Evidence for liquid-liquid phase separation during the early stages of Mg-struvite formation

We thank BAM and Helmholtz-Zentrum Berlin (HZB) for providing us with the beamtime at mySpot of BESSY II.The supplementary material document file contains the following items: Fig. S1. The time-resolved pH curve from the struvite precipitation reaction [Eq. (1)] combined with PHREEQC calculated equilibrated pH; Fig. S2. Cryo-TEM bright-field imaging from the reactant solution sampled after 5 s after mixing without any post-processing. Fig. S3. Sketch of the flow-through setup used for the scattering experiments; Supporting Note 1: We derive how the OZ correlation length compares with an equivalent radius of a sphere. We also include input (MgStruvite_01_input.pqi) and output (MgStruvite_output.pqo) files from PHREEQC 3, which contain information about the predicted speciation at equilibrium following the reaction from Eq. (1). These are regular text files and are human-readable.The precipitation of struvite, a magnesium ammonium phosphate hexahydrate (MgNH4PO4 · 6H2O) mineral, from wastewater is a promising method for recovering phosphorous. While this process is commonly used in engineered environments, our understanding of the underlying mechanisms responsible for the formation of struvite crystals remains limited. Specifically, indirect evidence suggests the involvement of an amorphous precursor and the occurrence of multi-step processes in struvite formation, which would indicate non-classical paths of nucleation and crystallization. In this study, we use synchrotron-based in situ x-ray scattering complemented by cryogenic transmission electron microscopy to obtain new insights from the earliest stages of struvite formation. The holistic scattering data captured the structure of an entire assembly in a time-resolved manner. The structural features comprise the aqueous medium, the growing struvite crystals, and any potential heterogeneities or complex entities. By analysing the scattering data, we found that the onset of crystallization causes a perturbation in the structure of the surrounding aqueous medium. This perturbation is characterized by the occurrence and evolution of Ornstein-Zernike fluctuations on a scale of about 1 nm, suggesting a non-classical nature of the system. We interpret this phenomenon as a liquid-liquid phase separation, which gives rise to the formation of the amorphous precursor phase preceding actual crystal growth of struvite. Our microscopy results confirm that the formation of Mg-struvite includes a short-lived amorphous phase, lasting >10 s.Helmholtz-Zentrum für Umweltforschung UF

High-Temperature Oxidation in Dry and Humid Atmospheres of the Equiatomic CrMnFeCoNi and CrCoNi High- and Medium-Entropy Alloys

Surface degradation phenomena of two model equiatomic alloys from the CrMnFeCoNi alloy system were investigated in 2% O-2 and 10% H2O (p(O2) = 0.02 and 10(-7) atm, respectively) at 800 degrees C for times up to 96 h. The crystallographic structures, morphologies, and chemical compositions of the corrosion layers developing on CrMnFeCoNi and CrCoNi were comparatively analyzed by mass gain analysis, X-ray diffraction, and scanning electron microscopy combined with energy-dispersive X-ray spectroscopy and electron backscatter diffraction. The oxidation resistance of CrMnFeCoNi is relatively poor due to the fast growth of porous Mn-oxide(s). CrCoNi forms an external chromia layer that is dense and continuous in a dry 2% O-2 atmosphere. This layer buckles and spalls off after exposure to 10% H2O atmosphere. Beneath the chromia layer, a Cr-depleted zone forms in the CrCoNi alloy in both environments. As the oxide scale spalls off in the H2O-containing atmosphere, a secondary chromia layer was observed and correspondingly enlarges the Cr-depleted zone. In contrast, as the chromia layer remains without significant spallation when CrCoNi is exposed to a dry oxidizing atmosphere, the region depleted in Cr is narrower

Synthesis of transition metal phosphate compounds as functional materials

In den letzten Jahrzehnten ist die Rückgewinnung wichtiger Elemente aus Abfallströmen wie Abwässern, Schlämmen und Abraum. Übermäßiger Bergbau, industrielle Prozesse und Überdüngung in der Landwirtschaft setzen Schadstoffe wie Phosphat, Ammonium und Übergangsmetalle in die Umwelt frei und bringen Ökosysteme aus dem Gleichgewicht. In dieser Dissertation wird die Kristallisation von Übergangsmetallphosphatverbindungen (TMPs) aus wässrigen Lösungen untersucht, darunter M-Struvit, M-Dittmarit und M-Phosphat-Octahydrat (NH4MPO4∙6H2O, NH4MPO4∙H2O, M3(PO4)2∙8H2O mit M = Ni, Co, NixCo1-x). Diese kristallinen Phasen ermöglichen die gemeinsame Ausfällung von PO43-, NH4+ und Übergangsmetallen und bieten einen vielversprechenden Weg zur Rückgewinnung von Phosphat und Übergangsmetallen aus industriellen und landwirtschaftlichen Abwässern. TMPs besitzen vielseitige Eigenschaften wie thermische und mechanische Stabilität, einfache Veränderlichkeit und Multifunktionalität, wodurch sie sich für fortschrittliche Energieumwandlungs- und -speicheranwendungen eignen. Deshalb stellt die Synthese von TMPs eine kombinierte Rückgewinnungs- und Upcycling-Methode für fortschrittliche Funktionsmaterialien dar. Detaillierte Untersuchungen des Bildungsprozesses aus wässriger Lösung wurden mit zeitaufgelösten ex- und in-situ-Elektronenbildern, spektroskopischen, spektrometrischen und beugungsbasierten Methoden durchgeführt. Die in dieser Dissertation enthaltenen Ergebnisse geben neue Einblicke in den nicht klassischen Kristallisationsmechanismus von TMPs, der eine kontrollierte Einstellung der Kristallitgröße und -morphologie ermöglicht. Darüber hinaus führt die thermische Behandlung von TMPs zu thermisch stabilen, mesoporösen und/oder protonenleitenden Materialien für elektrochemische Anwendungen. Die Ergebnisse tragen zum grundlegenden Verständnis von Keimbildung und Kristallisationsphänomenen bei und helfen bei der Entwicklung moderner Funktionsmaterialien für elektrochemische Anwendungen.A critical issue in the 21st century is the recovery of essential elements from waste streams like wastewaters, sludges, and tailings. Excessive mining, industrial processes, and overfertilization in agriculture release pollutants such as phosphate, ammonium, and transition metals into the environment, unbalancing ecosystems. This dissertation investigates the crystallization of transition metal phosphate (TMPs) compounds from aqueous solutions, including M-struvite, M-dittmarite, and M-phosphate octahydrate (NH4MPO4∙6H2O, NH4MPO4∙H2O, M3(PO4)2∙8H2O with M = Ni, Co, NixCo1-x). These crystalline phases allow for the co-precipitation of PO43-, NH4+, and transition metals, providing a promising route for phosphate and transition metal recovery from industrial and agricultural wastewaters. TMPs possess favorable properties like thermal and mechanical stability, tunability, and multifunctionality, making them suitable for advanced energy conversion and storage applications. Accordingly, the synthesis of TMPs represents a combined recovery and upcycling method towards advanced functional materials. Detailed investigations of the formation process from aqueous solution were carried out using time-resolved ex- and in-situ, electron imaging, spectroscopic, spectrometric, and diffraction-based techniques. The results contained in this dissertation reveal new insights into the non-classical crystallization mechanism of TMPs, allowing for controlled adjustment of crystallite size and morphology. Moreover, thermal treatment of TMPs compounds yields thermally stable, mesoporous, and/or proton-conductive materials for electrochemical applications. The findings, on the one hand, can contribute to the fundamental understanding of nucleation and crystallization phenomena in aqueous solutions in general and specifically for metal phosphates. On the other hand, my findings aid applied materials chemistry in the development of advanced functional materials for electrochemical uses

Ni- and Co-struvites: Revealing crystallization mechanisms and crystal engineering towards applicational use of transition metal phosphates

Industrial and agricultural waste streams, which contain high concentrations of NH4+, PO43- and transition metals are environmentally harmful and toxic pollutants. At the same time phosphorous and transition metals constitute highly valuable resources. Typically, separate pathways have been considered to extract hazardous transition metals or phosphate, independently from each other. Investigations on the simultaneous removal of multiple components have been studied only to a limited extent. Here, we report the synthesis routes for Co- and Ni-struvites (NH4MPO4.6H2O, M = Ni2+, Co2+ ), which allow for P, ammonia and metal co precipitation. By evaluating different reaction parameters, the phase and stability of transition metal struvites, as well as their crystal morphologies, and sizes could be optimized. Ni-struvite is stable in a wide reactant concentration range and at different metal/phosphorus (M/P) ratios, whereas Co-struvite only forms at low M/P ratios. Detailed investigations of the precipitation process using ex situ and in situ techniques provided insights into the crystallization mechanisms/crystal engineering of these materials. M-struvites crystallize via intermediate colloidal nanophases, which subsequently aggregate and condense to final crystals after extended reaction times. However, the exact reaction kinetics of the formation of a final crystalline product varies significantly depending on the metal cation involved in the precipitation process: several seconds (Mg) to minutes (Ni) to hours (Co). The achieved level of control over the morphology and size, makes precipitation of metal struvites a promising method for direct metal recovery and binding them in the form of valuable phosphate raw materials. Under this paradigm, the crystals can be potentially upcycled as precursor powders for electrochemical applications, which require transition metal phosphates (TMPs).Comment: Main manuscript 22 pages, SI 27 page

Non-classical crystallization pathway of transition metal phosphate compounds

Here, we elucidate non-classical multistep crystallization pathways of transition metal phosphates from aqueous solutions. We followed precipitation processes of M-struvites, NH4MPO4∙6H2O, and M-phosphate octahydrates, M3(PO4)2∙8H2O, where M = Ni, Co, NixCo1-x by using in-situ scattering and spectroscopy-based techniques, supported by elemental mass spectrometry analyses and advanced electron microscopy. Ni- and Co-phosphates crystallize via intermediate colloidal amorphous nanophases which subsequently change their complex structures while agglomerating, condensing, and densifying throughout the extended reaction times. We reconstructed the three-dimensional morphology of these precursors by employing cryo-electron tomography (cryo-ET). We found that the complex interplay between metastable amorphous colloids and proto-crystalline units determines the reaction pathways. Ultimately, the same crystalline structure, such as struvite, is formed. However, the multistep process stages vary in complexity and can last from a few minutes to several hours depending on the selected transition metal(s), their concentration, and the Ni:Co ratio

Template-free synthesis of mesoporous and amorphous transition metal phosphate materials

We present how mesoporosity can be engineered in transition metal phosphate (TMPs) materials in a template-free manner. The method involves a transformation of a precursor metal phosphate phase, M-struvite (NH4MPO4·6H2O, M = Mg2+, Ni2+, Co2+, Nix2+Co1-x2+), and it relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneously mesoporous phase, which forms while degassing of NH3 and H2O from crystals. The temporal evolution of mesoporous frameworks and the response of the metal coordination environment were followed with in-situ and ex-situ scattering and diffraction, as well as X -ray spectroscopy. Despite sharing the same precursor struvite structure, different amorphous and mesoporous structures were obtained. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions depending on a metal cation present in the analogous M-struvites. The amorphous structures of thermally decomposed Mg-, Ni- and NixCo1-x-struvites exhibit high surface areas and pore volumes (240 m²g-1 and 0.32 cm-3 g-1 for Mg and 90 m²g-1 and 0.13 cm-3 g-1 for Ni). We propose that the low-cost, environmentally friendly M-struvites could be obtained as recycling products from industrial and agricultural wastewaters. These waste products could be then upcycled into mesoporous TMPs through a simple thermal treatment for further applications, for instance, in in (electro)catalysis

Thermally processed Ni-and Co-struvites as functional materials for proton conductivity

Here, we describe how to synthesise proton-conductive transition metal phosphates (TMPs) by direct thermal processing of precursor M-struvites, NH4MPO4·6H2O, with M = Ni2+, Co2+. In the as-derived TMP phases their thermal history and bulk proton conductivity were linked with the structural information about the metal coordination, phosphate groups, and volatile compounds. These aspects were investigated with vibrational and synchrotron-based spectroscopic methods (FT-IR, FT-RS, XAS). We elucidated the structures of amorphous and crystalline Ni- and Co phosphate phases in association with different coordination changes and distortion degrees of the metal polyhedra as they developed upon heating. Ni-struvite transformed to a stable amorphous phase over a broad range of temperatures (90 °C 10−4 S cm−1 at room temperature. Even at low humidity, these values are comparable with those found for Nafion, MOFs, some perovskites or composite materials. Coprecipitation of phosphates and transition metal cations in the form of struvite is potentially a viable method to extract these elements from wastewater. Thus, we propose that recycled M-struvites could be potentially further directly upcycled into crystalline and amorphous TMPs useful for electrochemical applications

Solution-driven processing of calcium sulfate: the mechanism of the reversible transformation of gypsum to bassanite in brines

Here, we show that calcium sulfate dihydrate (gypsum) can be directly, rapidly and reversibly converted to calcium sulfate hemihydrate (bassanite) in high salinity solutions (brines). The optimum conditions for the efficient production of bassanite in a short time ( 4 M and maintaining a temperature, T > 80 °C. When the solution containing bassanite crystals is cooled down to around room temperature, eventually gypsum is formed. When the temperature is raised again to T > 80 °C, bassanite is rapidly re-precipitated. This contrasts with the typical behaviour of the bassanite phase in low salt environments. Traditionally, hemihydrate is obtained from gypsum through a solid state thermal treatment at 150 °C 4 M, and T > 80 °C gypsum becomes readily more soluble than bassanite, which induces the direct precipitation of the latter from gypsum. The fact that these transformations are controlled by the solution provides extensive opportunities for precise manipulation of crystal formation. Our experiments confirmed that bassanite remained the sole crystalline structure for many hours before reverting into gypsum. This property is extremely advantageous for practical processing and efficient crystal extraction in industrial scenarios

Evidence for liquid-liquid phase separation during the early stages of Mg-struvite formation

The precipitation of struvite, a magnesium ammonium phosphate hexahydrate (MgNH4PO4⋅6H2O) mineral, from wastewater is a promising method for recovering phosphorous. While this process is commonly used in engineered environments, our understanding of the underlying mechanisms responsible for the formation of struvite crystals remains limited. Specifically, indirect evidence suggests the involvement of an amorphous precursor and the occurrence of multi-step processes in struvite formation, which would indicate non-classical paths of nucleation and crystallization. In this study, we use synchrotron-based in situ X-ray scattering complemented by cryogenic transmission electron microscopy to obtain new insights from the earliest stages of struvite formation. The holistic scattering data captured the structure of an entire assembly in a time-resolved manner. The structural features comprise the aqueous medium, the growing struvite crystals, and any potential heterogeneities or complex entities. By analysing the scattering data, we found that the onset of crystallization causes a perturbation in the structure of the surrounding aqueous medium. This perturbation is characterized by the occurrence and evolution of Ornstein-Zernike fluctuations on a scale of about 1 nm, suggesting a non-classical nature of the system. We interpret this phenomenon as a liquid-liquid phase separation (LLPS), which gives rise to the formation of the amorphous precursor phase preceding actual crystal growth of struvite. Our microscopy results confirm that the formation of Mg-struvite includes a short-lived amorphous phase, lasting >10 seconds

Template-free synthesis of mesoporous and amorphous transition metal phosphate materials

We present how mesoporosity can be engineered in transition metal phosphate (TMPs) materials in a template-free manner. The method involves the transformation of a precursor metal phosphate phase, called M-struvite (NH4MPO4·6H2O, M = Mg2+, Ni2+, Co2+, NixCo1−x2+). It relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneously mesoporous phase, which forms during degassing of NH3 and H2O. The temporal evolution of mesoporous frameworks and the response of the metal coordination environment were followed by in situ and ex situ scattering and diffraction, as well as X-ray spectroscopy. Despite sharing the same precursor struvite structure, different amorphous and mesoporous structures were obtained depending on the involved transition metal. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions depending on the metal cation present in the analogous M-struvites. The amorphous structures of thermally decomposed Mg-, Ni- and NixCo1−x-struvites exhibit high surface areas and pore volumes (240 m2 g−1 and 0.32 cm−3 g−1 for Mg and 90 m2 g−1 and 0.13 cm−3 g−1 for Ni). We propose that the low-cost, environmentally friendly M-struvites could be obtained as recycling products from industrial and agricultural wastewaters. These waste products could be then upcycled into mesoporous TMPs through a simple thermal treatment for further application, for instance in (electro)catalysis