Fe Leaching Research Articles

Efficient purification and utilization of pyrite cinder for carbon-coated lithium iron phosphate synthesis

Nonferrous impurities such as Cu, Zn, and Co, along with inert materials such as gangue and silica in pyrite cinder (PyC), significantly limit its direct use as an iron source for battery-grade ferric phosphate (FP) or lithium iron phosphate (LFP). To address this issue, a new process using alkali excitation, mechanical activation, and aging to remove impurities from PyC was developed. Additionally, a novel method for preparing carbon-coated lithium iron phosphate (LFP@C) using purified PyC (p-PyC) as the iron source was explored. With 20% NaOH, 3h of ball milling activation, and aging at 200 ℃ for 4h, the Fe content in PyC increased to 55.14%, with a recovery rate of 95.43%. Compared with those in untreated PyC, the Fe leaching rate in p-PyC reached 98.25%, and the levels of Al, Cu, Zn, Co, and Si in the acid-leaching liquor were reduced by 96.62%, 96.67%, 99.85%, 75.96%, and 99.99%, respectively. The LFP@C cathode material was directly prepared via carbothermal reduction using acid-leaching liquor from p-PyC as the iron source. The LFP@C-30% crystal particles were well connected, and the surface was effectively coated with a carbon layer to form a conductive layer. At 0.1C, the specific capacity was 159.09 mAh·g−1, with 95.63% capacity retention after 100 cycles. LFP@C-30% presented the lowest charge transfer resistance and an apparent diffusion coefficient (DLi) of 2.33×10−11 cm2·s−1. This study offers a simple and effective method for removing impurities from PyC and presents a new approach for converting PyC into high-demand FPs or LFPs.

Iron-based nitrogen-rich metal-organic framework structure for activation of hydrogen peroxide and peroxymonosulfate for ultra-efficient tetracycline degradation

Fe-based metal–organic frameworks (Fe-MOFs) have been used to catalyze the degradation of organic pollutants; however, the underlying mechanism remains unclear. In this study, we prepared Fe-MOF catalysts featuring a three-dimensional ordered structure and active Fe-N4 coordination centers using self-designed polypyrazole compounds as ligands. Because the coordination centers are similar to the classical single-atom Fe-N4 active neutral structure, Fe-MOFs exhibit excellent performance in activating hydrogen peroxide (H2O2) and peroxymonosulfate (PMS) for the degradation of antibiotics. Moreover, the two adjacent nitrogen atoms in pyrazole strengthen the interaction with active neutral Fe, thereby enhancing the efficiency and selectivity of the catalytic sites. In the presence Fe-MOF/H2O2, a free radical process involving hydroxyl radicals (OH) is activated to achieve a degradation rate of 98.36 % for tetracycline (TC) within 10 min. In a Fe-MOF/PMS system, 97.01 % of TC can be degraded within 10 min through a non-free radical process with singlet oxygen (1O2) as the primary active species. The high degradation efficiency of Fe-MOF is primarily attributed to its highly catalytically active structure, which exerts a van der Waals force effect on the pollutants, thereby facilitating electron transfer between the pollutants and active centers. This shortens the distance between the pollutants and Fe catalytic center, enhances electron transfer, and promotes the chemical adsorption of H2O2 and PMS to form FeN4-H2O2 and FeN4-PMS, respectively. Additionally, the strong coordination within the Fe-N4 pyrazole structure significantly suppresses Fe leaching, facilitating a stable adsorption configuration.

Effective activation of PMS by encapsulating monodispersed Fe3O4 within N, S heteroatoms co-doped carbon chamber for ROX removal dominated by the non-radical pathway

Developing the eco-friendly catalyst-adsorption iron-based materials with improved catalytic activity and minimal Fe leaching is fascinating for roxarsone (ROX) removal. Herein, Fe3O4 nanoparticles were encapsulated in flexible N, S-modified carbon chamber (Fe3O4@NS4C) through the “hydrothermal + pyrolysis” process to form a catalyst with multi-active sites. ROX could be degraded nearly 100 % at pH 5.0 −11.0 and secondary inorganic As species concentration is lower than 0.09 mg/L by efficient adsorption. Especially, the Fe ion leaching concentration in Fe3O4@NS4C/PMS after ROX removal is decreased to 0.08 mg/L. Combined with quenching experiment, EPR, Raman spectroscopy and electrochemical analysis, the non-radical activation mechanism dominated by 1O2 and electron transfer was determined. The synergistic interaction between the N doped sites and the S anchored sites within the carbon matrix not only improves the adsorption of PMS on the catalyst but also facilitates the direct activation of PMS to 1O2, while the surface electron transfer improves the Fe2+/Fe3+ redox cycling in PMS activation. The active sites of ROX attacked by 1O2 were examined through Fukui function computations. Combined with HPLC-MS, the ROX degradation pathway was determined, and the toxicity of intermediates was evaluated. Furthermore, the removal performance of ROX in Fe3O4@NS4C/PMS system was also assessed in different environment for practical application, indicating that the advantages in the synergy between N, S co-doping carbon chamber and encapsulated iron oxide for water purification.

The effect of biopolymer stabilisation on biostimulated or bioaugmented mine residue for potential technosol production

Mine waste can be transformed into technosol as an ecological strategy. Despite its importance to soil functions, biological activity is often overlooked. Biopolymers can serve as innovative tools for bioremediation, facilitating chemical reactions and creating networks to encapsulate contaminants. This work aims to assess the use of bioleached and stabilised residues from a tungsten mine for technosol production. The first objective was to evaluate mine tailings for their bioleaching potential by biostimulation or bioaugmentation with strain Diaphorobacter polyhydroxybutyrativorans B2A2W2. The second was to evaluate the effect of Portland cement or biopolymers such as Carboxymethyl Cellulose (CMC) or Xanthan Gum (XG) on the stabilisation of bioleached residues. The impact of biopolymers on residues’ characteristics, such as metal leaching, number of cultivable microorganisms, compression strength and ecotoxicity was evaluated using flow systems. Over time, bioleached metallic elements decreased, except for iron (Fe). Biostimulated and stabilised residues exhibited similar trends; both CMC and cement showed low leaching rates and viable microorganisms in the same order (106 CFU × ml−1). However, bioaugmented residue stabilised with XG showed 106 CFU × ml−1 viable microorganisms and increased 2.2-fold Fe leaching than BA_Control. CMC addition to bioaugmented residue reduced 5.9-fold Fe leaching and increased 100-fold viable microorganisms. By utilising both biological and engineering approaches to characterise the technosol, this study contributes to advancing knowledge of technosol production. The residues biostimulated and stabilised with CMC produced a material useful for bio-applications, with low toxicity and metal leaching, useful for bio-applications. XG was the best stabiliser for geotechnical engineering applications, with improved compression strength. In conclusion, the study demonstrates the usefulness of biopolymer treatment for residues and emphasises the importance of selecting the appropriate biopolymer for the intended function of technosols.

ZIFs@MIL-101/urea-derived magnetic FeCo nitrogen-rich carbon as an effective and stable catalyst for peroxymonosulfate activation

High efficiency and stability are key issues in heterogeneous metal catalytic materials/peroxymonosulfate (PMS) systems during wastewater degradation. However, catalytic materials that are difficult to recover and metal leaching can cause secondary contamination of water bodies. Herein, we designed the magnetic FeCo nitrogen-rich carbon (FeCo-NC) obtained by layer-by-layer encapsulation, followed by urea encapsulation of in situ grown MOF-in-MOF and carbonization. The CoFe2O4 crystalline nature of FeCo-NC was confirmed by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and selected angle electron diffraction (SAED) results, which is responsible for the magnetic properties of FeCo-NC. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) present that the material's morphology transforms from dodecahedral ZIF-67 to spindle-shaped ZIF-67@MIL-101 and then to octahedral FeCo-NC. Compared with FeCo-C and ZIF-67@MIL-101, the removal efficiency of FeCo-NC was maintained at 78.6 % after 10 consecutive cycles, with only a 17 % loss of raw material. The Fe and Co leaching amounts in the FeCo-NC/PMS system were approximately 0.6 and 0.1 mg/L, respectively, much lower than China's Fe and Co emission standards. FeCo-NC characterization and TC degradation results demonstrated that magnetic CoFe2O4 nanoparticles formed on the surface or inside the FeCo-NC could effectively inhibit metal (Fe and Co) loss and be easily regenerated in multiple degradation cycles. The mechanism and degradation routes in the FeCo-NC/PMS/ TC system, including the radical/nonradical pathways, Fe/Co valence change, and electron transfer, were further investigated by electron paramagnetic resonance experiments, electrochemical analyses, in situ Raman spectroscopy, and HPLC–MS experiments.

Coordination Stabilization of Fe by Porphyrin‐Intercalated NiFe‐LDH Under Industrial‐Level Alkaline Conditions for Long‐Term Electrocatalytic Water Oxidation

AbstractThe durable and economic electrocatalysts with high current density under industrial alkaline conditions are critical for advancing the industrial production of hydrogen energy by water electrolysis. The industrial highly alkaline electrolyte exacerbates the Fe dissolution of NiFe layered double hydroxide (NiFe‐LDH), leading to the dramatic degradation of stability and activity. The NiFe‐LDH intercalated Tetrakis(4‐carboxyphenyl)porphyrin (TCPP) (NiFe‐TCPP), 1,4,7,10‐Tetraazacyclododecane‐1,4,7,10‐tetraacetic acid (DOTA) (NiFe‐DOTA) and CO32− (NiFe‐CO3) are fabricated respectively for electrocatalytic water oxidation under industrial alkaline conditions. In 10 m KOH, compared to NiFe‐DOTA (335.0 mV) and NiFe‐CO3 (499.2 mV), the resultant NiFe‐TCPP exhibits the lowest overpotentials of 290.2 mV at 1000 mA cm−2. The NiFe‐TCPP also operates continuously for 1000 h at 500 mA cm−2 with near‐zero attenuation. The theoretical and experimental studies reveal that the strong coordination between conjugated carboxylate ligand TCPP and Fe of the laminate inhibits the Fe leaching by increasing the dissolution energy barriers to 4.29 eV and improving the self‐healing ability, thus enhancing the stability. Furthermore, the charge redistribution induced by the strong coordination optimizes the d‐band centers (‐2.81 eV) and decreases the reaction energy barriers (1.47 eV), thereby increasing the catalytic activity.

Performance and reaction mechanism of montmorillonite/α-Fe2O3/starch bio-nanocomposite as high-efficiency photocatalytic degradation of acetaminophen: Characterization, feasibility, and pathway

The worldwide challenge of eliminating pharmaceutical contaminants requires immediate attention. Developing bio-based catalysts that are eco-friendly, reusable, and high-performance, employing starch (ST) and montmorillonite (MMT) as support, holds tremendous promise as a novel biocatalyst for pharmaceutical waste removal. In this study, a montmorillonite/α-Fe2O3/starch (MMT/α-Fe2O3/ST) bio-nanocomposite photocatalyst was successfully synthesized and used for acetaminophen (ACT) degradation under UVA-LED irradiation. The influence of operational factors, such as catalyst, ACT concentrations, and solution pH, on photocatalytic activity was examined in detail; catalyst: 0.75 g/L, pH: 7.1, leading to total ACT (10 mg/L) removal in ∼80 min. MMT/α-Fe2O3/ST showed excellent durability due to negligible Fe leaching. After four successive degradation cycles, ACT and TOC elimination efficiencies remained over 91 and 42.7 %. Compared to other anions studied, carbonate ions suppressed the most ACT degradation. Based on the radical scavenger experiments, hydroxyl and superoxide radicals and holes were involved in the MMT/α-Fe2O3/ST system. LC-MS results were used to propose ACT degradation pathways. This work illuminated the significance of biocatalysts in removing emerging pollutants from wastewater.

Influence of Oxygen Vacancies in La0.4Sr0.6FeO3-δ Perovskite Oxide Nanoparticles for the Oxygen Evolution Reaction

Iron incorporation is one of the key factors to generate highly active NiFe(OH)x electrocatalysts for the oxygen evolution reaction (OER). However, it remains controversial whether Fe(IV) is present during OER and how the oxygen vacancies in Fe(IV)-containing metal oxides affect their activities. In this work, we develop a facile approach to control oxygen vacancy content, via an ozone treatment under ambient pressure during cooling for the synthesis of La1-x Sr x FeO3-δ (0 ≤ x ≤ 1, 0 ≤ δ ≤ 0.5x) perovskite oxides - an important class of energy-related materials that contain a rare Fe(IV) oxidation state. We have initially synthesized a series of La1-x Sr x FeO3-δ compounds using a polymerized complex method. The concentration of oxygen vacancies and Fe(IV) are determined by redox titration, and the crystal structures are derived by analyzing X-ray diffraction patterns using Rietveld refinement. Significant amounts of oxygen vacancies are found in the as-synthesized compounds with x ≥ 0.8: La0.2Sr0.8FeO3-δ (δ = 0.066) and SrFeO3-δ (δ = 0.195). A subsequent ambient-pressure ozone treatment approach is able to substantially reduce the amount of oxygen vacancies in these compounds to achieve levels near the ideal oxygen stoichiometry of 3 for La0.2Sr0.8FeO3-δ (δ = 0.006) and SrFeO3-δ (δ = 0.021). The oxygenation/deoxygenation kinetics can be tuned by the cooling rate after annealing. As the oxygen vacancy concentration decreases, the structure of SrFeO3-δ evolves from orthorhombic to cubic, demonstrating that the crystal structures in metal oxides can be highly sensitive to the number of oxygen vacancies. We have further conducted a systematic evaluation of the OER activity and stability of La1-x Sr x FeO3-δ perovskites in 1 M KOH. Their initial OER activity first increases with increasing Sr content (from x = 0 to 0.8), and then decreases when the Sr content is increased to 1. Their stability, as evaluated by monitoring element leaching from the electrodes show that La does not leach at a detectable rate, but Sr and Fe leach substantially. The leaching of Sr occurs at similar rates under open circuit potential (OCP) and OER potential, suggesting a nonelectrochemical dissolution process. The leaching of Fe is, however, strongly dependent on the electrode potential. More Fe leaching is observed at the OER potential than OCP. Additionally, the electrode with higher initial OER activity leaches more Fe. These results indicate that OER facilitates the dissolution of Fe from the electrode. The leaching of Fe, in turn, is considered responsible for the activity loss of La1- x Sr x FeO3- δ during OER. This study brings new insight into the degradation mechanism of La1- x Sr x FeO3- δ and related metal oxides during electro-oxidation processes.

Exploring Fe Retention in Oxygen Evolution Reaction Catalysts Via Composition Engineering

The oxygen evolution reaction (OER) is an electrochemical half-reaction critical to electrolyzer and metal-air battery technologies. It is well established that Ni (oxy)hydroxides are state-of-the-art electrocatalysts for the OER in basic media when Fe impurities are present in these systems. Morphological studies have shown that these catalysts are prone to dramatic nanoscale reconstruction under electrochemical conditions, implying dissolution, migration and redeposition processes of the catalyst’s components. Processes involving the displacement of Fe are especially important to understand, as these impurities, while essential for high activity at the anode, are often associated with cathode fouling. Describing the parameters that govern Fe leaching is thus of interest for the design of materials aimed toward the maintenance of device performance and longevity. To study how the degree of restructuring relates to Fe dissolution and redeposition, we have prepared a series of electrolyte accessible Ni(z)Co(1-z)O(x)H(y) (z = 0, 0.2, 0.4, ...) thin film catalysts, whereby increased amounts of Co limit the material’s dynamic behavior. By introducing tertiary cations with trackable redox features, we map a parameter space of catalyst composition more or less capable of retaining surface active phases. Parallels with Ni-Co + Fe catalysts are then carried out in Fe-free electrolyte to disrupt absorption-desorption equilibria and connect host-structure dynamics to equilibrium concentrations of electrolyte impurities.

Hydrogen Peroxide Spillover on Platinum-Iron Hybrid Electrocatalyst for Stable Oxygen Reduction.

Iron-nitrogen-carbon (Fe-N-C) catalysts, although the most active platinum-free option for the cathodic oxygen reduction reaction (ORR), suffer from poor durability due to the Fe leaching and consequent Fenton effect, limiting their practical application in low-temperature fuel cells. This work demonstrates an integrated catalyst of a platinum-iron (PtFe) alloy planted in an Fe-N-C matrix (PtFe/Fe-N-C) to address this challenge. This novel catalyst exhibits both high-efficiency activity and stability, as evidenced by its impressive half-wave potential (E1/2) of 0.93 V versus reversible hydrogen electrode (vs RHE) and minimal 7 mV decay even after 50,000 potential cycles. Remarkably, it exhibits a very low hydrogen peroxide (H2O2) yield (0.07%) at 0.6 V and maintains this performance with negligible change after 10,000 potential cycles. Fuel cells assembled with this cathode PtFe/Fe-N-C catalyst show exceptional durability, with only 8 mV voltage loss at 0.8 A cm-2 after 30,000 cycles and ignorable current degradation at a voltage of 0.6 V over 85 h. Comprehensive in situ experiments and theoretical calculations reveal that oxygen species spillover from Fe-N-C to PtFe alloy not only inhibits H2O2 production but also eliminates harmful oxygenated radicals. This work paves the way for the design of highly efficient and stable ORR catalysts and has significant implications for the development of next-generation fuel cells.

Efficient Alkaline Water Oxidation Electrocatalysis Enabled via the Modulation of Sn‐Containing Anions towards NiFe Oxyhydroxide

AbstractDespite being considered as efficient non‐noble metal‐based electrocatalysts for alkaline oxygen evolution reaction (OER), NiFe (oxy)hydroxides (NiFeOxHy) typically fall short of meeting practical requirements. To address this challenge, herein, we introduce a facile in situ electrochemical incorporation technique to form Sn‐doped NiFe‐layered double hydroxide (NiFeSn‐LDH) precatalysts. Subsequently, under the alkaline OER process, the precatalyst evolves into stannate ion‐adsorbed NiFe oxyhydroxides (NiFeOOH). The presence of these stable stannate oxyanions plays a key role in mitigating Fe leaching, optimizing the electronic structure of NiFeOOH, and improving its reaction kinetics, thereby significantly enhancing alkaline OER performance. Notably, the nickel foam‐supported NiFeSn‐LDH demonstrates impressive results delivering a large current density of 100 mA cm−2 at an overpotential as low as ~260 mV and maintaining the industrial‐relevant ~500 mA cm−2 current density over 5 days with negligible activity decay, surpassing the performances of most of the transition metal‐based electrocatalysts. Comprehensive advanced characterizations of the precatalysts, before and after the OER reactions, have been performed to uncover stable residual stannate ions at the surface of NiFeOxHy and to determine their pivotal role in promoting alkaline OER.

Promoted surface reconstruction of pentlandite via phosphorus-doping for enhanced oxygen evolution reaction

The pentlandite Fe5Ni4S8(abbreviated as FNS) is not efficient for water splitting because of its inferior performance for the oxygen evolution reaction (OER). This issue originates from the low activity and instability of FNS during the OER process but can be solved through appropriate doping. Herein, a P-doping strategy based on annealing in the presence of NaH2PO2as a phosphorus source upstream was employed on FNS to enhance its activity and stability toward OER. The results demonstrated fine-tuned electronic structures of Fe and Ni in FNS through P-doping, resulting in suppressed Fe leaching,improved electrical conductivity of FNS, and easier formation of NiOOH on the surface of the catalyst. In turn, these features enhanced the OER activity and stability. The optimal P-doped FNS catalyst FNSP-40 exhibited a 4-fold greater electrochemical surface area compared to that of FNS, accompanied by an overpotential of 235 mV at 10 mA cm−2. The optimized FNSP-40 catalyst was used as an anode, and platinum-decorated FNS was used as a cathode. This combination demonstrated an electrolysis performance with a cell voltage of 1.57 V, reaching a current density of 100 mA cm−2,which indicates efficient operation. The advantages of P-doping engineering were also verified in simulated seawater with enhanced OER performance. Overall, the proposed strategy looks promising for the fabrication of pentlandite-structured catalysts for efficient alkaline water and seawater oxidation.

One-pot synthesis of magnetic oil shale semi-coke nanocomposite for Fenton-like catalytic organic dye degradation: Performance and mechanism

The conversion of oil shale semi-coke (OSC) is into high-value materials has been an attractive area in waste recycling. In this study, a novel Fenton-like catalyst (Fe3O4/POSC) was successfully prepared using in-situ one-pot oxidation precipitation method for degradation of Methylene Blue (MB). The composition, morphology and properties of the materials were characterized. It was found that Fe3O4/POSC was a mesoporous material with graphene-like structure. The synergistic effect among oxygen functional groups, oxygen vacancies, unsaturated bonds and Fe2+/Fe3+ cycling in Fe3O4/POSC improved the superior degradation performance of MB. Under the optimal conditions (catalyst 1.0 g/L, pH 3.0, and H2O2 25 mmol/L), Fe3O4/POSC exhibited highly efficient degradation (92.73 % in 30 min, 99.54 % in 180 min) and stability (89.72 % after 6 cycles) of MB with low Fe leaching(<0.505 mg/L), following pseudo-first order degradation kinetics. Free radical quenching experiments showed that both •O2-/ HO2• and OH• participated in Fenton-like system, and OH• was the dominant species in MB degradation. According the degradation products of MB by GC-MS, the possible mechanism was proposed. This paper provided a better way to solving the problem of dye wastewater through the effective application of OSC waste.

Photocatalytic and persulfate-facilitated tetracycline degradation using NiFe2O4/carbon/polymer membranes: Activity and stability during flow-through

We synthesized NiFe2O4/carbon composite nanoparticles through a straightforward co-precipitation method, and incorporated these particles into porous polyethersulfone (PES) membranes via casting solution blending and film casting cum phase separation. The resulting photocatalytic membranes were used for the oxidative degradation of tetracycline (TC) in flow–through. We could demonstrate a higher catalytic activity in acidic conditions, a photocatalytic enhancement under visible light irradiation, and a 3x higher TC removal by persulfate (PS) in comparison to H2O2. Moreover, we observed the leaching of all Ni from the incorporated NiFe2O4 after using a membrane for 30 h in the flow-through degradation of 5 ppm TC with PS. This was accompanied by a loss of the total organic carbon removal activity, suggesting that Ni plays an important role as mineralization promoter. However, no Fe leaching occurred and the in situ formed FexOy retained the high TC conversion activity of NiFe2O4 after 30 h contact to acidic conditions, highlighting an exceptional long-term stability. We further identified that substrate desorption, catalyst complexation, and metal leaching can be facilitated by the presence of radical scavengers. This significantly contributed to their inhibitory effects, illustrating that an altered substrate-catalyst interaction may frequently be overlooked during the detection of radical species.

Electron shuttle of carboxyl boosted Fe(III)-anchored carboxylated cellulose activating sodium perborate for organic pollutant abatement

The traditional Fenton application is limited by the disproportionation of hydrogen peroxide (H2O2) and the tardy reduction of Fe(III). To conquer these issues, we construct an enhanced Fenton-like process using a composite of citric acid-carboxylated microcrystalline cellulose complexing with Fe(III) (CA-Fe(III)@MCC) to activate sodium perborate (SPB), which can effectively eliminate antibiotic sulfamethoxazole (SMX, 89.2%, 0.035 min-1). The CA-Fe(III)@MCC composite significantly enhances the circulation of Fe(III)/Fe(II), leading to the generation of hydroxyl radicals and perboric radicals with excellent structural stability and minimal Fe leaching during CA-Fe(III)@MCC/SPB process. Systematic investigations reveal that the introduced carboxyl groups not only anchor Fe(III) to prevent its deactivation and leaching, but also regulate the coordination environment and serve as electron shuttles, driving the formation of reactive species and reduction of Fe(III). This process presents a novel, environmentally friendly, and sustainable strategy for utilizing natural cellulose and its industrial biomass product in advanced oxidation processes.

Enhancing oxygen evolution reaction via hydrogen plasma treatment: Unveiling the functionality of CN defects and the role of Fe in NiFe Prussian blue analogs

AbstractThe rational design of electronic and vacancy structures is crucial to regulating and enhancing electrocatalytic water splitting. However, creating novel vacancies and precisely controlling the number of vacancies in existing materials systems pose significant challenges. Herein, a novel approach to optimize the concentration of the CN vacancy (VCN) in the NiFe Prussian blue analog (PBA) nanocubes is designed by incorporating the H2 or O2 plasma treatment. The relationship between the VCN and catalysis is analyzed, and results show that a moderate concentration of VCN (6.5%) can enormously enhance oxygen evolution reaction (OER) activity of NiFe PBA. However, an excessive amount of VCN disrupts the crystal structure and hinders the transportation of charge carriers, consequently leading to inferior OER. Furthermore, the VCN significantly activates the activity of Fe sites, inducing preferential adsorption of OH− on Fe sites, followed by adsorption on Ni sites, thereby optimizing the reaction pathway and significantly promoting OER performance. In addition, VCN also suppresses Fe leaching, giving the catalyst excellent durability. This study reveals the feasibility of creating unconventional defects in nanomaterials and precisely controlling the number of vacancies for diverse catalytic and energy applications.

Fabrication of N-doped graphitic carbon encapsulated Fe3C/Fe nanoparticles with dual-reaction centers for highly effective Fenton-like degradation of organic pollutants

The highly active and durable design of heterogeneous catalysts holds vital importance in the popularization of Fenton-like process for wastewater remediation. In this study, we successfully fabricated magnetic N-doped graphitic carbon (NC) encapsulated Fe3C/Fe nanoparticles, designated as Fe3C/Fe@NC-2.8, with a two-step pyrolysis method. We employed chitosan as a green precursor of NC, which is used as a heterogeneous Fenton-like catalyst to degrade refractory organic pollutants. Density functional theory (DFT) calculations revealed that the built-in electric field from the shell to core promoted electron transfer from NC to Fe3C/Fe, and thereby improved regeneration of Fe(II) and H2O2 activation. Because of the strong synergistic effects of the dual-reaction regions of Fe and Fe3C, as well as the core-shell structure advantages, the optimized Fe3C/Fe@NC rapidly degraded the typical refractory organic pollutants, and showed a much higher activity than the reference Fe2O3 and Fe3O4 samples. The total organic carbon removal efficiency of bisphenol A reached 70 % after reaction for 60 min. In addition, Fe3C/Fe@NC-2.8 possessed trace Fe leaching and satisfactory magnetically separable ability. This work provides mechanistic and practical perspectives for the development of advanced catalysts for recalcitrant pollutant treatment.

Robust Activity and Stability of P-Doped Fe-Carbon Composites Derived from MOF for Bromate Reduction.

Iron-based materials are effective for the reductive removal of the disinfection byproduct bromate in water, while the construction of highly stable and active Fe-based materials with wide pH adaptability remains greatly challenging. In this study, highly dispersed iron phosphide-decorated porous carbon (Fe2P(x)@P(z)NC-y) was prepared via the thermal hydrolysis of Fe@ZIF-8, followed by phosphorus doping (P-doping) and pyrolysis. The reduction performances of Fe2P(x)@P(z)NC-y for bromate reduction were evaluated. Characterization results showed that the Fe, P, and N elements were homogeneously distributed in the carbonaceous matrix. P-doping regulated the coordination environment of Fe atoms and enhanced the conductivity, porosity, and wettability of the carbonaceous matrix. As a result, Fe2P(x)@P(1.0)NC-950 exhibited enhanced reactivity and stability with an intrinsic reduction kinetic constant (kint) 1.53-1.85 times higher than Fe(x)@NC-950 without P-doping. Furthermore, Fe2P(0.125)@P(1.0)NC-950 displayed superior reduction efficiency and prominent stability with very low Fe leaching (4.53-22.98 μg L-1) in a wide pH range of 4.0-10.0. The used Fe2P(0.125)@P(1.0)NC-950 could be regenerated by phosphating, and the regenerated Fe2P(0.125)@P(1.0)NC-950 maintained 85% of its primary reduction activity after five reuse cycles. The study clearly demonstrates that Fe2P-decorated porous carbon can be applied as a robust and stable Fe-based material in aqueous bromate reduction.

Facile fabrication of amorphous Al/Fe based metal-organic framework as effective heterogeneous fenton catalyst for environmental remediation.

This study presents a facile preparation and durable amorphous Fe and Al-based MOF nanoplate (AlFe-BTC MOFs) catalyst with notable stability in Fenton reactions. Rigorous characterization using XRD, HR-TEM, and BET confirms the amorphous nature of the synthesized AlFe-BTC MOFs, revealing mesopores (3.4nm diameter), a substantial surface area (232 m2/g), and a pore volume of 0.69cc/g. XPS analysis delineates distinct Al2p and Fe2p binding energy values, signifying specific chemical bonding. FE-SEM elemental mapping elucidates the distinctive distribution of Fe and Al within the framework of AlFe-BTC MOFs. In catalytic activity testing, the amorphous AlFe-BTC MOFs exhibited outstanding performance, achieving complete degradation of Methylene blue (MB) dye and 78% TOC removal over 45min of treatment under mild reaction conditions. The catalyst's durability was assessed, revealing about 75% TOC removal and complete dye decomposition over five successive recycles, with less than 1mg/L of Fe and Al leaching. UV-Vis spectra revealed the destruction of MB dye over multiple recycling studies. Based on this finding, the amorphous AlFe-BTC MOF nanoplates emerge as a promising solution for efficient dye removal from industrial wastewater, underscoring their potential in advanced environmental remediation processes.

A Base Layer of Ferrous Sulfate-Amended Pine Bark Reduces Phosphorus Leaching from Nursery Containers

Phosphorus (P) fertilizers applied to container-grown nursery crops readily leach through pine bark-based substrates and can subsequently runoff and contribute to surface water contamination. The objectives of this research were to determine the effect of adding a layer of FeSO4·7H2O-amended pine bark (FSB) to the bottoms of nursery containers on P leaching characteristics. Phosphorus and iron (Fe) leaching in response to FSB layer height (4 or 7.5 cm), FeSO4·7H2O rate (0.3, 0.6, or 1.2 kg·m−3 Fe), and form (i.e., granular versus liquid) used to formulate the FSB layer, and the inclusion of dolomite in the FSB layer were also investigated. Greenhouse studies lasting 15 and 19 weeks were conducted, in which 2.5 L nursery containers containing the FSB layer treatments below non-amended pine bark substrate were fertilized with 199 or 117 mg P from a soluble or controlled-release fertilizer, respectively. Leachate resulting from daily irrigation was collected and analyzed for P and Fe weekly. All FSB treatments leached less P than the control (non-amended pine bark only), with P reductions ranging from 22% (4 cm FSB with 0.3 kg·m−3 Fe) to 73% (7.5 cm FSB with 1.2 kg·m−3 Fe). Phosphorus leaching decreased linearly with an increase in Fe rate or layer height. The amount of Fe that leached from containers with FSB was &lt;5% of that applied, regardless of the Fe rate. Granular- and liquid-applied FeSO4·7H2O with or without dolomite were equally effective at reducing P leaching. Adding 0.6 kg·m−3 Fe to the bottom 500 cm3 of pine bark increased P adsorption by 0.053 mg·cm−3 P, which equates to 17.9 mg P adsorbed per gram of FeSO4·7H2O added. Results from this research suggest that including an FSB layer in the bottom of nursery containers is an effective strategy for reducing P runoff from container-based nursery production sites.