Reaction Of Iron Research Articles

A density functional theory analysis of the C-H activation reactivity of iron(IV)-oxo complexes with an 'O' substituted tetramethylcyclam macrocycle.

In this article, we present a meticulous computational study to foresee the effect of an oxygen-rich macrocycle on the reactivity for C-H activation. For this study, a widely studied nonheme Fe(IV)O molecule with a TMC (1,4,8,11-tetramethyl 1,4,8,11-tetraazacyclotetradecane) macrocycle that is equatorially attached to four nitrogen atoms (designated as N4) and acetonitrile as an axial ligand has been taken into account. For the goal of hetero-substitution, step-by-step replacement of the N4 framework with O atoms, i.e., N4, N3O1, N2O2, N1O3, and O4 systems, has been considered, and dihydroanthracene (DHA) has been used as the substrate. In order to neutralise the system and prevent the self-interaction error in DFT, triflate counterions have also been included in the calculations. The study of the energetics of these C-H bond activation reactions and the potential energy surfaces mapped therefore reveal that the initial hydrogen abstraction, which is the rate-determining step, follows the two-state reactivity (TSR) pattern, which means that the originally excited quintet state falls lower in the transition state and the product. The reaction follows the hydrogen atom transfer (HAT) mechanism, as indicated by the spin density studies. The results revealed a fascinating reactivity order, in which the reactivity increases with the enrichment of the oxygen atom in the equatorial position, namely the order follows N4 < N3O1 < N2O2 < N1O3 < O4. The impacts of oxygen substitution on quantum mechanical tunneling and the H/D kinetic isotope effect have also been investigated. When analysing the causes of this reactivity pattern, a number of variables have been identified, including the reactant-like transition structure, spin density distribution, distortion energy, and energies of the electron acceptor orbital, i.e., the energy of the LUMO (σ*z2), which validate the obtained outcome. Our results also show very good agreement with earlier combined experimental and theoretical studies considering TMC and TMCO-type complexes. The DFT predictions reported here will undoubtedly encourage experimental research in this biomimetic field, as they provide an alternative with higher reactivity in which heteroatoms can be substituted for the traditional nitrogen atom.

Influence of Equatorial Co-Ligands on the Reactivity of LFeIIIOIPh.

Previous biomimetic studies clearly proved that equatorial ligands significantly influence the redox potential and thus the stability/reactivity of biologically important oxoiron intermediates; however, no such studies were performed on FeIIIOIPh species. In this study, the influence of substituted pyridine co-ligands on the reactivity of iron(III)-iodosylbenzene adduct has been investigated in sulfoxidation and epoxidation reactions. Selective oxidation of thioanisole, cis-cyclooctene, and cis- and trans-stilbene in the presence of a catalytic amount of [FeII(PBI)3](OTf)2 with PhI(OAc)2 provide products in good to excellent yields through an FeIIIOIPh intermediate depending on the co-ligand (4R-Py) used. Several mechanistic studies were performed to gain more insight into the mechanism of oxygen atom transfer (OAT) reactions to support the reactive intermediate and investigate the effect of the equatorial co-ligands. Based on competitive experiments, including a linear free-energy relationship between the relative reaction rates (logkrel) and the σp (4R-Py) parameters, strong evidence has been observed for the electrophilic character of the reactive species. The presence of the [(PBI)2(4R-Py)FeIIIOIPh]3+ intermediates and the effect of the co-ligands was also supported by UV-visible measurements, including the color change from red to green and the hypsochromic shifts in the presence of co-ligands. This is another indication that the title iron(III)-iodosylbenzene adduct is able to oxygenate sulfides and alkenes before it is transformed into the oxoiron form by cleavage of the O-I bond.

Aerobic iron-oxidizing bacteria secrete metabolites that markedly impede abiotic iron oxidation.

Iron is one of the Earth's most abundant elements and is required for essentially all forms of life. Yet, iron's reactivity with oxygen and poor solubility in its oxidized form (Fe3+) mean that it is often a limiting nutrient in oxic, near-neutral pH environments like Earth's ocean. In addition to being a vital nutrient, there is a diversity of aerobic organisms that oxidize ferrous iron (Fe2+) to harness energy for growth and biosynthesis. Accordingly, these organisms rely on access to co-existing Fe2+ and O2 to survive. It is generally presumed that such aerobic iron-oxidizing bacteria (FeOB) are relegated to low-oxygen regimes where abiotic iron oxidation rates are slower, yet some FeOB live in higher oxygen environments where they cannot rely on lower oxygen concentrations to overcome abiotic competition. We hypothesized that FeOB chemically alter their environment to limit abiotic interactions between Fe2+ and O2. To test this, we incubated the secreted metabolites (collectively known as the exometabolome) of the deep-sea iron- and hydrogen-oxidizing bacterium Ghiorsea bivora TAG-1 with ferrous iron and oxygen. We found that this FeOB's iron-oxidizing exometabolome markedly impedes the abiotic oxidation of ferrous iron, increasing the half-life of Fe2+ 100-fold from ∼3 to ∼335 days in the presence of O2, while the exometabolome of TAG-1 grown on hydrogen had no effect. Moreover, the few precipitates that formed in the presence of TAG-1's iron-oxidizing exometabolome were poorly crystalline, compared with the abundant iron particles that mineralized in the absence of abiotic controls. We offer an initial exploration of TAG-1's iron-oxidizing exometabolome and discuss potential key contributors to this process. Overall, our findings demonstrate that the exometabolome as a whole leads to a sustained accumulation of ferrous iron in the presence of oxygen, consequently altering the redox equilibrium. This previously unknown adaptation likely enables these microorganisms to persist in an iron-oxidizing and iron-precipitating world and could have impacts on the bioavailability of iron to FeOB and other life in iron-limiting environments.

The Iron Chaperone Poly C Binding Protein 1 Regulates Iron Efflux through Intestinal Ferroportin in Mice

Iron is an essential nutrient required by all cells but used primarily for red blood cell production. Because humans have no effective mechanism for ridding the body of excess iron, the absorption of dietary iron must be precisely regulated. The critical site of regulation is the transfer of iron from the absorptive enterocyte to the portal circulation via the sole iron efflux transporter, ferroportin (FPN). Here we report that poly(rC)-binding protein 1 (PCBP1), the major cytosolic iron chaperone, is necessary for the regulation of iron flux through FPN in the intestine of mice. PCBP1 binds iron-glutathione complexes in the cytosol of cells and delivers the iron to ferritin, the iron storage protein, to iron centers in enzymes, and to iron-sulfur cluster chaperones. PCBP1 also limits the chemical reactivity of iron, thereby limiting iron-catalyzed oxidative damage in cells. To explore the role of PCBP1 in dietary iron absorption, we developed mice with an inducible, enterocyte-specific deletion of PCBP1. Mice lacking PCBP1 in the intestinal epithelium exhibit low levels of enterocyte iron, poor retention of dietary iron in enterocyte ferritin, and excess efflux of iron through FPN. Kinetic studies of iron transport using a stable isotope ( 57Fe) coupled with a mini-hepcidin that blocks FPN activity demonstrated that PCBP1 deletion had no effect of intestinal iron uptake but caused high rates of iron efflux through FPN. Surprisingly, excess iron efflux occurred despite lower levels of FPN protein in enterocytes and upregulation of the iron regulatory hormone hepcidin. PCBP1 deletion and the resulting unregulated dietary iron absorption led to poor growth, severe anemia on a low iron diet and liver oxidative stress with iron loading on a high iron diet. To investigate the roles of PCBP1 more precisely in enterocytes, we developed 3-D organoid cultures from intestinal epithelium which functionally expressed the major iron trafficking proteins: divalent metal transporter 1, PCBP1, ferritin, transferrin receptor 1 and FPN. Ex vivo culture of wild-type and PCBP1-depleted enteroids demonstrated normal patterns of FPN expression and hepcidin-mediated turnover. However, fluorescence measurements of kinetically labile iron pools in enteroids competent or blocked for FPN iron efflux indicated that PCBP1 dramatically altered efflux activity. PCBP1 functioned as a cytosolic buffer for iron, binding and retaining iron and thereby keeping “free” iron at very low levels. This low concentration of free iron limited its availability for FPN-mediated efflux and allowed hepcidin-mediated changes in FPN levels to regulate the amount of iron exported from the enterocyte. Thus, by binding enterocyte iron, PCBP1 reduces the concentration of unchaperoned, “free” iron to a low level. This low level of cytosolic free iron is necessary for hepcidin-mediated regulation of FPN activity.

Nitrogen modification enhances conductivity and reactivity of sulfidated zero-valent iron: Mechanism and Cr(VI) removal

The incorporation of electronegative elemental nitrogen into zero-valent iron (ZVI)/sulfidated zero-valent iron (S-ZVI) has emerged as an outstanding and promising way to improve decontamination performance. However, the impact of nitrogen modification on the electrical structure of ZVI/S-ZVI remains unclear. Herein, nitrogen-modified sulfidated zero-valent iron (S-N-ZVI) was successfully obtained utilizing cheap and accessible ammonium chloride as the nitrogen source. Raman spectra, FTIR, and density functional theory (DFT) calculations demonstrated that NH3 acts as the dominant nitrogen species. According to the projected density of states and charge-density difference calculations, N is successfully bound to Fe, resulting in a redistribution of surface charge and an increase in electron density of S-N-ZVI, which is reflected in the improved conductivity of S-N-ZVI. Compared with S-ZVI, S-N-ZVI demonstrates better performance in terms of Cr(VI) removal kinetics (kobs improved by 2.075 folds), resistance to air aging, reusability and ability to preserve FeSX stability. This study highlights that the electronic structure significantly impacts the physicochemical properties of S-ZVI and reveals the mechanism of nitrogen modification on the electronic structure of S-ZVI.

Coffee grounds modified zero-valent iron for efficient heavy metal removal

Surface modification is one of the most important approach for improving the reactivity of zero-valent iron. In this study, waste coffee grounds (CG) were chosen to modify zero-valent iron through a mechanochemical method. The synthesized CG-ZVI exhibited a 166 times faster Cr(VI) removal rate. Structural characterization and ATR-FTIR analysis indicated that CG modification endowed ZVI with abundant carboxylic acid groups, and accelerated the adsorption of Cr(VI) via the complexation effect of CG-COOH···HCrO4−. Moreover, the polyphenolic substances from CG-ZVI, as an electron shuttle, accelerated the electron transfer from the iron core to generated surfaced bound Fe2+, resulting in high efficiency of Cr(VI) removal. In addition, CG-ZVI selectively removed Cr(VI) in the presence of anions (Cl−, NO3−, SO42−) and acted as a permeable reactive barrier material for in situ treatment of heavy metal-contaminated water. This work demonstrates that CG modification can function as an excellent candidate for perfecting the reactivity of ZVI. More importantly, it opens up a new way for the utilization of discarded CG.

Elucidating the impact of sulfur precursors on the reactivity, toxicity, and colloidal stability of post-sulfidized nanoscale zerovalent iron

The sulfur precursor-induced sulfidation effectively enhances the nanoscale zerovalent iron (nZVI) reactivity. However, due to the batch-to-batch variation in synthesis and reaction conditions, the sulfur precursor that confers superior reactivity to sulfidized nZVI (S-nZVI) and its application potential are undetermined. This study evaluated the impact of six sulfur precursors (Na2S, Na2S2O4, S0, Na2S2O3, K2S6, and sulfate reduction effluent [a sulfide-containing effluent]) on the reactivity, toxicity, and colloidal stability of S-nZVI. The reactivity enhancement induced by sulfidation of the different sulfur precursors was inconsistent and dependent on the contaminant. In the removal of trichloroethylene (TCE) and hexavalent chromium Cr(VI) in aqueous solution, S-nZVI, with a high Fe0 content, hydrophobicity, and electron transfer properties (i.e., S-nZVINa2S and S-nZVINa2S2O3), yielded relatively high capacities. In the removal of tetracycline (TC) by S-nZVI, the performance was relatively unaffected by the sulfur precursors. The toxicity evaluation demonstrated that S-nZVIs showed a limited toxicity (less than 0.35-log) to Escherichia coli (E. coli) in simulated groundwater. Despite sulfidation marginally improving the colloidal stability of nZVI—by reducing the interparticle forces—, the S-nZVI particle settling was observed, within 60 min, at the bottom of the vial containing the suspension. Overall, none of the sulfur precursors was manifestly preferable to the others. Na2S, Na2S2O3, and SR-effluent were recommended for use in low sulfur content post-sulfidation processes considering the material performances and costs. These findings contribute to the understanding of the effect of the sulfur precursors on the reactivity and application potential of S-nZVI, thereby providing guidance for tuning S-nZVI properties and selecting suitable sulfur precursors for specific in situ remediation scenarios.

Revisiting the Role of Dissolved Silicate in Catalyzing the Hydrogen Peroxide Process with Iron-Bearing Minerals.

Injecting H2O2 into aquifers is a widely used in-situ chemical oxidation (ISCO) technology for groundwater remediation. Dissolved silicate was reported to decrease the reactivity of iron (Ⅲ)-bearing minerals toward H2O2. In this study, the effect of naturally occurring levels of dissolved silicate (≤1 mM) on the catalyzing hydrogen peroxide (CHP) with Fe(II) minerals is revaluated, and new observations that contradict with previous studies are reported. Specifically, dissolved silicate enhanced the CHP process by Fe(II) minerals. In the presence of Fe(II) minerals, siderite and ferrous oxide (FeO), which had a stronger dissolution tendency than Fe(III) minerals, dissolved silicate could prevent the dissolved iron species from precipitation through a coordinating effect, therefore reinforcing the homogeneous CHP process and the degradation of 2,4-dichlorophenol. The solution pH decreased due to the generation of degradation intermediates, and the solution acidification in turn promoted further dissolution of Fe(II) minerals. FeO particles exhibited the strongest silicate adsorption among the minerals, therefore a higher initial silicate concentration of 1 mM was needed to observe the enhancing effect. This study redefines the role of dissolved silicate on CHP process and provides clues to the design of efficient H2O2-based ISCO system for the remediation of groundwater.

Synergistic photocatalytic performance of Fe@Fe2O3 core-shell nanostructures supported on g-C3N4 nanosheets for RhB and phenol decolorization: Fabrication, characterization, and mechanistic insights

In this study, Fe@Fe2O3 core-shell nanoparticles were synthesized and adsorbed onto g-C3N4 nanosheets through a chemical adsorption process. The resulting Fe@Fe2O3/g-C3N4 nanocomposites exhibited a unique morphology and were characterized by a narrow dispersion of Fe@Fe2O3 nanostructures uniformly distributed on the g-C3N4 nanosheets. The impact of varying reaction parameters, such as reaction time and reducing agent concentration, on the reactivity and properties of iron was investigated. The enhanced photoactivity of Fe@Fe2O3/g-C3N4 nanocomposites for RhB and phenol was explored, and it was found that the heterojunction formed between Fe2O3 and g-C3N4 facilitated efficient charge partition, thereby reducing electron-hole recombination, and promoting the separation of photogenerated charges. Mechanistic insights into the degradation process of the pollutant RhB were gained using Fe@Fe2O3/g-C3N4 nanocomposites, and it was found that the holes (h+) and superoxide radicals (O2−) were the main active species involved in the degradation of RhB. The study highlights the potential of Fe@Fe2O3/g-C3N4 nanocomposites to eliminate contaminants.

Developing the Ascorbic Acid Test: A Candidate Standard Tool for Characterizing the Intrinsic Reactivity of Metallic Iron for Water Remediation

Granular metallic iron (gFe0) materials have been widely used for eliminating a wide range of pollutants from aqueous solutions over the past three decades. However, the intrinsic reactivity of gFe0 is rarely evaluated and existing methods for such evaluations have not been standardized. The aim of the present study was to develop a simple spectrophotometric method to characterize the intrinsic reactivity of gFe0 based on the extent of iron dissolution in an ascorbic acid (AA—0.002 M or 2 mM) solution. A modification of the ethylenediaminetetraacetic acid method (EDTA method) is suggested for this purpose. Being an excellent chelating agent for FeII and a reducing agent for FeIII, AA sustains the oxidative dissolution of Fe0 and the reductive dissolution of FeIII oxides from gFe0 specimens. In other words, Fe0 dissolution to FeII ions is promoted while the further oxidation to FeIII ions is blocked. Thus, unlike the EDTA method that promotes Fe0 oxidation to FeIII ions, the AA method promotes only the formation of FeII species, despite the presence of dissolved O2. The AA test is more accurate than the EDTA test and is considerably less expensive. Eight selected gFe0 specimens (ZVI1 through ZVI8) with established diversity in intrinsic reactivity were tested in parallel batch experiments (for 6 days) and three of these specimens (ZVI1, ZVI3, ZVI5) were further tested for iron leaching in column experiments (for 150 days). Results confirmed the better suitability (e.g., accuracy in assessing Fe0 dissolution) of the AA test relative to the EDTA test as a powerful screening tool to select materials for various field applications. Thus, the AA test should be routinely used to characterize and rationalize the selection of gFe0 in individual studies.

Integrated effect of bulk cations on nano-confined reactivity of clay-intercalated subnanoscale zero-valent iron in water-tetrahydrofuran mixtures

Smectite clay-intercalated subnanoscale zero-valent iron (CSZVI) exhibits superior reactivity toward contaminants due to the small iron clusters (∼0.5 nm) under nano-confinement, which however is significantly influenced by the solution chemistry e.g., various cations, of polluted soil and water. This work was undertaken to elucidate the mechanisms of solution chemistry effects on dehalogenation ability of CSZVI in water-tetrahydrofuran solution using decabromodiphenyl ether as a model contaminant. By combined spectroscopic characterization and molecular dynamics simulation, it was revealed that bulk cations, i.e., Na+, K+, Mg2+ and Ca2+ collectively affected the interlayer distance, water content and Brønsted acidity of CSZVI and thus its degradation efficiency. Although causing inter-particle aggregation, Mg2+ induced optimal nano-confined interlayers at concentration of 20 mM, exhibiting a superior debromination efficiency with rate constant 9.84 times larger than that by the common nano-sized ZVI. Conversely, K+ rendered the interlayers less reactive, but protected CSZVI from corrosion loss with higher electron utilization efficiency, which was 1.7 times higher than CSZVI in presence of Mg2+. The findings provide new strategies to manipulate the reactivity of nano-confined CSZVI for effective wastewater and contaminated soil remediation.

Removal of Cr(VI) by hollow micron zero-valent iron in groundwater containing different ions: Mechanisms and mineralized products

The development of zero-valent iron in-situ reactive zone technology is restricted by the poor mobility and reactivity of zero-valent iron. Hence，hollow micron zero-valent iron (H-mZVI) was prepared through rapid liquid reduction and used to remove Cr(VI) from aqueous solution. Scanning electron microscopy confirmed that H-mZVI had a hollow structure, particle size of approximately 1 µm, and rough surface. X-ray diffraction indicated that H-mZVI was mainly composed of ZVI. Brunauer–Emmett–Teller results showed that H-mZVI had a large specific surface area (25.54 m2/g) and pore volume (0.12 cm3/g). The Cr(VI) removal efficiency of H-mZVI was 6.18 times that of solid micron zero-valent iron (S-mZVI), and the removal reaction conformed to first-order reaction kinetics. Electrochemical test results revealed that the electron transport efficiency was stronger, Fe2+ concentration in aqueous solution was larger, and the decrease in oxidation–reduction potential was more obvious in H-mZVI than in S-mZVI. Desorption experiment and X-ray photoelectron spectroscopy showed that H-mZVI removed Cr(VI) primarily through reduction and secondarily through adsorption. The effects of conventional ions and humic acid (HA) on Cr(VI) removal by H-mZVI were in the order of PO43->HA>NO3->CO32->HCO3->Cl-=Mg2+=Ca2+. The corrosion products and their proportions varied in the presence of different ions.

Unraveling the neglected role of elemental sulfur in chromate removal by sulfidated microscale zero-valent iron

Elemental sulfur (S0), as an oxidation product of low-valent sulfur, is widely believed to inhibit the reactivity of sulfidated zero-valent iron (S-ZVI). However, this study found that the Cr(VI) removal and recyclability of S-ZVI with S0 as the dominant sulfur species were superior to those FeS or iron polysulfides (FeSx, x > 1) dominated ones. The more S0 directly mixed with ZVI, the better Cr(VI) removal obtained. This was ascribed to the formation of micro-galvanic cells, the semiconductor properties of cyclo-octasulfur S0 with sulfur atom substituted by Fe2+, and the in situ generations of highly reactive iron monosulfide (FeSaq) or polysulfides precursors (FeSx,aq). The Cr(VI) sequestration of FeSx,aq was 1.2–2 times that of FeSaq, and the reaction rate of amorphous iron sulfides (FexSy) in the removal of Cr(VI) by S-ZVI was 8- and 66-fold faster than that of crystalline FexSy and micron ZVI, respectively. The interaction of S0 with ZVI required direct contact and needed to overcome the spatial barrier caused by FexSy formation. These findings reveal the role of S0 in Cr(VI) removal by S-ZVI and guide the future development of in situ sulfidation technologies to utilize the highly reactive FexSy precursors for field remediation.

Performance Enhancement of Biogenetic Sulfidated Zero-Valent Iron for Trichloroethylene Degradation: Role of Extracellular Polymeric Substances.

Chemical sulfidation has been considered as an effective strategy to improve the reactivity of zero-valent iron (S-ZVI). However, sulfidation is a widespread biogeochemical process in nature, which inspired us to explore the biogenetic sulfidation of ZVI (BS-ZVI) with sulfate-reducing bacteria (SRB). BS-ZVI could degrade 96.3% of trichloroethylene (TCE) to acetylene, ethene, ethane, and dichloroethene, comparable to S-ZVI (97.0%) with the same S/Fe ratio (i.e., 0.1). However, S-ZVI (0.21 d-1) exhibited a faster degradation rate than BS-ZVI (0.17 d-1) based on pseudo-first-order kinetic fitting due to extracellular polymeric substances (EPSs) excreted from SRB. Organic components of EPSs, including polysaccharides, humic acid-like substances, and proteins in BS-ZVI, were detected with 3D-EEM spectroscopy and FT-IR analysis. The hemiacetal groups and redox-activated protein in EPS did not affect TCE degradation, while the acetylation degree of EPS increased with the concentration of ZVI and S/Fe, thus inhibiting the TCE degradation. A low concentration of HA-like substances attached to BS-ZVI materials promoted electron transport. However, EPS formed a protective layer on the surface of BS-ZVI materials, reducing its TCE reaction rate. Overall, this study showed a comparable performance enhancement of ZVI toward TCE degradation through biogenetic sulfidation and provided a new alternative method for the sulfidation of ZVI.

Stability and reactivity of dinuclear iron(III)-salen complexes as catalysts in ethylene polymerization: A computational approach

The increasing demand for olefin polymers has prompted extensive research on catalysis, processes, and structural characterization to explore their economic potential. In this study, N,N'-bis(salicylidene)-1,2-ethylenediamine (salen) was synthesized, complexed with Fe(III) ion, and the complex was bridged by simple condensation reaction with five different dicarboxylic acids to produce dinuclear complexes. Different methods, such as 1H NMR, FT-IR, UV–Vis, and EDX elemental analysis, were used to analyze and identify the ligand and complexes. Spectroscopic results supported by molecular modeling studies, revealed that the complexes had an octahedral geometry. Structural optimization of the ligand and metal complexes was performed using Avogadro (version 1.2.0) and the Universal Force Field molecular mechanics level. Density functional theory was used to conduct computational calculations on the stability and reactivity of the zeolite-supported and unsupported complexes as catalysts for the polymerization of ethylene. Interestingly, the supported complexes were found to exhibit lower stability and higher reactivity than the neat metal complexes. As such, the synthesized complexes are promising catalysts for the production of polyethylene, and their use could significantly reduce the cost of industrial polyethylene production.

Generic CD-MUSIC-eSGC model parameters to predict the surface reactivity of iron (hydr)oxides

The surface reactivity of iron (hydr)oxides plays a crucial role in controlling their interfacial reactions, for which various surface complexation models have been developed. The diversity of mineralogical properties of iron (hydr)oxides has resulted in a redundancy of model parameters, which hampers the modeling of iron (hydr)oxides in soils and sediments, where goethite, hematite and ferrihydrite dominate the iron (hydr)oxide mass fraction. To capture their combined surface reactivity, optimized generic protonation parameters of the Charge Distribution-Multisite Complexation (CD-MUSIC) extended-Stern-Gouy-Chapman (eSGC) model were derived by reanalyzing literature datasets and tested with some newly synthesized iron (hydr)oxides. It was observed that the proton and monovalent ion affinity constants of the different iron (hydr)oxides were located in a narrow range. For the singly- and triply-coordinated hydroxyl sites the obtained generic log(affinity constants) were 8.3 and 11.7 for the protonation reaction and -0.5 for the reaction with the monovalent background ions. Their combination with fixed site densities of singly-/triply-coordinated hydroxyl sites of 3.45/2.70, 5.00/2.50, and 5.80/1.40 sites/nm2 for goethite, hematite, and ferrihydrite, respectively, provided good results. The Stern layer capacitances of the inner and outer Stern layers were set equal and could be acquired by an empirical correlation with the sample specific surface area (SSA). The CD-MUSIC-eSGC model with the generic model parameters enables good quality predictions of the proton reactivity of iron (hydr)oxides in 1:1 electrolyte solutions regardless of the sample heterogeneity. The advantages of the generic CD-MUSIC-eSGC model are twofold: (1) protonation of iron (hydr)oxides can be described without making use of spectroscopic measurements and proton titrations, and (2) the model calculations are greatly simplified.

Aging and reactivity assessment of nanoscale zerovalent iron in groundwater systems

In this study, changes in the reactivity of nanoscale zerovalent iron (NZVI) in five different groundwater (GW) systems under anoxic and oxic conditions were examined over a wide range of aging time (0 − 60 d). p-nitrophenol (p-NP) was used as a redox-sensitive probe, whereas nalidixic acid (NA), a typical antibiotic found in the natural environment, was used as a sorbing compound. Investigation of the p-NP reduction in pure water systems showed that NZVI lost 41% and 98% of its reductive activity under anoxic and oxic conditions after 60 d, while enhancement of its reactivity was observed after short-term aging in GW (1 − 5 d), followed by a further decline. This behavior has been ascribed to the formation of secondary Fe(II)-bearing phases, including magnetite and green rust, resulting from NZVI aging in GW. Adsorption experiments revealed that GW-anoxic-aged NZVI samples exhibited a good affinity toward NA, and a greater NA adsorption (∼27 µmol g − 1) than that of pristine NZVI (∼2 µmol g − 1) at alkaline pH values. Surface complexation modeling showed that the enhanced adsorption of NA onto secondary minerals can be attributed to the Fe(II)-NA surface complexation. This considerable change in the reductive ability and the adsorption capacity of NZVI arising from groundwater corrosion calls for greater attention to be paid in assessment studies, where NZVI is injected for long-term remediation in groundwater.

Sophorolipid modification enables high reactivity and electron selectivity of nanoscale zerovalent iron toward hexavalent chromium

Nanoscale zero-valent iron is considered to be a promising nanostructure for environmental remediation, while increasing the electron selectivity of nanoscale zerovalent iron (nZVI) during target contaminant removal is still a challenge (electron selectivity, defined as the percentage of electrons transferred to the target contaminants over the number of electrons donated by nZVI). In this study, the strategy for increasing the reactivity and electron selectivity of nZVI via sophorolipid (SL-nZVI) modification was proposed. The results showed that the removal efficiency and electron selectivity of SL-nZVI toward Cr(VI) was 99.99% and 56.30%, which was higher than that of nZVI (61.16%, 25.91%). Meanwhile, the particles were well characterized and the mechanism for enhanced reactivity and electron selectivity was investigated. Specially, both the morphology and BET specific surface area characterization suggested that stability against aggregation was higher in SL-nZVI nanoparticles than in nZVI. Besides, X-ray photoelectron spectroscopy (XPS), Tafel polarization curves, and Electrochemical impedance spectroscopy also indicated that the introduction of sophorolipid successfully prevent the nanoparticles from oxidation and benefit the electron transferring. In addition, a water contact angle test revealed that SL-nZVI nanoparticles were less hydrophilic (contact angle = 34.8°) than nZVI (contact angle = 23.9°). Therefore, in terms of reactivity, sophorolipid modification inhibited the aggregation of the nanoparticles and enhanced the electrical conductivity. For electron selectivity, the introduction of sophorolipid not only benefited Cr(VI) adsorption and the electron transfer from Fe0 to the surface-adsorbed Cr(VI) that followed but also reduced the possibility of side reactions between Fe0 and H2O. This study demonstrates that the introduction of sophorolipid is an effective strategy for developing a highly efficient nZVI-based nanocomposite system and highlights the potential role of sophorolipid in improving the electron selectivity of nZVI.

Fabrication and Characterization of Bimetal Sulfide Hybrid Ag/S-ZVI for Dechlorination of Trichloroethylene

Sulfidated and bimetal modification can improve the reactivity and selectivity of zero-valent iron in contaminant removal. However, previous studies were focused on unilateral material approaches. In this article, a new hybrid composite Ag/S-ZVI was prepared by doping elemental silver on surface of sulfidated nanoscale zerovalent iron (S-nZVI). The results of X-Ray Diffraction (XRD), energy dispersive spectrometer (EDS) and X-ray Photoelectron Spectroscopy (XPS) indicated Ag was dispersed on the surface of S-nZVI. Scanning electron microscope (SEM) images displayed Ag/S-ZVI was irregular clusters with rough surfaces, small agglomeration, and quasi-spherical in shape. The removal of TCE by Ag/S-ZVI was 90.4% within 20 min. The reaction rate constant &lt;i&gt;K&lt;sub&gt;obs&lt;/sub&gt;&lt;/i&gt; of Ag/S-ZVI was 2.59 times or 1.85 times of nZVI or S-nZVI, respectively. Cycling experiments showed that Ag/S-ZVI had good recycling ability, and the removal rate of TCE reached 72.6% at the third cycle. The addition of Ag&lt;sup&gt;+&lt;/sup&gt; makes S-nZVI as an abundant and efficient source of reducing electrons. The Fe&lt;sup&gt;0&lt;/sup&gt; core can break C-Cl bonds by releasing electrons and the surface layer of Ag favors the transfer efficiency of electrons. Such study provides an efficient and robust ternary system for the remediation of TCE in groundwater.

Multistep synthesis, reactivity and X-ray structure of the anisole-terminated iron(II) polyhalogenoclathrochelates and their monoribbed-functionalized macrobicyclic derivatives

Multistep synthetic pathway towards a series of the anisoleboron-capped ribbed-functionalized iron(II) cage complexes was developed. Their hexachloroclathrochelate precursor was obtained by the template condensation of three dichloroglyoximate chelating ligand synthons with two molecules of 4-methoxyphenylboronic acid as a Lewis-acidic cross-linking agent on the iron(II) ion as a matrix. It easily underwent a stepwise nucleophilic substitution with S2- and O2-dinucleophilic aliphatic (ethanedithiolate) or aromatic (pyrocatecholate) agents, forming the stable X2 (X = S or O)-six-membered ribbed substituent(s) at a quasiaromatic cage framework. Performing these reactions under the different reaction conditions (i.e., at various hexachloroclathrochelate-to-nucleophile molar ratios, a wide range of temperatures and a series of the solvents) allowed to control a predominant formation of its mono-, di- or triribbed-substituted macrobicyclic derivatives. Thus obtained iron(II) di- and tetrachloroclathrochelates can undergo their post-synthetic transformations with active nucleophilic agents. The latter complexes underwent a further nucleophilic substitution with the anionic derivative of n-butanthiol, thus giving the hexasulfide macrobicyclic compound with two functionalizing n-alkyl substituents in one of its three chelate α-dioximate fragments and two apical biorelevant anisole substituents. The obtained iron(II) clathrochelates, possessing a low-spin electronic d6 configuration, were characterized using elemental analysis, MALDI-TOF mass spectrometry, UV–Vis, 1H and 13C{1H} NMR spectroscopies, and by the single-crystal X-ray diffraction experiments for the hexachloroclathrochelate precursor, its dichlorotetrasulfide macrobicyclic derivative and the monoribbed-functionalized hexasulfide cage complex. In all their molecules, the encapsulated iron(II) ion is situated in the centre of its FeN6-coordination polyhedron, the geometry of which is intermediate between a trigonal prism and a trigonal antiprism with the distortion angles φ from 21.4 to 23.4°. Halogen bonding between the polyhalogenoclathrochelate molecules in their crystals is observed.Graphical abstract