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Infrared nonlinear optical (IR NLO) materials play significant roles in laser technology. The novel functional building units (FBUs) are of great importance in constructing NLO materials with strong second harmonic generation (SHG). Herein, polysulfide anion [Sx]2- (x = 2, 3, 4, 5) units are investigated on NLO-related properties and structure-performance relationships. Theoretical calculations uncover that the [Sx]2- (x = 2, 3, 4, 5) units are potential IR NLO FBUs with large polarizability anisotropy (δ), hyperpolarizability (ß) and wide HOMO-LUMO gap. Fourteen crystals including [Sx]2- (x = 2, 3, 4, 5) units are calculated and analyzed. The results show that these units can result in a wide IR transmittance range, significant SHG effects, wide band gap Eg (Na2S4: Eg = 3.09 eV), and large birefringence Δn [BaS3 (P21212): Δn = 0.70]. More importantly, it is highlighted that the crystal materials including with [Sx]2- (x = 2, 3, 4, 5) groups are good candidates for the exploration of the outstanding IR NLO materials.
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Electroactive organic electrode materials exhibit remarkable potential in aqueous zinc ion batteries (AZIBs) due to their abundant availability, customizable structures, sustainability, and high reversibility. However, the research on AZIBs has predominantly concentrated on unraveling the storage mechanism of zinc cations, often neglecting the significance of anions in this regard. Herein, bipolar poly(thionine) is synthesized by a simple and efficient polymerization reaction, and the kinetics of different anions are investigated using poly(thionine) as the cathode of AZIBs. Notably, poly(thionine) is a bipolar organic polymer electrode material and exhibits enhanced stability in aqueous solutions compared to thionine monomers. Kinetic analysis reveals that ClO4 - exhibits the fastest kinetics among SO4 2-, Cl-, and OTF-, demonstrating excellent rate performance (109 mAh g-1 @ 0.5 A g-1 and 92 mAh g-1 @ 20 A g-1). Mechanism studies reveal that the poly(thionine) cathode facilitates the co-storage of both anions and cations in Zn(ClO4)2. Furthermore, the lower electrostatic potential of ClO4 - influences the strength of hydrogen bonding with water molecules, thereby enhancing the overall kinetics in aqueous electrolytes. This work provides an effective strategy for synthesizing high-quality organic materials and offers new insights into the kinetic behavior of anions in AZIBs.
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Enhancing active states on the catalyst surface by modulating the adsorption-desorption properties of reactant species is crucial to optimizing the electrocatalytic activity of transition metal-based nanostructured materials. In this work, an efficient optimization strategy is proposed by co-modulating the dual anions (C and S) in Ni3C/Ni3S2, the heterostructured electrocatalyst, which is prepared via a simple hot-injection method. The presence of Ni3C/Ni3S2 heterojunctions accelerates the charge carrier transfer and promotes the generation of active sites, enabling the heterostructured electrocatalyst to achieve current densities of 10/100 mA cm-2 at 1.37 V/1.53 V. The Faradaic efficiencies for formate production coupled with hydrogen evolution approach 100%, accompanied with a stability record of 350 h. Additionally, operando electrochemical impedance spectroscopy (EIS), in situ Raman spectroscopy, and density functional theory (DFT) calculations further demonstrate that the creation of Ni3C/Ni3S2 heterointerfaces originating from dual anions' (C and S) differentiation is effective in adjusting the d-band center of active Ni atoms, promoting the generation of active sites, as well as optimizing the adsorption and desorption of reaction intermediates. This dual anions co-modulation strategy to stable heterostructure provides a general route for constructing high-performance transition metal-based electrocatalysts.
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Hitherto, highly concentrated electrolyte is the overarching strategy for revitalizing the usage of amide - in lithium-metal batteries (LMBs), which simultaneously mitigates the reactivity of amide toward Li and regulates uniform Li deposition via forming anion-solvated coordinate structure. However, it is undeniable that this would bring the cost burden for practical electrolyte preparation, which stimulates further electrolyte design toward tailoring anion-abundant Li+ solvation structure in stable amide electrolytes under a low salt content. Herein, a distinct method is conceived to design anions-enriched Li+ solvation structure in dilute amide-electrolyte (1 m Li-salt concentration) with the aid of integrating perfluoropolyethers (PFPE-MC) with anion-solvating ability and B/F-involved additives. The optimized electrolyte based on N,N-Dimethyltrifluoroacetamide (FDMAC) exhibits outstanding compatibility with Li and NCM622 cathode, facilitates uniform Li deposition along with robust solid electrolyte interphase (SEI) formation. Accordingly, both the lab-level LMB coin cell and practical pouch cell based on this dilute FDMAC electrolyte deliver remarkable performances with improved capacity and cyclability. This work pioneers the feasibility of diluted amide as electrolyte in LMB, and provides an innovative strategy for highly stable Li deposition via manipulating solvation structure within diluent electrolyte, impelling the electrolyte engineering development for practical high-energy LMBs.
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Partial ligand substitution at the iron pentacarbonyl radical cation generates novel half-sandwich complexes of the type [Fe(η6-arene)(CO)2]â + (arene=1,3,5-tri-tert-butylbenzene, 1,3,5-trimethylbenzene, benzene and fluorobenzene). Of those, the bulkier 1,3,5-tri-tert-butylbenzene (mes*) derivative [Fe(mes*)(CO)2]â + was fully characterized by XRD analysis, IR, NMR, cw-EPR, Mössbauer spectroscopy and cyclic voltammetry as the [Al(ORF)4]- (RF=C(CF3)3) salt. Chemical electronation, i. e., the single electron reduction, with decamethylferrocene generates neutral [Fe(mes*)(CO)2], whereas further deelectronation under CO-pressure leads to a dicationic three-legged [Fe(mes*)(CO)3]2+ salt with [Al(ORF)4]- counterion. The full substitution of the carbonyl ligands in [Fe(CO)5]â +[Al(ORF)4]- mainly resulted in disproportionation reactions, giving solid Fe(0) and the dicationic bis-arene salts [Fe(η6-arene)2]2+([Al(ORF)4]-)2 (arene=1,3,5-trimethylbenzene, benzene and fluorobenzene). Only by employing the very large fluoride bridged anion [F-{Al(ORF)3}2]-, it was possible to isolate an open shell bis-arene cation salt [Fe(C6H6)2]â +[F-{Al(ORF)3}2]-. The highly reactive cation was characterized by XRD analysis, cw-EPR, Mössbauer spectroscopy and cyclic voltammetry. The disproportionation of [Fe(C6H6)2]â + salts to give solid Fe(0) and [Fe(C6H6)2]2+ salts was analyzed by a suitable cycle, revealing that the thermodynamic driving force for the disproportionation is a function of the size of the anion used and the polarity of the solvent.
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Photo-regulated transmembrane ionophores enable spatial and temporal control over activity, offering promise as targeted therapeutics. Key to such applications is control using bio-compatible visible light. Herein, we report red-shifted azobenzene-derived synthetic anionophores that use amber or red light to trigger (E)-(Z) photoisomerisation and activation of transmembrane chloride transport. We demonstrate that by tuning the thermal half-life of the more active, but thermodynamically unstable, Z isomer to relax on the timescale of minutes, transient activation of ion transport can be achieved by activating with solely with visible light and deactivating by thermal relaxation.
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Quantum chemical calculations using ab initio methods at the MRCI+Q(8,9)/def2-QZVPPD and CCSD(T)/def2-QZVPPD levels as well as using density functional theory are reported for the diatomic molecules AeN- (Ae=Ca, Sr, Ba). The anions CaN- and SrN- have electronic triplet (3Π) ground states with nearly identical bond dissociation energies De ~57â kcal/mol calculated at the MRCI+Q(8,9)/def2-QZVPPD level. In contrast, the heavier homologue BaN- has a singlet (1Σ+) ground state, which is only 1.1â kcal/mol below the triplet (3Σ-) state. The computed bond dissociation energy of (1Σ+) BaN- is 68.4â kcal/mol. The calculations at the CCSD(T)-full/def2-QZVPPD and BP86-D3(BJ)/def2-QZVPPD levels are in reasonable agreement with the MRCI+Q(8,9)/def2-QZVPPD data, except for the singlet (1Σ+) state, which has a large multireference character. The calculated atomic partial charges given by the CM5, Voronoi and Hirshfeld methods suggest small to medium-sized AeâN- charge donation for most electronic states. In contrast, the NBO method predicts for all species medium to large AeâN- electronic charge donation, which is due to the neglect of the (n)p AOs of Ae atoms as genuine valence orbitals. Neither the bond orders nor the bond lengths correlate with the bond dissociation energies. The EDA-NOCV calculations show that the heavier alkaline earth atoms Ca, Sr, Ba use their (n)s and (n-1)d orbitals for covalent bonding.
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The vertical detachment energy (VDE) is a vital factor for predicting the stability of anions that have important applications in the atom, molecule and cluster science. Due to the synthetic or characterization difficulty of anions, accurate and efficient predictions of VDE independent of laboratory data have always been an appealing task to remedy the experimental deficiencies. Unfortunately, the generally adopted CCSD(T) and electron propagator theory (EPT) methods have respectively been proven to be reliable but very cost-expensive, and cost-effective but sometimes problematic when Koopman's theorem is invalid. Here, we for the first time introduced and benchmarked a series of model chemistry composite methods (e. g., CBS-QB3, G4 and W1BD) on calculating VDE for 57 molecular anions. Notably, CBS-QB3 exceeds the accuracy of CCSD(T) while approaching the economy of EPT. Therefore, we highly recommend the composite method CBS-QB3 to compute VDEs for molecular anions in the attractive "killing two birds with one stone" manner.
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Chemical stability is closely associated with the transformations and bioavailabilities of engineered nanomaterials and is a key factor that governs broader and long-term application. With the growing utilization of molybdenum disulfide (MoS2) nanosheets in water treatment and purification processes, it is crucial to evaluate the stability of MoS2 nanosheets in aquatic environments. Nonetheless, the effects of anionic species on MoS2 remain largely unexplored. Herein, the stability of chemically exfoliated MoS2 nanosheets (ceMoS2) was assessed in the presence of inorganic anions. The results showed that the chemical stability of ceMoS2 was regulated by the nucleophilicities and the resultant charging effects of the anions in aquatic systems. The anions promote the dissolution of ceMoS2 by triggering a shift in the chemical potential of the ceMoS2 surface as a function of the anion nucleophilicity (i.e., charging effect). Fast charging with HCO3- and HPO42-/H2PO4- was validated by a phase transition from 1T to 2H and the emergence of MoV, and it promoted oxidative dissolution of the ceMoS2. Additionally, under sunlight, ceMoS2 dissolution was accelerated by NO3-. These findings provide insight into the ion-induced fate of ceMoS2 and the durability and risks of MoS2 nanosheets in environmental applications.
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Molibdeno , Nanoestructuras , DisulfurosRESUMEN
Vacuum-UV (185 nm, VUV) is widely applied to polish reverse osmosis permeate (ROP), such as the production of electronics-grade ultrapure water. In this study, the VUV oxidation of acetaldehyde, a common carbonyl in ROP, was found to be influenced by anions even at low concentrations. Interestingly, the influencing extent and mechanism varied depending on the anions. Bicarbonate minimally affected the VUV-photon absorption and â¢OH consumption, but at 5000 µg-C·L-1, it decreased the degradation of acetaldehyde by 58.7% possibly by scavenging organic radicals or other radical chain reactions. Nitrate strongly competed for VUV-photon absorption and â¢OH scavenging through the formation of nitrite, and at 500 µg-N·L-1, it decreased the removal rate of acetaldehyde degradation by 71.2% and the mineralization rate of dissolved organic carbon by 53.4%. Chloride competed for VUV-photon absorption and also generated reactive chlorine species, which did not affect acetaldehyde degradation but influenced the formation of organic byproducts. The radical chain reactions or activation of anions under VUV irradiation could compensate for the decrease in oxidation performance and need further investigation. In real ROPs, the VUV oxidation of acetaldehyde remained efficient, but mineralization was hindered due to nitrate and chloride anions. This study deepens the understanding of the photochemistry and feasibility of VUV in water with low concentrations of anions.
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NiFe layered double hydroxides (NiFe-LDH) exhibited an outstanding performance and promising application potential for removing ozone. However, the effect of interlayer anions on ozone removal remains ambiguous. Here, a series of NiFe-LDH with different interlayer anions (F-, Cl-, Br-, NO3-, CO32-, and SO42-) were prepared to investigate the effect of the interlayer anion on ozone removal for the first time. It was found that the interlayer anions are a key factor affecting the water resistance of the NiFe-LDH catalyst under moist conditions. NiFe-LDH-CO32- exhibited the best water resistance, which was much better than that of NiFe-LDH containing other interlayer anions. The in situ DIRFTS demonstrates that the carbonates in the interlayer of NiFe-LDH-CO32- will undergo coordination changes through the interaction with water molecules under moist conditions, exposing new metal sites. As a result, the newly exposed metal sites could activate water molecules into hydroxyl groups that act as active sites for catalyzing ozone decomposition. This work provides a new insight into the interlayer anions of LDH, which is important for the design and development of LDH catalysts with excellent ozone removal properties.
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Aniones , Hidróxidos , Ozono , Ozono/química , Hidróxidos/química , Catálisis , Aniones/químicaRESUMEN
Humic acid (HA) is ubiquitous in natural aquatic environments and effectively accelerates decontamination by permanganate (Mn(VII)). However, the detailed mechanism remains uncertain. Herein, the intrinsic mechanisms of HA's impact on phenolics oxidation by Mn(VII) and its intermediate manganese oxo-anions were systematically studied. Results suggested that HA facilitated the transfer of a single electron from Mn(VII), resulting in the sequential formation of Mn(VI) and Mn(V). The formed Mn(V) was further reduced to Mn(III) through a double electron transfer process by HA. Mn(III) was responsible for the HA-boosted oxidation as the active species attacking pollutants, while Mn(VI) and Mn(V) tended to act as intermediate species due to their own instability. In addition, HA could serve as a stabilizer to form a complex with produced Mn(III) and retard the disproportionation of Mn(III). Notably, manganese oxo-anions did not mineralize HA but essentially changed its composition. According to the results of Fourier-transform ion cyclotron resonance mass spectrometry and the second derivative analysis of Fourier-transform infrared spectroscopy, we found that manganese oxo-anions triggered the decomposition of C-H bonds on HA and subsequently produced oxygen-containing functional groups (i.e., C-O). This study might shed new light on the HA/manganese oxo-anion process.
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Sustancias Húmicas , Manganeso , Oxidación-Reducción , Fenoles , Manganeso/química , Fenoles/química , Aniones , Compuestos de Manganeso/química , Óxidos/química , Contaminantes Químicos del Agua/químicaRESUMEN
Detection of fluoride (F-), acetate (AcO-), and cyanide (CN-) anions is vital from the biological and environmental aspects. In the present contributions, we have introduced a simple Salen-type chromogenic sensor, BEN, to detect these biologically important anions. Changes in UV-visible absorption spectra and color of BEN solution from very pale yellow to pink color are similar for each of these anions and found to be reversible only in the case of F- ions in attendance of HSO4- ions. The estimated limit of detection of BEN solution for detecting F-, AcO-, and CN- anions is found to be below the micromolar (µM) concentration level. Our fabricated handy paper test kit is suitable for qualitatively naked-eye detection of the anions. An immediate quantitative estimation of these important anions is possible using our BEN employing a smartphone, avoiding any costly experimental setup.
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The decline in the quality of water resources in the Amazon is very rapid in cities suffering from unplanned urban growth. The region has two defined seasons, winter (wet) and summer (dry), which directly affect the behavior of contaminants in aquatic ecosystems. The aim of this study was to assess the ecological and human health risks associated with the use of the watershed. In addition, an ecological index was proposed: the Quality Index for Aquatic Life, for the risk of contaminants to aquatic life. Sampling was carried out at six points in the Juá watershed. Physicochemical parameters, major anions, metals and total phosphorus were analyzed at both stations between 2020 and 2021. The highest concentrations of contaminants were found in the rainy season, due to the washing away of the banks. In this sense, Cl presented a concentration more than 307 times higher than that permitted by Brazilian legislation (wet). The ecological index showed that the watershed has a high risk of metals such as Cr III and Cr VI for the biota. The human health risk analysis showed a low risk; however, the lack of basic sanitation in the city indicates that monitoring of urban water resources is necessary.
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Metales Pesados , Contaminantes Químicos del Agua , Humanos , Calidad del Agua , Monitoreo del Ambiente , Ecosistema , Contaminantes Químicos del Agua/análisis , Medición de Riesgo , Metales Pesados/análisis , Ríos , ChinaRESUMEN
This study refers to the intricate world of Acinetobacter baumannii, a resilient pathogenic bacterium notorious for its propensity at antibiotic resistance in nosocomial infections. Expanding upon previous findings that emphasised the bifunctional enzyme PaaY, revealing unexpected γ-carbonic anhydrase (CA) activity, our research focuses on a different class of CA identified within the A. baumannii genome, the ß-CA, designated as ð½-AbauCA (also indicated as CanB), which plays a crucial role in the resistance mechanism mediated by AmpC beta-lactamase. Here, we cloned, expressed, and purified the recombinant ð½-AbauCA, unveiling its distinctive kinetic properties and inhibition profile with inorganic anions (classical CA inhibitors). The exploration of ð½-AbauCA not only enhances our understanding of the CA repertoire of A. baumannii but also establishes a foundation for targeted therapeutic interventions against this resilient pathogen, promising advancements in combating its adaptability and antibiotic resistance.
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Acinetobacter baumannii , Aniones , Antibacterianos , Inhibidores de Anhidrasa Carbónica , Anhidrasas Carbónicas , Pruebas de Sensibilidad Microbiana , Acinetobacter baumannii/enzimología , Acinetobacter baumannii/efectos de los fármacos , Anhidrasas Carbónicas/metabolismo , Antibacterianos/farmacología , Antibacterianos/química , Antibacterianos/síntesis química , Aniones/farmacología , Aniones/química , Inhibidores de Anhidrasa Carbónica/farmacología , Inhibidores de Anhidrasa Carbónica/química , Inhibidores de Anhidrasa Carbónica/síntesis química , Relación Estructura-Actividad , Relación Dosis-Respuesta a Droga , Estructura MolecularRESUMEN
The ability of thermoresponsive polymers to respond to temperature with a reversible conformational change makes them promising 'smart' materials for solutions in medical and biotechnological applications. In this work, two such polymers and structural isomers were studied: poly(N-isopropyl acrylamide) (PNiPAm) and poly(2-isopropyl-2-oxazoline) (PiPOx). We compare the critical solution temperatures (CST) of these polymers in D2O and H2O in the presence of Hofmeister series salts, as results obtained under these different solvent conditions are often compared. D2O has a higher dipole moment and electronegativity than H2O, which could significantly alter the CST transition. We used two complementary methods to measure the CST, dynamic light scattering (DLS) and differential scanning calorimetry (DSC) and found that the CST decreased significantly in D2O compared to H2O. In the presence of highly concentrated kosmotropes, the CST of both polymers decreased in both solvents. The influence of the kosmotropic anions was smaller than the water isotope effect at low ionic strengths but considerably higher at physiological ionic strengths. However, the Hofmeister anion effect was quantitatively different in H2O than in D2O, with the largest relative differences observed for Cl-, where the CSTs in D2O decreased more than in H2O measured by DLS but less by DSC. PiPOx was more sensitive than PNiPAm to the presence of chaotropes. It exhibited much higher transition enthalpies and multistep transitions, especially in aqueous solutions. Our results highlight that measurements of thermoresponsive polymer properties in D2O cannot be compared directly or quantitatively to application conditions or even measurements performed in H2O.
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Polímeros , Solventes , Temperatura , Solventes/química , Polímeros/química , Rastreo Diferencial de Calorimetría , Resinas Acrílicas/química , Óxido de Deuterio/química , Agua/química , SolucionesRESUMEN
A comprehensive thermodynamic and structural study of the complexation affinities of tetra (L1), penta (L2), and hexaphenylalanine (L3) linear peptides towards several inorganic anions in acetonitrile (MeCN) and N,N-dimethylformamide (DMF) was carried out. The influence of the chain length on the complexation thermodynamics and structural changes upon anion binding are particularly addressed here. The complexation processes were characterized by means of spectrofluorimetric, 1H NMR, microcalorimetric, and circular dichroism spectroscopy titrations. The results indicate that all three peptides formed complexes of 1:1 stoichiometry with chloride, bromide, hydrogen sulfate, dihydrogen phosphate (DHP), and nitrate anions in acetonitrile and DMF. In the case of hydrogen sulfate and DHP, anion complexes of higher stoichiometries were observed as well, namely those with 1:2 and 2:1 (peptide:anion) complexes. Anion-induced peptide backbone structural changes were studied by molecular dynamic simulations. The anions interacted with backbone amide protons and one of the N-terminal amine protons through hydrogen bonding. Due to the anion binding, the main chain of the studied peptides changed its conformation from elongated to quasi-cyclic in all 1:1 complexes. The accomplishment of such a conformation is especially important for cyclopeptide synthesis in the head-to-tail macrocyclization step, since it is most suitable for ring closure. In addition, the studied peptides can act as versatile ionophores, facilitating transmembrane anion transport.
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Aniones , Termodinámica , Aniones/química , Péptidos/química , Péptidos/metabolismo , Enlace de Hidrógeno , Simulación de Dinámica Molecular , Acetonitrilos/química , Dimetilformamida/química , Dicroismo CircularRESUMEN
Quiescent batch experiments were conducted to evaluate the influences of Cl-, F-, HCO3-, HPO42-, and SO42- on the reactivity of metallic iron (Fe0) for water remediation using the methylene blue (MB) method. Strong discoloration of MB indicates high availability of solid iron corrosion products (FeCPs). Tap water was used as an operational reference. Experiments were carried out in graduated test tubes (22 mL) for up to 45 d, using 0.1 g of Fe0 and 0.5 g of sand. Operational parameters investigated were (i) equilibration time (0-45 d), (ii) 4 different types of Fe0, (iii) anion concentration (10 values), and (iv) use of MB and Orange II (O-II). The degree of dye discoloration, the pH, and the iron concentration were monitored in each system. Relative to the reference system, HCO3- enhanced the extent of MB discoloration, while Cl-, F-, HPO42-, and SO42- inhibited it. A different behavior was observed for O-II discoloration: in particular, HCO3- inhibited O-II discoloration. The increased MB discoloration in the HCO3- system was justified by considering the availability of FeCPs as contaminant scavengers, pH increase, and contact time. The addition of any other anion initially delays the availability of FeCPs. Conflicting results in the literature can be attributed to the use of inappropriate experimental conditions. The results indicate that the application of Fe0-based systems for water remediation is a highly site-specific issue which has to include the anion chemistry of the water.
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Contaminantes Químicos del Agua , Purificación del Agua , Hierro , Agua , Aniones , Contaminantes Químicos del Agua/análisis , Purificación del Agua/métodosRESUMEN
Sulfurized nanoscale zero-valent iron supported on biochar (BC-SNZVI) has been successfully synthesized for 2,4,6-trichlorophenol (2,4,6-TCP) removal, while was only effectively under acidic conditions. To obtain highly efficient removal of 2,4,6-TCP within a broader pH range, weak static magnetic fields (WMF) was applied in BC-SNZVI/2,4,6-TCP aqueous systems. Results showed 30 mT WMF supported the most extensive 2,4,6-TCP removal, and 87.4% of 2,4,6-TCP (initial concentration of 30 mg/L) was removed by 0.5 g/L BC-SNZVI at neutral pH (pH = 6.8) within 180 min, which was increased by 54.4% compared to that without WMF. The observed rate constant (Kobs) under 30 mT WMF was 2.1-fold greater than that without WMF. Although three typical anions (NO3- (0.5-10.0 mM), H2PO4- (0.05-0.5 mM), and HCO3- (0.5-5.0 mM)) still inhibited 2,4,6-TCP removal, WMF could efficiently alleviate the inhibitory effects. Moreover, 73.1% of 2,4,6-TCP was successfully removed by BC-SNZVI under WMF in natural water. WMF remarkably boosted the dechlorination of 2,4,6-TCP, increasing the 2,4,6-TCP dechlorination efficiency from 45.2% (in the absence of WMF) to 83.8% (in the presence of WMF) by the end of 300 min. And the complete dechlorination product phenol appeared within 10 min. Force analysis confirmed the magnetic field gradient force (FB) moved paramagnetic Fe2+ at the SNZVI surface along the direction perpendicular to the external applied field, promoting the mass-transfer controlled SNZVI corrosion. Corrosion resistance analysis revealed WMF promoted the electron-transfer controlled SNZVI corrosion by decreasing its self-corrosion potential (Ecorr). With the introduction of sulfur, the magnitude of FB doubled and the Ecorr decreased comparing with NZVI. Our findings provide a facile and viable strategy for treating chlorinated phenols at neutral pH.
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Carbón Orgánico , Clorofenoles , Hierro , Carbón Orgánico/química , Hierro/química , Clorofenoles/química , Concentración de Iones de Hidrógeno , Contaminantes Químicos del Agua/química , Campos MagnéticosRESUMEN
The aim of this study was a systematic analysis of the influence of anions (chloride and sulfate) on the electrochemical behavior of the Co-Sn system during codeposition from gluconate baths. The pH-dependent multiple equilibria in cobalt-tin baths were calculated using stability constants. The codeposition of the metals was characterized thermodynamically considering the formation of various CoxSny intermetallic phases. The alloys obtained at different potentials were characterized in terms of their elemental (EDS and anodic stripping) and phase compositions (XRD), the development of preferred orientation planes (texture coefficients), surface morphology (SEM), and wettability (water; diiodomethane; surface energy). The mass of the deposits and cathodic current efficiencies were strongly dependent on both the deposition potential and the bath composition. The morphology and composition of the alloys were mainly dependent on the deposition potential, while the effect of the anions was less emphasized. Two-phase alloys were produced at potentials -0.9 V (Ag/AgCl) and lower, and they consisted of a mixture of tetragonal tin and an uncommon tetragonal CoSn phase. The preferential orientation planes of tin grains were dependent on the cobalt incorporation into the deposits and anion type in the bath, while the latter did not affect the preferential orientation plane of the CoSn phase. The surface wettability of the alloys displayed hydrophobicity and oleophilicity originating from the hierarchical porous surface topography rather than the elemental or phase composition. The codeposition of the metals occurs within the progressive nucleation model, but at more electronegative potentials and in the presence of sulfate ions, a transition from progressive to instantaneous nucleation can be possible. This correlated well with the partial polarization curves of the alloy deposition and the texture of the tin phase.