Positively Charged Additives Facilitate Incorporation in Inorganic Single Crystals.

Incorporation of guest additives within inorganic single crystals offers a unique strategy for creating nanocomposites with tailored properties. While anionic additives have been widely used to control the properties of crystals, their effective incorporation remains a key challenge. Here, we show that cationic additives are an excellent alternative for the synthesis of nanocomposites, where they are shown to deliver exceptional levels of incorporation of up to 70 wt % of positively charged amino acids, polymer particles, gold nanoparticles, and silver nanoclusters within inorganic single crystals. This high additive loading endows the nanocomposites with new functional properties, including plasmon coupling, bright fluorescence, and surface-enhanced Raman scattering (SERS). Cationic additives are also shown to outperform their acidic counterparts, where they are highly active in a wider range of crystal systems, owing to their outstanding colloidal stability in the crystallization media and strong affinity for the crystal surfaces. This work demonstrates that although often overlooked, cationic additives can make valuable crystallization additives to create composite materials with tailored composition-structure-property relationships. This versatile and straightforward approach advances the field of single-crystal composites and provides exciting prospects for the design and fabrication of new hybrid materials with tunable functional properties.

Effects of metal cation substitution on hexavalent chromium reduction by green rust.

Chromium contamination is a serious environmental issue in areas affected by leather tanning and metal plating, and green rust sulfate has been tested extensively as a potential material for in situ chemical reduction of hexavalent chromium in groundwater. Reported products and mechanisms for the reaction have varied, most likely because of green rust's layered structure, as reduction at outer and interlayer surfaces might produce different reaction products with variable stabilities. Based on studies of Cr(III) oxidation by biogenic Mn (IV) oxides, Cr mobility in oxic soils is controlled by the solubility of the Cr(III)-bearing phase. Therefore, careful engineering of green rust properties, i.e., crystal/particle size, morphology, structure, and electron availability, is essential for its optimization as a remediation reagent. In the present study, pure green rust sulfate and green rust sulfate with Al, Mg and Zn substitutions were synthesized and reacted with identical chromate (CrO42-) solutions. The reaction products were characterized by X-ray diffraction, pair distribution function analysis, X-ray absorption spectroscopy and transmission electron microscopy and treated with synthetic δ-MnO2 to assess how easily Cr(III) in the products could be oxidized. It was found that Mg substitution had the most beneficial effect on Cr lability in the product. Less than 2.5% of the Cr(III) present in the reacted Mg-GR was reoxidized by δ-MnO2 within 14 days, and the particle structure and Cr speciation observed during X-ray scattering and absorption analyses of this product suggested that Cr(VI) was reduced in its interlayer. Reduction in the interlayer lead to the linkage of newly-formed Cr(III) to hydroxyl groups in the adjacent octahedral layers, which resulted in increased structural coherency between these layers, distinctive rim domains, sequestration of Cr(III) in insoluble Fe oxide bonding environments resistant to reoxidation and partial transformation to Cr(III)-substituted feroxyhyte. Based on the results of this study of hexavalent chromium reduction by green rust sulfate and other studies, further improvements can also be made to this remediation technique by reacting chromate with a large excess of green rust sulfate, which provides excess Fe(II) that can catalyze transformation to more crystalline iron oxides, and synthesis of the reactant under alkaline conditions, which has been shown to favor chromium reduction in the interlayer of Fe(II)-bearing phyllosilicates.

Direct Visualization of Arsenic Binding on Green Rust Sulfate.

"Green rust" (GR), a redox-active Fe(II)-Fe(III) layered double hydroxide, is a potential environmentally relevant mineral substrate for arsenic (As) sequestration in reduced, subsurface environments. GR phases have high As uptake capacities at circum-neutral pH conditions, but the exact interaction mechanism between the GR phases and As species is still poorly understood. Here, we documented the bonding and interaction mechanisms between GR sulfate and As species [As(III) and As(V)] under anoxic and circum-neutral pH conditions through scanning transmission electron microscopy (STEM) coupled with energy-dispersive X-ray (EDX) spectroscopy and combined it with synchrotron-based X-ray total scattering, pair distribution function (PDF) analysis, and As K-edge X-ray absorption spectroscopy (XAS). Our highly spatially resolved STEM-EDX data revealed that the preferred adsorption sites of both As(III) and As(V) are at GR crystal edges. Combining this data with differential PDF and XAS allowed us to conclude that As adsorption occurs primarily as bidentate binuclear (2C) inner-sphere surface complexes. In the As(III)-reacted GR sulfate, no secondary Fe-As phases were observed. However, authigenic parasymplesite (ferrous arsenate nanophase), exhibiting a threadlike morphology, formed in the As(V)-reacted GR sulfate and acts as an additional immobilization pathway for As(V) (∼87% of immobilized As). We demonstrate that only by combining high-resolution STEM imaging and EDX mapping with the bulk (differential) PDF and extended X-ray absorption fine structure (EXAFS) data can one truly determine the de facto As binding nature on GR surfaces. More importantly, these new insights into As-GR interaction mechanisms highlight the impact of GR phases on As sequestration in anoxic subsurface environments.

Surface Fatigue Behavior of a WC/aC:H Thin-Film and the Tribochemical Impact of Zinc Dialkyldithiophosphate.

In wind turbine gearboxes, (near-)surface initiated fatigue is attributed to be the primary failure mechanism. In this work, the surface fatigue of a hydrogenated tungsten carbide/amorphous carbon (WC/aC:H) thin-film was tested under severe cyclic tribo-contact using polyalphaolefin (PAO) and PAO + zinc dialkyldithiophosphate (ZDDP) lubricants. The film was characterized in terms of its structure and chemistry using X-ray diffraction, analytical transmission electron microscopy, including electron energy loss spectroscopy (EELS), as well as X-ray photoelectron spectroscopy (XPS). The multilayer carbon thin-film exhibited promising surface fatigue performance showing a slight change in the hybridization state of the aC:H matrix. Dehydrogenation of the thin-film and subsequent transformation of cleaved C-H bonds to nonplanar sp2 carbon rings were inferred from EELS and XPS results. While tribo-induced changes to the aC:H matrix were not influenced by a nanometer-thick ZDDP reaction-film, the rate of oxidation of WC and its oxidation state were affected. While accelerating surface fatigue on a steel surface, the ZDDP-tribofilm protected the WC/aC:H film from surface fatigue. In contrast to the formation of polyphosphates from ZDDP molecules on steel surfaces, it appeared that on the WC/aC:H thin film surface, ZDDP molecules decompose to ZnO, suppressing the oxidative degradation of WC.

A template-free and low temperature method for the synthesis of mesoporous magnesium phosphate with uniform pore structure and high surface area.

Mesoporous phosphates are a group of nanostructured materials with promising applications, particularly in biomedicine and catalysis. However, their controlled synthesis via conventional template-based routes presents a number of challenges and limitations. Here, we show how to synthesize a mesoporous magnesium phosphate with a high surface area and a well-defined pore structure through thermal decomposition of a crystalline struvite (MgNH4PO4·6H2O) precursor. In a first step, struvite crystals with various morphologies and sizes, ranging from a few micrometers to several millimeters, had been synthesized from supersaturated aqueous solutions (saturation index (SI) between 0.5 and 4) at ambient pressure and temperature conditions. Afterwards, the crystals were thermally treated at 70-250 °C leading to the release of structurally bound water (H2O) and ammonia (NH3). By combining thermogravimetric analyses (TGA), scanning and transmission electron microscopy (SEM, TEM), N2 sorption analyses and small- and wide-angle X-ray scattering (SAXS/WAXS) we show that this decomposition process results in a pseudomorphic transformation of the original struvite into an amorphous Mg-phosphate. Of particular importance is the fact that the final material is characterized by a very uniform mesoporous structure with 2-5 nm wide pore channels, a large specific surface area of up to 300 m2 g-1 and a total pore volume of up to 0.28 cm3 g-1. Our struvite decomposition method is well controllable and reproducible and can be easily extended to the synthesis of other mesoporous phosphates. In addition, the so produced mesoporous material is a prime candidate for use in biomedical applications considering that magnesium phosphate is a widely used, non-toxic substance that has already shown excellent biocompatibility and biodegradability.

The interfacial reactivity of arsenic species with green rust sulfate (GRSO4).

Arsenic (As) contamination in groundwater is a significant health and environmental concern worldwide because of its wide distribution and toxicity. The fate and mobility of As is greatly influenced by its interaction with redox-active mineral phases, among which green rust (GR), an FeII-FeIII layered double hydroxide mineral, plays a crucial role. However, the controlling parameters of As uptake by GR are not yet fully understood. To fill this gap, we determined the interfacial reactions between GR sulfate (GRSO4) and aqueous inorganic As(III) and As(V) through batch adsorption experiments, under environmentally-relevant groundwater conditions. Our data showed that, under anoxic conditions, GRSO4 is a stable and effective mineral adsorbent for the removal of As(III) and As(V). At an initial concentration of 10 mg L-1, As(III) removal was higher at alkaline pH conditions (~95% removal at pH 9) while As(V) was more efficiently removed at near-neutral conditions (>99% at pH 7). The calculated maximum As adsorption capacities on GRSO4 were 160 mg g-1 (pH 8-9) for As(III) and 105 mg g-1 (pH 7) for As(V). The presence of other common groundwater ions such as Mg2+ and PO43- reduces the efficiency of As removal, especially at high ionic strengths. Long-term batch adsorption experiments (up to 90 days) revealed that As-interacted GRSO4 remained stable, with no mineral transformation or release of adsorbed As species. Overall, our work shows that GRSO4 is one of the most effective As adsorbents among iron (oxyhydr)oxide phases.