1. The limits of detection and quantification were 0.18 and 0.50 µg L-1, respectively. Extraction recovery was 93.6%. The relative standard deviations were less than 4%. The effectiveness of the method was investigated by determination of Ag+ ions in water and wastewater samples.

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The in-situ generation of therapeutic agents in targeted lesions is promising for revolutionizing oncotherapy but is limited by the low production efficiency. Given the specific tumor microenvironment (TME) of colorectal cancer (CRC), i.e., mild acidity, overexpressed H2O2, glutathione (GSH) and H2S, we develop phycocyanin (PC) encapsulated PZTC/SS/HA nanocapsules (NCs) for TME-responsive, protein-assisted "turn-on'' therapy of CRC. The NCs are prepared by sequentially assembling Cu2+-tannic acid (TA) coordination shell, disulfide bond-bearing cross-linker, and hyaluronic acid (HA) on the sacrificial template ZIF-8, thus achieving pH-, GSH-responsiveness, and tumor targeting capability, respectively. Once reaching the CRC sites, the NCs can quickly disintegrate and release Cu2+ and PC, accompanied by subsequent endogenous H2S-triggered generation of copper sulfide (CuS). Significantly, the intracellular sulfidation process can be accelerated by PC, thereby enabling efficient photothermal therapy (PTT) under NIR-Ⅱ laser. Besides, Cu2+-associated chemodynamic therapy (CDT) can be simultaneously activated and enhanced by PTT-induced local hyperthermia and disulfide bond-induced GSH consumption. This CRC-targeted and TME-activated synergistic PTT/CDT strategy displays high therapeutic efficacy both in vitro and in vivo, which can open up a new avenue for biomolecule-assisted in-situ nanoagent generation and effective TME-responsive synergistic treatment of CRC.

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The in situ formation of a heterostructure delivers superior electrochemical properties as compared to the mechanical mixing, which shows great promise for developing new electrolytes for solid oxide fuel cells (SOFCs). Herein, in an SOFC constructed by the Ba5Nb4O15 electrolyte and Ni0.8Co0.15Al0.05LiO2-δ anode, an in situ formation of Ba3CoNb2O9/Ba5Nb4O15 heterostructure is designed by Co-ion diffusion from the anode to the electrolyte during cell operation, resulting in improved ion conductivity and fuel cell performance. An abnormal phenomenon is observed that the SOFC based on the Ba3CoNb2O9/Ba5Nb4O15 electrolyte delivered a peak power density of 703 mW/cm2 at 510 °C, which is higher than that at 550 °C. Characterization in terms of X-ray photoelectron spectroscopy and X-ray diffraction verifies that the operating temperature affected the Co doping concentrations, leading to different conducting behaviors of the heterostructure. Furthermore, it is found that the heterojunction of Ba3CoNb2O9 and Ba5Nb4O15 can restrict the electron migration to avoid current leakage of the cell and simultaneously enhance the proton conductivity. These findings manifest the developed in situ Ba3CoNb2O9/Ba5Nb4O15 heterostructure as a promising electrolyte for SOFCs.

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Development of new strategies in photoelectrochemical (PEC) sensors is an important way to realize sensitive detection of biomolecule. In this study, mesoporous silica nanospheres (MSNs)-assisted split-type PEC aptasensor with in situ generation of Bi2S3 was proposed to achieve reliable detection of prostate-specific antigen (PSA). To be more specific, this bioresponsive release system will release large amounts of Na2S by the reaction between PSA and aptamer that capped Na2S-loading MSNs. Next, the Na2S reacts with Bi to yield BiOI/BiOBr/Bi2S3 composite, which leads to an alteration in the electron-hole transfer pathway of the photoelectric material and a decrease in the response. As the PSA concentration increases, more Na2S can be released and lower photocurrent is obtained. The linear range under the optimal experimental conditions is 10 pg·mL-1-1 µg⋅mL-1, and the detection limit is 1.23 pg⋅mL-1, which has satisfactory stability and anti-interference.

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Inorganic nanocrystals possess unique physicochemical properties compared to their bulk counterparts. Stabilizing agents are commonly used for the preparation of inorganic nanocrystals with controllable properties. Particularly, colloidal polymers have emerged as general and robust templates for in situ formation and confinement of inorganic nanocrystals. In addition to templating and stabilizing inorganic nanocrystals, colloidal polymers can tailor their physicochemical properties such as size, shape, structure, composition, surface chemistry, and so on. By incorporating functional groups into colloidal polymers, desired functions can be integrated with inorganic nanocrystals, advancing their potential applications. Here, recent advances in the colloidal polymer-templated formation of inorganic nanocrystals are reviewed. Seven types of colloidal polymers, including dendrimer, polymer micelle, stare-like block polymer, bottlebrush polymer, spherical polyelectrolyte brush, microgel, and single-chain nanoparticle, have been extensively applied for the synthesis of inorganic nanocrystals. Different strategies for the development of these colloidal polymer-templated inorganic nanocrystals are summarized. Then, their emerging applications in the fields of catalysis, biomedicine, solar cells, sensing, light-emitting diodes, and lithium-ion batteries are highlighted. Last, the remaining issues and future directions are discussed. This review will stimulate the development and application of colloidal polymer-templated inorganic nanocrystals.

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Sulfidation of zerovalent iron (SZVI) can strengthen the decontamination ability by promoting the electron transfer from inner Fe0 to external pollutants by iron sulfide (FeSx). Although FeSx forms easily, the mechanism for the FeSx bonding on the ZVI surface through a liquid precipitation method is elusive. In this work, we demonstrate a key pathway for the sulfidation of ZVI, namely, the in situ formation of FeSx on ZVI surface, which leads to chemical bonding across two domains: the pristine ZVI and the newly formed FeSx phase. The two chemically bridged heterophases display superior activity in electron transportation compared to the physically coated SZVI, eventually bringing about the better performance in reducing Cr(VI) species. It is revealed that the formation of chemically bonded FeSx requires balancing the rates for the two processes of Fe(II) release and sulfidation, which can be achieved by tuning the pH and S(-II) concentration. This study elucidates a mechanism for surface generation of FeSx on ZVI, and it provides new perspectives to design high-quality SZVI for environmental applications.

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This review focuses on the opportunities provided by sol-gel chemistry for the production of silica/epoxy nanocomposites, with significant representative examples of the "extra situ" approach and an updated description of the "in situ" strategy. The "extra situ" strategy enables the creation of nanocomposites containing highly engineered nanoparticles. The "in situ" approach is a very promising synthesis route that allows us to produce, in a much easier and eco-friendly manner, properly flame-retarded silica/epoxy nanocomposites endowed with very interesting properties. The review highlights the recently proposed mechanism of nanoparticles formation, which is expected to help to design the synthesis strategies of nanocomposites, changing their composition (both for the nanoparticle and matrix nature) and with in situ-generated nanoparticles possibly more complex than the ones obtained, until today, through this route.

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A new concept to construct photoresponsive nanozyme through the in situ deposition of electron transporting material (ETM) on BiOBr nanoplates was proposed. That was, the spontaneous coordination of ferricyanide ions (i.e., [Fe(CN)6]3-) onto the surface of BiOBr formed electron transporting material (ETM), which efficiently prevented electron-hole recombination and led to efficient enzyme mimicking activity under light stimuli. Moreover, the formation of the photoresponsive nanozyme was regulated by pyrophosphate ions (PPi) due to the competitive coordination of PPi with [Fe(CN)6]3- onto the surface of BiOBr. This phenomenon allowed the construction of an engineerable photoresponsive nanozyme that was coupled with the rolling circle amplification (RCA) reaction to elucidate a novel bioassay for chloramphenicol (CAP, taken as a model analyte). The developed bioassay manifested the merits of label-free, immobilization-free and with efficiently amplified signal. Quantitative analysis of CAP in a wide linear range from 0.05 to 100 nM with the detection limit of 0.015 nM was realized, which endowed the methodology with sufficiently high sensitivity. It is expected to be a powerful signal probe in bioanalytical field by virtue of its switchable and fascinating visible-light-induced enzyme mimicking activity.

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Advanced optoelectronic devices have attracted extensive interdisciplinary interest but lags far behind in biomolecular detection. The nascent organic photoelectrochemical transistor (OPECT) is expected to become a versatile platform to this end. Herein, using biological derivation of type-I Ag2S/ZnIn2S4 heterojunction, a light-fueled high-efficacy OPECT system with zero-gate-biased operation is successfully developed for biomolecular detection. Exemplified by a sandwich immunocomplexing towards mouse IgG (MIgG) with Ag nanoparticles (Ag NPs) as the label, steering the acidolysis-release of Ag+ toward ZnIn2S4 could induce the in-situ formation of type-I Ag2S/ZnIn2S4 heterojunction, increasing the recombination of light-activated excitons and thus inhibiting the photo-responsibility of ZnIn2S4, as sensitively monitored by the amplified OPECT response. The proposed device could achieve good analytical performance in terms of high specificity and sensitivity, with a detection limit as low as 33.7 fg mL-1. This OPECT device based on bio-induced formation of type-I heterojunction can provide a novel route to biomolecular detection, and offered a new perspective for the optoelectronic sensors to be used in futuristic physiological and pathological detection.

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A stable cathode-electrolyte interface (CEI) is crucial for aqueous zinc-ion batteries (AZIBs), but it is less investigated. Commercial binder poly(vinylidene fluoride) (PVDF) is widely used without scrutinizing its suitability and cathode-electrolyte interface (CEI) in AZIBs. A water-soluble binder is developed that facilitated the in situ formation of a CEI protecting layer tuning the interfacial morphology. By combining a polysaccharide sodium alginate (SA) with a hydrophobic polytetrafluoroethylene (PTFE), the surface morphology, and charge storage kinetics can be confined from diffusion-dominated to capacitance-controlled processes. The underpinning mechanism investigates experimentally in both kinetic and thermodynamic perspectives demonstrate that the COO- from SA acts as an anionic polyelectrolyte facilitating the adsorption of Zn2+ ; meanwhile fluoride atoms on PTFE backbone provide hydrophobicity to break desolvation penalty. The hybrid binder is beneficial in providing a higher areal flux of Zn2+ at the CEI, where the Zn-Birnessite MnO2 battery with the hybrid binder exhibits an average specific capacity 45.6% higher than that with conventional PVDF binders; moreover, a reduced interface activation energy attained fosters a superior rate capability and a capacity retention of 99.1% in 1000 cycles. The hybrid binder also reduces the cost compared to the PVDF/NMP, which is a universal strategy to modify interface morphology.

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Conservation of sandstone-based cultural heritage has attracted a great deal of interest. We propose herein a novel protecting strategy, via in situ fabrication of bentonite-based hydrogels (B-H) inside sandstones, where the bentonite-based hydrogels serve as the underlying cement. To create bentonite-based hydrogels with controllable structure, possessing good mechanical and anti-swelling properties, we have optimized forming time, appearance, and viscosity. The hydrogel precursor penetrated into the pores of the sandstone; the hydrogel would then form within 3-5 h. As found by employing a fluorescent tracer, the precursor remained controllably in place without any apparent change in the sandstone morphology. The bentonite-based hydrogels that formed inside the sandstones presented strong hydrogen bonding, coordination, and ionic bonding, as well as strong mechanical interlocking to the sandstone matrix. As a result, the sandstones possessed enhanced mechanical compressive strength and excellent resistance to acid, salt, and freeze-thaw cycles. Our approach provides for a non-destructive, eco-friendly, easy-to-use, and long-term strategy for cultural preservation, one with excellent protection effects.

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With a direct band gap, superior charge carrier mobility, and uniformly distributed pores, graphdiyne (GDY) has stimulated tremendous interest from the scientific community. However, its broad application is greatly limited by the complicated multistep synthesis process including complex deprotection of hexakis-[(trimethylsilyl)ethynyl]benzene (HEB-TMS) and peeling of GDY from the substrates. Here, we describe a deprotection-free strategy to prepare GDY powder by directly using HEB-TMS as the monomer. When CuCl was used as the catalysts in DMF solvent, the yield of GDY powder reached ≈100 %. More interestingly, uniformly dispersed CuO nanoparticles with an average diameter of ≈2.9 nm were in situ formed on GDY after the reaction. The prepared CuO/GDY was demonstrated an excellent co-catalyst for photocatalytic hydrogen evolution, comparable to the state-of-art Pt co-catalyst. The deprotection-free approach will widen the use of GDY and facilitate its scaling up to industrial level.

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A novel signal-increased photoelectrochemical (PEC) biosensor for l-cysteine (L-Cys) was proposed based on the Bi2MoO6-Bi2S3 heterostructure formed in situ on the indium-tin oxide (ITO) electrode. To fabricate the PEC biosensor, Bi2MoO6 nanoparticles were prepared by a hydrothermal method and coated on a bare ITO electrode. When L-Cys existed, Bi2S3 was formed in situ on the interface of the Bi2MoO6/ITO electrode by a chemical displacement reaction. Under the visible light irradiation, the Bi2MoO6-Bi2S3/ITO electrode exhibited evident enhancement in photocurrent response compared with the Bi2MoO6/ITO electrode, owing to the signal-increased sensing system and the excellent property of the formed Bi2MoO6-Bi2S3 heterostructure such as the widened light absorption range and efficient separation of photo-induced electron-hole pairs. Under the optimal conditions, the sensor for L-Cys detection has a linear range from 5.0 × 10-11 to 1.0 × 10-4 mol L-1 and a detection limit of 5.0 × 10-12 mol L-1. The recoveries ranging from 90.0% to 110.0% for determining L-Cys in human serum samples validated the applicability of the biosensor. This strategy not only provides a method for L-Cys detection but also broadens the application of the PEC bioanalysis based on in situ formation of photoactive materials.

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In this study, an in situ nanostructured copper tungsten carbide composite was synthesized by mechanical alloying (MA) and the powder metallurgy route. The microstructure and phase changes of the composite were characterized by X-ray diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy. Tungsten carbide phases (WC and W2C) were only present after MA and combination of sintering. Higher energy associated with a longer milling time was beneficial for the formation of WC. Formation of W2C and WC resulted from internal refinement due to heavy plastic deformation in the composite. The solubility of the phases in the as-milled and sintered composite was described by the changes of the lattice parameter of Cu. Chemical analysis of the surface of a composite of W 4f and C 1s revealed that the increased defects introduced by MA affect the atomic binding of the W-C interaction.