A billion-year shift in the formation of Earth's largest ore deposits.

Banded iron formations (BIFs) archive the relationship between Earth's lithosphere, hydrosphere, and atmosphere through time. However, constraints on the origin of Earth's largest ore deposits, hosted by BIFs, are limited by the absence of direct geochronology. Without this temporal context, genetic models cannot be correlated with tectono-thermal and atmospheric drivers responsible for BIF upgrading through time. Utilizing in situ iron oxide U-Pb geochronology, we provide a direct timeline of events tracing development of all the giant BIF-hosted hematite deposits of the Hamersley Province (Pilbara Craton, Western Australia). Direct dating demonstrates that the major iron ore deposits in the region formed during 1.4 to 1.1 Ga. This is one billion to hundreds of millions of years later than previous age constraints based upon 1) the presence of hematite ore clasts in conglomerate beds deposited before ~1.84 Ga, and 2) phosphate mineral dating, which placed the onset of iron mineralization in the Province at ~2.2 to 2.0 Ga during the great oxidation event. Dating of the hematite clasts verified the occurrence of a ~2.2 to 2.0 Ga event, reflecting widespread, but now largely eroded iron mineralization occurring when the Pilbara and Kaapvaal cratons were proximal. No existing phosphate mineral dates overlap with obtained hematite dates and therefore cannot be related to hematite crystallization and ore formation. New geochronology conclusively links all major preserved hematite deposits to a far younger (1.4 to 1.1 Ga) formation period, correlated with the amalgamation of Australia following breakup of the Columbia supercontinent.

Ru-P pair sites boost charge transport in hematite photoanodes for exceeding 1% efficient solar water splitting.

Fast transport of charge carriers in semiconductor photoelectrodes are a major determinant of the solar-to-hydrogen efficiency for photoelectrochemical (PEC) water slitting. While doping metal ions as single atoms/clusters in photoelectrodes has been popularly used to regulate their charge transport, PEC performances are often low due to the limited charge mobility and severe charge recombination. Here, we disperse Ru and P diatomic sites onto hematite (DASs Ru-P:Fe2O3) to construct an efficient photoelectrode inspired by the concept of correlated single-atom engineering. The resultant photoanode shows superior photocurrent densities of 4.55 and 6.5 mA cm-2 at 1.23 and 1.50 VRHE, a low-onset potential of 0.58 VRHE, and a high applied bias photon-to-current conversion efficiency of 1.00% under one sun illumination, which are much better than the pristine Fe2O3. A detailed dynamic analysis reveals that a remarkable synergetic ineraction of the reduced recombination by a low Ru doping concentration with substitution of Fe site as well as the construction of Ru-P bonds in the material increases the carrier separation and fast charge transportation dynamics. A systematic simulation study further proves the superiority of the Ru-P bonds compared to the Ru-O bonds, which allows more long-lived carriers to participate in the water oxidation reaction. This work offers an effective strategy for enhancing charge carrier transportation dynamics by constructing pair sites into semiconductors, which may be extended to other photoelectrodes for solar water splitting.

Particle-based hematite crystallization is invariant to initial particle morphology.

SignificanceMany crystallization processes occurring in nature produce highly ordered hierarchical architectures. Their formation cannot be explained using classical models of monomer-by-monomer growth. One of the possible pathways involves crystallization through the attachment of oriented nanocrystals. Thus, it requires detailed understanding of the mechanism of particle dynamics that leads to their precise crystallographic alignment along specific faces. In this study, we discover a particle-morphology-independent oriented attachment mechanism for hematite nanocrystals. Independent of crystal morphology, particles always align along the [001] direction driven by aligning interactions between (001) faces and repulsive interactions between other pairs of hematite faces. These results highlight that strong face specificity along one crystallographic direction can render oriented attachment to be independent of initial particle morphology.

Unassisted Photoelectrochemical H2O2 Production with In Situ Glycerol Valorization Using α-Fe2O3.

Photoelectrochemical (PEC) H2O2 production via two-electron O2 reduction is promising for H2O2 production without emitting CO2. For PEC H2O2 production, α-Fe2O3 is an ideal semiconductor owing to its earth abundance, superior stability in water, and an appropriate band gap for efficient solar light utilization. Moreover, its conduction band is suitable for O2 reduction to produce H2O2. However, a significant overpotential for water oxidation is required due to the poor surface properties of α-Fe2O3. Thus, unassisted solar H2O2 production is not yet possible. Herein, we demonstrate unassisted PEC H2O2 production using α-Fe2O3 for the first time by applying glycerol oxidation, which requires less bias compared with water oxidation. We obtain maximum Faradaic efficiencies of 96.89 ± 0.6% and 100% for glycerol oxidation and H2O2 production, respectively, with high stability for 25 h. Our results indicate that unassisted and stable PEC H2O2 production is feasible with in situ glycerol valorization using the α-Fe2O3 photoanode.

Efficient Acidic Photoelectrochemical Water Splitting Enabled by Ru Single Atoms Anchored on Hematite Photoanodes.

Photoelectrochemical (PEC) water splitting in acidic media holds promise as an efficient approach to renewable hydrogen production. However, the development of highly active and stable photoanodes under acidic conditions remains a significant challenge. Herein, we demonstrate the remarkable water oxidation performance of Ru single atom decorated hematite (Fe2O3) photoanodes, resulting in a high photocurrent of 1.42 mA cm-2 at 1.23 VRHE under acidic conditions. Comprehensive experimental and theoretical investigations shed light on the mechanisms underlying the superior activity of the Ru-decorated photoanode. The presence of single Ru atoms enhances the separation and transfer of photogenerated carriers, facilitating efficient water oxidation kinetics on the Fe2O3 surface. This is achieved by creating additional energy levels within the Fe2O3 bandgap and optimizing the free adsorption energy of intermediates. These modifications effectively lower the energy barrier of the rate-determining step for water splitting, thereby promoting efficient PEC hydrogen production.

Hematite Hollow-Sphere-Array Photoanodes for Efficient Photoelectrochemical Water Splitting.

Constructing 3D nanophotonic structures is regarded as an effective method to realize efficient solar-to-hydrogen conversion. These photonic structures can enhance the absorbance of photoelectrodes by the light trapping effect, promote the charge separation by designable charge transport pathway and provide a high specific surface area for catalytic reaction. However, most 3D structures reported so far mainly focused on the influence of light absorption and lacked a systematic investigation of the overall water splitting process. Herein, hematite hollow-sphere-array photoanodes are fabricated through a facile hydrothermal method with polystyrene templates. Validating by simulations and experiments, the hollow sphere array is proved to enhance the efficiency of light harvesting, charge separation and surface reaction at the same time. With an additional annealing treatment in oxygen, a photocurrent density of 2.26 mA cm-2 at 1.23 V versus reversible hydrogen electrode can be obtained, which is 3.70 times larger than that with a planar structure in otherwise the same system. This work gains an insight into the photoelectrochemical water splitting process, which is valuable for the further design of advancing solar driven water splitting devices.

Ge-Doped Hematite with FeCoNi-Bi as Cocatalyst for High-Performing Photoelectrochemical Water Splitting.

Hematite is a promising photoanode material for photoelectrochemical water-splitting technology. However, the low current density associated with the low conductivity, low charge carrier mobility, and poor oxygen evolution catalytic activity is a challenging issue for the material. In this study, the challenge is addressed by introducing Germanium (Ge) doping, coupled with the use of FeCoNi-Bi as a co-catalyst. Ge doping not only increases the conductivity and charge carrier concentration of the hematite photoanode, but also induces nanopores, thereby expanding its electrochemical reactive surface area to facilitate the oxygen evolution reaction. In the meantime, the FeCoNi-Bi cocatalyst electrodeposited onto the surface of Ge-doped hematite, improves the oxygen evolution reaction performance. As a result, the obtained photoanode achieves a photocurrent density of 2.31 mA cm-2 at 1.23 VRHE, which is three times higher than that of hematite (0.72 mA cm-2). Moreover, a new analytical method is introduced to scrutinize both the positive and negative effects of Ge doping and FeCoNi-Bi cocatalyst on the photoanode performance by decoupling the photoelectrochemical process steps. Overall, this study not only enhances the performance of hematite photoanodes but also guides their rational design and systematic assessment.

Uncovering Energetic Positions of Surface Trap States in α-Fe2O3 Treated with Cobalt Phosphate (Co-Pi) Using Charge Carrier-Selective Heterodyne Transient Grating Technique.

Near-field heterodyne transient grating (NF-HD-TG) responses of hematite (α-Fe2O3) treated with cobalt phosphate (Co-Pi) were measured with the burn lasers inducing the depletion of the response by the removal of the trapped charge carriers in the target state, which is called charge carrier-selective heterodyne transient grating (CS-HD-TG) spectroscopic technique. We found that two distinct trap states co-existed in Co-Pi loaded on the surface of α-Fe2O3. One of them named r-SS2, of which potential was similar to that of r-SS1 in the surface of α-Fe2O3, acted as a recombination centre but could increase the lifetime of the trapped holes by the charge separation. We also revealed that the energetic position of the other (i-SS2), which has been regarded as the intermediate state for oxygen evolution reaction with low overpotential, was higher than that of i-SS1 in α-Fe2O3 but lower than those of r-SS1 and r-SS2.

Photolysis of Dissolved Organic Matter over Hematite Nanoplatelets.

Solar photoexcitation of chromophoric groups in dissolved organic matter (DOM), when coupled to photoreduction of ubiquitous Fe(III)-oxide nanoparticles, can significantly accelerate DOM degradation in near-surface terrestrial systems, but the mechanisms of these reactions remain elusive. We examined the photolysis of chromophoric soil DOM coated onto hematite nanoplatelets featuring (001) exposed facets using a combination of molecular spectroscopies and density functional theory (DFT) computations. Reactive oxygen species (ROS) probed by electron paramagnetic resonance (EPR) spectroscopy revealed that both singlet oxygen and superoxide are the predominant ROS responsible for DOM degradation. DFT calculations confirmed that Fe(II) on the hematite (001) surface, created by interfacial electron transfer from photoexcited chromophores in DOM, can reduce dioxygen molecules to superoxide radicals (•O2-) through a one-electron transfer process. 1H nuclear magnetic resonance (NMR) and electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) spectroscopies show that the association of DOM with hematite enhances the cleavage of aromatic groups during photodegradation. The findings point to a pivotal role for organic matter at the interface that guides specific ROS generation and the subsequent photodegradation process, as well as the prospect of using ROS signatures as a forensic tool to help interpret more complicated field-relevant systems.

Optimization of hematite nanoparticles from natural ore as novel imaging agents: A Green Chemistry approach.

In this research, we propose an environmentally friendly method for producing hematite nanoparticles (H-NPs) from natural hematite ore, focusing on their application as efficient contrast agents in x-ray and computed tomography (CT) imaging for medical purposes. The process involves the reduction of iron oxide within the ore to attain the desired hematite phase, crucial for synthesizing H-NPs. To ensure sustainability, we adopted a Green Chemistry approach, utilizing a combination of carbon soot and limestone for the purification process, thereby achieving eco-conscious production. The produced H-NPs were thoroughly characterized using various analytical techniques, such as x-ray fluorescence (XRF), x-ray diffraction (XRD), Fourier transmission infrared spectroscopy (FT-IR), and FESEM-EDX (field emission scanning electron microscopy-energy-dispersive x-ray spectroscopy). XRD analysis confirmed the crystalline rhombohedral hexagonal lattice structure, while FT-IR spectra indicated the presence of characteristic Fe-O stretching modes in line with the expected molecular composition. FESEM-EDX imaging unveiled agglomerated particles, ranging in size from 54.6 to 149.9 nm for iron ore and 22 nm for H-NPs. These particles were primarily composed of iron (Fe) and oxygen (O). The magnetic properties of the H-NPs were investigated through vibrating sample magnetometer (VSM) studies, highlighting their distinct ferromagnetic behavior. Of particular significance, the H-NPs demonstrated exceptional performance as contrast agents in both x-ray and CT imaging. Even at minimal concentrations, they exhibited remarkable x-ray absorption capabilities. CT scans further validated their exceptional absorptive capacity. These findings emphasize the potential of H-NPs as valuable assets in medical imaging, serving as sustainable tools for enhanced diagnostic applications. The study showcases an eco-conscious approach to harnessing natural resources, paving the way for a greener and more effective utilization of H-NPs in the medical imaging landscape.

Hematite reconstruction of Late Triassic hydroclimate over the Colorado Plateau.

Hematite is the most abundant surficial iron oxide on Earth resulting from near-surface processes that make it important for addressing numerous geologic problems. While red beds have proved to be excellent paleomagnetic recorders, the early diagenetic origin of hematite in these units is often questioned. Here, we validate pigmentary hematite ("pigmentite") as a proxy indicator for the Late Triassic environment and its penecontemporaneous origin by analyzing spectrophotometric measurements of a 14.5-My-long red bed sequence in scientific drill core CPCP-PFNP13-1A of the Chinle Formation, Arizona. Pigmentite concentrations in the red beds track the evolving pattern of the Late Triassic monsoon and indicate a long-term rise in aridity beginning at ∼215 Ma followed by increased oscillatory climate change at ∼213 Ma. These monsoonal changes are attributed to the northward drift of the Colorado Plateau as part of Laurentia into the arid subtropics during a time of fluctuating CO2 Our results refine the record of the Late Triassic monsoon and indicate significant changes in rainfall proximal to the Adamanian-Revueltian biotic transition that thus may have contributed to apparent faunal and floral events at 216 to 213 Ma.

Fully Dispersed IrOx Atomic Clusters Enable Record Photoelectrochemical Water Oxidation of Hematite in Acidic Media.

Ir-based materials are still the benchmark catalysts for various reactions in acidic environment, but the high loading and low atom utilization limit their large-scale deployment. Herein, we report an effective strategy for implanting fully dispersed iridium-oxide atomic clusters onto hematite for boosting photoelectrochemical water oxidation in acidic solution. The resulting photoanode achieves a record-high photocurrent of 1.35 mA cm-2 at 1.23 V, corresponding to a mass activity of 172.70 A g-1 (3 times higher than electrodeposited control sample) and demonstrating the merits from the high atomic utilization of Ir. The systematically experimental and theoretical results reveal that the performance improvement correlates with the modulated electronic structure including the adjusted Fermi level and d-band center, which significantly enhances charge separation efficiency and promotes the conversion from intermediate *O into *OOH.

Tropical soil remediation from pyrene: Release the power of natural iron content in soil for the efficient oxidant's activation.

Natural soil minerals often contain numerous impurities, resulting in comparatively lower catalytic activity. Tropical soils are viewed as poor from soil organic matter, cations, and anions, which are considered the main impurities in the soil that are restricted to utilizing natural minerals as a catalyst. In this regard, the dissolved iron and hematite crystals that presented naturally in tropical soil were evaluated to activate oxidants and degrade pyrene. The optimum results obtained in this study were 73 %, and the rate constant was 0.0553 h-1 under experimental conditions [pyrene] = 300 mg/50 g, pH = 7, T = 55 °C, airflow = 260 mL/min, [Persulfate (PS)] = 1.0 g/L, and humic acid (HA) ( % w/w) = 0.5 %. The soil characterization analysis after the remediation process showed an increase in moieties and cracks of the soil aggregate, and a decline in the iron and aluminium contents. The scavengers test revealed that both SO4•- and O2•- were responsible for the pyrene degradation, while HO• had a minor role in the degradation process. In addition, the monitoring of by-products, degradation pathways, and toxicity assessment were also investigated. This system is considered an efficient, green method, and could provide a step forward to develop low-cost soil remediation for full-scale implementation.

Ferrihydrite transformation impacted by coprecipitation of lignin: Inhibition or facilitation?

Lignin is a common soil organic matter that is present in soils, but its effect on the transformation of ferrihydrite (Fh) remains unclear. Organic matter is generally assumed to inhibit Fh transformation. However, lignin can reduce Fh to Fe(II), in which Fe(II)-catalyzed Fh transformation occurs. Herein, the effects of lignin on Fh transformation were investigated at 75°C as a function of the lignin/Fh mass ratio (0-0.2), pH (4-8) and aging time (0-96 hr). The results of Fh-lignin samples (mass ratios = 0.1) aged at different pH values showed that for Fh-lignin the time of Fh transformation into secondary crystalline minerals was significantly shortened at pH 6 when compared with pure Fh, and the Fe(II)-accelerated transformation of Fh was strongly dependent on pH. Under pH 6, at low lignin/Fh mass ratios (0.05-0.1), the time of secondary mineral formation decreased with increasing lignin content. For high lignosulfonate-content material (lignin:Fh = 0.2), Fh did not transform into secondary minerals, indicating that lignin content plays a major role in Fh transformation. In addition, lignin affected the pathway of Fh transformation by inhibiting goethite formation and facilitating hematite formation. The effect of coprecipitation of lignin on Fh transformation should be useful in understanding the complex iron and carbon cycles in a soil environment.

Facet-dependent activation of oxalic acid over hematite nanocrystals under the irradiation of visible light for efficient degradation of pollutants.

Naturally occurring hematite has been widely studied in the Fenton-like system for water pollutant remediation due to its abundance and non-toxicity. However, its inadequate catalytic activity results in difficulty in effectively degrading pollutants in the catalytic degradation system that it constitutes. Thus, we constructed a photochemical system composed of hematite with {001} facet of high activity facet and low-cost and non-toxic oxalic acid (OA) for the removal of various types of pollutants. The removal rate for the degradation of metronidazole, tetracycline hydrochloride, Rhodamine B, and hexavalent chromium by hematite nanoplate with the exposed {001} facet activating OA under visible light irradiation was 4.75, 2.25, 2.33, and 2.74 times than that by the exposed {110} facet, respectively. Density functional theory (DFT) calculation proved that the OA molecule was more easily adsorbed on the {001} facet of hematite than that on the {110} facet, which would favor the formation of the more Fe(III)-OA complex and reactive species. In addition, the reactive site of metronidazole for the attraction of radicals was identified on the basis of the DFT calculation on the molecular occupied orbitals, and the possible degradation pathway for metronidazole included carbon chain fracture, hydroxyethyl-cleavage, denitrogenation, and hydroxylation. Thus, this finding may offer a valuable direction in designing an efficient iron-based catalyst based on facet engineering for the improved activity of Fenton-like systems such as OA activation.

First-principles study on the heterogeneous formation of environmentally persistent free radicals (EPFRs) over α-Fe2O3(0001) surface: Effect of oxygen vacancy.

Metal oxides with oxygen vacancies have a significant impact on catalytic activity for the transformation of organic pollutants in waste-to-energy (WtE) incineration processes. This study aims to investigate the influence of hematite surface oxygen point defects on the formation of environmentally persistent free radicals (EPFRs) from phenolic compounds based on the first-principles calculations. Two oxygen-deficient conditions were considered: oxygen vacancies at the top surface and on the subsurface. Our simulations indicate that the adsorption strength of phenol on the α-Fe2O3(0001) surface is enhanced by the presence of oxygen vacancies. However, the presence of oxygen vacancies has a negative impact on the dissociation of the phenol molecule, particularly for the surface with a defective point at the top layer. Thermo-kinetic parameters were established over a temperature range of 300-1000 K, and lower reaction rate constants were observed for the scission of phenolic O-H bonds over the oxygen-deficient surfaces compared to the pristine surface. The negative effects caused by the oxygen-deficient conditions could be attributed to the local reduction of FeIII to FeII, which lower the oxidizing ability of surface reaction sites. The findings of this study provide us a promising approach to regulate the formation of EPFRs.

Roles of Cobalt-Coordinated Polymeric Perylene Diimide in Hematite Photoanodes for Improved Water Oxidation.

Interfacial charge recombination is a permanent issue that impedes the photon energy utilization in photoelectrochemical (PEC) water splitting. Herein, a conjugated polymer, urea linked perylene diimide polymer (PDI), is introduced to the designation of hematite-based composite photoanodes. On account of its unique molecule structure with abundant electronegative atoms, the O and N atoms with lone electron pairs can bond with Fe atoms at the surface of Zr4+ doped α-Fe2 O3 (Zr:Fe2 O3 ) and thus establish charge transfer channels for expediting hole separation and migration. Meanwhile, PDI molecules can passivate the surface states in Zr:Fe2 O3 , which is in favor of suppressing carrier recombination. Particularly, Co2+ is used to coordinate with PDI (Co-PDI) to accelerate hole extraction as well as utilization, and the as-obtained Co-PDI form type-II heterojunction with Zr:Fe2 O3 . Such a photoanode configuration takes advantage of the unique molecule structure of PDI, and the target Co-PDI/Zr:Fe2 O3 photoanodes eventually attain a photocurrent density of 2.17 mA cm-2 , which is inspirational for unearthing the potential use of conjugative molecules in PEC fields.

Synergy of Ultrathin CoOx Overlayer and Nickel Single Atoms on Hematite Nanorods for Efficient Photo-Electrochemical Water Splitting.

To solve surface carrier recombination and sluggish water oxidation kinetics of hematite (α-Fe2 O3 ) photoanodes, herein, an attractive surface modification strategy is developed to successively deposit ultrathin CoOx overlayer and Ni single atoms on titanium (Ti)-doped α-Fe2 O3 (Ti:Fe2 O3 ) nanorods through a two-step atomic layer deposition (ALD) and photodeposition process. The collaborative decoration of ultrathin CoOx overlayer and Ni single atoms can trigger a big boost in photo-electrochemical (PEC) performance for water splitting over the obtained Ti:Fe2 O3 /CoOx /Ni photoanode, with the photocurrent density reaching 1.05 mA cm-2 at 1.23 V vs. reversible hydrogen electrode (RHE), more than three times that of Ti:Fe2 O3 (0.326 mA cm-2 ). Electrochemical and electronic investigations reveal that the surface passivation effect of ultrathin CoOx overlayer can reduce surface carrier recombination, while the catalysis effect of Ni single atoms can accelerate water oxidation kinetics. Moreover, theoretical calculations evidence that the synergy of ultrathin CoOx overlayer and Ni single atoms can lower the adsorption free energy of OH* intermediates and relieve the potential-determining step (PDS) for oxygen evolution reaction (OER). This work provides an exemplary modification through rational engineering of surface electrochemical and electronic properties for the improved PEC performances, which can be applied in other metal oxide semiconductors as well.

Surface Self-Transforming FeTi-LDH Overlayer in Fe2 O3 /Fe2 TiO5 Photoanode for Improved Water Oxidation.

Integrating hematite nanostructures with efficient layer double hydroxides (LDHs) is highly desirable to improve the photoelectrochemical (PEC) water oxidation performance. Here, an innovative and facile strategy is developed to fabricate the FeTi-LDH overlayer decorated Fe2 O3 /Fe2 TiO5 photoanode via a surface self-transformation induced by the co-treatment of hydrazine and NaOH at room temperature. Electrochemical measurements find that this favorable structure can not only facilitate the charge transfer/separation at the electrode/electrolyte interface but also accelerate the surface water oxidation kinetics. Consequently, the as-obtained Fe2 O3 /Fe2 TiO5 /LDH photoanode exhibits a remarkably increased photocurrent density of 3.54 mA cm-2 at 1.23 V versus reversible hydrogen electrode (RHE) accompanied by an obvious cathodic shift (≈140 mV) in the onset potential. This work opens up a new and effective pathway for the design of high-performance hematite photoanodes toward efficient PEC water oxidation.

Photoelectrochemical degradation of selected organic substances on Fe2O3 photoanodes: a comparison with TiO2.

The photoelectrochemical degradation of selected aromatic substances, acid orange 7 (AO7), salicylic acid (SA), benzoic acid (BA), and 4-chlorophenol (4-CP) was studied on hematite (α-Fe2O3) and compared with titanium dioxide (TiO2), both deposited as thin films on conducting substrates (FTO/glass). Batch type reactors were used under backside and front side illumination. Electrical bias was applied on the semiconducting electrodes, such that only valence band processes leading to oxidative pathways were followed. The initial Faradaic efficiency, f0, of degradation processes was determined from the UV-Vis absorbance decrease of the starting materials. f0 for 1 mM AO7 degradation in 0.01 M sulphuric acid was found to be 7.5%. When the pH of the solution was neutral (pH 7.2) or alkaline (pH 13), f0 decreased to 1.7%. For 1 mM SA, f0 was 6.2% on hematite photoanodes and 6.1% on titanium dioxide. For 1 mM benzoic acid and 4-chlorophenol, f0 was an order of magnitude lower, but only on hematite. This is ascribed to the lack of OH· radical formation on hematite, which seems to be essential for the photooxidation of these compounds.