Iron Oxyhydroxides Research Articles

One‐Step Electrodeposition of Iron Oxyhydroxide Onto 3D Porous Graphene Substrates for on Chip Asymmetric Micro‐Supercapacitors

AbstractElectrochemical capacitors based on redox active materials can achieve greater capacitance values than traditional electric double layer composites. Herein, electrodeposition of iron oxyhydroxide from a mildly acidic acetate precursor is reported. The one‐step deposition resulted in a submicron film composed of FeOOH phase, which was confirmed via Raman and x‐ray photoelectron spectroscopy. The capacitance increased linearly with loading amount and achieved a maximum at 1600 mC deposition with 120 mF cm−2 at 25 mV s−1 after which the film became more resistive, limiting electrolyte access to the porous graphene substrate. The deposited FeOOH demonstrated promising rate capability and good cycling stability, without phase changes, retaining 82 % of the initial capacitance after 5000 consecutive charge/discharge cycles. The charge storage mechanism of FeOOH was determined via in situ Raman spectroscopy, which followed reversible iron oxygen vibration changes upon cycling which become more intense upon reduction as a result of sodium ion intercalation. Furthermore, an asymmetric configuration full cell combining FeOOH/MnO2 allowed the working voltage to be extended to 2 V, maintaining an ideal capacitor behaviour, and achieving a maximum energy and power density of 21 μWh cm−2 and 2.5 mW cm−2 respectively.

Application of iron oxide and its composites containing carbon nanoparticles to the solution of environmental problems

The radioactive materials and the secondary waste after a nuclear power plant accident pose a big environmental problem. The nontoxic iron oxide and iron oxyhydroxide, and their composites with carbon materials were applied to solve the problem. Coal oxide produced by modified Brodie method using coal, NaOH, and γ-Fe2O3 were treated by a hydrothermal process. When the diluted dispersion mixture was treated with SrCl2, the composite particles were attracted to a magnet. On the other hand, the composite without SrCl2 was not attracted. This means only the SrCl2-adsorbed composite can be recovered by a magnet. Hematite doped with various amounts of Nb was synthesized. Its catalytic activities for photo-Fenton reaction were investigated for degradation of methylene blue (MB) in the presence of H2O2 under visible light. Nb-doped hematite calcined at 600 ºC produced smaller particles and showed higher catalytic activity than those calcined at 700 ºC. It was shown that the sample with higher Nb doping showed a better catalytic activity, i.e., the sample with 40 atomic percent of Nb calcined at 600 ºC has the highest catalytic activity. The hematite with 7.4 atomic percent of Nb calcined at 600 ºC showed unique characteristics since it has rapid decomposition rate of MB as well as ferrimagnetic-like characteristics, which makes it separable by a magnet. The polymorphism of iron(III) oxyhydroxide was controlled by adding acetic acid, ethylenediamine, and citric acid. The lepidocrocite obtained by adding the additive of citric acid resulted in the presence of citric acid in the particles and revealed a large specific surface area and negative Zeta potential, which showed an extremely high catalytic activity of MB decomposition for photo-Fenton reaction.

Dual-Ligand-Driven Dark Reactive Oxygen Species Generation on Iron Oxyhydroxides: Implications for Environmental Remediation.

The dark generation of reactive oxygen species (ROS), particularly hydroxyl radicals (·OH), is crucial in the oxidative transformation of various pollutants. However, the mechanisms behind this process are predominantly linked to direct O2 activation by reduced substances such as Fe(II) and natural organic matter. In this study, we introduce a previously overlooked dual-ligand mechanism that significantly amplifies ·OH generation on iron oxyhydroxides, facilitated by cysteine and pyrophosphate. Our findings reveal that these ligands collaboratively boost ·OH generation by 99.5-125.7% compared to Fe(II) alone. This enhancement occurs through a two-step electron transfer (ET) process, where cysteine transfers electrons to O2 through iron oxyhydroxides. The complexation of pyrophosphate with iron oxyhydroxides further reduces the thermodynamic barriers, notably promoting this ET process and significantly improving the electron utilization efficiency for O2 activation by the electron donor cysteine. Such a process has shown its great potential for effectively driving the oxidative transformation of various pollutants, including As(III), dichlorophenol, and carbamazepine. These findings offer valuable insights for nature-based pollutant mitigation in soil and subsurface environments.

Morphogenetic varieties of iron oxyhydroxides in shimmering smokers-diffusers of the Rainbow hydrothermal field (36°13′ N, 33°54′ W, Mid-Atlantic Ridge): LA-ICP-MS data for the development of halmyrolysis theory

Research subject. Iron oxyhydroxides covering and replacing the chimneys of shimmering water smokers-diffusers of the Rainbow hydrothermal field (MAR). Aim. To identify features of the concentration and associations of chemical elements in varieties of iron oxyhydroxides to recognize patterns of geochemical differentiation under conditions of halmyrolysis of sulfide chimneys-diffusers. Materials and methods. Samples were collected during a dive to a depth of 2300 m using the manual manipulator of the Mir-2 manned vehicle (travel No. 50, research vessel Akademik Mstislav Keldysh, 2005). Varieties of iron ohyhydroxides were identified using electron microscopes (REMMA-202М with LZ-5 Link system, Tescan Vega 3 sbu with an Oxford Instruments X-act energy-dispersive analyzer, and Jeol Superprobe 733 with an EDA Oxford Instruments INCAx-sight) and a powder X-ray diffractometer (SHIMADZU XRD-6000, CuK-α radiation with monochromator). Further, a mass spectrometry with inductively coupled plasma and laser ablation (LA-ICP-MS) analysis was conducted at the South Urals Federal Scientific Center of Mineralogy and Geoecology, Ural Branch of the Russian Academy of Sciences. Results. Microlayered goethite aggregates containing admixtures of barite, calcite, aragonite, native sulfur, covellite, sphalerite, and an X-ray amophoric oxyhydroxide phase of iron cover the shimmering diffusers. Towards the inner parts of the chimney walls, they are replaced by pseudomorphs of lepidocrocite after pyrite and pyrrhotite, and then by radial and bacteriomorphic crustifications of lepidocrocite. The use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) showed that goethite varieties have the increased contents of Zn and Co associated with other elements of medium-temperature hydrothermal fluids (Cd, Mn, Ni, Ga, Sn, Pb and Sb) in the absence of significant concentrations of a high-temperature hydrothermal association (Se, Bi, Te). The role of elements of seawater association (Mg, Na, K, Sr, U, V, As, Mo, Ni, P, B, W, Cs, REE) decreases from the surface layered goethite aggregates to crustification varieties of lepidocrocite. Different scenarios of accumulation under conditions of sulfide halmyrolysis and precipitation on local reduction barriers are proposed for elements with different valences (U, V, Mo, As, Cr, Eu). It is assumed that some of the microelements (Sr, V, As, P, REE) found in goethite are products of sorption on iron hydroxides or are part of invisible Fe-Ca hydroxyphosphates. Conclusion. The influence of sulfide halmyrolysis on the differentiation of chemical elements has been revealed.

Superparamagnetic Relaxation in Ensembles of Ultrasmall Ferrihydrite Nanoparticles

The paper examines the impact of interparticle interactions on the superparamagnetic relaxation of ultrasmall nanoparticle ensembles, using Fe2O3∙nH2O iron oxyhydroxide (ferrihydrite) nanoparticles as an example. Two samples were analyzed: ferrihydrite of biogenic origin (with an average particle size of d ≈ 2.7 nm) with a natural organic shell, and a sample (with d ≈ 3.5 nm) that underwent low-temperature annealing, during which the organic shell was partially removed. The DC and AC magnetic susceptibilities (χ′(T), χ′′(T)) in a small magnetic field in the superparamagnetic (SPM) blocking region of the nanoparticles were measured. The results show that an increase in interparticle interactions leads to an increase in the SPM blocking temperature from 28 to 52 K according to DC magnetization data. It is shown that below the SPM blocking temperature, magnetic interactions of nanoparticles lead to the formation of a collective state similar to spin glass in bulk materials. The scaling approach reveals that the dynamics of correlated magnetic moments on the particle surface slow down with increasing interparticle interactions. Simulation of χ′′(T) dependence has shown that the dissipation of magnetic energy occurs in two stages. The first stage is directly related to the blocking of the magnetic moment of nanoparticles, while the second stage reflects the spin-glass behavior of surface spins and strongly depends on the strength of interparticle interactions.

Geochemical Characteristics and Environmental Risks of Cu in the Soil of A Sloping Vineyard (Phu Tho Province, Vietnam)

In the vineyards, the intensive use of cupric fungicides and fertilizers has resulted in Cu enrichment in the soils. Specifically, in sloping vineyards, the mobility of Cu can contribute to intensify the environmental risks. The research on geochemical characteristics of Cu is a key solution to explore the distribution of Cu in different geochemical fractions and understand the mobility and toxicity of this element in the environment. In this study, we aim to investigate the geochemical properties of Cu in the vineyard topsoil (0-20 cm) and subsoil (20-40-60 cm), using the improved three-step sequential extraction procedure developed by the Commission of the European Communities Bureau of Reference (BCR). In addition, the environmental risk is calculated by the environmental risk code (RAC) based on the percentage of Cu in the acid-soluble fraction. The results reveal that the mobility of Cu in the acid-soluble fraction (F1) and reducible fraction (Cu associated with the iron and manganese oxyhydroxides) (F2) tends to decrease with increasing soil depth. The major portion of Cu mostly exists in the strong bond with silicate clays (F4), accounting for 84% of total Cu content on average. Contrarily, the minor propotion of Cu associates with soil organic matter (F3) (3% on average). On the other hand, the content and proportion of Cu in the soil fractions are largerly influenced by basic soil properties (organic matter contents and fine soil particles). In addition, under the impact of soil erosion, higher percentages of F1 and F2 fractions of Cu are observed in the surface soil layers at the top of the hill compared to those at the backslope of the hill. The mean calculated RAC of 10.66%, 5.76%, and 5.38% for the 0-20 cm, 20-40 cm, and 40-60 cm soil layers, respectively, demonstrate a low risk to medium environmental risk level in the studied vineyard. Although an overall low risk level is observed for Cu in the studied vineyard soil, the deposition of Cu originating from repeated Cu-based pesticides and erosion is of particular concern in the vineyard soils.

Black powder and mineral deposits in the LPG production and processing line: Analytical study and formation mechanisms

The accumulation of mineral deposits such as black powder causes severe impacts throughout the gas production and transport process. The phenomenon takes place from gas wells to LNG/LPG treatment plants and terminals. The complexity lies in understanding the mechanisms by which these materials are formed in random quantities, as well as their varied nature. The aim of this study is to monitor black powder and other mineral deposits formation in a chain of gas production and processing situated in the south of Algeria and unravel their root causes. To that extent, an analytical study was carried out on four samples of both mineral deposits and black powder taken from an LPG processing and production unit. The adopted analytical approach included an exploration of the textural and structural properties. It also involves a composition characterizations related to the content of metallic elements, moisture, organic and mineral matter. The particle distribution is also determined. The analytical study was conducted using gravimetric determination, XRD, XRF, SEM/EDX and Raman spectroscopy. Particle distribution was given by Laser granulometry technique. The results of the DRX/FRX and EDX characterization primarily revealed that the samples contain a variety of mineral components such as iron oxides; magnetite Fe3O4 and hematite Fe2O3, iron oxy-hydroxide FeO(OH), iron sulphide FeS2, calcite CaCO3, SiO2 and halite NaCl. The presence distribution of these components depends on the location of the sample in gas line. Granulometry study shows that black powder contamination can be spread over a wide spectrum of particle sizes ranging from 1.51 µm to 678.50 µm. This study has allowed to elucidate the nature and distribution of particles deposited at different positions in the LPG production chain and to propose probable mechanisms for their formation.

Synergistic Effect of Cobalt/Ferrocene as a Catalyst for the Oxygen Evolution Reaction.

There is a great deal of interest in the development of electrocatalysts for the oxygen evolution reaction (OER) that are stable and have high activity because this anodic half-reaction is the main bottleneck in water splitting and other key technologies. Cobalt and iron oxide and oxyhydroxide electrocatalysts constitute a cheaper alternative to the highly active and commonly used Ir- and Ru-based catalysts. Most of the described electrocatalysts require tedious synthetic and expensive preparation procedures. We report here a facile and straightforward preparation of an electrocatalyst by a combination of commercial compounds, such as cobalt chloride and ferrocene. A highly active and stable OER electrocatalyst is obtained, which shows a low overpotential in the alkaline medium as a consequence of a synergistic effect between both compounds and is inexpensive.

Impact of Fe3+/Polyphenol Ratio in Iron-gall Ink on Superoxide Formation: Rationalizing Historic Recipes from a Kinetic Study.

Iron-gall inks, a vital part of our written cultural heritage, are at risk of complete loss due to degradation, a potential loss that we must urgently address. These inks are based on Fe3+-complexes with phenolic compounds, which grow to form a complex network of iron oxyhydroxides. Over time, these black inks turn into brownish tones, with extensive degradation in paper support leading to extensive breaking. The kinetics of iron-gall ink preparation explains the use of iron sulfate, FeSO4, in all ancient recipes to obtain a stable amorphous ink. The novelty of this work shows that a low ratio of Fe3+/polyphenol is a crucial factor in allowing the ink's growth without its degradation. This ratio also prevents the formation of superoxide. This was achieved through a comprehensive research methodology involving spectroscopic techniques in the visible and the near-infrared regions, stopped-flow spectrometry and electrochemical studies.

Molecular fractionation mediates genotoxicity evolution of hydrochar-derived dissolved organic matter at the iron oxyhydroxides-water interface

Adsorption fractionation of dissolved organic matter (DOM) induced by soil minerals is a common geochemical process, which has been widely documented on natural DOM. Hydrochar is a promising functional material in soil remediation but can continuously release abundant endogenic DOM with potential biotoxicity. However, adsorption fractionation at molecular level and its influence on toxicity evolution of hydrochar-derived DOM (HDOM) at genetic level at the soil-water interface remain poorly understood. Herein, we investigated the molecular fractionation of HDOM on three typical soil iron minerals (i.e., ferrihydrite, goethite, and hematite). Results from ultrahigh-resolution mass spectrum showed that HDOM molecules with high molecular weight and high contents of unsaturated oxidized or aromatic structures (e.g., unsaturated phenolic compounds, polyphenols, and organic acids) were preferentially absorbed by iron oxyhydroxides, while aliphatic molecules and poorly oxygenated compounds (e.g., hydrocarbon, phenols, and alcohols) were retained in aqueous phase. Furthermore, we quantitatively evaluated their genotoxicity variation using a toxicogenomics assay using green fluorescence protein-fused whole-cell array, and results showed that oxidative, protein, membrane, and DNA stresses were primary responses upon exposure to original HDOM. Interface fractionation induced by iron oxyhydroxides significantly reduced genotoxicity of HDOM, especially for oxidative, membrane and DNA stresses. Overall, the selective absorption of HDOM molecules by iron oxyhydroxides shifted its biotoxicity, which might change the ecological effects of hydrochar amendment, e.g., microbial community structure, environmental pollutant transformation, and even the ecological function of terrestrial and aquatic ecosystems. These findings would contribute to unraveling the environmental geochemistry process of HDOM in the natural soil-water interface and provide a new insight into the biotoxicity of hydrochar usage to terrestrial and aquatic environments.

Synergistic release of Cd(II) and As(V) from ternary sorption systems containing ferrihydrite nanoparticles: The role of binary and ternary surface complexes

Cadmium (Cd) and arsenic (As) generally exhibit mutually beneficial co-sorption behavior on iron oxyhydroxides through multiple mechanisms, including surface precipitation, ternary surface complexes, and electrostatic interactions. However, the numerous factors that control the immobilization of Cd and As in turn complicated the processes and mechanisms involved in their co-desorption from iron minerals, which hindered the full understanding of their geochemical behaviors. Here, the simultaneous release of Cd(II) and As(V) from newly precipitated ferrihydrite nanoparticles by either Ca or P was investigated through kinetics and isothermal desorption experiments. We showed that the Cd(II) and As(V) present two-phase desorption processes (rapid desorption and slow desorption) in both binary (Fe–Cd or Fe–As alone) and ternary systems (Fe–Cd–As co-presence). Compared to their binary counterparts, Cd(II) and As(V) in the ternary systems are more prone to detachment from ferrihydrite. Further desorption of Cd(II) and As(V) at different co-presence scenarios (different initial concentrations) demonstrated mutual promotion behaviour towards their counterparts; the co-presence of Cd(II) facilitates the desorption of As(V), while the co-presence of As(V) also promotes the desorption of Cd(II). XPS and FTIR results demonstrated that either Ca or P showed minor effects on the binding environment of Cd and As. Further results from the in-situ ATR-FTIR experiment and second derivative peak fitting analysis indicate that the enhanced detachment of Cd(II) and As(V) from the ternary system may be due to the synergistic desorption of the ternary surface complexes and other surface complex species. Our results provide new insights into the prediction of the environmental behaviour of the coexistence of Cd(II) and As(V) in iron-rich geological settings. The potential environmental risks of iron-based remediation methods should be considered due to the enhanced bioavailability of Cd(II) and As(V) in co-presence circumstances.

Fabrication of Cu-doped iron oxyhydroxide for phosphate removal: A comprehensive spectroscopic, equilibrium, and thermodynamic approach

Fabrication of Cu-doped iron oxyhydroxide for phosphate removal: A comprehensive spectroscopic, equilibrium, and thermodynamic approach

Obtaining granular adsorbents based on biopolymers and clay minerals

The development of granular, low-cost adsorbents represents an important environmental challenge. Natural clay minerals show promise in this area, as they exhibit adsorption capacity a range of pollutants. Nevertheless, the high dispersion of aluminosilicates limits their widespread use. To enhance the processability of these materials, they are subjected to granulation using natural biopolymers, such as sodium alginates. Concurrently, the adsorption capacity of the granules can be increased by the application of modifiers to the surface of natural silicates, in particular iron oxyhydroxides, which are efficacious in the removal of heavy metals from water. The aim of this study is to obtain granular adsorbents based on saponite and biopolymer that are stable in water and capable of removing heavy metal ions from the water environment. The rheological behavior of the suspensions was investigated in order to ascertain the optimal conditions for high-quality granulation. The phase composition of the modified saponite was determined by X-ray diffraction analysis. The structural-sorption characteristics of the samples were investigated using the method of low-temperature nitrogen adsorption-desorption, and their thermal properties were studied by differential thermal and thermal gravimetric analyses. The present study demonstrates that the viscosity of saponite and sodium alginate-based suspensions with varying mass ratios is dependent on the clay mineral content of the mixture, at a fixed polymer quantity. The conditions for granulation were determined, and it was established that the stability of the granules in the aqueous medium is influenced by the quantity of sodium alginate incorporated into the mixture. It was established that the specific surface area of the modified sample decreases during the granulation process. This value is 109 m2/g, which is less than the 173 m2/g that observed for the powdered adsorbent. The processes and phase transformations occurring in granular materials during heating were studied. As a result of the study of the rheological characteristics of suspensions based on saponite and sodium alginate, it was found that these systems are thixotropic. It was also discovered that the stability of the granules in an aqueous medium is significantly affected by the amount of sodium alginate added to the suspension. The potential applications of the obtained adsorbents in the purification of water from heavy metal ion contamination are shown.

Enhanced geological and radioactive mapping of Gabal Abu Ashayir-Gabal El Bakriyah area, central Eastern Desert, Egypt, using remotely sensing data

AbstractThe primary goal of this work is to integrate airborne gamma-ray spectrometry with multispectral data from ASTER and Landsat-8 for mapping of the geology, radiometric data, and types of alterations of Gabal Abu Ashayir-Gabal El Bakriyah area, central Eastern Desert, Egypt. Utilizing various image processing techniques like color band composites (CBC), principal component analysis (PCA), band ratios (BR), and minimum noise fraction (MNF), it is possible to map the hydrothermal alterations zones and identify the lithological units under investigation. By identifying the various lithological units and alteration types, these results are validated and verified in the field. These methods’ outputs are combined to create an accurate geological map of the research region and tracing the propylitic, phyllic and iron oxy-hydroxides alterations. These rock units are ophiolitic mélange (oldest), arc metavolcanics, arc granitoids, younger gabbro, late-collision granites (monzogranites, syenogranites and alkali feldspar granites) and Nubian Sandstone (Taref formation and Quseir Formation) youngest, Furthermore, the radioactive anomalies are primarily associated with ferrugination zones (iron oxy-hydroxides alteration) at Gabal El Bakriyah monzogranite and alkali feldspar granite. The radioactive minerals are uranothorite, thorite and fergusonite. The opaque minerals that encountered at the rock units of Gabal Abu Ashayir-Gabal El Bakriyah are chromite, ilmenite, magnetite, chalcopyrite and chalcocite, whereas the non-opaque minerals comprises titanite, rutile, fluorite, garnet, zircon, apatite and barite.

Sustainable synthesis of iron oxide nanopigments: Enhancing pigment quality through combined air oxidation and cavitation techniques

This study investigates the synthesis and characterization of iron oxide pigments through various methods, including air oxidation, co-precipitation, and hydrodynamic cavitation. The infrared (IR) spectral analysis revealed key functional groups and metal-oxide bonds indicative of goethite, with bands associated with O–H stretching and Fe–O vibrations. The study also explores how different conditions, such as temperature, pH, and reactant ratios, affect the color, yield, and particle size of the pigments produced. Through batch and continuous synthesis processes, it was found that cavitation offers a more controlled particle size distribution compared to other methods. The experiments highlight the influence of parameters like temperature, pH, and NaOH concentration on the final pigment properties, with optimized conditions yielding high-quality pigments. The comparison of synthetic methods demonstrates the trade-offs in terms of reaction complexity, particle size control, and yield, emphasizing the potential of hydrodynamic cavitation for efficient and scalable pigment production. The study concludes by summarizing the versatile reactions of FeSO4 and NaOH in producing various iron oxide and oxyhydroxide materials, which are valuable in industrial and environmental applications.

The dual gain strategy of introducing nickel doping and anchoring amorphous iron oxyhydroxide nanosheets on ZIF-67 achieves an efficient oxygen evolution reaction

A ZIF-67@Ni@FeOOH composite material was synthesized using nickel-doped ZIF-67 as a precursor and was electrochemically characterized as an efficient oxygen evolution reaction (OER) catalyst. The results indicated that Ni doping preserved the polyhedral structure of ZIF-67 while enhancing its OER activity. The introduction of amorphous FeOOH nanosheets allowed ZIF-67@Ni@FeOOH to not only retain its original polyhedral structure but also develop a hollow interior and self-remodeling surface, resulting in numerous defects. These features contribute to improved charge transfer efficiency and enhanced conductivity of the material. The dual enhancement effect is achieved by combining the doping strategy with structural defect engineering. The synergistic effects of Co, Ni, and Fe species further boost OER performance. The ZIF-67@Ni@FeOOH catalyst exhibited remarkable OER efficacy, with the lowest overpotential at a current density of 10 mA cm−2 being 329 mV and a low Tafel slope of 42.95 mV dec−1. In situ Raman spectroscopy revealed that high-valence hydroxyl oxides, specifically NiOOH and CoOOH, present on the composite surface were the active species for OER. This study offers a promising approach for developing economically viable electrocatalysts with superior efficiency for OER.

Activation of peroxymonosulfate by β-FeOOH@Cia-MoS2 for enhancing degradation of tetracycline: Significant roles of surface functional groups and Fe/Mo redox reactions

Vertically oriented interstitial atom carbon-anchored molybdenum disulfide (Cia-MoS2) nanospheres loaded with iron oxyhydroxide (β-FeOOH) were proposed for modulating the surface catalytic activity and stability of the unsaturated catalytic system. The β-FeOOH@Cia-MoS2 efficiently activated peroxymonosulfate (PMS) to degrade 95.4% of tetracycline (TC) within 30 min, owing to the more sulfur vacancies, higher surface hydroxyl density, redox ability and electronic transmission rate of β-FeOOH@Cia-MoS2. According to the characterization and analysis data, the multiple active sites (Fe, Mo and S sites) and oxygen-containing functional groups (CO, –OH) of β-FeOOH@Cia-MoS2 could promote the activation of PMS to form reactive oxygen species (ROS). The oxidation cycle of Fe(II)/Fe(III) and Mo(IV)/Mo(VI), the electron transfer mediator of rich sulfur vacancies, as well as oxygen-containing functional groups on the surface of β-FeOOH@Cia-MoS2 synergistically promoted the formation of ROS (1O2, FeIVO, SO4•- and •OH), among which 1O2 was the main active oxidant. In particular, the β-FeOOH@Cia-MoS2/PMS system could still degrade pollutants efficiently and stably after five recycling cycles. Furthermore, this system had a strong anti-interference ability in the actual water body. This study provided a promising strategy for the removal of difficult-to-degrade organic pollutants.

Leptothrix ochracea genomes reveal potential for mixotrophic growth on Fe(II) and organic carbon.

Winogradsky's observations of L. ochracea led him to propose autotrophic iron oxidation as a new microbial metabolism, following his work on autotrophic sulfur-oxidizers. While much culture-based research has ensued, isolation proved elusive, so most work on L. ochracea has been based in the environment and in microcosms. Meanwhile, the autotrophic Gallionella became the model for freshwater microbial iron oxidation, while heterotrophic and mixotrophic iron oxidation is not well-studied. Ecological studies have shown that Leptothrix overtakes Gallionella when dissolved organic carbon content increases, demonstrating distinct niches. This study presents the first near-complete genomes of L. ochracea, which share some features with autotrophic iron oxidizers, while also incorporating heterotrophic metabolisms. These genome, metabolic modeling, and transcriptome results give us a detailed metabolic picture of how the organism may combine lithoautotrophy with organoheterotrophy to promote Fe oxidation and C cycling and drive many biogeochemical processes resulting from microbial growth and iron oxyhydroxide formation in wetlands.

Preparation of Oriented Nanoporous Magnetite Films by a Template-Free Solution Process from Iron Oxyhydroxide Films

Nanoporous oxide films composed of nanocrystal assemblies with an aligned crystallographic orientation are key nanostructures for efficient interfacial reactions. However, a simple, template-free method for their formation remains a challenge. Layered metal hydroxide (LMH) films are a promising precursor for spontaneous formation of nanoporous oxide films.[1-4] LMHs have a layered structure comprising 2D sheets of edge-shared octahedral hydroxide, i.e., brucite structure, with or without interlayer anions and water molecules. Calcination of LMH results in dehydration, anion elimination, and volume shrinkage, leading to the spontaneous formation of nanoporous oxides.In this study, we have prepared nanoporous and ferrimagnetic magnetite (Fe3O4) films by using layered iron hydroxides, namely, green rust (GR), as a precursor. Generally, GR has a brucite-type structure containing Fe2+ and Fe3+ ions, and is highly susceptible to oxidation by oxygen in water and air, leading to the formation of iron oxyhydroxides (FeOOH). Here, GR films were electrochemically deposited on FTO substrates in an aqueous solution containing Fe2+ and NO3 − ions at room temperature. Drying the GR films in air resulted in the formation of two-type FeOOH films, depending on the electrodeposition condition. Characterization using X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and FT-IR spectroscopy revealed that one is [010]-oriented γ-FeOOH films, and the other is [001]-oriented δ-FeOOH films. The obtained FeOOH films had a mille-feuille like morphology with 500–700 nm thickness. Heat treatment of these two-type FeOOH films under vacuum at 500 °C resulted in the formation of [110]- and [111]-oriented nanoporous Fe3O4 films. The obtained Fe3O4 films showed a ferrimagnetic behavior in VSM measurements and had a nanoporous structure comprising nanoparticles with 50–100 nm diameter.Finally, a possilble interpretation for the observed orientation relationships between the FeOOH and Fe3O4 was also discussed on the basis of pyrolysis intermediates of FeOOH and similarity in their atomic arrangements. References T. Shinagawa, M. Watanabe, T. Mori, J.-i. Tani, M. Chigane and M. Izaki, Inorg. Chem., 57, 13137 (2018).T. Shinagawa, M. Chigane and M. Izaki, ACS Omega, 6, 2312 (2021).T. Shinagawa, M. Chigane and M. Takahashi, Cryst. Growth Des., 22, 4122 (2022).T. Shinagawa, N. Kotobuki and A. Ohtaka, Nanoscale Adv., 5, 96 (2023). Figure 1

Electrolyte-Induced Fe-Doping of LaNiO3 Model Surfaces for Water Electrolysis

Renewable energy needs to be store in different energy forms for the energy transition away from fossil fuels. One of most promising forms is chemicals such as H2 and C-based fuels obtained via electrochemical reactions. The common hinderance in such reactions is the sluggish oxygen evolution reaction (OER), which causes low energy efficiency in conversion devices. Developing highly active, earth-abundant OER electrocatalysts in alkaline media is necessary to boost the performance of such devices. Fe ion content in electrolyte is known to influence the OER-activity of metal oxide electrocatalysts. For example, the Fe incorporation in NiOOH is a well-established and important effect for OER.[1] Here, we present the effect of absorbed Fe on the OER activity of the epitaxial Ni-surface terminated LaNiO3 thin films. The correlation between surface species and OER activity of electrocatalysts was investigated using surface-sensitive low-energy ion scattering and X-ray photoemission spectroscopies. We observe more than an order-of-magnitude boost in OER activity during initial cycling, from 0.15 mAcm-2 to 3.40 mAcm-2 at 1.60 V vs. reversible hydrogen electrode. The activity increase was mainly caused by the incorporation of up to 5 % Fe at the top surface of LaNiO3 film (less than ~1 nm) even though only a very trace amount of Fe ion, 30 ppb, is present in the 0.1 M electrolyte of high purity KOH 99.99 %. Our results demonstrate that the disordered active surface phase, which develops even on single crystalline surfaces, is a complex interplay between the as-prepared (surface) crystalline structure, composition of the solid electrocatalyst and the liquid electrolyte, and has strong impact on the final OER activity, implying that we need to think differently about the crystalline electrocatalysts: crystalline bulk and dynamically changing surface layer.[1] L. Trotochaud, S.L. Young, J.K. Ranney, S.W. Boettcher, Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation, J. Am. Chem. Soc. 136 (2014) 6744–6753.