Differences In Oxidation State Research Articles

Strong Catalyst-Support Interaction in WOx Nanowires Supported Iridium Nanocatalysts: A Pathway to Efficient Water Electrolysis

This paper investigates the use of sub-stoichiometric tungsten oxide nanowires (WOxNW) as a support material for Ir nanocatalysts in the oxygen evolution reaction (OER) for proton exchange membrane water electrolysis (PEMWE). The results demonstrate that Ir@WOxNW has exceptional activity and durability, which paves the way for large-scale PEMWE deployment. The catalyst-support interaction plays a crucial role in explaining this performance boost.The preparation and characterization of Ir@WOxNW involved loading ultra-fine Ir nanoparticles onto WOxNW through hydrothermal treatment. High-resolution transmission electron microscopy (HR-TEM) and energy-dispersive X-ray spectroscopy (EDS) mapping analysis revealed that the iridium nanoparticles were uniformly loaded on the WOxNW support material, indicating efficient loading and dispersion. X-ray photoelectron spectroscopy (XPS) analysis showed that the supported Ir catalysts had a mixed valence state of Ir0 and Ir4+. Ir@WOxNW was compared with three other Ir-based OER catalysts, outperforming them in terms of activity and durability.The Ir@WOxNW catalyst demonstrated superior OER activity compared to the other three catalysts, with a mass activity of 812 A/gIr at 1.55 V vs reversible hydrogen electrode (RHE). The Tafel slopes of the OER catalysts were grouped into two categories: Ir Black and Ir@WOxNW showed smaller values (about 40 mV/dec), and larger values for Ir@ATO and Ir Oxide (about 120 mV/dec), respectively. Electrochemical impedance spectroscopy (EIS) measurements indicated that the high mass activity of Ir@WOxNW was due to a high population of catalytic sites with fast intrinsic kinetics from the dispersed ultra-fine Ir catalyst on WOxNW. The durability of all catalysts was investigated using an accelerated durability test (ADT), and the Ir@WOxNW catalyst demonstrated unexpectedly high durability compared to the other catalysts.The postmortem XPS analysis showed that the Ir@WOxNW catalyst exhibited a subtle change in Ir0/Ir4+ ratio after the ADT, indicating suppressed Ir oxidation and greater stability compared to the other catalysts. Additionally, non-destructive depth profile analysis by synchrotron based XPS was conducted on the supported ultrafine Ir catalysts before and after the ADT test. The difference in oxidation state increased as the supported Ir catalysts were probed deeper into the core. The results showed that after oxidation potential cycles ADT, the WOxNW-supported Iridium exhibited strong resistance to oxidation. The core location remained a high percentage of metal peak, in contrast to the other three control catalysts.Density functional theory calculations suggested that the oxygen-deficient WOxNW support helps to maintain the OER-active metal@metal oxide core@shell-like form of the Ir catalyst particles by enhancing electron transfer from the WOxNW to the Ir surface, thereby weakening the binding of oxygen to the Ir surface and enhancing the oxidation resistance of the Ir metal to oxides.In conclusion, ultrafine Ir nanoparticles supported on WOxNW have significant potential for practical applications in electrochemical water splitting. The high activity and durability of Ir@WOxNW make it a promising candidate for large-scale PEMWE deployment.

Long-range A-site cation disorder in NaA(MO4)2 (M = Mo, W) double scheelite oxides

Synchrotron X-ray and neutron powder diffraction methods have been used to obtain accurate long-range average structures of some double scheelite compounds of the type NaA(BO4)2 (A ​= ​La, Pr, Nd, Sm, Lu, and Bi; B = Mo, W) at room temperature. Phase pure samples were synthesized using standard solid-state methods. Rietveld refinements using combined synchrotron X-ray diffraction (SXRD) and neutron diffraction (NPD) revealed a random distribution of the Na and A-type cations regardless of the presence of 6s2 lone pairs (such as Bi3+) and the difference in oxidation states and ionic radii between the cations. The NaA(BO4)2 (A ​= ​La, Pr, Nd, Sm, Lu, and Bi) series displayed linear trends in lattice parameters and AO8 polyhedra volume with the ionic radius of the A-type cation for the lanthanoids, but a deviation from the trend was observed for A ​= ​Bi3+. The NaBi(BO4)2 structure has a smaller than expected unit cell volume than based on extrapolation from the corresponding NaLn(BO4)2 series, possibly due to short-range ordering of the 6s2 lone pair electrons.

Investigation on the predictive power of tolerance factor τ for A-site double perovskite oxides.

We have used a recently introduced new tolerance factor τ to create a stability map of all possible A-site double perovskite titanates AA'Ti2O6 and niobates AA'Nb2O6. The predictive power of τ is relatively good based on comparisons with available experimental data for A-site double perovskites. We carried out quantum chemical calculations on two hypothetical double perovskite compositions CsScTi2O6 and YRbTi2O6, where τ predicts high probability for their existence. In both cases, we found limits in the predictive power of the new tolerance factor for ion combinations on the A and A' site which are very different in size. A difference in oxidation state may decrease the accuracy, as well. Overall, the A-site double perovskite stability mapping provides a starting point for the discovery of novel A-site double perovskites.

Effect of a Plateau Environment on the Oxidation State of the Heart and Liver through AMPK/p38 MAPK/Nrf2-ARE Signaling Pathways in Tibetan and DLY Pigs.

Simple SummaryPlateau stress is a main factor limiting pig production. There are great differences in oxidation state and antioxidant defense between Tibetan pigs (TPs) and DLY pigs exposed to a plateau environment. However, there are limited reports on the mechanism of adaptation of TPs and DLY pigs to the plateau environment involving a signal pathway related to oxidation state. In the present study, we found that TPs exhibit a stronger heart and liver antioxidant stress capacity than DLY pigs through AMPK/p38 MAPK/Nrf2-ARE signaling pathways under a plateau hypoxic environment.This study evaluated the effect of a plateau environment on the heart and liver oxidation state of Tibetan pigs (TPs) and DLY pigs through analyzing AMPK, p38 MAPK, and Nrf2 signaling pathways. Twelve 120-day-old TPs and twelve 120-day-old DLY pigs were randomly divided into two groups in a plateau environment for three weeks. Exposed to a plateau environment, TPs exhibited a lower (p < 0.05) malondialdehyde level but higher (p < 0.05) glutathione, superoxide dismutase (SOD), glutathione peroxidase (GSH-Px), and total antioxidant capacity (T-AOC) activities in the liver and heart than those observed in DLY pigs. TPs also showed higher (p < 0.05) mRNA levels of SOD and GSH-Px in the liver and heart compared with those of DLY pigs. The TPs showed higher (p < 0.05) mRNA and protein levels of AMPK and Nrf2 in the liver and heart compared with those of DLY pigs. Furthermore, TPs showed higher (p < 0.05) mRNA and protein levels of p38 MAPK in the heart and higher mRNA levels of p38 MAPK in the liver compared with those of DLY pigs under a plateau environment. In summary, TPs possess a stronger antioxidant capacity in the heart and liver than that of DLY pigs in a plateau environment through AMPK/p38 MAPK/Nrf2-ARE signaling pathways.

Electrochemical Oxidation and Speciation of Lanthanides in Potassium Carbonate Solution

Increasing lanthanide demand to support clean energy goals drives the need to develop more efficient approaches to separate adjacent lanthanides. Most approaches for lanthanide separations are not very selective and are based on small differences in lanthanide ionic radii. Concentrated potassium carbonate media has shown some potential to enable oxidation of praseodymium (Pr) and terbium (Tb) to their tetravalent states, which could ultimately enable a separation based on differences in oxidation states, but very little is known regarding the system’s chemistry. This work completes a detailed examination of cerium (Ce) redox chemistry in concentrated carbonate media to support the development of Pr and Tb oxidation studies. The half-wave potential (E1/2) of the Ce(III)/(IV) redox couple is evaluated under various solution conditions and computational modeling of carbonate coordination environments is discussed. Cyclic voltammetry shows higher carbonate concentrations and temperatures can lower the potential required to oxidize Ce(III) by 54 mV (3.5 to 5.5 M) and 39 mV (from 10 °C to 70 °C). Chronoabsorptometry shows Ce(III) and Ce(IV) carbonate complexes are chemically stable and reversible. Computational modelling suggests the most likely coordination environment for the Ce(IV) complex is Ce(CO3)4(OH)5− which is less entropically favorable than the lowest energy Ce(III) complex, Ce(CO3)4 5−.

Determining the oxidation state of elements by X-ray crystallography.

Protein-mediated redox reactions play a critical role in many biological processes and often occur at centres that contain metal ions as cofactors. In order to understand the exact mechanisms behind these reactions it is important to not only characterize the three-dimensional structures of these proteins and their cofactors, but also to identify the oxidation states of the cofactors involved and to correlate this knowledge with structural information. The only suitable approach for this based on crystallographic measurements is spatially resolved anomalous dispersion (SpReAD) refinement, a method that has been used previously to determine the redox states of metals in iron-sulfur cluster-containing proteins. In this article, the feasibility of this approach for small, non-iron-sulfur redox centres is demonstrated by employing SpReAD analysis to characterize Sulfolobus tokodaii sulerythrin, a ruberythrin-like protein that contains a binuclear metal centre. Differences in oxidation states between the individual iron ions of the binuclear metal centre are revealed in sulerythrin crystals treated with H2O2. Furthermore, data collection at high X-ray doses leads to photoreduction of this metal centre, showing that careful control of the total absorbed dose is a prerequisite for successfully determining the oxidation state through SpReAD analysis.

DFT study of electronic properties of N-doped ZnO and ZnO/Cu(111) bilayer films

The electronic properties of N-doped ZnO/Cu(111) bilayer films have been studied by using the DFT+U method including dispersion contributions and compared to that of free-standing ZnO bilayer films. The substitution of a lattice O ion in free-standing ZnO bilayer by a N atom results in oxidation state of N of -2, while the oxidation state of N becomes -3 when it replaces a lattice O in a ZnO/Cu(111) bilayer film. The extra negative charge of N in N:ZnO/Cu(111) compared to freestanding N:ZnO is due to an electron transfer from the Cu support. The difference in oxidation state of the N dopant is demonstrated by the analysis of the Bader charge, of the magnetization, and of the density of states. The changes in electronic properties of the doped ZnO films were evaluated by adsorbing CO and H2 molecules. The results show that the adsorption energies are significantly enhanced in N-doped ZnO/Cu(111) compared to the unsupported N:ZnO bilayer counterpart. This reflects the effect of the ZnO/Cu(111) interface in improving adsorption and possibly catalytic properties and the role of the N-dopant in activating the oxide film.

Effect of nonequivalent substitution of Pr3+/4+ with Ca2+ in PrBaCoFeO5+δ as cathodes for IT-SOFC

We used a Ca doping strategy with PrBaCoFeO5+δ (PBCF) to prepare a novel double-perovskite Pr1–xCaxBaCoFeO5+δ (PCBCF). x = 0.05 and x = 0.1 samples exhibited a single phase with layered double-perovskite structure, combined with good chemical compatibility with common electrolyte materials. X-ray photoelectron spectroscopy profiles of PCBCF were compared to that of PBCF to detect differences in oxidation states. The substitution of Ca2+ for Pr ions in PCBCF effectively reduces the thermal expansion coefficient and material costs. Though the introduction of Ca2+ reduced the electrical conductivity, it improved the oxygen catalytic activity. The improved electrochemical performance was attributed to the increased oxygen vacancy concentration in the lattice. The optimal composition x = 0.1 cathode exhibited the best catalytic activity and durability. The polarization impedance and maximum power density of the 0.1 cathode were 0.027 Ω cm2 and 728 mW cm−2 at 800 °C, respectively. Distribution of relaxation time analysis demonstrated that the 0.1 cathode electrochemical reactions under oxygen partial pressures involved at least three processes and confirmed that the transfer process of oxide ions and charge transfer process are the major rate-determining steps of the oxygen reduction reaction. The combination of experimental and analysis results indicated that the 0.1 sample has considerable potential as part of a cathode for application in intermediate-temperature solid oxide fuel cells.

Nanotoxicity of different sizes of graphene (G) and graphene oxide (GO) in vitro and in vivo

Graphene family nanomaterials (GFNs) have attracted significant attention due to their unique characteristics and applications in the fields of biomedicine and nanotechnology. However, previous studies highlighted the in vitro and in vivo toxicity of GFNs with size and oxidation state differences are still elusive. Therefore, we prepared graphene (G) and graphene oxide (GO) of three different sizes (S-small, M-medium, and L-large), and characterized them using multiple surface-sensitive analytical techniques. In vitro assays using HEK 293T cells revealed that the small and large sizes of G and GO significantly reduced the cell viability and increased DNA damage, accompanying with activated reactive oxygen species (ROS) generation and induced various expressions of associated critical genetic markers. Moreover, the bacterial assays highlighted that G and GO caused strong acute toxicity on Tox2 bacteria. Effects of G were higher than GO and showed size dependent effect: L > M > S, while the medium size of GO induced mild genetic toxicity on RecA bacteria. In vivo assays revealed that exposure to G and GO caused the developmental toxicity, induced ROS generation, and activated related pathways (specifically GO) in zebrafish. Taken together, G showed stronger ability to decrease the survival rate and induce the acute toxicity, while GO showed obvious toxicity in terms of DNA damages, ROS generation, and abnormal gene expressions. Our findings highlighted that G and GO differentially induced toxicity based on their varying physical characteristics, especially sizes and oxidation state, and exposure concentrations and sensitivity of the employed in vitro and in vivo models. In short, this study provided deep insights on the negative effects of GFNs exposure.

Geochemical behaviour of rare earth elements (REE) along a river reach receiving inputs of acid mine drainage

Total and dissolved rare earth elements (REE) were studied in a river reach affected by several inputs of acid mine drainage. The first four acidic discharges were of lesser importance compared to the last (Agrio River, coming from the Río Tinto mines), which transported high loads of Fe and Al (2.1 and 4.2 ton/day, respectively) together with REE (16.4 kg/day) and other trace elements. In the acid mine drainage (AMD) sources, practically all the REE were dissolved and the North American Shale Composite (NASC)-normalized patterns showed an enrichment in medium REE, although some differences exist between the patterns of each source. The pH values in the river reach upstream of the confluence with the Agrio River ranged between 8.01 and 7.03, and most of the Fe and Al from the AMD sources precipitated. Downstream of this acidic discharge, the pH decreased to 2.98. Upstream of the first AMD input, the dissolved and total concentrations of ΣREE were very low (<0.6 μg/L). In the river reach affected by AMD that maintains pH values >7, concentrations of ΣREE increased (up to 25 μg/L), mainly transported by the particulate phase. In the reach downstream of the Agrio River with acidic conditions, REE behaved conservatively. The REE NASC-normalized patterns of the river samples resemble that of the AMD sources, although an enrichment of heavy REE in the dissolved phase is observed linked to complexation by carbonates. Cerium and particularly La also show higher dissolved percentages, similar to HREE, which must be due to the lower affinity of these elements to be sorbed onto Fe oxyhydroxides. Variations in Ce and Eu anomalies are observed along the river reach as a consequence of the different AMD inputs. However, the values of the Ce anomaly are higher in total samples than in dissolved samples. Speciation results indicate that these differences are not caused by differences in oxidation states but by slight differences in the hydrogeochemical behaviour of Ce with respect to La and Nd.

Redox dependent behaviour of molybdenum during magmatic processes in the terrestrial and lunar mantle: Implications for the Mo/W of the bulk silicate Moon

We present results of high-temperature olivine-melt, pyroxene-melt and plagioclase-melt partitioning experiments aimed at investigating the redox transition of Mo in silicate systems. Data for a series of other minor and trace elements (Sc, Ba, Sr, Cr, REE, Y, HFSE, U, Th and W) were also acquired to constrain the incorporation of Mo in silicate minerals. All experiments were carried out in vertical tube furnaces at 1 bar and temperatures ranging from ca. 1220 to 1300 °C. Oxygen fugacity was controlled via CO–CO2 gas mixtures and varied systematically from 5.5 log units below to 1.9 log units above the fayalite–magnetite–quartz (FMQ) redox buffer thereby covering the range in oxygen fugacities of terrestrial and lunar basalt genesis. Molybdenum is shown to be volatile at oxygen fugacities above FMQ and that its compatibility in pyroxene and olivine increases three orders of magnitude towards the more reducing conditions covered in this study. The partitioning results show that Mo is dominantly tetravalent at redox conditions below FMQ-4 and dominantly hexavalent at redox conditions above FMQ. Given the differences in oxidation states of the terrestrial (oxidized) and lunar (reduced) mantles, molybdenum will behave significantly differently during basalt genesis in the Earth (i.e. highly incompatible; average DMoperidotite/melt∼0.008) and Moon (i.e. moderately incompatible/compatible; average DMoperidotite/melt∼0.6). Thus, it is expected that Mo will strongly fractionate from W during partial melting in the lunar mantle, given that W is broadly incompatible at FMQ-5. Moreover, the depletion of Mo and the Mo/W range in lunar samples can be reproduced by simply assuming a primitive Earth-like Mo/W for the bulk silicate Moon. Such a lunar composition is in striking agreement with the Moon being derived from the primitive terrestrial mantle after core formation on Earth.

Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane

Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn3O4, Mn2O3, and MnO2), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explain and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides.

The importance of iron speciation (Fe+2/Fe+3) in determining mineral assemblages: an example from the high‐grade aluminous metapelites of southeastern Madagascar

AbstractMetapelitic granulites from the Anosyen domain of southeastern Madagascar are exposed in three intercalated formations: the Amparihy, Bakika and Ihosy formations. Although mineralogically distinct from each other, the rocks from these formations show very similar bulk‐rock compositions when measured on a FeT basis. The preserved mineral assemblages thus do not reflect differences in the ratios of the main rock‐forming oxides (i.e. Al2O3:FeT:MgO), but instead reflect variations in the pre‐metamorphic oxidation state of the protolith rocks. These differences in oxidation state are manifested via differences in iron speciation – either Fe+2 or Fe+3. The relatively reduced rocks of the Amparihy Formation preserve the assemblage bi–sp–sill–g–cd, which contrasts markedly with the mostly garnet and spinel‐absent bi–cd–sill–mt assemblages preserved in the strongly oxidized rocks of the Ihosy Formation. Compositionally intermediate rocks of the Bakika Formation are garnet bearing, but sillimanite‐absent, and contain the assemblage sp–g–cd–mag. Modelling of these rocks in the Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O system suggests that they evolved along a heating and cooling P–T path with only limited decompression accompanying cooling on the retrograde path. Peak temperatures and pressures of ∼880–920 °C and 6–6.5 kbar are inferred for the majority of the Anosyen domain, with slightly lower peak temperatures (∼840 °C) estimated in the extreme northwest of the area. The high‐temperature and relatively low‐pressure nature of metamorphism suggests high geothermal gradients existed during orogenesis, which in southern Madagascar is related to the amalgamation of Gondwana (580–520 Ma). Although metamorphic temperatures may have been augmented via thermal advection from the emplacement of the syn‐ to post‐tectonic Ambalavao suite, the high geothermal gradients nevertheless suggest thin and consequently hot lithosphere existed prior to orogenesis.

ChemInform Abstract: Extreme Differences in Oxidation States: Synthesis and Structural Analysis of the Germanide Oxometallates A10[Ge9]2[WO4] as well as A10+x[Ge9]2 [W1‐xNbxO4] with A = K and Rb Containing [Ge9]4‐ Polyanions.

AbstractSemitransparent dark‐red or ruby‐red single crystals of K10.35Ge18W0.65Nb0.35 O4, Rb10.35Ge18W0.65Nb0.35 O4, K10Ge18WO4, and Rb10Ge18WO4 are synthesized by solid state reactions using K, Rb, Ge, W, WO3, K2WO4, Rb2WO4, GeO2 and HgO as starting materials (Nb crucible, 800 °C, 120 h).

Use of X-ray Absorption Spectroscopy To Speciate Manganese in Airborne Particulate Matter from Five Counties Across the United States

The purpose of this study is to characterize manganese oxidation states and speciation in airborne particulate matter (PM) and describe how these potentially important determinants of PM toxicity vary by location. Ambient PM samples were collected from five counties across the US using a high volume sequential cyclone system that collects PM in dry bulk form segregated into "coarse" and "fine" size fractions. The fine fraction was analyzed for this study. Analyses included total Mn using ICP-MS and characterization of oxidation states and speciation using X-ray absorption spectroscopy (XAS). XAS spectra of all samples and ten standard compounds of Mn were obtained at the National Synchrotron Light Source. XAS data was analyzed using Linear Combination Fitting (LCF). Results of the LCF analysis describe differences in composition between samples. Mn(II) acetate and Mn(II) oxide are present in all samples, while Mn(II) carbonate and Mn(IV) oxide are absent. To the best of our knowledge, this is the first paper to characterize Mn composition of ambient PM and examine differences between urban sites in the US. Differences in oxidation state and composition indicate regional variations in sources and atmospheric chemistry that may help explain differences in health effects identified in epidemiological studies.

Investigation of Surface Oxidation Processes on Manganese Oxide Electrocatalysts Using Electrochemical Methods and Ex Situ X-ray Photoelectron Spectroscopy

Recently, we developed a promising non-precious metal catalyst with bifunctional activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), two important energy conversion reactions with relevance to fuel cells and water-splitting. Having previously identified the catalyst as a manganese (III) oxide with alpha-Mn2O3 crystallinity, in this study we further characterize the catalyst surface to understand changes in the surface chemistry under different reaction conditions. We identify key electrochemical features of the catalyst using cyclic voltammetry and then probe the changes in the surface oxidation state of manganese in the potential region between the ORR and the OER using ex-situ X-ray photoelectron spectroscopy (XPS). Despite the surface sensitivity of XPS, these measurements do not reveal any differences in surface oxidation state between samples tested at ORR potentials and those examined at potentials relevant to the OER. We show, however, that electrochemical methods can discern a difference in oxidation states of the two samples upon re-insertion of the samples into an electrochemical cell after the completion of ex-situ XPS measurements. These results suggest that oxidative processes on the catalyst surface are extremely shallow, which we quantify based on the experimental results and theoretical modeling of the XPS spectra.

Characterization and Functional Modification of StaC and RebC, Which Are Involved in the Pyrrole Oxidation of Indolocarbazole Biosynthesis

The diversity of indolocarbazole natural products results from the differences in oxidation states of the pyrroline ring moiety. In the biosynthetic pathways for staurosporine and rebeccamycin, two homologous enzymes having 64% identity, StaC and RebC, are responsible for the selective production of K252c, which has one oxo group at the pyrroline ring, and arcyriaflavin A, which has two. Although StaC has a FAD-binding motif, most StaC molecules do not contain FAD, and the protein cannot be reconstituted with FAD in vitro. In this study, we mutated Ala-118 in StaC by replacing a glutamine that is conserved in FAD monooxygenases, resulting in increased FAD content as well as catalytic activity. In addition, mutations around the substrate-binding sites of StaC and RebC can change the product selectivity. Specifically, StaC-N244R-V246T and RebC-F216V-R239N mutants produced substantial amounts of arcyriaflavin A and K252c, respectively.

Effects of changing solution chemistry on Fe 3+/Fe 2+ isotope fractionation in aqueous Fe–Cl solutions

The range in 56Fe/ 54Fe isotopic compositions measured in naturally occurring iron-bearing species is greater than 5‰. Both theoretical modeling and experimental studies of equilibrium isotopic fractionation among iron-bearing species have shown that significant fractionations can be caused by differences in oxidation state (i.e., redox effects in the environment) as well as by bond partner and coordination number (i.e., nonredox effects due to speciation). To test the relative effects of redox vs. nonredox attributes on total Fe equilibrium isotopic fractionation, we measured changes, both experimentally and theoretically, in the isotopic composition of an Fe 2+–Fe 3+–Cl–H 2O solution as the chlorinity was varied. We made use of the unique solubility of FeCl 4 − in immiscible diethyl ether to create a separate spectator phase against which changes in the aqueous phase could be quantified. Our experiments showed a reduction in the redox isotopic fractionation between Fe 2+- and Fe 3+-bearing species from 3.4‰ at [Cl −] = 1.5 M to 2.4‰ at [Cl −] = 5.0 M, due to changes in speciation in the Fe–Cl solution. This experimental design was also used to demonstrate the attainment of isotopic equilibrium between the two phases, using a 54Fe spike. To better understand speciation effects on redox fractionation, we created four new sets of ab initio models of the ferrous chloride complexes used in the experiments. These were combined with corresponding ab initio models for the ferric chloride complexes from previous work. At 20 °C, 1000 ln β ( β = 56Fe/ 54Fe reduced partition function ratio relative to a dissociated Fe atom) values range from 6.39‰ to 5.42‰ for Fe(H 2O) 6 2+, 5.98‰ to 5.34‰ for FeCl(H 2O) 5 +, and 5.91‰ to 4.86‰ for FeCl 2(H 2O) 4, depending on the model. The theoretical models predict ferric–ferrous fractionation about half as large (depending on model) as the experimental results. Our results show (1) oxidation state is likely to be the dominant factor controlling equilibrium Fe isotope fractionation in solution and (2) nonredox attributes (such as ligands present in the aqueous solution, speciation and relative abundances, and ionic strength of the solution) can also have significant effects. Changes in the isotopic composition of an Fe-bearing solution will influence the resultant Fe isotopic signature of any precipitates.

Low temperature water–gas shift: Differences in oxidation states observed with partially reduced Pt/MnOX and Pt/CeOX catalysts yield differences in OH group reactivity

The Pt–ceria synergy may be described as the dehydrogenation of formate formed on the surface of the partially reducible oxide (PRO), ceria, by Pt across the interface, with H2O participating in the transition state. However, due to the rising costs of rare earth oxides like ceria, replacement by a less expensive partially reducible oxide, like manganese oxide, is desirable. In this contribution, a comparison between Pt/ceria and Pt/manganese oxide catalysts possessing comparable Pt dispersions reveals that there are significant differences and certain similarities in the nature of the two Pt/PRO catalysts. With ceria, partial reduction involves reduction of the oxide surface shell, with Ce3+ at the surface and Ce4+ in the bulk. In the case of manganese oxide, partial reduction results in a mixture of Mn3+ and Mn2+, with Mn2+ located at the surface. With Pt/CeOX, a high density of defect-associated bridging OH groups react with CO to yield a high density of the formate intermediate. With Pt/MnOX, the fraction of reactive OH groups is low and much lower formate band intensities result upon CO adsorption; moreover, there is a greater fraction of OH groups that are essentially unreactive. Thus, much lower CO conversion rates are observed with Pt/MnOX during low temperature water–gas shift. As with ceria, increasing the Pt loading facilitates partial reduction of MnOX to lower temperature, indicating metal–oxide interactions should be taken into account.

AuI: an alternative and potentially better precursor than AuIII for the synthesis of Au nanostructures

This article provides an overview of current developments with regard to the use of AuI compounds as precursors in the synthesis of Au nanostructures with controlled shapes or morphologies. We begin with a brief description of the difference between AuI and AuIII compounds, followed by a discussion on how the solubility and stability of a AuI compound can be improved by forming a coordination complex with a ligand (X). We then focus on a range of recent studies that have been directed towards the use of AuI-X complexes as precursors to elemental Au, in an effort to produce Au nanostructures with a variety of shapes, including icosahedral nanoparticles, truncated decahedrons, nanowires or nanorods, branched nanostructures, hybrid nanostructures, nanoboxes, nanocages, and nanoframes. In these syntheses, the AuI-X complexes offer a number of attractive features for generating Au nanostructures as compared to the conventional AuIII compounds, mostly due to their differences in oxidation state and aurophilic effect. The ability to control AuI chemistry therefore provides a great opportunity to systematically investigate the syntheses, physical properties, and applications of Au nanostructures.