Oxidation State Of Iron Research Articles

Defect Engineering with Rational Dopants Modulation for High-Temperature Energy Harvesting in Lead-Free Piezoceramics

HighlightsThe solution limit of manganese ion in BiFeO3–BaTiO3 (BF–BT) was determined by combining multiple advanced characterization methods.The defect engineering associated with fine doping can realize the co-modulation of polarization configuration, iron oxidation state and domain orientation.The BF–BT–0.2Mn piezoelectric energy harvester shows excellent power generation capacity at 250 °C, which is an important breakthrough for lead-free piezoelectric devices.

Unveiling the magnetic structure of BaFeO3-y: Shedding light on the elusive magnetic behavior

This work provides a comprehensive examination of the structural and magnetic properties of 6H-BaFeO2.96 over a wide temperature range (10 K < T < 300 K) using neutron and synchrotron X-ray diffraction. Additionally, the local oxidation state of iron is examined using electron energy loss spectroscopy. No structural changes that could indicate a charge-order transition are observed in spite of a reported possible charge disproportionation of Fe4+ into Fe(4+δ)+ and Fe(4-δ)+ phenomenon at low temperature. According to the magnetic characterization, BaFeO2.96 orders antiferromagnetically at TN=156 K. The application of external magnetic fields strongly influences the magnetic behavior; the transition temperature shifts to lower values with the applied magnetic field and the long-range magnetic order melts with an applied field of 14 T. The magnetocaloric effect clearly shows at TN a change from negative to positive magnetic entropy. The Rietveld refinement of the neutron powder diffraction data collected at 10 K, gives a magnetic ordering with propagation vector [0, 0, ½] and three magnetically distinct sites for the Fe atoms. This magnetic structure consists of ferromagnetic Fe-sheets perpendicular to the c-axis with the magnetic moments along the [110] direction coupled both ferromagnetic and antiferromagnetically along the c-axis. The magnetic moment values of the three Fe ions are very different evidencing a delicate equilibrium of competing magnetic interactions.

Biogenic Sulfide-Mediated Iron Reduction at Low pH

Acid mine drainage (AMD) pollutes natural waters, but some impacted systems show natural attenuation. We sought to identify the biogeochemical mechanisms responsible for the natural attenuation of AMD. We hypothesized that biogenic sulfide-mediated iron reduction is one mechanism and tested this in an experimental model system. We found sulfate reduction occurred under acidic conditions and identified a suite of sulfate-reducing bacteria (SRB) belonging to the groups Desulfotomaculum, Desulfobacter, Desulfovibrio, and Desulfobulbus. Iron reduction was not detected in microcosms when iron-reducing bacteria or SRB were selectively inhibited. SRB also did not reduce iron enzymatically. Rather, the biogenic sulfide produced by SRB was found to be responsible for the reduction of iron at low pH. Addition of organic substrates and nutrients stimulated iron reduction and increased the pH. X-ray diffraction and an electron microprobe analysis revealed that the polycrystalline, black precipitate from SRB bioactive samples exhibited a greater diversity of iron chalcogenide minerals with reduced iron oxidation states, and minerals incorporating multiple metals compared to abiotic controls. The implication of this study is that iron reduction mediated by biogenic sulfide may be more significant than previously thought in acidic environments. This study not only describes an additional mechanism by which SRB attenuate AMD, which has practical implications for AMD-impacted sites, but also provides a link between the biogeochemical cycling of iron and sulfur.

Charge Transfer in n-FeO and p-α-Fe2O3 Nanoparticles for Efficient Hydrogen and Oxygen Evolution Reaction.

This study aims to explore the n-FeO and p-α-Fe2O3 semiconductor nanoparticles in hydrogen (HER) and oxygen (OER) evolution reactions and a combined full cell electrocatalyst system to electrolyze the water. We have observed a distinct electrocatalytic performance for both HER and OER by tuning the interplay between iron oxidation states Fe2+ and Fe3+ and utilizing phase-transformed iron oxide nanoparticles (NPs). The Fe2+ rich n-FeO NPs exhibited superior HER performance compared to p-α-Fe2O3 and Fe(OH)x NPs, which is attributed to the enhancement in n-type semiconducting nature under HER potential, facilitating the electron transfer for the reduction in H+ ions. In contrast, p-α-Fe2O3 NPs demonstrated excellent OER activity. An H-cell constructed using n-FeO||p-α-Fe2O3 NPs as cathode and anode achieved a cell voltage of 1.87 V at a current density of 50 mA/cm2. The cell exhibited remarkable stability after 30 h of activation and maintained the high current density of 100 mA/cm2 for 80 h with a negligible increase in cell voltage. This work highlights the semiconducting properties of n-FeO and p-α-Fe2O3 for the electrochemical water splitting system using the band bending phenomenon under the applied potential.

Effect of iron oxidation state on the catalytic performance of Fe/C in liquid phase flow hydrogenation of 2-butyne-1,4-diol

Cis-2-butene-1,4-diol and 1,4-butanediol are crucial precursors in producing bioplastics and biodegradable plastics. Moreover, cis-2-butene-1,4-diol is used in the production of vitamins A and B6, fungicides and insecticides. On an industrial scale, they are produced by hydrogenation of 2-butyne-1,4-diol with Ni Raney as catalyst at > 160 °C and > 15 MPa. Herein, the effect of mesoporous carbon, iron loading (2, 6, 10 and 14 wt%), and metal oxidation state on the activity and selectivity of iron catalysts in the liquid phase continuous flow 2-butyne-1,4-diol hydrogenation at mild conditions (at temperature range 10–65 °C and pressure range 1–20 bar) was performed. Catalytic investigations supported by statistical modeling and physicochemical characterization (TPR, H2-TPD, physisorption, TEM, XPS, and Mössbauer spectroscopy), showed that the activity of the Fe/C can be determined by the presence of functional groups in mesoporous support which are responsible for high metal dispersion and strong metal-support interaction, which boosts the catalytic activity of iron catalysts. Additionally, the formation of metastable iron carbides which are active in hydrogenation cannot be excluded. All of the catalysts showed 100% selectivity toward cis-2-butene-1,4-diol at the lowest temperature. However, the best compromise between selectivity and activity (TOF=336 h−1) was achieved with 2 wt% Fe at 1 bar and 25 °C.

Production and characterization of nano-magnetic material through different red mud reduction processes

Red mud (RM), is an industrial waste deriving from the production of primary aluminium, with about 200 Mtons generated annually. In this work, the reduction of RM for obtaining magnetic products with particular chemical-physical characteristics has been explored. RM reduction was carried out in a semi-closed reducing environment at a high processing temperature (750–1100 °C) in the presence of carbon-rich ash (CA) resulting from a commercial pyro-gasification plant and by using an H2 atmosphere. All the materials were characterized by elemental analysis, XRD diffraction technique, SEM/EDX microscopy, thermogravimetry and infrared spectroscopy. The materials obtained under the different conditions have in common the presence of small iron-magnetic domains (with different iron oxidation states), in the order of hundreds of nanometres, and by the ferro-magnetic or paramagnetic response to an external magnetic field. In particular, the material pre-treated with HCl (enriched in iron) and reduced with H2 showed very good magnetic responses, more iron in reduced oxidative states showing high ferro-magnetic responses to the external field. The synthesised materials are quite differents each others and appear to have several potential fields of application, as sorbents for specific wastewater pollutants, as materials for CO2 capture, for catalysis and (bio)sensing applications. Nevertheless, the high interconnection between the magnetic and non-magnetic phases limit the direct separation or the iron enrichment. Further efforts should be focused on the functional studies and subsequent LCA and LCC analyses.

Does the 57Fe Mössbauer isomer shift depend on the oxidation state of iron?

The 57Fe Mössbauer isomer shift is not directly related to the oxidation state of iron, and therefore the evaluation of the oxidation state of iron from the isomer shift is problematic. The oxidation state affects the isomer shift only to the extent that it affects the Fe–X bond lengths. The isomer shift can be estimated based on the average Fe–X interatomic distance.

Magnetotelluric imaging of an iron-oxide copper gold (IOCG) deposit under thick cover

The presence of thick (>100 m) and electrically conductive (< 10 Ω.m) ground cover is a major impediment in mineral exploration of deep resources. Iron-oxide copper gold (IOCG) systems in Australia are often associated with a pronounced potential field anomaly, depending on the oxidation state of iron, but the gravity and magnetic field signatures have little vertical resolution unless constrained by drill hole petrophysics. Additionally, IOCG systems have deep magmatic sources, with their conductivity anomalies extending at least to the lithospheric mantle. The Vulcan IOCG prospect lies about 30 km northeast of the Olympic Dam IOCG mine and is defined by a significant gravity anomaly associated with brecciated haematite beneath 850 m of sedimentary cover sequences. To image the physical properties and structural geometry of the Vulcan IOCG prospect, a 100-site broadband MT and passive seismic array was deployed in a 1 km grid over a 9 by 9 km area. Three-dimensional inversion of MT responses resolve structure in three distinct domains. Firstly, broad limestone-quartzite-shale stratigraphy (1–30 Ω.m) in the 850 m cover is delineated in resistivity and corresponds well with changes in shear-wave velocity. Secondly, the region of brecciated haematite below the cover sequences is shown to have lower resistivity (< 60 Ω.m) than surrounding country rock (> 100 Ω.m). Thirdly, a more electrically conductive (< 30 Ω.m) vertical zone that extends > 5 km is imaged a few kilometers to the northeast of the Vulcan haematite breccia, and appears to be linked by a region of low shear-wave velocity in the depth range 1–2 km. Two-dimensional inversion of more regional MT responses along a 200-km line passing through the Vulcan prospect suggest this vertical region of low resistivity links to the lower-crust with anomalous resistivity of < 60 Ω.m in a similar way as imaged beneath the Olympic Dam mine. It is suggested that this conductive region is associated with graphite precipitated from magmatically derived CO2-rich fluids cooling in a reducing environment.

Exploring the Limits of Fe-Rich Chemistries in Na-Based CaFe2O4-Type Postspinel Oxides.

Structural trends, physical properties, and electrochemical performances of the NaFexRu2-xO4 system have been investigated. Synthesis attempts using both conventional solid-state routes and high-pressure methods were explored for the compositional range 1.0 ≤ x ≤ 1.67. Based on Rietveld refinements against powder X-ray diffraction data, analyses of 57Fe Mössbauer spectroscopy data, and elemental analysis by electron microprobe, the existence of a confined compositional solid solution (1 ≤ x ≤ 1.3) adopting the CaFe2O4-type postspinel structure is demonstrated. This is contrasted with the NaFexTi2-xO4 system, for which no evidence of a solid solution is observed. However, for all explored synthetic routes of NaFexRu2-xO4 compositions, a trivalent iron oxidation state is maintained. Structural analysis and qualitative bond valence energy landscape models reveal that the progressive integration of iron into the postspinel framework results in narrowed sodium ion diffusion channels, restricting electrochemical deintercalation of sodium. Consequently, the CaFe2O4-type iron-rich compounds explored in this study demonstrate limited potential as positive electrode materials for sodium batteries. It is expected that this fundamental insight will help guide the exploration of alternative NaM2O4-based positive electrode materials with similar structure types.

Enhanced PMS activation and NSAID degradation selectivity by hydrophobic microenvironment regulation on Fe3+@Cu-MOF

In this study, the activation of peroxymonosulfate (PMS) and selective degradation of nonsteroidal anti-inflammatory drugs were investigated using hydrophobically modified Fe3+@Cu-MOF. The Fe3+@Cu-MOF-CTAB/PMS system demonstrated high-efficiency, achieving near-complete degradation of diclofenac within 120 min. The degradation rate constants for diclofenac, ibuprofen, and naproxen were 0.0048, 0.00103, and 0.00046 min−1, respectively, positively correlated with their hydrophobicity. Longer hydrophobic surfactant chains in Fe3+@Cu-MOFs lead to greater initial adsorption of diclofenac, enhancing degradation efficiency upon the introduction of PMS. The Fe3+@Cu-MOF-CTAB/PMS system removes over 80 % of diclofenac in various water matrices, showing optimal efficiency in acidic environments but reduced effectiveness with competing anions. Post-degradation changes in the oxidation states of copper and iron in the MOF structure indicated a synergistic redox mechanism essential for PMS activation. The hydroxylation and C-N bond cleavage in diclofenac were key degradation pathways. This study highlights the potential of hydrophobically modified Fe3+@Cu-MOFs in water treatment, providing insights into the interplay between material design, hydrophobic interactions, and catalytic performance.

Highly sensitive and selective chemiresistive temperature-dependent trace formalin sensor using hydrothermally grown hexagonal yttrium ferrite

Formalin (HCHO) is widely employed in industries such as furniture, food processing, textiles, construction, printing, and cleaning. The presence of formalin both in environment and adulterated food can give rise to significant health perils, involving damage to the eyes, kidneys, respiratory, and nervous system. This study demonstrates a trace formaldehyde sensor using hydrothermally prepared yttrium ferrite (YFeO3). The synthesized material was characterized using sophisticated tools. XRD analysis confirms the formation of hexagonal phase with crystallite size ∼30 nm. FESEM, TEM micrographs show agglomerated microstructure is formed. Bandgap energy and surface area have been estimated using UV–Vis, and BET surface area analysis which are ∼2 eV and 10.4 m2/gm respectively. XPS investigation corroborates the existence of bivalent oxidation states of iron as well as oxygen vacancies within the sample. The sensor delineates a remarkably strong p-type response (∼3.12 folds) to 1 ppm formalin with an exceptionally rapid response time of 3 s. Furthermore, it achieved a lower detection limit of 500 ppb, at the optimum temperature of 240 °C. The sensor also showed an admirable ability to respond selectively to formalin, even when subjected to a variety of interfering chemicals (such as acetylene, ammonia, NO2, toluene, etc.), maintaining sensitivity value almost unchanged for a continuous 100 days. The enhanced formalin sensing performance of the hexagonal YFeO3 (YFO) based sensor can be ascribed to a synergistic influence arising from several factors, encompassing augmented surface area, lower bandgap energy, the presence of bivalent oxidation states of iron and oxygen defects.

Probing the Oxidation State of Ocean Worlds with SUDA: Fe (ii) and Fe (iii) in Ice Grains

Characterizing the geochemistry of Europa and Enceladus is a key step for astrobiology investigations looking for evidence of life in their subsurface oceans. Transition metals with several oxidation states, such as iron, may be tracers of the oxidation state of icy ocean moon interiors. Their detection, as well as the characterization of their oxidation states, on the moons’ (plume) ice grains would bring valuable new information about the geochemistry of both the subsurface oceans and surface processes. Impact ionization mass spectrometers such as the SUDA instrument on board Europa Clipper can analyze ice grains ejected from icy moons’ surfaces and detect ocean-derived salts therein. Here we record mass spectra analogs for SUDA using the Laser Induced Liquid Beam Ion Desorption technique for Fe2+ and Fe3+ salts (both sulfates and chlorides). We show that impact ionization mass spectrometers have the capability to detect and differentiate ferrous (Fe2+) from ferric (Fe3+) ions in both cation and anion modes owing to their tendency to form distinct ionic complexes with characteristic spectral features. Peaks bearing Fe3+, such as [Fe3+ (OH)2]+ and [Fe3+ (OH) a Cl b ]−, are particularly important to discriminate between the two oxidation states of iron in the sample. The recorded analog spectra may allow the characterization of the oxidation state of the oceans of Europa and Enceladus with implications for hydrothermal processes and potential metabolic pathways for life forms in their subsurface oceans.

X‐Ray Fluorescence Determination of FeII/Fetotal Ratios in Sediments and Soils

The two most common oxidation states of iron can be determined by wavelength‐dispersive X‐ray fluorescence spectrometry relatively fast with an accuracy comparable to that of alternative methods. Main advantages for the analysis of sediments and soils are that organic matter does not interfere and solid samples can be analysed directly with minimal preparation effort. The limited availability of appropriate reference materials with certified data on their ferrous iron content turned out to be the major obstacle to implementing the method. For this reason and because no influence of the analysed geological materials on the intensity ratios of the closely adjacent Fe Kβ5 / Fe Kβ1,3 lines became evident, several rock types were selected in addition to sediments and soils to broaden and improve the calibration. Nevertheless, most reference data for calibration had to be determined by 57Fe Mössbauer spectroscopy. Plotting Fe Kβ5/Fe Kβ1,3 intensity ratios versus w FeO/w Fe2O3total ratios resulted in a correlation with R2 = 0.962 for the linear regression of all calibration data.

The relationship between iron redox states and H2O contents in back-arc basin basaltic glasses from the North Fiji Basin

Island-arc basalts (IAB) from convergent plate margins tend to have both higher iron oxidation states (higher Fe3+/Fe2+) and higher H2O contents than the mid-ocean ridge basalts (MORB) produced by seafloor spreading, which raises the question of whether these two characteristics are causally related. Back-arc basin basalts (BABB) may help with this question, in that they are products of seafloor spreading, like MORB, but sourced from supra-subduction mantle, like IAB. Here we examine the relationship between Fe3+/Fe2+ (determined by XANES spectroscopy) and H2O contents in BABB glasses from the North Fiji Basin (NFB). The glasses cover a range of compositions from 6.1 to 8.5 wt% MgO, and from 0.16 to 1.6 wt% H2O, and have also been analysed for trace elements and Sr-Nd-Pb-isotopes. Measured Fe3+/Fe2+ range from MORB-like to slightly higher values and are positively correlated with H2O and heavy-halogen contents (Cl, Br and I). The correlation is due to lower Fe2+ rather than higher Fe3+ compared to the MORB array. This suite of BABBs is not significantly enriched in trace elements other than H2O and the heavy halogens, with MORB-like Ba/Th and other incompatible-element ratios, suggesting that the H2O and halogens may have come from dehydration of subducted lithospheric serpentinites under subsolidus conditions. Na2O is unusually variable for a suite of samples from such a limited area, and is not correlated with H2O, precluding a relationship between H2O and degree of melting. The link between H2O and low Fe2+ may be explained by H2O-rich fluids entering the transcrustal magma plumbing system, where they increase the proportion of olivine and augite to plagioclase crystallizing during the crustal evolution of the magmas. In this situation, relatively small additions of H2O can have an enhanced effect on major-element chemistry if the crustal evolution proceeds by cycles of replenish-mix-tap-crystallize (RMTX) rather than by simple fractional crystallization without repeated replenishment and tapping. The absence of any increase in Fe3+ with H2O, together with the lack of any correlation between H2O and Fe3+/Fe2+ in MORB glasses generally, suggest that various mechanisms, including more extensive olivine fractionation, were responsible for elevating Fe3+/Fe2+ in H2O-rich basalts from convergent margin settings. Proxy methods based on concentrations of elements with redox-variable partition coefficients (V, Eu) are not sensitive enough to record the subtle variations in Fe3+/Fe2+ observable by XANES spectroscopy.

A redox switch allows binding of Fe(II) and Fe(III) ions in the cyanobacterial iron-binding protein FutA from Prochlorococcus

The marine cyanobacterium Prochlorococcus is a main contributor to global photosynthesis, whilst being limited by iron availability. Cyanobacterial genomes generally encode two different types of FutA iron-binding proteins: periplasmic FutA2 ABC transporter subunits bind Fe(III), while cytosolic FutA1 binds Fe(II). Owing to their small size and their economized genome Prochlorococcus ecotypes typically possess a single futA gene. How the encoded FutA protein might bind different Fe oxidation states was previously unknown. Here, we use structural biology techniques at room temperature to probe the dynamic behavior of FutA. Neutron diffraction confirmed four negatively charged tyrosinates, that together with a neutral water molecule coordinate iron in trigonal bipyramidal geometry. Positioning of the positively charged Arg103 side chain in the second coordination shell yields an overall charge-neutral Fe(III) binding state in structures determined by neutron diffraction and serial femtosecond crystallography. Conventional rotation X-ray crystallography using a home source revealed X-ray-induced photoreduction of the iron center with observation of the Fe(II) binding state; here, an additional positioning of the Arg203 side chain in the second coordination shell maintained an overall charge neutral Fe(II) binding site. Dose series using serial synchrotron crystallography and an XFEL X-ray pump-probe approach capture the transition between Fe(III) and Fe(II) states, revealing how Arg203 operates as a switch to accommodate the different iron oxidation states. This switching ability of the Prochlorococcus FutA protein may reflect ecological adaptation by genome streamlining and loss of specialized FutA proteins.

Photoinduced Cleavage of a Strained N-C Bond in an Iron Complex Supported by Super-Bulky Amidinate and Guanidinate Ligands.

The reaction of Fe2(mes)4 with the super-bulky amidines and guanidines HLAr*-R (LAr*-R = [(Ar*N)2C(R)]-, Ar* = 2,6-bis(diphenylmethyl)-4-tert-butylphenyl), R = Me (LAr*-Me), tBu (LAr*-tBu), Ph (LAr*-Ph), NiPr2 (LAr*-iPr2N), and Pip (LAr*-Pip)) gives access to the three-coordinate iron-mesityl complexes (LAr*-R)Fe(mes) only where LAr*-R = LAr*-Me, LAr*-Ph, or LAr*-Pip. Subsequent protonolysis with the N-atom transfer reagent Hdbabh (Hdbabh = 2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-diene) is limited in success, providing in one instance a few crystals of four-coordinate (LAr*-Me)Fe(dbabh)(Hdbabh), while three-coordinate (LAr*-Pip)Fe(dbabh) is synthesized reproducibly. Complexes (LAr*-Me)Fe(dbabh)(Hdbabh) and (LAr*-Pip)Fe(dbabh) are thermally insensitive in solution to temperatures of up to 100 °C. On the other hand, both (LAr*-Me)Fe(dbabh)(Hdbabh) and (LAr*-Pip)Fe(dbabh) show sensitivity to blue LED light (395 nm), undergoing photochemical transformations. For instance, the photolysis of (LAr*-Me)Fe(dbabh)(Hdbabh) leads to N-C bond scission and C-C bond coupling across the -dbabh moieties to give four-coordinate (LAr*-Me)Fe(N=dbabh-dbabhNH2). Photolyzing pyridine-d5 (py-d5) solutions of (LAr*-Pip)Fe(dbabh) at -5 °C produces a new paramagnetic photoproduct, [P]. Due to the thermal sensitivity of compound [P], it has eluded structural characterization; yet, Evans' method measurements suggest that the iron(II) oxidation state is maintained, thereby pointing to the -dbabh moiety as the locus of chemical change. In line with this assessment, addition of excess Me3SiCl to solutions of [P] produces the iron(II) complex (LAr*-Pip)FeCl(py-d5) as shown by 1H NMR spectroscopy. Gas chromatography/mass spectrometry analysis of the solutions of [P] shows a peak in the chromatogram with a molecular mass corresponding to a formulation of C14H11N that cannot be attributed to Hdbabh. This provides evidence for the photochemical-induced isomerization of the -dbabh ligand, revealing a heretofore unknown photochemical sensitivity of this N atom transfer reagent.

Waste-derived catalysts for tar cracking in hot syngas cleaning

Catalytic tar cracking is a promising technique for hot syngas cleaning unit in gasification plants because it can preserve tars chemical energy, so increasing the syngas heating value. The cost associated with catalyst preparation is a key issue, together with its deactivation induced by coke deposition. Iron is a cheap and frequently used catalyst, which can also be found in some industrial wastes. The study aims to assess the catalytic efficiency for tar cracking of two waste-derived materials (red mud and sewage sludge) having high content of iron. The catalysts were supported on spheres of γ-Al2O3, and their efficiency was compared to that of a pure iron catalyst. The role of support was investigated by testing pure red mud, with and without the support. A series of long-term tests using naphthalene as tar model compound were carried out under different values of process temperatures (750 °C-800 °C) and steam concentrations (0 %-7.5 %). The waste derived catalysts showed lower hydrogen yields compared to pure iron catalyst, due to their lower content of iron. On the other hand, the conversion efficiencies of all the tested catalysts resulted rather similar, since the Alkali and Alkaline-Earth Metallic species present on the surface of waste-derived catalyst help in preventing coke deposition. The iron oxidation state appears to play an important role, with reduced iron more active than its oxidised form in the tar cracking reactions. This indicates the importance of tuning steam concentration to keep constant the reduced state of iron while limiting coke deposition.

WD‐XRF technique for speciation of iron and quantification of its oxidation states in geological samples using L‐series of iron X‐ray spectrum

AbstractWavelength dispersive X‐ray fluorescence (WD‐XRF) spectrometry is a fast and widely used technique for elemental analysis of geological samples from Na to U. However, it has seldom been applied for quantitative determination of oxidation states of elements in complex matrices. In this study, we present a method to determine the oxidation states of iron in geological samples by WD‐XRF. We used the FeLα1,2 fluorescence line as a tool for iron speciation and Fe(II)/Fetotal ratio determination. We found that the normalized intensity (peak height) of FeLα1,2 fluorescence line was linearly correlated with the spin multiplicity (2S + 1) of ferrous and ferric content in the samples. To account for the matrix effects of chemical environment (matrix and chemical bonding) on FeLα1,2 fluorescence line, we introduced a chemical index factor (μ) that enabled accurate determination of Fe(II)/Fetotal ratio in different types of geological samples. The method was validated using international certified reference materials and their mixtures and obtained promising results, with only 6 out of 55 determinations showing relative error more than 5% of the certified values.

Unravelling the role of iron and manganese oxides in colouring Late Antique glass by micro-XANES and micro-XRF spectroscopies

This research aims to understand colouring technologies in 5th–7th centuries glass imported to Atlantic Britain by correlating the iron (Fe) and manganese (Mn) ratios and oxidation states with colour. Despite having a similar matrix chemical composition and concentrations of Fe and Mn oxides, these vessels display different colours (from green to yellow/amber, sometimes with purple streaks). Colour changes can be induced by controlling the reduction-oxidation reactions that occur during glass production, which are influenced by the raw materials, furnace and melt atmosphere, and recycling. To evaluate these parameters, reference glasses were prepared, following the composition of Late Antique archaeological glass recovered from Tintagel (UK) and Whithorn (UK). A corpus of archaeological and experimental glass samples was analysed using bulk Fe and Mn K-edge x-ray absorption near edge structure (XANES) spectroscopy, micro-XANES and micro x-ray fluorescence (μ-XRF) at beamline ID21, at the European Synchrotron Radiation Facility. Fe and Mn XANES spectra of the archaeological glass indicate that Fe and Mn are in a similar oxidation state in all the yellow samples, predominantly Fe3+ and Mn2+. No detectable difference in Mn and Fe oxidation state occurs in the purple streaks compared to the yellow glass bulk but μ-XRF maps of the distribution of Fe and Mn show that Mn is more concentrated in the purple streaks. This indicates that the purple colour of the streaks is mainly due to a higher Mn/Fe ratio and persistence of more oxidised manganese in the purple areas, even though it is difficult to detect. Many archaeological fragments appear pale green in transmitted light but amber in reflected light. XANES studies detected the presence of surface layers where manganese is more oxidised. This layer is believed to scatter transmitted and reflected light differently and might be responsible for the optical features of the archaeological glass.

Modulating positive charge sites generations and iron oxidation state transitions in FeP4/CoP/C p-n heterojunction toward efficient oxygen evolution

Promoting the formation of positive charge active sites and high oxidation state FeOOH in the heterojunction electrocatalyst can enhance its intrinsic activity for oxygen evolution reaction (OER). However, the current synthesis methods that can simultaneously achieve both properties remain a great challenge. In this work, a feasible strategy for concurrently promoting the generation of positive charge active sites and high oxidation state metal species by constructing a heterojunction between FeP4 and CoP is proposed. Specifically, the p-n heterojunction between FeP4 and CoP is constructed by pyrolysis of MIL88A@FeCoLDH prepared by introducing Co through cation exchange using MIL88A as a template. The experimental and density functional theory calculation analyses suggest the construction of p-n heterojunction can effectively modulate the electron structure, optimize the d-band center, induce the generation of strong space charge region, and shorten the bond length of Fe-O, thus promoting the formation of positive charge active sites and high active species FeOOH and the adsorption ability of oxygen-containing intermediates for enhancing the OER performance. Benefiting from the synergistic effect between positive charge active sites and FeOOH, the obtained FeP4/CoP/C electrocatalyst exhibits a low overpotential of 258 mV for the OER at a current density of 10 mA cm−2 and superior stability at 20 mA cm−2 for 52 h. This work gives insights into the charge regulation effect in the heterojunction for enhancing the OER catalytic activity and provides a general strategy for designing more efficient oxygen evolution electrocatalysts.