Complexation mechanism of Pb2+ on Al-substituted hematite: A modeling study and theoretical calculation.

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.

Adsorption Mechanisms of Glyphosate on Ferrihydrite: Effects of Al Substitution and Aggregation State.

Ferrihydrite is one of the most reactive iron (Fe) (oxyhydr)oxides in soils, but the adsorption mechanisms of glyphosate, the most widely used herbicide, on ferrihydrite remain unknown. Here, we determined the adsorption mechanisms of glyphosate on pristine and Al-substituted ferrihydrites with aggregated and dispersed states using macroscopic adsorption experiments, zeta potential, phosphorus K-edge X-ray absorption near-edge structure spectroscopy, in situ attenuated total reflectance Fourier transform infrared spectroscopy coupled with two-dimensional correlation spectroscopy, and multivariate curve resolution analyses. Aggregation of ferrihydrite decreases the glyphosate adsorption capacity. The partial substitution of Al in ferrihydrite inhibits glyphosate adsorption on aggregated ferrihydrite due to the decrease of external specific surface area, while it promotes glyphosate adsorption on dispersed ferrihydrite, which is ascribed to the increase of surface positive charge. Glyphosate predominately forms protonated and deprotonated, depending on the sorption pH, monodentate-mononuclear complexes (MMH1/MMH0, 77-90%) on ferrihydrites, besides minor deprotonated bidentate-binuclear complexes (BBH0, 23-10%). Both Al incorporation and a low pH favor the formation of the BB complex. The adsorbed glyphosate preferentially forms the MM complex on ferrihydrite and preferentially bonds with the Al-OH sites on Al-substituted ferrihydrite. These new insights are expected to be useful in predicting the environmental fate of glyphosate in ferrihydrite-rich environments.

Effects of Al(3+) doping on the structure and properties of goethite and its adsorption behavior towards phosphate.

Al substitution in goethite is common in soils, and has strong influence on the structure and physicochemical properties of goethite. In this research, a series of Al-doped goethites were synthesized, and characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The adsorption behavior of these samples towards PO4(3-) was also investigated. Characterization results demonstrated that increasing Al content in goethite led to a reduction in crystallinity, increase in specific surface area (SSA), and morphology change from needle-like to granular. Rietveld structure refinement revealed that the lattice parameter a remained almost constant and b slightly decreased, but c was significantly reduced, and the calculated crystal density increased. EXAFS analysis demonstrated that the Fe(Al)-O distance in the structure of the doped goethites was almost the same, but the Fe-Fe(Al) distance decreased with increasing Al content. Surface analysis showed that, with increasing Al content, the content of OH groups on the mineral surface increased. The adsorption of phosphate per unit mass of Al-doped goethite increased, while adsorption per unit area decreased owing to the decrease of the relative proportion of (110) facets in the total surface area of the minerals. The results of this research facilitate better understanding of the effect of Al substitution on the structure and properties of goethite and the cycling of phosphate in the environment.

Aluminum substitution stabilizes organic matter in ferrihydrite transforming into hematite: A molecular analysis.

The association of soil organic matter (SOM) with iron (Fe) oxyhydroxides, particularly ferrihydrite, plays a pivotal role in the biogeochemical cycling of carbon (C) in both terrestrial and aquatic environment. The aging of ferrihydrite to more crystalline phases can impact the stability of associated organic C, a process potentially influenced by aluminum (Al) substitution due to its abundance. However, the molecular mechanisms governing the temporal and spatial distribution of SOM during the aging process of Al-substituted Fe oxyhydroxides remain unclear. This study aims to bridge this knowledge gap through a comprehensive approach, utilizing batch experiments, solid characterization techniques, and atomic force microscopy (AFM) based peak-force quantitative nanomechanical mapping (PF-QNM). Batch experiments revealed that humic acid (HA) was released into the aqueous phase during aging, with Al inhibiting this release. Various solid characterization methods collectively suggested that Al hindered the crystalline transformation of ferrihydrite and significantly preserved HA on the surface of newly formed hematite, rather than it being occluded within the interior of the new minerals. Results from 3-Dimensional fluorescence spectroscopy (3D-EEM) and Fourier-transform infrared spectroscopy (FTIR) indicated that the structure of HA remained constant, with the carboxyl-rich and hydroxyl-rich portions of HA fixed at the mineral interface during the aging period. Furthermore, we developed AFM-based PF-QNM to both quantify and visualize the interactions between Fe oxyhydroxides and HA, demonstrating variations in HA affinity among different Fe oxyhydroxides and highlighting the influence of the Al substitution rate.

Mineralogical fingerprint and human health risk from potentially toxic elements of Fe mining tailings from the Fundão dam.

In 2015, >50 million cubic meters of Fe mining tailings were released into the Doce River basin from the Fundão dam, raising the question of its consequences on the affected ecosystems. This study aimed to establish a mineralogical-(geo)chemical association of potentially toxic elements (PTEs) from Fe mining tailings from the Fundão dam, collected seven days after the failure, through a multidisciplinary approach combining assessment of the risk to human health, environmental geochemistry, and mineralogy. Thus, eleven tailings samples were collected with the support of the Brazilian Military Police Fire Department. Granulometry, magnetic measurements, optical microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and sequential chemical extraction of PTEs analyses were performed. Contamination indexes, assessment of risk to human health, and Pearson correlation were calculated using the results of sequential chemical extraction of PTEs. The predominance of goethite in Fe oxyhydroxide concentrates from the mud indicates that the major source of hematite may not be from tailings, but from pre-existing soils and sediments, and/or preferential dissolution of hematite in deep flooded zones of the tailings column of the Fundão dam. Moreover, the high correlation of most carcinogenic PTEs with their crystallographic variables indicates that goethite is the primary source of contaminants. Goethites from Fe mining tailings showed high specific surface area and Al-substitution, and due to their greater stability and reactivity, the impacts on PTE sorption phenomena and bioavailability may be maintained for long periods. However, their lower dissolution rate, and the consequent release of heavy metals would promote greater resilience for affected ecosystems, preventing significant PTE inputs under periodic reduction conditions. More specific studies, involving the crystallographic characteristics of Fe oxyhydroxides should be developed since they may provide another critical component of this set of complex and dynamic variables that interfere with the bioavailability of metals in ecosystems.

Pt-O-Ce interaction enhanced by Al substitution to promote the acetone degradation through accelerating the breaking of CC bond in acetic acid intermediate.

The reaction rate of volatile organic compounds (VOCs) oxidation is controlled by the rate-limiting step in the total reaction process. This study proposes a novel strategy, by which the rate-limiting step of acetone oxidation is accelerated by enhanced chemical bond interaction with more electrons transfer through Al-substituted CeO2 loaded Pt (Pt/Al-CeO2). Results indicate that the rate-limiting step in the process of acetone oxidation is the decomposition of acetic acid. Al substitution enhances the Pt-O-Ce interaction that transfers more electrons from Pt/Al-CeO2 to acetic acid, promoting the breaking of its CC bond with a lower free energy barrier. Attributing to these, the reaction rate of Pt/Al-CeO2 is 13 times as high as that of Pt/CeO2 and its TOFPt value is 11 times as high as that of Pt/CeO2 at 150 °C. Moreover, the CO2 selectivity of Pt/Al-CeO2 also increases by 22 %. This work establishes the relationship between Pt-O-Ce interaction and acetone oxidation that provides novel perspectives on the development of efficient materials for VOCs oxidation.

Role of Al substitution in the reduction of ferrihydrite by Shewanella oneidensis MR-1.

Substitution of aluminum under natural environmental conditions has been proven to inhibit the transformation of weakly crystalline iron (oxyhydr)-oxides towards well crystalline iron oxides, thereby enhancing their long-term stability. However, exploration on the role of aluminum substitution in bacteria-mediated iron oxides transformation is relatively lacking, especially in the anaerobic underground condition where iron (oxyhydr)-oxides are easy to reduced. In this study, we selected four different levels of substitution aluminum prevalent in iron oxides under natural conditions, which are 0 mol%, 10 mol%, 20 mol%, and 30 mol% (mol Al/mol (Al + Fe)) respectively. With the presence of Shewanella oneidensis MR-1, we conducted a 15-day anaerobic microcosm experiment in simulated groundwater conditions. The experiment data suggested that aluminum substitution result in a decrease in bio-reduction rate constants of ferrihydrite from 0.24 in 0 mol% Al to 0.17 in 30 mol% Al. Besides, when containing substituted aluminum, secondary minerals produced by biological reduction of ferrihydrite changed from magnetite to akaganeite. These results were attributed to the surface coverage of Al during the reduction process, which affects the contact between S. oneidensis MR-1 and the unexposed Fe(III), thus inhibiting the further reduction of ferrihydrite. Since iron (oxyhydr)-oxides exhibit a strong affinity on multiple kinds of pollutants, results in this study may contribute to predicting the migration and preservation of contaminants in groundwater systems.

Complexation mechanism of Pb2+ at the ferrihydrite-water interface: The role of Al-substitution.

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.

Effects of Al substitution on sorption of diclofenac to Fe(III) (hydr)oxides: roles of phase transition and sorption mechanisms.

Fe(III) (hydr)oxides commonly contained many metal impurities such as Al. The incorporation of Al might change the properties of minerals and consequently affect sorption behaviors of pollutants with polar functional groups (e.g., diclofenac (DCF)). In this study, batch experiments and microscale characterization were conducted to investigate the DCF sorption mechanisms to goethite and Al-substituted minerals. Goethite and Al-substituted products (including Al-goethite, Al-goethite-hematite, and Al-hematite) were synthesized with different Al contents (i.e., 0%, 5%, 10%, and 15% (in mol)) by co-precipitation method. Due to difference of ionic radius between Al and Fe and formation of excessive -OH, Al substitution resulted in deviation of cell parameters from the Vegard line. Al substitution caused increasing -OH in Al-goethite and phase transformation caused decreasing -OH in Al-hematite. The total -OH in minerals was positively related to DCF sorption capacity. In the lower initial concentration range (0.4-9 mg/L), the sorption distribution coefficient (Kd) values of goethite, Al-goethite, and Al-hematite were 21.98, 22.25, and 21.18 L/kg, respectively. Desorption characteristics and ion strength effects indicated that DCF sorption to minerals occurred mainly through outer-sphere complexation. Fourier transform infrared analyses revealed that H-bonds could be formed through -OH of minerals and -COOH of DCF, and the H-bond strength on Al-hematite was stronger than that on goethite/Al-goethite. In the normal environmental pH (e.g., 6.0 to 8.0), Kd values of DCF decreased linearly with increasing pH. These findings are helpful for understanding of DCF migration in environment involving Al-substituted minerals.

Determination of Band Structure of Naturally Occurring Goethite with Al Substitution: A Case Study of Zhushan Iron Zone.

The photocatalytic property of Fe oxide minerals has long been considered to play an important role in shaping modern terrestrial environments. However, due to the complexity of natural settings, a precise determination of the band structure of natural goethite has not been achieved. In this work, the mineralogical characteristics of natural goethite samples obtained from Zhushan, China, were systematically studied through X-ray diffraction, transmission electron microscopy, X-ray energy dispersive spectroscopy, and X-ray fluorescence spectroscopy. Afterward, the band structure for both natural and synthetic goethite samples was determined by synchrotron-based X-ray absorption and emission spectra and photoelectron spectroscopy. The band gap of natural goethite (2.25 eV) was narrower than that of its synthetic counterpart (2.55 eV), and the valence band position of natural goethite was slightly lifted (-5.06 eV) compared to that of synthetic goethite (-5.38 eV). Al doping in natural goethite crystal, as revealed by the mineralogical tests, was the main reason that contributed to this difference. The theoretical calculation showed the narrowed band gap was caused by the contribution of Al-2p orbits at the top of the valence band. Therefore, free electrons can be created under light irradiation with a shorter wavelength. The experiments showed that natural goethite can photo-catalytically degrade methyl orange, and the degradation efficiency was better (47.5%) than that of the synthetic goethite group (31.5%). This study, for the first time, revealed the band structure and confirmed the photocatalytic properties of natural goethite, which should play an important role in surface substance evolution and elemental cycling.

Low-Cost Al-Doped Layered Cathodes with Improved Electrochemical Performance for Rechargeable Sodium-Ion Batteries.

O3-NaNi0.25Fe0.5Mn0.25O2 layered oxide is considered one of the most promising cathode candidates for sodium-ion batteries because of its advantages, such as its large capacity and low cost. However, the practical application of this material is limited by its poor cyclic stability and insufficient rate capability. Here, a strategy to substitute the Fe3+ in NaNi0.25Fe0.5Mn0.25O2 with Al3+ is adopted to address these issues. The substitution of Fe3+ with Al3+ enhances the framework stability and phase transition reversibility of the parent NaNi0.25Fe0.5Mn0.25O2 material by forming a stronger TM-O bond, which improves the cycling stability. Moreover, partial Al3+ substitution increases the interslab distance, providing a spacious path for Na+ diffusion and resulting in fast diffusion kinetics, which lead to improved rate capability. Consequently, the target NaNi0.25Fe0.5-xAlxMn0.25O2 sample with optimal x = 0.045 exhibits a remarkable electrochemical performance in a Na-ion cell with a large reversible capacity of 131.7 mA h g-1, a stable retention of approximately 81.6% after cycling at 1C for 100 cycles, and a rate performance of 81.3 mA h g-1 at 10C. This method might pave the way for novel means of improving the electrochemical properties of layered transitional-metal oxides and provide insightful guidance for the design of low-cost cathode materials.

Promotional effects of calcination temperature and H2O on the catalytic activity of Al-substituted MnAlO catalysts for low-temperature acetone oxidation.

In order to enhance the role of Al in the materials, Al-substituted MnAlO catalysts were synthesized via the hydrothermal-redox method at different calcination temperatures for acetone oxidation. There were Al-substituted α-MnO2 and amorphous aluminum oxide existed with homogeneous dispersion of elements in the catalysts. The surface property, reaction rate, CO2 yield and water resistance of MnAlO catalysts were greatly affected by calcination temperatures. MnAlO-450 catalyst exhibited the best catalytic performance (acetone conversion of 90% at 165 °C) with CO2 yield higher than 99.7%, which was mainly related to the weaker Mn-O bond strength, lower temperature reducibility and abundant Lewis acid sites. The acetone conversion of MnAlO-450 increased by as much as 16% in the presence of 1 vol% H2O compared to that in the absence of H2O at T50 (the temperature for 50% conversion of acetone). The acceleration consumption of ethanol as the main by-product by H2O improved the catalytic performance. This work would shed light on the Al substitution based catalysts for OVOC oxidation with highly efficient and water resistance.

Microstructure of Al-substituted goethite and its adsorption performance for Pb(II) and As(V).

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.

Adsorption of Cr(VI) on Al-substituted hematites and its reduction and retention in the presence of Fe2+ under conditions similar to subsurface soil environments.

Aluminum substitution is common in iron (hydr)oxides in subsurface environments, and can significantly modify mineral interactions with contaminants. However, few studies investigate Cr(VI) adsorption and its subsequent mobility on Al-substituted iron (hydr)oxide surfaces. Here shows that Al substitution gradually modifies hematite crystals from {101}, {112}, {110} and {104} faceted rhombohedra to {001} faceted plates, resulting in a general decrease in Cr(VI) adsorption density and favoring of monodentate mononuclear over bidentate binuclear Cr(VI) adsorption complexes. Consequently, the mobility of Cr(VI) might be increased in environments with an abundance of Al-containing iron (hydr)oxides. However, pre-adsorption of Fe2+ on hematite promotes Cr(VI) adsorption, reduction and fixation, and Al-substituted hematite removes more Cr(VI) than pure hematite. Similarly, although addition of Fe2+ to Cr(VI)-adsorbed hematite remobilizes a small proportion of Cr, it greatly increases the proportion of Cr fixed. As the coexistence of Fe2+ and iron (hydr)oxides is common in subsurface environments, Al-containing iron (hydr)oxides will promote Cr(VI) uptake and retention, with a significant proportion fixed as Cr(III), limiting Cr mobility and toxicity. These results offer new insights into how iron (hydr)oxides might control the behaviors of other high-valence redox-sensitive contaminants, and provide a platform for modeling such processes in complex soil and sediment systems.

Effects of Al3+ Substitution on Structural and Magnetic Behavior of CoFe2O4 Ferrite Nanomaterials.

A sol-gel autocombustion method was used to synthesize Al3+ ion-substituted cobalt ferrite CoAlxFe2-xO4 (x = 0⁻1.5). According to X-ray diffraction analysis (XRD), cobalt ferrite was in a single cubic phase after being calcined at 1000 °C for 3 h. Moreover, the lattice constant decreased with increase in aluminum substituents. When the sample was analyzed by Scanning Electron Microscopy (SEM), we found that uniformly sized, well-crystallized grains were distributed in the sample. Furthermore, we confirmed that Al3+ ion-substituted cobalt ferrite underwent a transition from ferrimagnetic to superparamagnetic behavior; the superparamagnetic behavior was completely correlated with the increase in Al3+ ion concentration at room temperature. All these findings were observed in Mössbauer spectra. For the cobalt ferrite CoAlxFe2-xO4, the coercivity and saturation magnetization decrease with an increase in aluminum content. When the annealing temperature of CoAl0.1Fe1.9O4 was steadily increased, the coercivity and saturation magnetization initially increased and then decreased.