Capturing Lacunary Iron–Oxo Keggin Clusters and Insight Into the Keggin-Fe13 Cluster Rotational Isomerization

The formation mechanism of ferrihydrite is the key to understand its treatment of pollutants in waste water and purification of surface water and groundwater. Although emerging evidence suggests that formation of the ferrihydrite occurs through the aggregation of prenucleation clusters, rather than classical atom-by-atom growth, its formation mechanism remains unclear. Herein, an iron–oxo anionic cluster of [Fe₂₂(μ₄-O)₈(μ₃-OH)₂₀(μ₂-OH)₁₈(CH₃COO)₁₆(H₂O)₂]⁴⁻ viewed as a dimer of bivacant β-Keggin-Fe₁₃ clusters was for the first time obtained by using lanthanide ions as stabilizers. Upon dissolution in a mixed solution of isopropanol and water, the lacunary β-Keggin-Fe₁₃ cluster can transform into an α-Keggin-Fe₁₃ cluster, distinctly demonstrating that the Keggin-Fe₁₃ cluster rotational isomerization can be realized through the vacant Keggin-Fe₁₃ cluster.     

Prenucleation formations in control over synthesis of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanocrystalline powders

Nanocrystalline cobalt ferrite powders were synthesized by hydrothermal treatment of co-precipitated hydroxides in the conditions of an external heating of the autoclave and under microwave heating of the reaction medium. In the microwave-heating mode, the prenucleation clusters formed under ultrasonic treatment of a suspended mixture of cobalt and iron hydroxides is transformed into CoFe₂O₄ nanocrystals during the first minute of synthesis at a temperature satisfying the equilibrium-existence conditions of cobalt ferrite. In the case of a slow external heating of the autoclave, there is no effect of this kind, which is attributed to the disintegration of the prenucleation clusters before the dehydration of the hydroxides to give crystalline cobalt ferrite becomes thermodynamically favorable. The main factor determining the increase in the formation rate of crystallites of CoFe₂O₄ nanopowders and the decrease in their size is the generation of prenucleation centers in the starting mixture of cobalt and iron hydroxides.     

Mechanism of removal of arsenic by bead cellulose loaded with iron oxyhydroxide (beta-FeOOH): EXAFS study

Bead cellulose loaded with iron oxyhydroxide (BCF) with 47 mass% Fe content was prepared and was successfully applied to the elimination of arsenic from aqueous solutions. A clearer understanding of the arsenic removal mechanism will provide accurate prediction of the arsenic adsorptive properties of the new adsorbent. To study the mechanism of the adsorption process, we measured the extended X-ray absorption fine structure (EXAFS) spectra of arsenite and arsenate sorbed onto the adsorbent with different surface coverages. Both arsenite and arsenate were strongly and specifically adsorbed by akaganéite adsorptive centers on BCF by an inner-sphere mechanism. There was no change in oxidation state following interaction between the arsenic species and the BCF surface. The dominant complex of arsenic species adsorbed on akaganéite was bidentate binuclear corner-sharing ((2)C) between As(V) tetrahedra (or As(III) pyramids) and adjacent edge-sharing FeO(6) octahedra. On the basis of the results from EXAFS spectra, the adsorptive characteristics of arsenic, such as the effects of pH and competing anions, were satisfactorily interpreted.     

Heat capacity studies of the iron oxyhydroxides akaganéite (β-FeOOH) and lepidocrocite (γ-FeOOH)

The iron oxides and iron oxyhydroxides exist as several different polymorphs, and a thermodynamic understanding of these polymorphs can provide us with an understanding of their relative stability and chemical reactivity. This study provides heat capacity measurements for lepidocrocite (γ-FeOOH) over the temperature range (0.8 to 38) K and akaganéite (β-FeOOH) over the range (0.7 to 302) K. Fits of the heat capacity of the two samples below T = 15 K showed similar behavior to previously published fits of goethite (α-FeOOH), which required a linear term and an anisotropic gap parameter to model accurately the antiferromagnetic spin–wave contributions. The akaganéite measurements were compared to previously reported measurements all of which showed significant disagreement. It is believed that the measurements reported here are the most reliable. Also, the presence of adsorbed water contributes significantly to the heat capacity of akaganéite, and the standard molar entropy at T = 298.15 K of the hydrated form was calculated to be (81.8 ± 2) J · mol^?1 · K^?1.     

Liquid Phase Hydrogenolysis of Biomass‐derived Lactate to 1,2‐Propanediol over Silica Supported Cobalt Nanocatalyst

Liquid phase hydrogenolysis of ethyl lactate to 1,2‐propanediol was performed over silica supporting cobalt catalysts prepared by two different methods: precipitation‐gel (PG) technique and deposition‐precipitation (DP) procedure. The cobalt species (Co₃O₄/cobalt phyllosilicate) present in the corresponding calcined PG and DP catalysts were different as a consequence of the preparation methods, and Co OH Co olation and Si O Co oxolation molecular mechanisms were employed to elucidate the chemical phenomena during the different preparation procedures. In addition, the texture (BET), reduction behavior (TPR and in‐situ XRD), surface dispersion and state of cobalt species (XPS), and catalytic performance differ greatly between the samples. Because of small particle size, high dispersion of cobalt species and facile reducibility, the Co/SiO₂ catalyst prepared by precipitation‐gel method presented a much higher activity than the catalyst prepared by deposition‐precipitation method. Metallic cobalt is assumed to be the catalytically active site for the hydrogenolysis reaction according to the catalytic results of both cobalt samples reduced at different temperatures and the structure changes after reaction.     

The transformation of ferrihydrite into goethite or hematite, revisited

During the oxidation of iron, poorly crystallized phases are firstly formed: 2- and 6-line ferrihydrite, which presents for the last phase, a similarity with wustite FeO but also with hematite α-Fe₂O₃. Crystallization increases with time and the solid phase obtained is dependent on temperature and pH. Obviously, high temperature favours the formation of the oxide hematite α-Fe₂O₃. As for the pH factor, it is more complicated. Low and high values of pH (2-5 and 10-14) favour the formation of goethite α-FeOOH, while obtaining hematite is favoured at neutral pH (values around 7). Goethite or hematite are obtained either through a dissolution-crystallization process or in the solid state, through a topotactic transformation.Given the structural relationships observed between ferrihydrite and wustite and hematite, it is allowed to think that a structural continuity could exist between wustite Fe_(1−x)O and hematite via ferrihydrite.     

Development and Evaluation of a Nanoporous Iron (Hydr)oxide Electrode for Phosphate Sensing

Nanoporous iron (hydr)oxide electrodes are evaluated as phosphate sensors using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The intensity of the reduction peak current (I_cp) of the ferrihydrite working electrode is tied to phosphate concentration at low pH; however, a hematite electrode combined with the use of EIS provided reliable sensing data at multiple pH values. Nanoporous hematite working electrodes produced an impedance phase component (θ) that shifts with increasing phosphate, and, at chosen frequencies, θ values were fitted for the range 1 nM to 0.1 mM phosphate at pH 4 and pH 7 in 5 mM NaClO₄.     

Distinct Short‐Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (<2 nm)

Amorphous intermediate phases are vital precursors in the crystallization of many biogenic minerals. While inherent short‐range orders have been found in amorphous calcium carbonates (ACCs) relating to different crystalline forms, it has never been clarified experimentally whether such orders already exist in very small clusters less than 2 nm in size. Here, we studied the stability and structure of 10,12‐pentacosadiynoic acid (PCDA) protected ACC clusters with a core size of ca. 1.4 nm consisting of only seven CaCO₃ units. Ligand concentration and structure are shown to be key factors in stabilizing the ACC clusters. More importantly, even in such small CaCO₃ entities, a proto‐calcite short‐range order can be identified but with a relatively high degree of disorder that arises from the very small size of the CaCO₃ core. Our findings support the notion of a structural link between prenucleation clusters, amorphous intermediates, and final crystalline polymorphs, which appears central to the understanding of polymorph selection.     

Transformation of ferrihydrite in the presence or absence of trace Fe(II): The effect of preparation procedures of ferrihydrite

Two-line ferrihydrite was prepared by two different procedures. In procedure 1, which is widely used, ferrihydrite (named as ferrihydrite-1) was prepared by droping NaOH solution into Fe(III) solution. In procedure 2, which is rarely reported, ferrihydrite (named as ferrihydrite-2) was prepared by adding Fe(III) and NaOH solutions into a certain volume of water simultaneously. The results showed that mixing procedures of Fe(III) and alkaline were critical in the sub-microstructures and the conversion mechanisms of ferrihydrites in the presence or absence of trace Fe(II). The sub-microstructure of ferrihydrite-1 favored the mechanism of its dissolution re-crystallization and hematite nanoparticles with rough surface were obtained. The sub-microstructure of ferrihydrite-2 favored the solid state transformation from ferrihydrite to hematite and hematite nanoparticles with smooth surface were formed. These research results will be helpful for us to control the synthesis of hematite nanoparticles with different surface state.     

Organolead Halide Perovskite Nanocrystals: Branched Capping Ligands Control Crystal Size and Stability

CH₃NH₃PbBr₃ perovskite nanocrystals (PNCs) of different sizes (ca. 2.5–100 nm) with high photoluminescence (PL) quantum yield (QY; ca. 15–55 %) and product yield have been synthesized using the branched molecules, APTES and NH₂‐POSS, as capping ligands. These ligands are sterically hindered, resulting in a uniform size of PNCs. The different capping effects resulting from branched versus straight‐chain capping ligands were compared and a possible mechanism proposed to explain the dissolution–precipitation process, which affects the growth and aggregation of PNCs, and thereby their overall stability. Unlike conventional PNCs capped with straight‐chain ligands, APTES‐capped PNCs show high stability in protic solvents as a result of the strong steric hindrance and propensity for hydrolysis of APTES, which prevent such molecules from reaching and reacting with the core of PNCs.     

Channeling Exciton Migration into Electron Transfer in Formamidinium Lead Bromide Perovskite Nanocrystal/Fullerene Composites

Hydrophobically capped nanocrystals of formamidinium lead bromide (FAPbBr₃) perovskite (PNC) show bright and stable fluorescence in solution and thin‐film states. When compared with isolated PNCs in a solution, close‐packed PNCs in a thin film show extended fluorescence lifetime (ca. 4.2 μs), which is due to hopping or migration of photogenerated excitons among PNCs. Both fluorescence quantum efficiency and lifetime decrease in a PNC thin film doped with fullerene (C₆₀), which is attributed to channeling of exciton migration into electron transfer to C₆₀. On the other hand, quenching of fluorescence intensity of a PNC solution is not accompanied by any change in fluorescence lifetime, indicating static electron transfer to C₆₀ adsorbed onto the hydrophobic surface of individual PNCs. Exciton migration among close‐packed PNCs and electron transfer to C₆₀ places C₆₀‐doped PNC thin films among cost‐effective antenna systems for solar cells.     

Fe(II)-induced transformation from ferrihydrite to lepidocrocite and goethite

The transformation of Fe(II)-adsorbed ferrihydrite was studied. Data tracking the formation of products as a function of pH, temperature and time is presented. The results indicate that trace of Fe(II) adsorbed on ferrihydrite can accelerate its transformation obviously. The products are lepidocrocite and/or goethite and/or hematite, which is different from those without Fe(II). That is, Fe(II) not only accelerates the transformation of ferrihydrite but also leads to the formation of lepidocrocite by a new path. The behavior of Fe(II) is shown in two aspects—catalytic dissolution-reprecipitation and catalytic solid-state transformation. The results indicate that a high temperature and a high pH(in the range from 5 to 9) are favorable to solid-state transformation and the formation of hematite, while a low temperature and a low pH are favorable to dissolution-reprecipitation mechanism and the formation of lepidocrocite. Special attentions were given to the formation mechanism of lepidocrocite and goethite.     

An evaluation of least-squares fitting methods in XAFS spectroscopy: Iron-based SBA-15 catalyst formulations

A detailed comparison has been made of determinations by ⁵⁷Fe Mössbauer spectroscopy and four different XAFS spectroscopic methods of %Fe as hematite and ferrihydrite in 11 iron-based SBA-15 catalyst formulations. The four XAFS methods consisted of least-squares fitting of iron XANES, d(XANES)/dE, and EXAFS (k³chi and k²chi) spectra to the corresponding standard spectra of hematite and ferrihydrite. The comparison showed that, for this particular application, the EXAFS methods were superior to the XANES methods in reproducing the results of the benchmark Mössbauer method in large part because the EXAFS spectra of the two iron-oxide standards were much less correlated than the corresponding XANES spectra. Furthermore, the EXAFS and Mössbauer results could be made completely consistent by inclusion of a factor of 1.3 ± 0.05 for the ratio of the Mössbauer recoilless fraction of hematite relative to that of ferrihydrite at room temperature (293 K). This difference in recoilless fraction is attributed to the nanoparticle nature of the ferrihydrite compared to the bulk nature of the hematite. Also discussed are possible alternative non-least-squares XAFS methods for determining the iron speciation in this application as well as criteria for deciding whether or not least-squares XANES methods should be applied for the determination of element speciation in unknown materials.     

Distinguishing metal halide molecular clusters from perovskite magic sized clusters in the synthesis of metal halide perovskite nanostructures

Background

Research into perovskite nanocrystals (PNCs) has uncovered interesting properties compared to their bulk counterparts, including tunable optical properties due to size-dependent quantum confinement effect (QCE). More recently, smaller PNCs with even stronger QCE have been discovered, such as perovskite magic sized clusters (PMSCs) and ligand passivated PbX₂ metal halide molecular clusters (MHMCs) analogous to perovskites.

Objective

This review aims to present recent data comparing and contrasting the optical and structural properties of PQDs, PMSCs, and MHMCs, where CsPbBr₃ PQDs have first excitonic absorption around 520 nm, the corresponding PMSCS have absorption around 420 nm, and ligand passivated MHMCs absorb around 400 nm.

Results

Compared to normal perovskite quantum dots (PQDs), these clusters exhibit both a much bluer optical absorption and emission and larger surface-to-volume (S/V) ratio. Due to their larger S/V ratio, the clusters tend to have more surface defects that require more effective passivation for stability.

Conclusion

Recent study of novel clusters has led to better understanding of their properties. The sharper optical bands of clusters indicate relatively narrow or single size distribution, which, in conjunction with their blue absorption and emission, makes them potentially attractive for applications in fields such as blue single photon emission.     

Chelatometric titration of bismuth with hedta

A new chelatometric method for the determination of Bi in bismuth-base alloys, low-melting alloys and reagent-grade bismuth salts is proposed. It is based on the chelation of Bi(III) with HEDTA, which is added in substoichiometric amount in perchloric acid medium to eliminate the interfering side-reactions of olation and oxolation, followed by pH adjustment and titration at pH 2 with Semi-Xylenol Orange as indicator. It is more selective than the classical EDTA method, and the accuracy and precision are enhanced. The coefficient of variation was found to be ˜ 0.1%.     

Mechanisms and efficiency of the simultaneous removal of metals and cyanides by using ferrate(VI): crucial roles of nanocrystalline iron(III) oxyhydroxides and metal carbonates

The reaction of potassium ferrate(VI), K₂FeO₄, with weak‐acid dissociable cyanides—namely, K₂[Zn(CN)₄], K₂[Cd(CN)₄], K₂[Ni(CN)₄], and K₃[Cu(CN)₄]—results in the formation of iron(III) oxyhydroxide nanoparticles that differ in size, crystal structure, and surface area. During cyanide oxidation and the simultaneous reduction of iron(VI), zinc(II), copper(II), and cadmium(II), metallic ions are almost completely removed from solution due to their coprecipitation with the iron(III) oxyhydroxides including 2‐line ferrihydrite, 7‐line ferrihydrite, and/or goethite. Based on the results of XRD, Mössbauer and IR spectroscopies, as well as TEM, X‐ray photoelectron emission spectroscopy, and Brunauer–Emmett–Teller measurements, we suggest three scavenging mechanisms for the removal of metals including their incorporation into the ferrihydrite crystal structure, the formation of a separate phase, and their adsorption onto the precipitate surface. Zn and Cu are preferentially and almost completely incorporated into the crystal structure of the iron(III) oxyhydroxides; the formation of the Cd‐bearing, X‐ray amorphous phase, together with Cd carbonate is the principal mechanism of Cd removal. Interestingly, Ni remains predominantly in solution due to the key role of nickel(II) carbonate, which exhibits a solubility product constant several orders of magnitude higher than the carbonates of the other metals. Traces of Ni, identified in the iron(III) precipitate, are exclusively adsorbed onto the large surface area of nanoparticles. We discuss the relationship between the crystal structure of iron(III) oxyhydroxides and the mechanism of metal removal, as well as the linear relationship observed between the rate constant and the surface area of precipitates.     

氨和有机胺对羰基硫与α-Fe2O3非均相反应的影响

利用原位漫反射傅里叶红外光谱(DRIFTS), 考察了室温下羰基硫(COS)在经氨气和有机胺预吸附的α-Fe₂O₃上的非均相反应, 并同时比较了氨气和不同有机胺(甲胺、三甲胺、三乙胺、苯胺、吡啶和吡咯)对反应活性的影响及其反应动力学. 结果表明, 经碱性物质预吸附后, COS可在α-Fe₂O₃表面发生氧化反应, 主要产物为气态CO₂、表面HCO₃^-、表面CO₃^2-和表面SO₄^2-, 且α-Fe₂O₃表面预吸附的碱性物质大大提高了COS在α-Fe₂O₃上的反应能力, 在碱性物质的影响中, 甲胺对反应的促进能力最大, 相比纯α-Fe₂O₃反应的反应活性提高了约4.5倍, 然而苯胺和吡咯对COS的反应影响不是很明显.观察到的不同碱性物质对COS的转化能力依次为: 甲胺>三甲胺>氨气>三乙胺>吡啶>吡咯>苯胺≈纯样品, 受碱性物质的影响, COS的反应级数由一级转变为二级. 此外, 研究也发现碱性物质的覆盖度和表面吸附水对COS转化能力存在一定的影响. 这些实验结果表明在碱性物质存在下,表面M―O^-是COS在α-Fe₂O₃发生氧化反应的关键活性位点, 对反应活性的贡献较大, 并在此基础上探讨碱性条件下COS的反应转化机制.     

Catalytic activity of water molecules in gas-phase glycine dimerization

The dimerization of glycine is the simplest oligomerization of amino acids and plays an important role in biology. Although this reaction is thermodynamically unfavorable in the aqueous phase, it has been shown to be spontaneous in the gas phase and proceeds via two different concerted reaction mechanisms known as cis and trans. This may have profound implications in prebiotic chemistry as common atmospheric prenucleation clusters are thought to have participated in gas-phase reactions in the early Earth's atmosphere. We hypothesize that particular arrangements of water molecules in these clusters could lead to lowering of the reaction barrier of amino acid dimerization and could lead to abiotic catalysis toward polypeptides. We test our hypothesis on a system of the cis transition state of glycine dimerization solvated by one to five water molecules using a combination of a genetic algorithm-based configurational sampling, density functional theory geometries, and domain-based local pair natural orbital coupled-cluster electronic structure. First, we discuss the validity of the model chemistries used to obtain our results. Then, we show that the Gibbs free energy barrier for the concerted cis mechanism can indeed be lowered by the addition of up to five water molecules, depending on the temperature.     

Ferrihydrite的亚微观结构对反应活性的影响

以Fe(III)盐为原料、NaOH为沉淀剂、采用三种方法调控制备了ferrihydrite, 借助X射线衍射(XRD)、红外光谱(IR)、差热分析(DTA)及其在稀盐酸中的溶解速率等手段对其结构进行了表征, 探讨了ferrihydrite的形成环境对其亚微观结构及其反应活性的影响. 结果表明, 不同方法制备的ferrihydrite的亚微观结构不同, 恒pH条件下制备的ferrihydrite结构与α-Fe2O3结构最为相似, 更易转化为α-Fe2O3粒子.     

Ion-pair evaporation from ionic liquid clusters

A differential mobility analyzer (DMA) is used in atmospheric pressure N₂ to select a narrow range of electrical mobilities from a complex mix of cluster ions of composition (CA)_n(C⁺)_z. The clusters are introduced into the N₂ gas by electrospraying concentrated (～20 mM) acetonitrile solutions of ionic liquids (molten salts) of composition CA (C⁺ = cation, A^? = anion). Mass analysis of these mobility-selected ions reveals the occurrence of individual neutral ion-pair evaporation events from the smallest singly charged clusters: (CA)_nC⁺→(CA)_{n? 1}C⁺+CA. Although bulk ionic liquids are effectively involatile at room temperature, up to six sequential evaporation events are observed. Because this requires far more internal energy than available in the original clusters, substantial heating (～10 eV) must take place in the ion guides leading to the mass analyzer. The observed increase in IL evaporation rate with decreasing size is drastic, in qualitative agreement with the exponential vapor pressure dependence predicted by Kelvin’s formula. A single evaporation event is barely detectable at n = 13, while two or more are prominent for n ≤ 9. Magic number clusters (CA)₄C⁺ with singularly low volatilities are found in three of the four ionic liquids studied. Like their recently reported liquid phase prenucleation cluster analogs, these magic number clusters could play a key role as gas-phase nucleation seeds. All the singularly involatile clusters seen are cations, which may help understand commonly observed sign effects in ion-induced nucleation. No other charge-sign asymmetry is seen on cluster evaporation.