RESUMO
Hematite nanoparticles commonly undergoes isomorphic substitution of Al3+ in nature, while how the Al-substitution-induced morphological change, defective structure and newly generated Al-OH sites affect the adsorption behavior of hematite for contaminants remains poorly understood. Herein, the interfacial reactions between Al-substituted hematite and Pb2+ was investigated via CD-MUSIC modeling and DFT calculations. As the Al content increased from 0% to 9.4%, Al-substitution promoted the proportion of (001) facets and caused Fe vacancies on hematite, which increased the total active site density of hematite from 5.60 to 17.60 sites/nm2. The surface positive charge of hematite significantly increased from 0.096 to 0.418 C/m2 at pH 5.0 due to the increases in site density and proton affinity (logKH) of hematite under Al-substitution. The adsorption amount of hematite for Pb2+ increased from 3.92 to 9.74 mmol/kg at pH 5.0 and 20 µmol/L initial Pb2+ concentration with increasing Al content. More Fe vacancies may lead to a weaker adsorption energy (Ead) of hematite for Pb2+, while the Ead was enhanced at higher Al content. The adsorption affinity (logKPb) of bidentate Pb complexes slightly increased while that of tridentate Pb complexes decreased with increasing Al content due to the presence of ≡ AlOH-0.5 and ≡ Fe2AlO-0.5 sites. Tridentate Pb complexes were dominant species on the surface of pure hematite, while bidentate ones became more dominant with increasing Al content. The obtained model parameters and molecular scale information are of great importance for better describing and predicting the environmental fate of toxic heavy metals in terrestrial and aquatic environments.
Assuntos
Alumínio , Compostos Férricos , Chumbo , Modelos Químicos , Chumbo/química , Compostos Férricos/química , Adsorção , Alumínio/química , Alumínio/análiseRESUMO
Metal-organic frameworks (MOFs) are promising adsorbents for legacy per-/polyfluoroalkyl substances (PFASs), but they are being replaced by emerging PFASs. The effects of varying carbon chains and functional groups of emerging PFASs on their adsorption behavior on MOFs require attention. This study systematically revealed the structure-adsorption relationships and interaction mechanisms of legacy and emerging PFASs on a typical MOF MIL-101(Cr). It also presented an approach reflecting the average electronegativity of PFAS moieties for adsorption prediction. We demonstrated that short-chain or sulfonate PFASs showed higher adsorption capacities (µmol/g) on MIL-101(Cr) than their long-chain or carboxylate counterparts, respectively. Compared with linear PFASs, their branched isomers were found to exhibit a higher adsorption potential on MIL-101(Cr). In addition, the introduction of ether bond into PFAS molecule (e.g., hexafluoropropylene oxide dimeric acid, GenX) increased the adsorption capacity, while the replacement of CF2 moieties in PFAS molecule with CH2 moieties (e.g., 6:2 fluorotelomer sulfonate, 6:2 FTS) caused a decrease in adsorption. Divalent ions (such as Ca2+ and SO42-) and solution pH have a greater effect on the adsorption of PFASs containing ether bonds or more CF2 moieties. PFAS adsorption on MIL-101(Cr) was governed by electrostatic interaction, complexation, hydrogen bonding, π-CF interaction, and π-anion interaction as well as steric effects, which were associated with the molecular electronegativity and chain length of each PFAS. The average electronegativity of individual moieties (named Me) for each PFAS was estimated and found to show a significantly positive correlation with the corresponding adsorption capacity on MIL-101(Cr). The removal rates of major PFASs in contaminated groundwater by MIL-101(Cr) were also correlated with the corresponding Me values. These findings will assist with the adsorption prediction for a wide range of PFASs and contribute to tailoring efficient MOF materials.
Assuntos
Fluorocarbonos , Estruturas Metalorgânicas , Adsorção , Fluorocarbonos/química , Estruturas Metalorgânicas/química , Carbono/química , Poluentes Químicos da Água/químicaRESUMO
Hematite is a common iron oxide in natural environments, which has been observed to influence the transport and fate of arsenate by its association with hematite. Although oxygen vacancies were demonstrated to exist in hematite, their contributions to the arsenate immobilization have not been quantified. In this study, hematite samples with tunable oxygen vacancy defect (OVD) concentrations were synthesized by treating defect-free hematite using different NaBH4 solutions. The vacancy defects were characterized by positron annihilation lifetime spectroscopy, Doppler broadening of annihilation radiation, extended X-ray absorption fine structure (EXAFS), thermogravimetric mass spectrometry (TG-MS), electron paramagnetic resonance (EPR), and X-ray photoelectron spectroscopy (XPS). The results revealed that oxygen vacancy was the primary defect type existing on the hematite surface. TG-MS combined with EPR analysis allowed quantification of OVD concentrations in hematite. Batch experiments revealed that OVDs had a positive effect on arsenate adsorption, which could be quantitatively described by a linear relationship between the OVD concentration (Cdef, mmol m-2) and the enhanced arsenate adsorption amount caused by defects (ΔQm, µmol m-2) (ΔQm = 20.94 Cdef, R2 = 0.9813). NH3-diffuse reflectance infrared Fourier transform (NH3-DRIFT) analysis and density functional theory (DFT) calculations demonstrated that OVDs in hematite were beneficial to the improvement in adsorption strength of surface-active sites, thus considerably promoting the immobilization of arsenate.
Assuntos
Arseniatos , Compostos Férricos , Compostos Férricos/química , AdsorçãoRESUMO
Combined pollution of cadmium (Cd) and lead (Pb) occurs frequently in agriculture lands, which has received increasing research attention. However, little is known about the interaction behaviors of Cd and Pb at various concentrations in the mixture. This study evaluated the single and combined effects of Cd and Pb on rice (Oryza sativa L.) root elongation through acute exposure test. The combined pollution was analyzed with the concentration addition (CA) model, independent action (IA) model and mathematical statistical methods. The dose-response results revealed that the interaction could weaken the toxicity of both Pb and Cd, and Cd had a more significant inhibitory effect on Pb toxicity. The predicted values of CA and IA models were consistently lower than the observed values in the relative root elongation range of 0-60%. Further, combining the CA or IA model with mathematical statistical methods, the interaction of Pb and Cd at similar concentrations showed a significant antagonistic effect on rice root elongation. At low Pb concentrations (Cd > 0.0195, Pb < 0.015 mg/L), there was a synergistic effect of the mixture on rice root; at high Pb concentrations (Cd < 0.225, Pb ≥ 1.25 mg/L), Pb dominated the toxicity on rice root. This is the first report of a systematic method for assessing heavy metal interaction at different concentration levels, which may facilitate the formulation of control standards of heavy metal combined pollution in agricultural land.
Assuntos
Metais Pesados , Oryza , Poluentes do Solo , Cádmio/toxicidade , Cádmio/análise , Chumbo/toxicidade , Chumbo/análise , Poluentes do Solo/toxicidade , Poluentes do Solo/análise , Metais Pesados/análise , SoloRESUMO
Accurate prediction of the environmental fate of Pb depends on the understanding of Pb coordination to mineral surfaces. Here, the proton and Pb adsorption and speciation on hematite nanocrystals with different exposed crystallographic facets were investigated. High-resolution transmission electron microscopy images revealed that hematite nanoplates (HNP) were of 75.3 ± 9.5% (001) facets and 24.6 ± 9.3% (012) facets, while hematite nanocubes (HNC) were of 76.0 ± 11.1% (012) facets and 24.0 ± 3.2% (110) facets. Our modeling results revealed that the proton affinity constant (log KH) of ≡FeOH-0.5 and ≡Fe3O-0.5 was 7.8 and 10.8 on hematite (012) facets, and changed to 7.7 and 11.7 on (110) facets, respectively. Owing to the different atomic arrangements, (012) facets not only have higher adsorption performance for Pb, but also present a greater dependence on pH than (110) facets. Additionally, our modeling further indicated that (012) facets bind Pb via both bidentate and tridentate complexes, while (110) facets bind Pb only through bidentate complexes at pH 3.0-6.5. These results facilitate a more detailed understanding of the complex species of Pb on hematite surface while also provide new insight into the reactivity mechanism of individual hematite facets.
Assuntos
Música , Nanopartículas , Adsorção , Chumbo , Nanopartículas Magnéticas de Óxido de FerroRESUMO
OMS-2 is one of the most promising catalysts for carcinogenic benzene elimination, and single-type alkali metals are typically introduced into the OMS-2 tunnels to modify its catalytic activity. Here, we reported a novel approach for significantly increasing the catalytic activity of OMS-2 via the simultaneous introduction of K+ and Rb+ into the tunnels. The catalytic results demonstrated that K+ and Rb+ codoped OMS-2 showed catalytic activity for benzene oxidation that exceeded those of K+ and Rb+ single-doped OMS-2, as evidenced by enormous decreases (â³T50 = 106 °C and â³T90 > 132 °C) in catalytic temperatures T50 and T90 (which correspond to benzene conversion percentages of 50% and 90%, respectively). The origin of the effect of K+ and Rb+ codoping on the catalytic activity of OMS-2 was experimentally and theoretically investigated via 18O2 isotope labeling, CO temperature-programmed reduction, and density functional theory calculation. The higher catalytic activity of K+ and Rb+ codoped OMS-2 was attributed to its higher lattice oxygen activity as well as its higher oxygen vacancy defect concentrations compared to the single-doped OMS-2 cases.
Assuntos
Benzeno , Oxigênio , Catálise , OxirreduçãoRESUMO
In the context of growing arsenic (As) contamination in the world, there is an urgent need for an effective treatment approach to remove As from the environment. Industrial wastewater is one of the primary sources of As contamination, which poses significant risks to both microorganisms and human health, as the presence of As can disrupt the vital processes and synthesis of crucial macromolecules in living organisms. The global apprehension regarding As presence in aquatic environments persists as a key environmental issue. This review summarizes the recent advances and progress in the design, strategy, and synthesis method of various manganese-based adsorbent materials for As removal. Occurrence, removal, oxidation mechanism of As(III), As adsorption on manganese oxide (MnOx)-based materials, and influence of co-existing solutes are also discussed. Furthermore, the existing knowledge gaps of MnOx-based adsorbent materials and future research directions are proposed. This review provides a reference for the application of MnOx-based adsorbent materials to As removal.
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Hematite is an iron oxide commonly found in terrestrial environments and plays an essential role in controlling the migration of heavy metal(loid)s in groundwater and sediments. Although defects were shown to exist both in naturally occurring and laboratory-synthesized hematite, their influences on the immobilization of heavy metal(loid)s remain poorly understood. In this study, hematite samples with tunable vacancy defect concentrations were synthesized to evaluate their adsorption capacities for the cation Pb(II) and for the oxyanion As(V). The defects in hematite were characterized using XRD, TEM-EDS mapping, position annihilation lifetime spectroscopy, and XAS. The surface charge characteristics in defective hematite were investigated using zeta potential measurements. We found that Fe vacancies were the primary defect type in the hematite structure. Batch experiments confirmed that Fe vacancies in hematite promoted As(V) adsorption, while they decreased Pb(II) adsorption. The reason for the opposite effects of Fe vacancies on Pb(II) and As(V) immobilization was investigated using DFT calculations and EXAFS analysis. The results revealed that Fe vacancies altered As-Fe coordination from a monodentate to a bidentate complex and increased the length of the Pb-Fe bond on the hematite surface, thereby leading to an increase in As(V) bonding strength, while decreasing Pb(II) adsorption affinity. In addition, the zeta potential analysis demonstrated that the presence of Fe vacancies led to an increase in the isoelectric point (IEP) of hematite samples, which therefore decreased the attraction for the cation Pb(II) and increased the attraction for the oxyanion As(V). The combination of these two effects caused by defects contributed to the contrasting difference between cation Pb(II) and oxyanion As(V) immobilization by defective hematite. Our study therefore provides new insights into the migration and fate of toxic heavy metal(loid)s controlled by iron minerals.
Assuntos
Compostos Férricos , Chumbo , Compostos Férricos/química , Ferro/química , Minerais/química , AdsorçãoRESUMO
OMS-2 nanorods with tunable K(+) concentration were prepared by a facile hydrothermal redox reaction of MnSO4, (NH4)2S2O8, and (NH4)2SO4 at 120 °C by adding KNO3 at different KNO3/MnSO4 molar ratios. The OMS-2 nanorod catalysts are characterized by X-ray diffraction, transmission electron microscopy, N2 adsorption and desorption, inductively coupled plasma, and X-ray photoelectron spectrometry. The effect of K(+) concentration on the lattice oxygen activity of OMS-2 is theoretically and experimentally studied by density functional theory calculations and CO temperature-programmed reduction. The results show that increasing the K(+) concentration leads to a considerable enhancement of the lattice oxygen activity in OMS-2 nanorods. An enormous decrease (ΔT50 = 89 °C; ΔT90 > 160 °C) in reaction temperatures T50 and T90 (corresponding to 50 and 90% benzene conversion, respectively) for benzene oxidation has been achieved by increasing the K(+) concentration in the K(+)-doped OMS-2 nanorods due to the considerable enhancement of the lattice oxygen activity.
Assuntos
Benzeno/química , Nanotubos/química , Potássio/análise , Adsorção , Monóxido de Carbono/química , Catálise , Modelos Moleculares , Nanotubos/ultraestrutura , Oxirredução , Oxigênio/química , Espectroscopia Fotoeletrônica , Teoria Quântica , Temperatura , Difração de Raios XRESUMO
The surface reactivity of iron (hydr)oxides plays a crucial role in controlling their interfacial reactions, for which various surface complexation models have been developed. The diversity of mineralogical properties of iron (hydr)oxides has resulted in a redundancy of model parameters, which hampers the modeling of iron (hydr)oxides in soils and sediments, where goethite, hematite and ferrihydrite dominate the iron (hydr)oxide mass fraction. To capture their combined surface reactivity, optimized generic protonation parameters of the Charge Distribution-Multisite Complexation (CD-MUSIC) extended-Stern-Gouy-Chapman (eSGC) model were derived by reanalyzing literature datasets and tested with some newly synthesized iron (hydr)oxides. It was observed that the proton and monovalent ion affinity constants of the different iron (hydr)oxides were located in a narrow range. For the singly- and triply-coordinated hydroxyl sites the obtained generic log(affinity constants) were 8.3 and 11.7 for the protonation reaction and -0.5 for the reaction with the monovalent background ions. Their combination with fixed site densities of singly-/triply-coordinated hydroxyl sites of 3.45/2.70, 5.00/2.50, and 5.80/1.40 sites/nm2 for goethite, hematite, and ferrihydrite, respectively, provided good results. The Stern layer capacitances of the inner and outer Stern layers were set equal and could be acquired by an empirical correlation with the sample specific surface area (SSA). The CD-MUSIC-eSGC model with the generic model parameters enables good quality predictions of the proton reactivity of iron (hydr)oxides in 1:1 electrolyte solutions regardless of the sample heterogeneity. The advantages of the generic CD-MUSIC-eSGC model are twofold: (1) protonation of iron (hydr)oxides can be described without making use of spectroscopic measurements and proton titrations, and (2) the model calculations are greatly simplified.
Assuntos
Ferro , Música , Óxidos , Prótons , Adsorção , Compostos Férricos/química , MineraisRESUMO
Relative to total cadmium (Cd) content, bioavailable Cd in paddy soil is regarded as a more reasonable indicator for the risk of Cd bioaccumulation in rice. However, there is still a lack of approach to accurately predict the content of bioavailable Cd in paddy soil due to its heterogeneity and complexity. Here, multi-surface speciation model (MSM) was employed to predict the bioavailable Cd and Cd immobilization effect. Moreover, a precise remediation strategy was designed based on screening and scenario simulation of the sensitive factors with MSM. The results demonstrated that MSM can well predict Cd bioaccumulation risk in rice. The contribution of pH to Cd bioavailability was quantified under three analysis scenarios, accounting for 87.51% of the total variance of bioavailable Cd. In addition, the pH alert value (6.31 ± 0.52) for Cd risk was acquired for each rice field on a county scale. A precise map for the application amount of lime materials was constructed by taking CaCO3 (3.38-15.75 t ha-1) as a recommended economical and green immobilization agent. This study provides a potentially effective approach for risk assessment of Cd contamination in rice and important reference for precise Cd remediation in paddy soil.
Assuntos
Oryza , Poluentes do Solo , Cádmio/química , Oryza/química , Solo/química , Disponibilidade Biológica , Poluentes do Solo/análiseRESUMO
Ferrihydrite is a poorly crystalline iron (hydr)oxide and highly efficient adsorbent for heavy metals. Al-substitution in ferrihydrite is ubiquitous in nature. However, the effect of Al-substitution on the surface reactivity of ferrihydrite remains unclear due to its low crystallinity. The present study aims to clarify the microstructure and interfacial reaction of Al-substituted ferrihydrite. Al-substitution had little effect on the morphology and surface site density of ferrihydrite, while the presence of ≡AlOH-0.5 sites resulted in higher proton affinity and surface positive charge of ferrihydrite. Besides, the affinity constant of Pb2+ adsorption on the surface of ferrihydrite decreased at higher Al content, which further decreased the adsorption performance of ferrihydrite for Pb2+. The modeling results revealed that bidentate complex was the dominant Pb complexation species on the surface of ferrihydrite, which was less affected by Al-substitution. The present study provides important insights into the effect of Al-substitution on the interfacial reaction at the ferrihydrite-water interface. The obtained parameters may facilitate the future advance of surface complexation model.
Assuntos
Chumbo , Metais Pesados , Adsorção , Compostos Férricos/química , Ferro , Óxidos , Prótons , ÁguaRESUMO
Background: The prognosis for patients with chronic hepatitis B virus (HBV)-related subacute liver failure is poor. Thus, accurate prognostication would facilitate management and optimize liver allocation. This study aimed to explore the risk factors for HBV-related subacute liver failure and establish a risk model. Methods: A total of 192 patients with HBV-related subacute liver failure treated at the First Affiliated Hospital of Xi'an Jiaotong University during January 2018 to January 2019 were selected and divided into the survival group (n=113) and the death group (n=79) based on their status within 6 months. Patient information were collected, including age, sex, body mass index, complications, hepatitis B e antigen (HBeAg), hepatic encephalopathy, hepatorenal syndrome, infections, ascites, HBV-DNA, Model for End-Stage Liver Disease (MELD), liver function tests, international normalized ratio (INR), serum creatinine and total cholesterol. Binary logistic regression was employed to identify risk factors for risk model establishment. The predictive value of the risk model was assessed with a receiver operating characteristic (ROC) curve. Results: Compared with the survival group, the patient age, incidence of hepatic encephalopathy and hepatorenal syndrome, infection and ascites rate, MELD score, and alanine aminotransferase (ALT), aspartate aminotransferase (AST), alkaline phosphatase (ALP), INR, and serum creatinine levels were significantly elevated, whereas the total cholesterol level was significantly decreased in the death group (all P<0.05). Patient age [odds ratio (OR) =1.11, P=0.03], hepatic encephalopathy (OR =8.31, P=0.02), infection (OR =4.27, P=0.005), ascites (OR =4.54, P=0.006), MELD score (OR =1.39, P<0.001), INR (OR =5.89, P=0.001), and total cholesterol (OR =0.31, P=0.002) were identified as prognostic factors affecting patient mortality. Although both the MELD score and the risk model established in the present study could differentiate patient outcomes, the area under the curve (AUC) (0.94 vs. 0.82, P<0.001) and sensitivity (91.1% vs. 58.2%, P<0.001) of the established risk model were significantly higher than those of the MELD score. Conclusions: Patient age, hepatic encephalopathy, infection, ascites, MELD score, INR, and total cholesterol level were independent prognostic factors. The prognostic model established based on these risk factors may have favorable predictive value.
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Goethite is a commonly found iron (hydr)oxide in soils and sediments that has been proven to possess abundant defects in structures. However, the underlying impact of these defects in goethite on arsenic immobilization remains unclear. In this study, goethite samples with abundant, moderate, and sparse defects were synthesized to evaluate their arsenic adsorption capacities. The characteristics of the defects in goethite were investigated by extended X-ray absorption fine structure (EXAFS), high angle annular dark field-scanning transmission electron microscopy-energy dispersion spectrum (HAADF-STEM-EDS) mapping, vibrating-sample magnetometry (VSM), and electron spin resonance (ESR). The characterization analysis revealed that the defects in as-synthesized goethite primarily existed in the form of Fe vacancies. Batch experiments demonstrated that the adsorption capacities of defect-rich goethite for As(V) and As(III) removal were 10.2 and 22.1 times larger than those of defect-poor goethite, respectively. The origin of the impact of Fe defects on arsenic immobilization was theoretically elucidated using density functional theory (DFT) calculations. The enhanced adsorption of goethite was attributed to the improvement of the arsenic affinity due to the Fe vacancy defect, thus considerably promoting arsenic immobilization. The findings of this study provide important insight into the migration and fate of arsenic in naturally occurring iron (hydr)oxides.
Assuntos
Arsênio , Compostos de Ferro , Arsênio/análise , Adsorção , Compostos de Ferro/química , Minerais/química , Ferro/química , Óxidos/análise , Solo , Compostos Férricos/químicaRESUMO
The fate of As(V) in subsurface environments is strongly affected by ubiquitous iron oxides. Defects are commonly present in natural hematite, while the impacts of defects on the active sites and complexation mechanism of hematite for As(V) remain poorly understood. In this study, the defect-rich hematite was employed to investigate the surface charge characteristics and As(V) adsorption behavior using potentiometric acid-base titration and CD-MUSIC model in comparison with corresponding defect-poor hematite. The total arsenate-active site density (5.7 sites/nm2) on defective hematite includes 1.2 sites/nm2 of original sites and 4.5 sites/nm2 of Fe vacancy-induced sites. The result revealed that the vacant Fe3+ sites in defective hematite was compensated by the protons in solution, thus resulting in a considerable increase in site density as well as positive charge. The CD-MUSIC modeling results demonstrated that the presence of Fe vacancies in hematite is beneficial to the improvement in affinity constants for both monodentate and bidentate arsenate complexes. The high adsorption capacity of defective hematite (2.60 µmol/m2) compared to defect-free hematite (1.33 µmol/m2) is attributed to its large affinity constants as well as its more active surface sites, thereby playing a vital role in reducing the threats of heavy metals in the environment.
Assuntos
Compostos Férricos , AdsorçãoRESUMO
Naturally occurring goethite commonly undergoes Al-substitution, while how changes in microstructure induced by Al-substitution affect the interactive reaction of Pb(II) or As(V) at the goethite-water interface remains poorly understood. This study reveals the structural properties of Al-substituted goethite and its adsorption behavior for Pb(II) and As(V) by multiple characterization techniques and Charge Distribution-Multisite Surface Complexation (CD-MUSIC) modeling. Al-substitution caused an obvious decrease in the length-to-width ratio in goethite particles and a slight decrease in the proportion of (110) facets. The presence of Al-O sites and higher surface roughness induced by Al-substitution contributed to a higher inner Stern layer capacitance (C1) and surface charge density of goethite. CD-MUSIC modeling results further revealed that the affinity constant of Pb(II) complex (log KPb) at the goethite-water interface and the adsorption capacity of goethite for Pb(II) decreased with increasing amount of Al-substitution, while an opposite tendency was observed for As(V) adsorption. The dominant species of both Pb(II) and As(V) on goethite were bidentate complexes, and Al-substitution had a minor impact on the abundance of Pb(II) and As(V) complexes on the surface of goethite. Overall, these experimental and modeling results provide new and important insights into the interfacial reactivity of Al-substituted goethite and facilitate the prediction of the environmental fate of heavy metals.
Assuntos
Compostos de Ferro , Chumbo , Adsorção , MineraisRESUMO
Fe-Mn binary oxide has received increasing interest in treating As(III)-containing polluted groundwater due to its low cost and environmental friendliness. Although the stability of Fe-Mn binary oxide is as important as its adsorption ability, little is known about whether and why Fe-Mn binary oxide is stable during As(III) removal. In this study, five successive cycles were conducted to evaluate the stability of Fe-Mn binary oxide for As(III) removal. As(III) oxidation/adsorption kinetics and the speciation distribution of the released Fe and Mn elements within single Fe oxide, Mn oxide, and Fe-Mn binary oxide were investigated by using characterization techniques of TEM-EDS mapping, selected area electron diffraction (SAED), and XPS combined with a binary component reactor, where Fe and Mn oxides were separated by a semipermeable membrane. The results revealed that Fe-Mn binary oxide could maintain excellent stability, although As(III) oxidation/adsorption behavior was coupled with the release of Fe and Mn ions from its surface. The great stability of Fe-Mn binary oxide for As(III) removal was attributed to the rapid return of aqueous Fe(II) and Mn(II) to the solid surface, which subsequently formed new mineral phases mediated by Fe and Mn oxides, thus considerably decreasing the loss of released Mn(II) and Fe(II).
Assuntos
Arsênio , Água Subterrânea , Poluentes Químicos da Água , Adsorção , Compostos de Manganês , Oxirredução , Óxidos , Poluentes Químicos da Água/análiseRESUMO
Cryptomelane-type octahedral molecular sieve (OMS-2) is one of the most promising catalysts for VOCs oxidation, and introduction of metal ions in OMS-2 tunnel is widely used for tailoring its catalytic activity. Here, different types of alkali earth metal ions with the same X/Mn atomic ratio of approximately 0.012 (X represents Mg2+, Ca2+, and Sr2+) were successfully introduced into OMS-2 tunnel by a one-step redox reaction. The catalytic test showed that introducing alkali earth metal ions into tunnels had a considerable effect on the catalytic performance of OMS-2 for benzene oxidation. The Sr2+ doped OMS-2 catalyst exhibited the better catalytic activity compared with those of Mg-OMS-2 and Ca-OMS-2 samples, and was also superior to a commercial 0.5% Pt/Al2O3 catalyst, as evidenced by its low reaction temperatures of T50 = 200 °C and T90 = 223 °C (corresponding to benzene conversions at 50% and 90%, respectively). The origin of the considerable effect of alkali earth metal doping on the catalytic activity of OMS-2 catalysts was experimentally and theoretically investigated by an 18O2 isotopic labeling experiment, CO temperature-programmed reduction, O2 temperature-programmed oxidation, and density functional theory calculations. The greatest catalytic activity of Sr-OMS-2 compared with those of Mg-OMS-2 and Ca-OMS-2 samples was attributed to its highest lattice oxygen activity as well as its largest surface area. By introducing alkali earth metal ions into the OMS-2 tunnel, we developed a low-cost and highly efficient catalyst that could be used as alternative to noble metal catalysts.
Assuntos
Benzeno/química , Metais Alcalinoterrosos/química , Modelos Químicos , Álcalis , Catálise , Cicloexanos , Íons , Oxirredução , Oxigênio , TemperaturaRESUMO
Cryptomelane-type manganese oxides (OMS-2) have been intensively investigated for application in the catalytic oxidation of carcinogenic benzene, and doping metal ions in the OMS-2 tunnels are widely used for modifying its catalytic activity. In this study, we reported a novel strategy of enhancing catalytic activity of OMS-2 for carcinogenic benzene elimination by tuning Sr2+ concentration in the tunnels. The catalytic activity result revealed that an obvious decrease (â³T50 = 27 °C and â³T90 = 37 °C) in T50 and T90 (corresponding to benzene conversions at 50 % and 90 %, respectively; initial benzene concentration was 2000 mg m-3; contact time was 1.5 s) had been observed by increasing the Sr2+ concentration in the OMS-2 tunnels. The origin of Sr2+ doping effect on catalytic activity was theoretically and experimentally investigated by CO temperature-programmed reduction, 18O2 isotope labeling, and density functional theory calculations. The result confirmed that increasing Sr2+ concentration in the tunnels not only promoted the lattice oxygen activity, but also facilitated the generation of more oxygen vacancy defects, thus considerably improving the catalytic activity of OMS-2.
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Cryptomelane-type octahedral molecular sieve manganese oxide (OMS-2) possesses high redox potential and has attracted much interest in its application for oxidation arsenite (As(III)) species of arsenic to arsenate (As(V)) to decrease arsenic toxicity and promote total arsenic removal. However, coexisting ions such as As(V) and phosphate are ubiquitous and readily bond to manganese oxide surface, consequently passivating surface active sites of manganese oxide and reducing As(III) oxidation. In this study, we present a novel strategy to significantly promote As(III) oxidation activity of OMS-2 by tuning K+ concentration in the tunnel. Batch experimental results reveal that increasing K+ concentration in the tunnel of OMS-2 not only considerably improved As(III) oxidation kinetics rate from 0.027 to 0.102 min-1, but also reduced adverse effect of competitive ion on As(III) oxidation. The origin of K+ concentration effect on As(III) oxidation was investigated through As(V) and phosphate adsorption kinetics, detection of Mn2+ release in solution, surface charge characteristics, and density functional theory (DFT) calculations. Experimental results and theoretical calculations confirm that by increasing K+ concentration in the OMS-2 tunnel not only does it improve arsenic adsorption on K+ doped OMS-2, but also accelerates two electrons transfers from As(III) to each bonded Mn atom on OMS-2 surface, thus considerably improving As(III) oxidation kinetics rate, which is responsible for counteracting the adverse adsorption effects by coexisting ions.