Fe Compounds Research Articles

High-Entropy Magnet Enabling Distinctive Thermal Expansions in Intermetallic Compounds.

The high-entropy strategy has gained increasing popularity in the design of functional materials due to its four core effects. In this study, we introduce the concept of a "high-entropy magnet (HEM)", which integrates diverse magnetic compounds within a single phase and is anticipated to demonstrate unique magnetism-related properties beyond that of its individual components. This concept is exemplified in AB2-type layered Kagome intermetallic compounds (Ti,Zr,Hf,Nb,Fe)Fe2. It is revealed that the competition among individual magnetic states and the presence of magnetic Fe in originally nonmagnetic high-entropy sites lead to intricate magnetic transitions with temperature. Consequently, unusual transformations in thermal expansion property (from positive to zero, negative, and back to near zero) are observed. Specifically, a near-zero thermal expansion is achieved over a wide temperature range (10-360 K, αv = -0.62 × 10-6 K-1) in the A-site equal-atomic ratio (Ti1/5Zr1/5Hf1/5Nb1/5Fe1/5)Fe2 compound, which is associated with successive deflection of average Fe moments. The HEM strategy holds promise for discovering new functionalities in solid materials.

Effect of transition metals (Fe, Ru and Os) on the elastic, thermodynamic, electronic, magnetic and thermoelectric properties of three Nd-filled arsenide skutterudites based on first-principles computations

Elastic, electronic, magnetic, thermodynamic, and thermoelectric properties of three neodymium-filled skutterudites NdT4As12 (T = Fe, Ru and Os) have been investigated using density functional theory. The bulk moduli increase with the atomic numbers of the transition metals. All materials are stiff, while the Os compound is the stiffest. A considerable ionic contribution is seen in their inter-atomic bonding. The Fe compound possesses the highest Debye temperature, while the Os compound has the highest melting temperature. GGA+U formalism predicts the semimetallic nature of all the compounds, but their total DOS differs near the Fermi level in both spin channels. The contributions of the Nd-f and T-d electrons differ in the three compounds and two methods. GGA+U predicts the highest magnetic moment in the Fe compound, followed by the Ru and Os compounds. The thermoelectric figure of merit shows no systematic variation with z of the transition metals and in the high temperature region it increases with temperature pretty fast. The highest value of ZT is 0.32 in the Ru compound in the spin-down channel while it is 0.24 in the spin-up channel in the Fe compound, both at 1000 K.

Investigating structural, optoelectronic, and mechanical properties of novel Tungsten-based oxides double-perovskites compounds Sr2XWO6 (X= Mn, Fe): A DFT approach

We employ PF-LAPW (full-potential linear augmented plane-wave) integrated within DFT (density functional theory) for a comprehensive exploration of the structural, optoelectronic, and mechanical properties of novel Tungsten-based oxides double-perovskites compounds Sr2XWO6 (X= Mn, Fe) through the quantum mechanical WIEN2K simulation package. All the computations are done by considering TB-mBJ (Tran-Blaha modified Becke-Johnson potential) and GGA (generalized gradient approximation) as the exchange-correlation potential. The stability and formation of the Sr2XWO6 (X= Mn, Fe) compounds in a cubic structure are validated through structural optimization and the tolerance factor. The analysis of elastic constants and Born-Huang stability criteria predict that the interested oxide double perovskites are ductile, mechanically stable, hard to scratch, anisotropic, and possess a dominant covalent bonding. Both Sr2MnWO6 and Sr2FeWO6 materials are indirect semiconductors with a band gap of 2.05 eV for Sr2FeWO6 and 1.98 eV for Sr2MnWO6 from W-L symmetry points within the 1st Brillouin zone. The small values of band gap and various parameters of optical properties, specifically the broad monotonically increasing absorption spectra, reveal that novel Tungsten-based oxides double-perovskites compounds Sr2XWO6 (X= Mn, Fe) exhibit great potential for optoelectronic properties.

Extensive reference set and refined computational protocol for calculations of 57Fe Mössbauer parameters.

Mössbauer spectroscopy is a powerful technique for probing the local electronic structure of iron compounds, because it reports in an element-selective manner on both the oxidation state and coordination environment of the Fe ion. Computational prediction of the two main Mössbauer parameters, isomer shift (δ) and quadrupole splitting (ΔEQ), has long been targeted by quantum chemical studies, and useful protocols based on density functional theory have been proposed. Here we present an extensive curated reference set of Fe compounds that is considerably larger and more diverse than literature precedents. We make a distinction between low-temperature and high-temperature experimental subgroups. This set is employed for optimizing a refined computational protocol utilizing the scalar version of the exact 2-component (X2C) Hamiltonian with the finite nucleus approximation. Attention is devoted to having an accurate and flexible all-electron basis set for Fe. We assess the performance of several DFT methods that cover all representative families and rungs of functionals and find that hybrid functionals with ca. 25-30% exact exchange offer the best accuracy for isomer shifts. The work establishes a refined general protocol of wide applicability that achieves good performance for the prediction of isomer shifts in a wider variety of systems than before, but the limitations of DFT for quadrupole splittings are also highlighted. Finally, comparison of calculated values with high-temperature experimental results shows that the use of an empirical correction factor is required to account for the second-order Doppler shift and to achieve the same quality of correlation as with the low-temperature data.

Electrochemical and corrosion behavior of steel rebars in concrete exposed to industrial SO2 and CO2 environment

Investigation into the corrosion mechanism of steel rebars in concrete under the combined influence of SO2 and CO2 is crucial for addressing the corrosion issues in reinforced concrete structures exposed to industrial environments. This study investigated the electrochemical and corrosion behavior of steel rebars in concrete under the combined influence of SO2 and CO2 using electrochemical methods, pH and SO42- concentration tests at the concrete/steel matrix interface, and surface analysis. During the corrosion process, a competitive chemical reaction between SO2 and CO2 occurs. The electrical resistance (Rc) of the concrete cover layer undergoes initial rapid growth, followed by slower increments, and then another period of rapid growth before eventually stabilizing. However, Rc sharply decreases over time, corrosion-induced damage in the concrete cover layer. CO2 diffuses to the vicinity of the rebar before SO2, inducing rebar depassivation. As rust severity increases, significant changes in the rust products are observed, with Fe(III) compounds transforming into Fe(II) compounds, and FeSO4·4H2O and FeSO4·7 H2O are prevalent in the rust products. Furthermore, the formation of ferrous sulfate compounds can lead to local acidification, thereby accelerating the corrosion rate, and hastening the aging and deterioration of the structure, posing a serious threat to the safety of the building structure.

Effects of doping with magnetic cations on the hybrid improper ferroelectricity in Sr3Sn2O7

We here report the structural, magnetic and electrical properties of Sr2.9La0.1Sn1.9M0.1O7 (M= Cr, Mn or Fe) compounds. This La/M codoping of the hybrid improper ferroelectric Sr3Sn2O7, allows introducing magnetic cations into the perovskite layers of this Ruddlesden-Popper phase. The doping induces minor structural changes, preserving the polar structure with space group A21am of the undoped compound. The perovskite tolerance factor of all doped samples is slightly lower than in Sr3Sn2O7, which preserves the tilts and rotations of SnO6 octahedra. Doped samples exhibit a paramagnetic behavior down to 5 K and obey the Curie-Weiss law above 200 K. The effective paramagnetic moments agree with the expected spin-only values of the respective magnetic M3+ cations. All samples show a ferroelectric hysteresis loop at room temperature, but the doped samples show larger coercive fields. Additionally, the doping with magnetic cations has important effects on the dielectric properties: a strong decrease of the temperature of the ferroelectric transition together with a smoothing of the anomaly in the dielectric permittivity. These results suggest that the disorder produced by the two aliovalent substitutions is detrimental for the ferroelectric properties due to point charge defects but, at the same time, the prevalence of the structural distortion (tilts and rotations) preserves the ferroelectricity in the investigated doping regime.

Comparative analysis of carotenoids, fatty acids, minerals, tastes, and odor in the skin of wild versus farmed large yellow croaker: Superior nutritional benefits with elevated heavy metal risks

People commonly consume large yellow croaker with skin, yet comprehensive studies on the skin's nutritional value, flavor, and health risks are lacking. The skin from wild fish and those from five main farming areas, nearly representing all fish in the market, were analyzed. The study revealed that the skin of all tested fish exhibited high levels of carotenoids, EPA, DHA, Σn-3/Σn-6 PUFA, Fe, Se, Cu, Zn, and various flavor compounds including free amino acids, 5′-nucleotides, and odor substances, and low levels of atherosclerotic and thrombogenic indices, suggesting health benefits. Notably, the wild fish skin was yellower with high carotenoid accumulation and nutritionally superior in fatty acids but showed a high heavy metal risk. Additionally, this research has, for the first time, elucidated that carotenoid storage in the skin of large yellow croaker depends on lutein esterification with oleic, palmitic, and decanoic acids. In summary, the current study indicates that the skin of farmed fish offers significant nutritional value and favorable flavor profiles, making it safe for consumption. However, while the skin of wild large yellow croaker is more nutritionally advantageous, it also presents a non-negligible risk of heavy metal contamination.

Ammonia Decomposition By Microwave Plasma Discharges

The global discourse focuses on future energy vectors, with hydrogen emerging as a robust candidate owing to its established industrial applications. However, a current challenge lies in storing and transporting hydrogen-based fuels. This research focuses on advancing efficient and environmentally friendly techniques for large-scale hydrogen production, leveraging its widespread industrial presence. Ammonia, identified as a promising energy vector, offers advantages in storage and transport over hydrogen. It capitalizes on existing global infrastructures, with approximately 20 million metric tons traded annually, contributing to a total production of 150 million tons annually. If many works focus on producing ammonia by electrical discharges [1], only a few are devoted to ammonia cracking and generally concentrate on catalysis [2]. In this study, we propose an investigation into the decomposition of ammonia by applying microwave (MW) plasma. Utilizing a MW cavity that confines an electromagnetic field excited at 2.45 GHz, we induce electrodeless plasma within a fused silica tube where pure ammonia (NH3) gas flow. At first, the plasma discharge was characterized with Fourier Transform Infrared Spectroscopy (FTIR). This preliminary part of the study exhibited that, for fixed input power (300 W) and fixed working pressure (100 mbar), NH3 decomposition decreased with a flow rate ranging from 0.4 to 2.4 SLM. It also showed that for fixed input power (300 W) and fixed flow rate (2.4 SLM), the NH3 dissociation increased with pressure ranging from 40 to 140 mbar. These experiments exhibited the predominant role of the residence time of ammonia but also reactive species in plasma. To further understand the NH3 cracking mechanisms, we performed optical emission spectroscopy (OES). This technique allowed us to determine the various light-emitting species produced during NH3 dissociation in the discharge and their physical parameters, such as temperatures and relative densities, as a function of different experimental parameters. We study the influence of gas flow rate ranging from 1 to 15 SLM, input power and near-atmospheric pressure on NH3 cracking and hydrogen (H2) recombination mechanisms. Gas chromatography (GC) was employed to measure the dissociation yield of NH3 and assess the efficiency of the H2 production process. In parallel, we synthesize iron (Fe) and nickel (Ni) nanoparticles through a plasma solution process. Both metals are abundant and inexpensive; hence, they are good candidates as catalysts for potential industrial applications. In the experimental setup, a pair of tungsten electrodes, connected by a high-voltage cathode, was submerged in an aqueous solution containing Fe and Ni chlorides. One electrode was the high-voltage cathode, while the other was the grounded anode. Pulsed discharges were generated to produce Fe and Ni compounds. The resulting Fe-Ni nanoparticles (NPs) were characterized by transmission electron microscopy (TEM) to determine their shape, size and composition, which depends on the concentrations of the metal chlorides in the electrolyte solution. Those NPs were then coated on silica tubes inserted in the MW reactor at various positions to establish their influence on the NH3 decomposition and H2 recombination processes. The primary goal of this study is to compare the dissociation of NH3 with and without catalysts, aiming to achieve optimal results for H2 production. This study investigates the impact of experimental parameters on ammonia cracking efficiency within a microwave plasma combined with catalysis. We compare these factors with ruthenium-catalyzed and non-catalyzed thermal processes, recognized as leading methods for ammonia cracking. The goal is to gain insights into the mechanisms of ammonia decomposition in microwave plasmas and evaluate the efficiency of our proposed methodology relative to established thermal processes, contributing to the advancement of sustainable and optimized ammonia cracking practices and decarbonated hydrogen production. Acknowledgements The authors would like to thank the Department of Physics, College of Science, Jazan University, Jazan 45142, Saudi Arabia, for the financial support to M. Awaji and SAKOWIN for the financial support to L. Pentecoste.

Resonant inelastic x-ray scattering in warm-dense Fe compounds beyond the SASE FEL resolution limit

Resonant inelastic x-ray scattering (RIXS) is a widely used spectroscopic technique, providing access to the electronic structure and dynamics of atoms, molecules, and solids. However, RIXS requires a narrow bandwidth x-ray probe to achieve high spectral resolution. The challenges in delivering an energetic monochromated beam from an x-ray free electron laser (XFEL) thus limit its use in few-shot experiments, including for the study of high energy density systems. Here we demonstrate that by correlating the measurements of the self-amplified spontaneous emission (SASE) spectrum of an XFEL with the RIXS signal, using a dynamic kernel deconvolution with a neural surrogate, we can achieve electronic structure resolutions substantially higher than those normally afforded by the bandwidth of the incoming x-ray beam. We further show how this technique allows us to discriminate between the valence structures of Fe and Fe2O3, and provides access to temperature measurements as well as M-shell binding energies estimates in warm-dense Fe compounds.

Impact of ligand substituents on the spiral arrangement in glutarohydrazide-based binuclear-iron(II) helicates

Coordination-driven self-assembly, particularly, helical metal complexes are quite interesting considering their distinctive architectures. Herein, we assemble new Fe(II) compounds namely, [Fe2(L1)2](BF4)4·2H2O, 1 and [Fe2(L2)2](BF4)4, 2 from flexible glutarohydazide ligands featuring helical-like di-nuclear arrays. Structurally, in all the compounds, the two chelating ligands were arranged differently, i.e. inverted U-shaped conformation for 1 and a twisted spiral arrangement for 2 were observed respectively. Interestingly, the observed structural variations of all compounds are a result of the ligand substituents in the six positions of the pyridyl moiety in which the relatively bulky methyl group substituted ligand resists the spiral arrangement which was observed in the Br substituted analog. Magnetic investigations revealed that compounds 1 and 2 are in the high spin state at all the measured temperature ranges. Further ligand fine-tunings in the pyridyl-aldehyde moiety for the presented helical-like arrays bearing relatively strong ligand field strength are suggested for achieving the spin crossover (SCO) event.

Modified Ordered Mesoporous Carbons for Cr(VI) Removal from Wastewater.

The pristine CMK-3 carbon was ozonized and then chemically modified by the Zr and Fe compounds. The synthesized carbonaceous materials were characterized with physicochemical methods. The obtained carbons had a high specific surface area (ca. 800 m2 g-1) and an acidic surface. The Cr(VI) adsorption properties of the oxidized and Zr/Fe-modified carbon were studied. The highest static adsorption capacity towards Cr(VI) ions was evaluated for Zr/Fe-modified carbon (50.1 mg g-1) at pHeq = 5.8 after 240 min. The Elovich and Freundlich theoretical models were well fitted to the Cr(VI) adsorption kinetic and isotherm data on the Zr/Fe-modified CMK-3-type carbon. The leading Cr(VI) adsorption mechanism acting on the Zr/Fe-modified carbon was probably based on the redox reactions between Cr(VI) and the carbonaceous surface. Electrostatic attraction and surface complexation processes could also occur during Cr(VI) adsorption in the studied system. The effect of the competitive anions on the concentration level, such as in the galvanic wastewater for Cr(VI) adsorption onto chemically modified carbon, was negligible. The HCl and HNO3 media were insufficient for the Zr/Fe-modified carbon regeneration after Cr(VI) adsorption. The Zr/Fe-modified carbon was successfully applied for the efficient (>90%) Cr(VI) removal from the model galvanic wastewater.

Exploring the molecular structure and in vitro biological potential of newly synthesized Fe(III), Co(II), and Ni(II) coordination compounds with 2-(pyridin-2-yl)-1H-benzimidazole and phenylalanine ligands

This study presents a thorough investigation into the synthesis, characterization, computational analysis, and biological evaluation of FePBZPHA, CoPBZPHA, and NiPBZPHA mixed-ligand complexes. They were synthesized in high yields via reactions between chloride salts of Iron, Cobalt, or Nickel with 2-(pyridin-2-yl)-1H-benzimidazole (PBZ) and Phenylalanine (PHA). They underwent extensive spectroscopic, elemental, conductivity, magnetic, and thermal analysis to confirm their formation. Molar conductivity measurements indicated their non-electrolytic nature, with UV–vis spectra revealing distinct absorption bands for PBZ and PHA ligands, shifting significantly upon metal ion coordination. Stoichiometry determination confirmed the 1:1:1 (M:PBZ:PHA) ratio, while FT-IR spectra comparison elucidated intricate binding modes, supported by mass spectra and elemental analysis. Thermal analysis revealed their thermal stability and decomposition pathways. DFT calculations unveiled octahedral coordination geometries and enhanced electron affinity, electronegativity, and reactivity of metal complexes. Biological evaluation showcased significantly enhanced efficacy of metal complexes in antimicrobial, anti-inflammatory, and antioxidant activities, with FePBZPHA exhibiting the highest potency. Molecular docking analysis highlighted their potential as therapeutic agents, with metal complexation enhancing binding affinity and interaction versatility. Overall, this study provides comprehensive insights into the synthesis, characterization, computational analysis, and biological evaluation of FePBZPHA, CoPBZPHA, and NiPBZPHA mixed-ligand complexes, suggesting promising applications in biomedicine and materials science.

Construction of Spin Crossover‐Fluorescent Bifunctional Cyclic Chain‐Like Fe(II) Compounds from Carbazole Ligands

AbstractThe incorporation of fluorescent properties into spin‐crossover (SCO) materials, aiming at controlling fluorescence via spin‐state transitions for applications in magneto‐optical switching and information processing, represents an appealing research direction. In this study, we prepared two examples of one‐dimensional cyclic chain‐like Fe(II) coordination polymers, denoted as [Fe(DPPC)2(NCS)2]⋅CH3OH⋅o‐C6H4Cl2 (1, DPPC=3,6‐di‐4‐pyridinyl‐9‐[4‐(4‐pyridinyl)phenyl]‐9H‐carbazole) and [Fe(PDPC)2(NCS)2] (2, PDPC=3,6‐di(pyridin‐4‐yl)‐9‐phenyl‐9H‐carbazole). Analyses through single‐crystal X‐ray studies and magnetic measurements validate the two‐step SCO behavior of 1 within the temperature range of 50~200 K. Additionally, when combined with temperature‐dependent fluorescence emission spectroscopy, the results demonstrate the coexistence of SCO and fluorescence in 1.

A fibrous Ir-doped NiFeOx on two-dimensional materials for high efficiency oxygen evolution reaction (OER)

As a clean and renewable energy, hydrogen gas can be generated from water electrolysis which also involves the sluggish oxygen evolution reaction (OER). The main commercial catalysts for OER are Ir and Ru based but have the problems of high cost and poor cycling stability. Herein, we designed a new electrocatalyst based on Ni, Fe and Ir compounds loaded on a unique two-dimensional carbon material, which can efficiently catalyze OER with high stability in alkaline solution. The composite was prepared by physical vapor deposition, showing a fibrous microscopic morphology with uniform particle size distribution. The fibrous structure ensured the exposure of active sites, which further improved OER activity. The loading of metallic iridium in the material is only 0.0858 mg cm−2. The catalytic activity of OER was maintained for 54 h under alkaline conditions at a current density of 50 mA cm−2 without significant changes in current density. Characterization showed that the excellent activity and stability of the catalysts originated from the Ir insertion into the NiFe2O4 lattice.

Adsorption of Residual Pesticide Glyphosate Isopropylamine in Surface Water by Modified Biomass Materials

Effective treatment of pesticide residue-induced pollution in the aqueous environment is the key to improving the water quality of rivers and lakes. Modified biomass material (Fe-Al-PS) was successfully prepared by impregnating Fe and Al bimetallic compounds to peanut shell powder for adsorption of glyphosate isopropylamine salt herbicide residues in aqueous environments. Fe-Al-PS reached adsorption equilibrium for 10 mg·L-1 of glyphosate isopropylamine salt at the adsorbent dosage and adsorption time of 0.14 g and 10 min, respectively, and the removal rates were stabilized at 99.9 % and 99.6 %, respectively. The adsorption process followed the pseudo-secondary kinetic and Freundlich adsorption isotherm models and belonged to multi-molecular layer chemisorption. The removal of glyphosate isopropylamine salt by Fe-Al-PS was greater than 95 % in a wide range of pH (2-11). The thermodynamic results indicated that the adsorption was a spontaneous exothermic process. Fe-Al-PS materials were easy to access and involved simple synthesis and low energy consumption, had high anti-interference ability, were reusable, and could be used not only for the effective removal of glyphosate isopropylamine salt herbicide in real water bodies but also for the removal of inorganic phosphorus.

Overview of Hemoglobin Levels in Construction Workers in Tanjungsari Village, Sukaresik District, Tasikmalaya Regency

Background & Objective: Hemoglobin is a tetrametric protein that binds iron (Fe) compounds that have an important role in the body, namely transporting oxygen from the organs of respiration throughout the body, and exchanging it with carbon dioxide from peripheral tissues to be released through the organs of respiration. Hemoglobin levels can be influenced by several factors, one of which is moderate to heavy-intensity physical activity. This study aims to determine haemoglobin levels in construction workers. Method: This research is a descriptive study with a total sampling technique conducted in May 2023. Respondents in this study were 35 construction workers. Sampling was carried out in Tanjungsari Village, Sukaresik District, Tasikmalaya Regency and the examination was carried out at the Hematology Laboratory of STIKes Muhammadiyah Ciamis. Measurement using the Cyanmethemoglobin method with the instrument used is a photometer. The examination results were processed and displayed in table format for narration. Result: This study found normal haemoglobin levels in 23 respondents (66%), and 12 respondents (34%) with abnormal or below-normal haemoglobin levels in construction workers. Conclusion: It can be concluded that the average results of haemoglobin levels in construction workers are normal. Future research is expected to research the relationship between working duration and haemoglobin in heavy workers.

Phenoxide coordination to Fe(III) tetraphenylporphyrin: Exploring antibacterial and electrocatalytic HER activity

Herein, we report synthesis, solid and solution state structure as well as properties of three five coordinate (unsubstituted, 4-NO2 substituted and 2,4,6 trinitro substituted) phenoxide axially ligated to Fe(III)-tetraphenyl porphyrins. Spectroscopic characterization revealed high-spin (S = 5/2) nature of the phenoxide bound Fe(III) porphyrins (Fe1 and Fe2). However, the 2,4,6 trinitro substituted phenoxide axially ligated Fe(III) porphyrin (Fe3) demonstrate spin admixed nature (S = 5/2, 3/2) with predominate high spin contribution. (Phenolato)(porphinato)iron(III) complexes merit attention owing to structural analogy with the catalase enzyme. In this study we investigated their antibacterial as well as electrocatalytic hydrogen evolution reaction (HER) activity. Fe1 demonstrate potent antibacterial activity against gram-negative E. coli (MTCC 443) and gram-positive Staphylococcus aureus (MTCC 3160) human pathogenic bacteria. It also produce catalytic current for electrocatalytic HER activities upon gradual addition of PTSA (para-tolunesulphonic acid) as proton source. Compounds Fe2 and Fe3 also produce enhanced catalytic wave which originate possibly from reduction of proton coupled with reduction of –NO2 group.

A heterostructured ternary transition metal oxide composite as an efficient electrocatalyst for the hydrogen evolution reaction

A key method for hydrogen production is water electrolysis involving the oxygen and hydrogen evolution reactions. The efficiency of these processes is largely dependent on the use of effective electrode catalysts. Despite the high water-splitting catalytic activity of noble metals such as Pt, Ru, and Ir, their scarcity and costliness pose significant challenges. Although Fe and Fe-based compounds have recently been identified as promising alternative catalysts due to their abundance, affordability, and low toxicity, particularly under the alkaline conditions required for the hydrogen evolution reaction, both can be reduced to unstable forms during the reaction. To address this, the focus of the present study is on developing a ternary transition metal oxide electrocatalyst comprising Ni, Fe, and Co oxides. Thereby, we leveraged the synergistic interactions among them to provide a heterogeneous electrocatalyst for the hydrogen evolution reaction with a sufficiently low overpotential of 45 mV and suitably high Tafel kinetics of 44.99 mV dec−1 and long-term stability. The ternary transition metal oxide electrode showcased superior performance compared to one comprising binary transition metal oxides by achieving a lower overpotential and a better Tafel slope while maintaining catalytic stability even for 100 h at a current density of 1000 mA cm−2. This innovative approach offers a highly efficient alternative catalyst to Fe, which is known to have stability issues for hydrogen production, especially at high current density.

Enhanced Fe(OH)2-driven reductive Dechlorination via shortened Fe-O bonds and colloidal medium

Fe2+ is usually adsorbed to the surface of iron-bearing clay, and iron (hydr)oxide in groundwater. However, the reductive activity of Fe(OH)2, a prevalent intermediate during the transformation of Fe2+, remains unclear. In this study, high-purity Fe(OH)2 was synthesized and tested for its activity in the degradation of carbon tetrachloride (CT). XRD data confirm that the synthesized material is a pure Fe(OH)2 crystal, exhibiting sharp peaks of (001) and (100) facets. Zeta potential analysis confirms that the off-white Fe(OH)2 is a colloidal suspension with a positive charge of ∼+35-50 mV. FTIR spectra reveal the formation of a coordination compound Fe2+ with OH−/OD−, derived from NaOH/OD. SEM and HRTEM results demonstrate that the Fe(OH)2 crystal has a regular octahedral structure with a size of ∼30-70 nm and average lattice spacings of 2.58 Å. Mössbauer spectrum verifies that the Fe2+ in Fe(OH)2/Fe(OD)2 is hexacoordinated with six Fe-O bonds. XAFS data demonstrate that the Fe-O bonds become shorter as the OH−:Fe(II) ratios increase. DFT results indicate that the (100) crystal face of Fe(OH)2 more readily transfers electrons to CT. In addition to being adsorbed to iron compounds, structural Fe2+ compounds such as Fe(OH)2 could also accelerate the electron transfer from Fe2+ to CT through shortened Fe-O bonds. The rate constant of CT reduction by Fe(OH)2 is as high as 0.794 min−1 when the OH−:Fe(II) ratio is 2.5 in water. This study aims to enhance our understanding of the structure-reactivity relationship of Fe2+ compounds in groundwater, particularly in relation to electron transfer mechanisms.

Unraveling the intrinsic mechanism behind the retention of arsenic in the co-gasification of coal and sewage sludge: Focus on the role of Ca and Fe compounds

Minimizing the emission of arsenic (As) is one of the urgent problems during co-gasification of Shenmu coal (SM) and sewage sludge (SS). The intrinsic mechanism of As retention was obtained by analyzing the effect of different SM addition ratios on the As form transformation during co-gasification at 1000 °C under CO2 atmosphere. The results showed that the addition of SM effectively promoted the enrichment of As in the co-gasified residues. Especially, the best As retention rate of 65.71% was achieved with the 70 wt% addition ratio of SM. The addition of SM promoted the adsorption and chemical oxidation of As(III) to the less toxic As(V) through the coupling of Ca and Fe compounds in the co-gasified residues. XRD and XPS results indicated that Fe2O3 adsorbed As2O3(g) after partial conversion to Fe3O4 by the Boudouard reaction, while part of As2O3 was oxidized to As2O5 by lattice oxygen. Finally, the generated As2O5 was successively trapped by CaO and Fe2O3 to form stable Ca3(AsO4)2 and FeAsO4. HRTEM and TEM analysis comprehensively proved that As(III) was stabilized by the lattice cage of CaAl2Si2O8. In conclusion, the co-oxidation of Ca and Fe compounds and lattice stabilization simultaneously played a crucial role in the retention of As2O3(g) during co-gasification.