Metastable Precursor Research Articles

A novel organic-inorganic hybrid polyoxometalate-based 3D framework constructed by organo-functionalized [As2W21O72(mal)2]18 − units and Ce3 + ions

A novel organic-inorganic hybrid polyoxometalate-based 3D framework K5H4{Ce3(H2O)9[As2W21O72(mal)2]}·20H2O (1) (mal=malic acid) has been synthesized by the metastable precursor [As2W19O67(H2O)]14−, which was further characterized by IR spectrum, thermogravimetric analysis (TGA), and X-ray single-crystal diffraction. Structural analysis revealed that 1 consists of the organo-functionalized [As2W21O72(mal)2]18− units linked together by the Ce3+ ions resulting in 3D network-like architecture. Magnetic property studies indicate that obvious antiferromagnetic interactions exist in three Ce3+ ions.

Growth of organic crystals via attachment and transformation of nanoscopic precursors

A key requirement for the understanding of crystal growth is to detect how new layers form and grow at the nanoscale. Multistage crystallization pathways involving liquid-like, amorphous or metastable crystalline precursors have been predicted by theoretical work and have been observed experimentally. Nevertheless, there is no clear evidence that any of these precursors can also be relevant for the growth of crystals of organic compounds. Herein, we present a new growth mode for crystals of DL-glutamic acid monohydrate that proceeds through the attachment of preformed nanoscopic species from solution, their subsequent decrease in height at the surface and final transformation into crystalline 2D nuclei that eventually build new molecular layers by further monomer incorporation. This alternative mechanism provides a direct proof for the existence of multistage pathways in the crystallization of molecular compounds and the relevance of precursor units larger than the monomeric constituents in the actual stage of growth.

Synthesis and Use of Reactive Molecular Precursors for the Preparation of Carbon Nanomaterials

AbstractThe use of reactive molecular carbon precursors is required if the preparation of carbon nanostructures and nanomaterials is to be achieved under conditions that are sufficiently benign to control their nanoscopic morphology and tailor their chemical functionalization. Recently, oligoyne precursors have been explored for this purpose, as they are sufficiently stable to be available in tangible quantities but readily rearrange in reactions that yield other forms of carbon. In this chapter, we briefly discuss available synthetic routes toward higher oligoynes that mostly rely on transition metal-mediated coupling reactions. Thereafter, a comprehensive overview of the use of oligoyne derivatives as precursors for carbon nanostructures and nanomaterials is given. While the non-templated conversion of simple oligoynes into carbonaceous matter exemplifies their potential as metastable carbon precursors, the more recent attempts to use functionalized oligoynes in host–guest complexes, self-assembled aggregates, thin films, colloids or other types of supramolecular structures have paved the way toward a new generation of carbon nanomaterials with predictable nanoscopic morphology and chemical functionalization.

Feathery and network-like filamentous textures as indicators for the re-crystallization of quartz from a metastable silica precursor at the Rusey Fault Zone, Cornwall, UK

Abstract. Hydrothermal quartz crystals, which occur in the Rusey Fault Zone (Cornwall, UK), show feathery textures and network-like filamentous textures. Optical hot-cathodoluminescence (CL) analysis and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) investigations on quartz samples revealed that positions exhibiting feathery textures (violet luminescence) contain higher amounts of Al and Li than quartz positions without feathery textures (blue luminescence), while concentrations of Al and Li are significantly lower in feathery textures. Both Al and Li correlate negatively with Si. Raman spectroscopy investigations revealed the presence of a weak peak at 507–509 cm−1 in quartz affected by feathery textures, which we attribute to the presence of ≤ 5 % moganite, a microcrystalline silica polymorph, intergrown with chalcedony. The combined occurrence of feathery textures and network-like filamentous textures in quartz samples from the Rusey Fault Zone points to the presence of a metastable silica precursor (i.e., amorphous silica or silica gel) before or during the crystallization.

Soil genesis and mineralogy across a volcanic lithosequence

Lithology is a principle state factor of soil formation, interacting with climate, organisms, topography and time to define pedogenesis. A lithosequence of extrusive igneous lithologies (rhyolite obsidian, dacite, andesite and basalt) was identified in the Clear Lake Volcanic Field in the Coast Range of northern California to determine the effects of lithology on pedogenesis, clay mineralogy and soil physiochemical properties. Based on regional landscape erosion rates (0.2–0.5mmyr−1), the soil residence times for the investigated pedons (~150cm deep) were of the order of 3000 to 7500years indicating that the soils developed under the relatively stable Holocene mesic/xeric climate regime. Soils from all lithologies developed to a similar Xeralf taxonomy with remarkably consistent physiochemical properties. Although total (Fet) and dithionite-citrate extractable (Fed) iron concentrations diverged across lithologies, the degree of weathering as assessed by the Fed/Fet ratio was similar across the lithosequence. In spite of large differences in silica content of the parent materials, the clay mineralogical assemblage of all lithologies was dominated by kaolin minerals (kaolinite and/or halloysite). All pedons displayed an increase in halloysite and the degree of halloysite hydration with increasing depth, except the basalt pedon, which was dominated by kaolinite with only trace halloysite. We attribute this lack of halloysite in the basalt pedon to the lower silica activities associated with this silica-poor lithology. There was a lack of nanocrystalline minerals across all lithologies as inferred from selective dissolution. The dominance of crystalline materials is a function of the xeric soil moisture regime whereby summer soil profile desiccation promotes dehydration and crystallization of metastable nanocrystalline precursors. Further, the pronounced summer dry period results in dehydration of halloysite (1.0nm) to halloysite (0.7nm; also referred to as meta halloysite in some literature), together with transformation to kaolinite, in the upper soil profile. In spite of the relatively young soil residence times of these soils (Holocene age), the effects of lithology persisted only in differences in Fe oxide concentrations (Fed), as well as a lack of significant halloysite in basalt pedons. The overwhelming effect of climate in these highly weatherable parent materials narrowed the trajectory of pedogenesis, resulting in soils from contrasting lithologies converging on kaolin mineralogy, a lack of nanocrystalline constituents, and similar soil physiochemical properties.

Synthesis of Metastable Co4N, Co3N, Co2N, and CoO0.74N0.24 from a Single Azide Precursor and Intermediates in CoBr2 Ammonolysis

Metastable cobalt nitrides Co4N, Co3N, Co2N, and cobalt oxide nitride CoO0.74N0.24 were synthesized by ammonolysis of one single metastable azide precursor, [Co(NH3)5N3]Cl2, in high purity by controlled variation of the reaction conditions (temperature, duration, gas atmosphere, and flow rate). The alternative route towards cobalt nitrides by ammonolysis of CoBr2 proceeds via [Co(NH3)6]Br2 and Co(NH3)2Br2 to exclusively yield Co3N. For Co3N1.1 a complex magnetic behavior is observed: dominating ferromagnetic ordering at low temperatures and a small coercive field of 10 mT. Co2N orders antiferromagnetically below 10 K. Electronic structure calculations [DFT, generalized‐gradient approximation (GGA)+U] on CoO0.75N0.25 reveal that the experimentally observed rock‐salt structure is less stable than the sphalerite‐type polymorph by about 30 kJ mol–1 and possesses an antiferromagnetically ordered ground state.

Effect of pH on Amorphous Calcium Carbonate Structure and Transformation

A number of organisms produce crystalline calcium carbonate via a metastable precursor phase termed amorphous calcium carbonate (ACC). ACC also forms during production of CaCO3 for industrial purposes, e.g., paper manufacturing and synthesis of fillers for polymers. Previous studies suggest that the local structure of ACC controls crystallization kinetics and pathways, i.e., the crystalline polymorph(s) that form(s) in the process. We used pair distribution function (PDF) analysis to provide evidence that the local structure of ACC gradually changes as the pH of the synthesis solutions is increased from 10.6 to 12.7, at ambient conditions. These changes correlate with the mole fraction of incorporated hydroxide ions, which varies gradually from negligible at pH 10.6 to 0.12 at pH 12.7. At lower pH (10.5), vaterite and calcite formed in less than 2 min, but as the pH increased, the lifetime of ACC increased, and it transformed directly to calcite (i.e., no vaterite intermediate). Although higher pH led to ...

Nucleation of FAU and LTA Zeolites from Heterogeneous Aluminosilicate Precursors

The nucleation of many natural, biogenic, and synthetic crystals involves the initial formation of metastable precursors that provides a kinetic pathway for an amorphous-to-crystalline transformation. This nonclassical mechanism is believed to be the dominant crystallization pathway for microporous zeolites. Despite significant research on zeolite growth mechanisms, molecular level details regarding the assembly, physicochemical properties, and structural evolution of amorphous (alumino)silicate precursors remain elusive. Here we use a combination of diffraction, scattering, and microscopy techniques to characterize the amorphous precursors that assemble and evolve during the synthesis of zeolites FAU and LTA – two materials that are widely used in commercial applications such as catalysis, adsorption, separations, and ion-exchange. Nucleation occurs by a two-step mechanism involving the initial formation of aggregates that serve as heterogeneous sites for nucleation. Using colloidal silica as a reagent, ...

Observations of nanocrystalline cubic boron nitride formed with plasma spraying

Cubic boron nitride (c-BN) has superior hardness and strength as compared to other ceramics that are commonly used as abrasives and in cutting tool applications. Cubic BN powders are generally produced under high pressures, usually greater than 10 GPa. Here, we report on the synthesis of nanocrystalline c-BN from metastable precursors without high external pressures using a novel plasma spray processing technique. Transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) measurements indicate that the initial metastable precursor particles are amorphous and comprised of boron, carbon, nitrogen and oxygen with weak interatomic bonding that may easily undergo phase transformations during plasma spraying. Postmortem X-ray diffraction and TEM analysis of plasma spray deposits reveal the formation of crystalline phases of BN, and high-resolution TEM observations demonstrate that c-BN can be induced during the plasma spray process with the addition of appropriate catalysts. These observations point to a novel pathway for facilitating the transition from a low-density amorphous state to the high-density cubic BN phase.

Freeze-drying synthesis of an amorphous Zn2+complex and its transformation to a 2-D coordination framework in the solid state

An amorphous and metastable precursor for a Zn two-dimensional coordination framework was synthesised via freeze drying. The precursor comprises randomly packed discrete clusters of a Zn complex. The amorphous-to-crystalline framework transformation, which was triggered by the gentle application of heat or pressure, was accompanied by a change in the coordination geometry of the Zn(2+) ions from tetrahedral to octahedral symmetry.

Tuning the composition of metastable CoxNiyMg100−x−y(OH)(OCH3) nanoplates for optimizing robust methane dry reforming catalyst

Finding controllable, low-cost, and scalable ways to generate Ni-based catalysts is the bottleneck for methane dry reforming catalyst design. A new method for generating trimetallic CoxNiyMg100−x−yO solid solution platelets enclosed by (111) facets has been developed from the topotactic pyrolysis of the metastable precursor CoxNiyMg100−x−y(OH)(OCH3) derived from solvothermal synthesis. The catalyst composition and reaction conditions have been modulated to achieve maximum coke resistance and catalyst stability. Long-term stability for 1000h time on stream at 800°C has been achieved for the optimized Co0.075Ni7.425Mg92.5O catalyst. The role of Co in the catalyst has been disclosed through kinetic measurements and detailed characterization of the spent catalysts. Co is enriched on the Co–Ni alloy surface under reforming conditions and accelerates the gasification of coke intermediates. Co also enhances the chemisorption of oxygen and reduces the activation energy for methane fragmentation, which is the rate-determining step for the overall reaction.

Energetic Insight into the Formation of Solids from Aluminum Polyoxocations

AbstractThe ε‐Keggin [AlO4Al12(OH)24(H2O)12]7+ ion (AlAl127+) is a metastable precursor in the formation of aluminum oxyhydroxide solids. It also serves as a useful model for the chemistry of aluminous mineral surfaces. Herein we calculate the enthalpies of formation for this aqueous ion and its heterometal‐substituted forms, GaAl127+ and GeAl128+, using solution calorimetry. Rather than measuring the enthalpies of the MAl127/8+ ions directly from solution hydrolysis, we measured the metathesis reaction of the crystallized forms with barium chloride creating an aqueous aluminum solution monospecific in MAl127/8+. Then, the contributions to the heat of formation from the crystallized forms were subtracted using referenced states. When comparing the aqueous AlAl127+ ion to solid aluminum (oxy)‐hydroxide phases, we found that this ion lies closer in energy to solid phases than to aqueous aluminum monomers, thus explaining its role as a precursor to amorphous aluminum hydroxide phases.

Energetic Insight into the Formation of Solids from Aluminum Polyoxocations.

The ε-Keggin [AlO4Al12(OH)24(H2O)12](7+) ion (AlAl12(7+)) is a metastable precursor in the formation of aluminum oxyhydroxide solids. It also serves as a useful model for the chemistry of aluminous mineral surfaces. Herein we calculate the enthalpies of formation for this aqueous ion and its heterometal-substituted forms, GaAl12(7+) and GeAl12(8+), using solution calorimetry. Rather than measuring the enthalpies of the MAl12(7/8+) ions directly from solution hydrolysis, we measured the metathesis reaction of the crystallized forms with barium chloride creating an aqueous aluminum solution monospecific in MAl12(7/8+). Then, the contributions to the heat of formation from the crystallized forms were subtracted using referenced states. When comparing the aqueous AlAl12(7+) ion to solid aluminum (oxy)-hydroxide phases, we found that this ion lies closer in energy to solid phases than to aqueous aluminum monomers, thus explaining its role as a precursor to amorphous aluminum hydroxide phases.

Effect of Mn addition on the thermal stability and magnetic properties of rapidly-quenched L10 FePt alloys

Nano-composite magnets with L10 structure derived from binary FePt alloys and prepared as melt-spun ribbons are of current interest due to their higher operating temperature and the ability to be cast as a two-phase magnet with exchange spring magnetic properties, as both soft and hard magnetic phase may emerge from the same metastable precursor, i.e. the disordered cubic A1 phase. The present paper studies the effect of Mn addition on the thermal stability and phase structure, on the abundance of the hard magnetic phase and relative proportion of the soft ones, on the microstructure of the alloy as a function of temperature and on the overall magnetic properties. The interplay of the various magnetic sublattices in the ordering of the L10 phases as a consequence of introducing antiferromagnetically coupled Mn atoms in the alloy composition is discussed and interpreted in terms of microstructural changes induced by this addition as revealed by high resolution transmission electron microscopy and X-ray diffraction. The temperature evolution of the phase composition and structural parameters is monitored using synchrotron radiation powder diffraction, while the compositional aspects are investigated using proton-induced X-ray emission and energy dispersive X-ray spectroscopy. Magnetic measurements reveal the magnetic parameters of interest (coercivity, remanence, Curie temperature, saturation magnetization), as well as the exchange-coupled two-phase nature of these magnets and provide information that hints at possible spin reorientation transitions in the Mn-containing planes of the L10 superlattice.

Thermal stability, thermal expansion and grain-growth in exchange-coupled Fe–Pt–Ag–B bulk nanocomposite magnets

Rare-earth free (RE-free) exchange coupling nanocomposite magnets are intensively studied nowadays due to their potential use in applications demanding stable high-temperature operation and corrosion resistance. In this respect, the FePt alloy system is one of the most actively addressed potential permanent magnet solutions. In FePt alloys, promising magnetic features arise from the co-existence of hard magnetic L10 FePt and soft magnetic L12 Fe3Pt phases emerged from the same metastable precursor. The present work deals with an in-situ temperature-resolved synchrotron radiation study of the thermal stability, thermal expansion and microstructure evolution in exchange-coupled FePtAgB alloys. The as-cast microstructural state as well as the optimized magnetic behavior are given as reference and correlated to the observed microstructural evolution with temperature. The melt-spun Fe48Pt28Ag6B18 alloy ribbons were examined in situ by synchrotron X-ray powder diffraction from ambient temperature up to 600°C. The FePt–Fe3Pt exchange-coupled microstructure achieved by rapid solidification is not significantly altered during the high temperature exposure. The thermal expansion of the FePt L10 unit cell has been found to be strongly anisotropic, being essentially an in-plane expansion which may be seen as an anisotropic invar effect. For the FePt L10 phase, a significant deviation from linear thermal expansion is observed at the Curie temperature TC=477°C. This non-linear behavior above TC is tentatively linked to a diffusion/segregation mechanism of Ag. The promising hard magnetic properties as well as the direct formation of the L10 phase from the as-cast state are directly related to the presence of Ag in the intergranular regions.

Selective formation of metastable ferrihydrite in the chiton tooth.

Metastable precursors are thought to play a major role in the ability of organisms to create mineralized tissues. Of particular interest are the hard and abrasion-resistant teeth formed by chitons, a class of rock-grazing mollusks. The formation of chiton teeth relies on the precipitation of metastable ferrihydrite (Fh) in an organic scaffold as a precursor to magnetite. In vitro synthesis of Fh under physiological conditions has been challenging. Using a combination of X-ray absorption and electron paramagnetic resonance spectroscopy, we show that, prior to Fh formation in the chiton tooth, iron ions are complexed by the organic matrix. In vitro experiments demonstrate that such complexes facilitate the formation of Fh under physiological conditions. These results indicate that acidic molecules may be integral to controlling Fh formation in the chiton tooth. This biological approach to polymorph selection is not limited to specialized proteins and can be expropriated using simple chemistry.

In situ imaging of silicalite-1 surface growth reveals the mechanism of crystallization.

The growth mechanism of silicalite-1 (MFI zeolite) is juxtaposed between classical models that postulate silica molecules as primary growth units and nonclassical pathways based on the aggregation of metastable silica nanoparticle precursors. Although experimental evidence gathered over the past two decades suggests that precursor attachment is the dominant pathway, direct validation of this hypothesis and the relative roles of molecular and precursor species has remained elusive. We present an in situ study of silicalite-1 crystallization at characteristic synthesis conditions. Using time-resolved atomic force microscopy images, we observed silica precursor attachment to crystal surfaces, followed by concomitant structural rearrangement and three-dimensional growth by accretion of silica molecules. We confirm that silicalite-1 growth occurs via the addition of both silica molecules and precursors, bridging classical and nonclassical mechanisms.

Functional carbon nanosheets prepared from hexayne amphiphile monolayers at room temperature.

Carbon nanostructures that feature two-dimensional extended nanosheets are important components for technological applications such as high-performance composites, lithium-ion storage, photovoltaics and nanoelectronics. Chemical functionalization would render such structures better processable and more suited for tailored applications, but typically this is precluded by the high temperatures needed to prepare the nanosheets. Here, we report direct access to functional carbon nanosheets of uniform thickness at room temperature. We used amphiphiles that contain hexayne segments as metastable carbon precursors and self-assembled these into ordered monolayers at the air/water interface. Subsequent carbonization by ultraviolet irradiation in ambient conditions resulted in the quantitative carbonization of the hexayne sublayer. Carbon nanosheets prepared in this way retained their surface functionalization and featured an sp(2)-rich amorphous carbon structure comparable to that usually obtained on annealing above 800 °C. Moreover, they exhibited a molecularly defined thickness of 1.9 nm, were mechanically self-supporting over several micrometres and had macroscopic lateral dimensions on the order of centimetres.

Designed synthesis of hydroxyapatite nanostructures: bullet-like single crystal and whiskered hollow ellipsoid

Hydroxyapatite (HAp) nanostructures of whiskered hollow ellipsoid and bullet-like single crystal were synthesized under mild reaction conditions by using a template-free "one pot" synthetic method. Immersing calcium carbonate precursor into ammonium phosphate solution resulted in the HAp phase. Formed HAp crystals were characterized by X-ray diffraction and transmission electron microscopy techniques. The stability and phase composition of calcium carbonate influenced the morphology and crystallinity of HAp. The transformation of the most stable calcite precursor yielded the bullet-like HAp single crystal of 300-600 nm in length, ~40 nm in tip diameter and ~80 to ~100 nm in bottom diameter. The metastable vaterite precursor showed the formation of the whiskered hollow ellipsoid nanostructures composed of HAp nanorods of ~10 nm in diameter. The driving force for the whole transformation process was the difference in solubility of calcium carbonate and HAp. At the same time, Kirkendall effect and Ostwald ripening played important roles in the formation of the different HAp nanostructures.

Preparation of magnesium phosphate cement by recycling the product of thermal transformation of asbestos containing wastes

Asbestos containing wastes have been employed for the first time in the formulation of magnesium phosphate cements. Two samples were mixed with magnesium carbonate and calcined at 1100 and 1300°C. Under these conditions, complete destruction of asbestos minerals is known to occur. The product, containing MgO, after reaction with water-soluble potassium di-hydrogen phosphate, led to the formation of hydrated phases at room temperature. Crystalline and amorphous reaction products were detected, with the latter being likely the metastable precursor of the former. Measured strengths were found to be in line with data from the literature, suggesting that this material may be used as cement. The process here described represents a viable recycling opportunity for this class of hazardous wastes. Simultaneous destruction of asbestos minerals and formation of reactive MgO during thermal treatment, bring benefits in terms of energy requirements and preservation of natural resources in cement manufacturing.