Precursor Phase Research Articles

Exploring Biomineralization Processes Using In Situ Liquid Transmission Electron Microscopy: A Review.

Liquid transmission electron microscopy (TEM) is a newly established technique broadly used to study reactions in situ. Since its emergence, complex and multifaceted biomineralization processes have been revealed with real-time resolution, where classical and non-classical mineralization pathways have been dynamically observed primarily for Ca and Fe-based mineral systems in situ. For years, classical crystallization pathways have dominated theories on biomineralization progression despite observations of non-traditional routes involving precursor phases using traditional- and cryo-TEM. The new dynamic lens provided by liquid TEM is a key correlate to techniques limited to time-stamped, static observations - helping shift paradigms in biomineralization toward non-classical theories with dynamic mechanistic visualization. Liquid TEM provides new insights into fundamental biomineralization processes and essential physiological and pathological processes for a wide range of organisms. This review critically reviews a summary of recent in situ liquid TEM research related to the biomineralization field. Key liquid TEM preparation and imaging parameters are provided as a foundation for researchers while technical challenges are discussed. In future, the expansion of liquid TEM research in the biomineralization field will lead to transformative discoveries, providing complementary dynamic insights into biological systems.

A room temperature chemical process for homogeneous mixing of precursor phases for low temperature tetracalcium phoshate preparation

The aim of this study was to prepare phase pure tetracalcium phosphate (TTCP) from the precursor phase mixtures homogeneous at the nano/microscale level at lower heat treatment temperatures in much shorter dwell times.Two different precursor powder mixtures were prepared by reacting CaCO3 with H3PO4 in ethanol or water. The resultant precursor powder mixtures were heat treated at temperatures in the 1200–1350 °C range for 2 and 5 h. Phase structures of the powders were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) and Raman spectroscopy analysis. Scanning electron microscopy (SEM) was used for the investigation of powder particle sizes and morphology. Powders synthesized by the heat treatment of both of the starting powder mixtures prepared in ethanol or water with 2 and 5 h of dwell times at 1350 °C were determined to be phase pure TTCP. SEM analysis along with the phase identification showed that the precursor powder prepared in ethanol had micron sized plates formed by aggregation of sub-micron sized thin CaHPO4 plates covering CaCO3 particles. The precursor powder prepared in water contained large aggregates of sub-micron sized CaCO3 particles whose surface was covered by precipitated nano-sized hydroxyapatite. TTCP powders were composed of large irregularly shaped particles formed by sintering of smaller equiaxed grains. Average grain and particles sizes of the TTCP powders synthesized from the precursor powder prepared in ethanol were 3.2–3.9 and 8.1–8.4 μm, respectively. Average grain and particle sizes of the TTCP powders synthesized from the precursor powder prepared in water however were measured to be 3.3–5.1 and 11.2–11.6 μm, respectively.The TTCP preparation method presented in this study provides homogeneous and well-mixed precursor powders prepared from cheap and commonly available precursors without milling and decreases the heat treatment time to 2 h at 1350 °C.

The Cahn–Hilliard model of coherent lamellar microstructure: application to alkali feldspar

The temporal evolution of coherent lamellar microstructures is significantly influenced by their elastic properties, particularly when the exsolved phases are coherent. This research utilizes the Cahn–Hilliard model to examine the morphological and energetic evolution of binary alkali feldspar, integrating anisotropic elastic energy into the Gibbs energy equation. The Cahn–Hilliard model successfully simulated the orientation of lamellae observed in natural samples and the elastic strain was consistent with previous research. We also computed the coherent solvus from the annealing simulation of various precursor compositions and temperatures. The temperature difference (ΔT\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Delta T$$\\end{document}) between the strain-free solvus and the coherent solvus was ΔT=85∘C\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Delta T = 85\\,{}^\\circ \ ext {C}$$\\end{document}, which is slightly lower than previously reported values obtained from similar parameters. This discrepancy is likely due to the presence of non-planar lamellae at the onset of phase separation, which are more stable than planar ones. We also simulated the binodal curves of the coherent solvi for different precursor phase compositions. The computed solvi were not unique but varied depending on the precursor composition. Our model is flexible because it does not assume any specific shapes for the lamellar interfaces and is applicable to various coherent binary systems.

Seeding as a Decisive Tool for Increasing Space-Time-Yields in the Preparation of High-Quality Cu/ZnO/ZrO2 Catalysts

Aging is one of the key steps in the preparation of highly active Cu/ZnO-based catalysts for use in the production of methanol. If certain pH and temperature specifications are met, an initially amorphous precipitate transforms into the crystalline precursor phase of zincian malachite, which is characterized by a periodic arrangement of Cu and Zn atoms and has proven advantageous for the quality of the final catalyst. However, aging generally takes between 30 min and multiple hours until the desired phase transformation is completed. With our study, we show that aging can be significantly accelerated by seeding the freshly precipitated suspension with already aged zincian malachite crystals: the necessary aging time was reduced by 41% for seeding mass fractions as low as 3 wt.% and from 83 min to less than 2 min for 30 wt.% seeds. No negative influence of seeding on the phase composition, specific surface area, molar metal ratios, or the morphology of the aged precursor could be identified. Consequently, the catalyst performance in the synthesis of methanol from CO2, as well as from a CO/CO2 mixture, was identical to a catalyst from an unseeded preparation and showed small advantages compared to a commercial sample. Thus, we conclude that seeding is a vital tool to accelerate the preparation of all Cu/Zn-based catalysts while maintaining product quality, presumably also on an industrial scale.

The roles of amorphous phase on Ca–Mg carbonate mineralization under the action of bacteria and EPS

Amorphous Ca–Mg carbonate (ACMC) is an important precursor phase of carbonate, and it is of great significance for understanding the process of microbial induced carbonate mineralization and the synthesis of new biomimetic mineral materials. Currently, the biomineralization role of ACMC remains controversial. Therefore, this study conducted experiments on ACMC-induced mineralization under the action of bacteria and their extracellular polymeric substances (EPS). The results show that bacteria and their secretion of EPS contributed to the formation and stability of hydrated Mg-rich ACMC, and affected the polymorphism and morphology of minerals. Bacterial cells and EPS could provide nucleation sites for ACMC precipitation, and they could also be easily adsorbed or encapsulated by ACMC and mineral particles. EPS, Mg2+, or both were conducive to the formation of aqueous amorphous phase, and could stabilize ACMC through surface adsorption and incorporation. The results of this study help to reveal the biomineralization role of ACMC and promote understanding of the formation and transformation process of Ca-Mg carbonate.

Antibody persistence and safety of a live-attenuated chikungunya virus vaccine up to 2 years after single-dose administration in adults in the USA: a single-arm, multicentre, phase 3b study

Chikungunya virus infection can lead to long-term debilitating symptoms. A precursor phase 3 clinical study showed high seroprotection (defined as a 50% plaque reduction of chikungunya virus-specific neutralising antibodies on a micro plaque reduction neutralisation test [μPRNT] titre of ≥150 in baseline seronegative participants) up to 6 months after a single vaccination of the chikungunya virus vaccine VLA1553 (Valneva Austria, Vienna, Austria) and a good safety profile. Here we report antibody persistence and safety up to 2 years. In this single-arm, multicentre, phase 3b study, we recruited participants from the precursor phase 3 trial from professional vaccine trial sites in the USA. Participants (aged ≥18 years) were eligible if they had completed the previous study and received VLA1553. Chikungunya virus-specific neutralising antibodies were evaluated at 28 days, 6 months, and 1 year and 2 years after vaccination. The primary outcome was the proportion of seroprotected participants (ie, μPRNT50 titre of ≥150) at 1 and 2 years, assessed in all eligible participants who had at least one post-vaccination immunogenicity sample available, overall and by age group at the time of vaccination (18-64 years and ≥65 years). Adverse events of special interest at the time of transition from the previous study to the current study (ie, at 6 months) and serious adverse events during the current study were recorded (ie, between 6 months and 2 years). All analyses were descriptive. This study is registered with ClinicalTrials.gov, NCT04838444, and immunogenicity follow-up is ongoing. In the precursor study, participants were screened between Sept 17, 2020, and April 10, 2021; data cutoff for this analysis was March 31, 2023. Of 2724 participants in the precursor study who received one dose of VLA1553, 363 participants were analysed in this study (310 [85%] aged 18-64 years and 53 [15%] aged ≥65 years at enrolment in the precursor study; mean age 47·7 years [SD 14·2], 207 [57%] of 363 participants were female, 156 [43%] were male, 280 [77%] were White, and 314 [87%] were not Hispanic or Latino). Strong seroprotection was observed at 1 year (98·9% [356 of 360 assessable participants; 97·2-99·7]) and 2 years (96·8% [306 of 316; 94·3-98·5]) after vaccination, and was very similar between those aged 18-64 years (at 1 year: 98·7% [303 of 307; 96·7-99·6]; at 2 years: 96·6% [256 of 265; 93·7-98·4]) and those aged 65 years and older (at 1 year: 100% [53 of 53; 93·3-100]; at 2 years: 98·0% [50 of 51; 89·6-100]) at each timepoint. No adverse events of special interest were ongoing at the time of transition. Ten serious adverse events occurred in nine (2%) participants between the 6-month and 2-year timepoints, including one death (due to drug overdose) that was determined to not be related to VLA1553. After a single VLA1553 vaccination, chikungunya virus-neutralising antibodies above the threshold considered to be protective persisted up to 2 years and there were no long-term serious adverse events related to vaccination. VLA1553 is an efficient and safe intervention that offers high seroprotection against chikungunya virus infection, a virus likely to spread globally with an urgent demand for long-lasting prophylaxis. Valneva Austria, Coalition for Epidemic Preparedness Innovation, and EU Horizon 2020.

Fabricating Ion Sieves by 3D Printing for Selective Lithium Adsorption from Brines

AbstractThis work presents the formation of a stable 3D monolith based on manganese oxide for the adsorption of lithium from brine. The precursor phase was prepared by microwave‐assisted hydrothermal synthesis and a subsequent calcination process to achieve the desired crystalline phase LiMn2O4. The monolith was formed using additive manufacturing, which allowed its size and shape to be controlled. Subsequently, this monolith was washed with a HCl solution to generate adsorption sites for lithium. The prepared materials were characterized by XRD, FTIR, TGA, N2 physisorption, and SEM‐EDS. Analysis confirmed that the 3D monolith retained its crystalline structure throughout the process. The kinetic characteristics of the adsorption process were evaluated using pseudo‐first and pseudo‐second order equations, as well as Freundlich and Langmuir equations, to describe thermodynamic equilibrium. Monoliths were able to capture lithium up to 13.84 mg/g and the Freundlich equation described the equilibrium (R2=0.9751), while the second‐order equation better described the kinetic behavior (R2=0.9130). Results showed that monoliths are selective towards lithium in the presence of competing cations. The stability of the materials was evaluated in adsorption‐desorption cycles, demonstrating a competitive reuse after five cycles. This research presents a promising new approach for developing efficient lithium extraction methods from brine.

Effect of Active Phase Precursor on Structural, Textural and Catalytic Properties of the Model NiOx/CeO2 System Active in Dry Reforming of Methane

The current paper is devoted to the synthesis of ceria-supported nickel-based catalysts starting from different precursors of the nickel active phase. Thermal decomposition of metal-containing precursors, deposited onto stable supports by dry impregnation, belongs to the industrially preferred, simple ways of catalyst preparation. The synthesized series of NiOx/CeO2 catalysts have been tested in dry methane reforming (DMR), in which two greenhouse gases, i.e., CO2 and CH4, are simultaneously converted into syngas. Both reaction progress and stability of the catalyst strongly depend on nickel speciation, which in turn can be determined by the nature of the chosen precursor. Contrary to relatively many studies focused on the importance of synthetic methods and conditions on nickel speciation, the effect of precursor nature on structural, textural, and functional properties of catalytic systems has neither been discussed much nor fully understood. The main goal of this paper was to elucidate the effect of precursors on the properties of NiOx/CeO2. Consequences of the use of various nickel precursors (simple inorganic salts, organometallic complexes, and chelates) have been analyzed in detail from the viewpoint of their beneficial influence on the catalytic performance of NiOx/CeO2 system (containing 3 wt. % of Ni) tested in DMR.

Ion association behaviors in the initial stage of calcium carbonate formation: An ab initio study

In this work, we performed static density functional theory calculations and ab initio metadynamics simulations to systematically investigate the association mechanisms and dynamic structures of four kinds of ion pairs that could be formed before the nucleation of CaCO3. For Ca2+–HCO3− and Ca2+–CO32− pairs, the arrangement of ligands around Ca2+ evolves between the six-coordinated octahedral structure and the seven-coordinated pentagonal bipyramidal structure. The formation of ion pairs follows an associative ligand substitution mechanism. Compared with HCO3−, CO32− exhibits a stronger affinity to Ca2+, leading to the formation of a more stable precursor phase in the prenucleation stage, which promotes the subsequent CaCO3 nucleation. In alkaline environments, excessive OH− ions decrease the coordination preference of Ca2+. In this case, the formation of Ca(OH)+–CO32− and Ca(OH)2–CO32− pairs favors the dissociative ligand substitution mechanism. The inhibiting effects of OH− ion on the CaCO3 association can be interpreted from two aspects, i.e., (1) OH− neutralizes positive charges on Ca2+, decreases the electrostatic interactions between Ca2+ and CO32−, and thus hinders the formation of the CaCO3 monomer, and (2) OH− decreases the capacity of Ca2+ for accommodating O, making it easier to separate Ca2+ and CO32− ions. Our findings on the ion association behaviors in the initial stage of CaCO3 formation not only help scientists evaluate the impact of ocean acidification on biomineralization but also provide theoretical support for the discovery and development of more effective approaches to manage undesirable scaling issues.

Superconductivity in Freestanding Infinite-Layer Nickelate Membranes.

The observation of superconductivity in infinite-layer nickelates has attracted significant attention due to its potential as a new platform for exploring high-Tc superconductivity. However, thus far, superconductivity has only been observed in epitaxial thin films, which limits the manipulation capabilities and modulation methods compared to two-dimensional exfoliated materials. Given the exceptionally giant strain tunability and stacking capability of freestanding membranes, separating superconducting nickelates from the as-grown substrate is a novel way to engineer the superconductivity and uncover the underlying physics. Herein, this work reports the synthesis of the superconducting freestanding La0.8Sr0.2NiO2 membranes ( ), emphasizing the crucial roles of the interface engineering in the precursor phase film growth and the quick transfer process in achieving superconductivity. This work offers a new versatile platform for investigating superconductivity in nickelates, such as the pairing symmetry via constructing Josephson tunneling junctions and higher Tc values via high-pressure experiments.

The key role of water on the transformation of the precursors to nano-crystalline C–S–H

The mechanism of multi-step nucleation, which means that a precursor phase exists before the formation of the final crystal, has undergone significant development as an advanced strategy for the production of high-performance structural materials and the mitigation of carbon emissions. This study investigated the potential transformation of C–S–H precursors in water, 98 % RH, and high-temperature environments. The findings suggest that C–S–H precursors, produced by disrupting the two-step nucleation process, can transform in both aqueous and 98%RH conditions, while high temperature alone is insufficient to induce the transformation. The progress of the transformation under 98%RH was impeded by the limited mass transport resulting from the constrained formation of nano-crystalline C–S–H in adsorbed water on the external surface and the pores. This study emphasizes the crucial role of water in facilitating the transformation process, presenting potential opportunities for the nanoengineering of C–S–H-based composites and cementitious materials.

Exploring the role of surface and porosity in CO2 capture by CaO-based adsorbents through response surface methodology (RSM) and artificial neural networks (ANN)

In this study, synthetic CaCO3 materials were utilized as precursors for CaO-based CO2 sorbents. The investigation examined how various operating parameters—such as synthesis temperature (ST), stirring rate (SR), and surfactant percentage (SP)—impact the properties of the adsorbents. Samples were firstly characterized by X-ray diffraction and Scanning Electron Microscopy (SEM), which revealed that the prevalence of calcite or aragonite crystal phases in the synthetic CaCO3 precursors can be tuned by adequately choosing the dose of surfactant (Triton-X100®), so that it can be used as a crystal habit and growth modifier. The calcination process applied to the CaCO3 precursors leads to the formation of partially sinterized cubic crystals of CaO, accompanied by minor quantities (< 5 %) of additional compounds like Ca(OH)2 or CaSO4. Specific surface area (SBET) and porosity were determined by measuring the N2 adsorption isotherms. A CaCO3 sample with an unprecedented value of SBET as large as 116 m2/g was prepared operating under optimal conditions. SBET and pore volumes were successfully correlated with the CO2 uptake capacity of the samples. SBET is more influential for experiments carried out under diluted CO2 atmosphere. When pure CO2 is used, the influence of meso- and micropore volumes (Vme and Vmi) is clearly predominant, which suggests that in this latter case diffusion through the porous texture of the samples plays a more remarkable role. A double-way approach through Response Surface Methodology (RSM) and the use of Artificial Neural Networks (ANNs) has been used to analyze the CO2 uptake capacity of the samples. Within the operational interval, excellent results were obtained for pure and diluted CO2 flow, and RSM and ANNs have demonstrated to be a very efficient tool to correlate the behavior of the CaO-based materials as CO2 sorbents with the surface area and pore volumes of the samples. Valuable information on (i) the importance of the different factors under study; (ii) their influence on the surface and porosity of the CaO-derived sorbents; and (iii) the subsequent CO2 capture performance of the sorbents has been obtained. The results suggest that four parameters have a statistically significant influence on CO2 uptake. These parameters are SR, the square of SR, its interaction with SP, and the square of SP. Additionally, the study assessed the stability of the CaO-based sorbents over 11 consecutive calcination-carbonation cycles. By adequately choosing the synthesis strategy and conditions, an almost negligible shrinkage effect can be achieved, resulting in a more sustained uptake capacity throughout the cycles.

Strip Casting of Sm2TM17-Type Alloys for Production of the Metastable SmTM7 Phase

Conventional book casting of Sm2TM17-type alloys (where TM = Co, Fe, Cu, Zr) leads to a coarse, highly segregated microstructure, predominantly due to the slow, variable cooling rate from the mould surface towards the centre of the ingot. These cast alloys require a long homogenisation treatment to remove this segregation and develop a super-saturated, metastable SmTM7-type hexagonal phase. This SmTM7 phase is a vital precursor phase required during magnet production to develop the complex cellular structure responsible for high magnetic properties. In this work, strip casting was employed to facilitate rapid solidification to develop thin flakes (&lt;0.5 mm thick) with a columnar grain structure. Rapid cooling has the potential to produce a homogenous microstructure consisting predominantly of the metastable SmTM7 phase. This could remove or significantly reduce the need for the energy-intensive homogenisation treatment usually required in conventional magnet manufacture. This paper investigates the effect of wheel speed (and hence cooling rate) on flake thickness, microstructure, and phase balance of the cast alloys. It was shown that for wheel speeds between 1.1 and 3.0 m/s, the microstructure showed large variation; however, in all cases, evidence of the columnar SmTM7 phase was presented. The adhesion between the melt and the wheel was deemed to be critical for the nucleation and subsequent columnar growth of SmTM7 grains, where the wheel speed controlled both the flow of the alloy onto the wheel and the thickness of the resultant flake. It was determined that in order to achieve a homogenous columnar SmTM7 structure, the maximum flake thickness should be limited to 270 μm to avoid the formation of equiaxed Sm2TM17 grains through insufficient cooling.

A global SS precursor method for imaging discontinuities: the Moho and beyond

SUMMARY Imaging seismic velocity discontinuities within the Earth's interior offers important insight into our understanding of the tectonic plate, associated mantle dynamics, and the evolution of the planet. However, imaging velocity discontinuities in locations where station coverage is sparse, is sometimes challenging. Here we demonstrate the effectiveness of a new imaging approach using deconvolved SS precursor phases. We demonstrate its effectiveness by applying it to synthetic seismograms. We also apply it to ∼1.6 M SS precursor waveforms from the global seismic database (1990–2018) for comparison with CRUST1.0. We migrate to depth and stack the data in circular 6° bins. The synthetic tests demonstrate that we can recover Moho depths as shallow as 20 km. Globally, the Moho is resolved at 21–67 km depth beneath continental regions. The Moho increases in depth from 21 km ± 4 km beneath the continental shelf to 45–50 km beneath the continental interiors and is as deep as 67 ± 4 km beneath Tibet. We resolve the Moho in 77 percent of all continental bins, within 10 km of CRUST1.0, with all outliers located in coastal regions. We also demonstrate the feasibility of using this method to image discontinuities associated with the mantle transition zone with both synthetic and real data. Overall, the approach shows broad promise for imaging mantle discontinuities.

Structural and Functional Analysis of the Amorphous Calcium Carbonate-Binding Protein Paramyosin in the Shell of the Pearl Oyster, Pinctada fucata.

Amorphous calcium carbonate (ACC) is an important precursor phase for the formation of aragonite crystals in the shells of Pinctada fucata. To identify the ACC-binding protein in the inner aragonite layer of the shell, extracts from the shell were used in the ACC-binding experiments. Semiquantitative analyses using liquid chromatography-mass spectrometry revealed that paramyosin was strongly associated with ACC in the shell. We discovered that paramyosin, a major component of the adductor muscle, was included in the myostracum, which is the microstructure of the shell attached to the adductor muscle. Purified paramyosin accumulates calcium carbonate and induces the prism structure of aragonite crystals, which is related to the morphology of prism aragonite crystals in the myostracum. Nuclear magnetic resonance measurements revealed that the Glu-rich region was bound to ACC. Activity of the Glu-rich region was stronger than that of the Asp-rich region. These results suggest that paramyosin in the adductor muscle is involved in the formation of aragonite prisms in the myostracum.

In Situ Synthesized Low-Dimensional Perovskite for >25% Efficiency Stable MA-Free Perovskite Solar Cells.

Developing an additive to effectively regulate the perovskite crystallization kinetics for the optimized optoelectronic properties of perovskite film plays a vital role in obtaining high efficiency and stable perovskite solar cells (PSCs). Herein, a new additive is designed and directly synthesized in perovskite precursor solution by utilizing an addition reaction between but-3-yn-1-amine hydrochloride (BAH) and formamidinium iodide. It is found that its product may control the intermediate precursor phase for regulating perovskite nucleation, leading to advantageous 2D perovskite to induce growth of perovskite along the preferred [001] orientation with not only released lattice strain but also strong interaction with perovskite to passivate its surface defects. By taking advantage of the above synergistic effects, the optimized PSC delivers an efficiency of 25.19% and a high open-circuit voltage (VOC) of 1.22 V. Additionally, the devices demonstrate good stability, remaining over 90% of their initial efficiencies under ambient atmosphere conditions for 60 days, high temperature of 85°C for 200 h, or maximum power point tracking for 500 h.

Mechanistic Study of the Influence of Reactant Type and Addition Sequence on the Microscopic Morphology of α-Al2O3

To perform an in-depth study of the crystal growth habits and phase changes of alumina and its precursors in reaction systems, this paper studied the effects of reactant type and addition order on the morphology of alumina using hydrothermal methods with different precipitants and aluminum sources as reactants. Research has shown that sodium bicarbonate and ammonium bicarbonate can be used as precipitants to prepare adhered spherical alumina and irregular short rod alumina, while potassium bicarbonate can be used as a precipitant to prepare hexagonal flake alumina. Using aluminum sulfate octahydrate, aluminum chloride hexahydrate, and aluminum nitrate, nine hydrates were prepared as aluminum sources, and agglomerated alumina, irregular short rod-shaped alumina, and fused alumina were obtained. The order of reactant addition affects the precursor phase of alumina, thereby affecting the microstructure of alumina after calcination, resulting in flake alumina with pores and short rod alumina. The results of this paper will provide theoretical guidance for the preparation of alumina with different micromorphologies.

Colloidal pathways of amorphous calcium carbonate formation lead to distinct water environments and conductivity.

CaCO3 is the most abundant biomineral and a major constituent of incrustations arising from water hardness. Polycarboxylates play key roles in controlling mineralization. Herein, we present an analytical and spectroscopic study of polycarboxylate-stabilized amorphous CaCO3 (ACC) and its formation via a dense liquid precursor phase (DLP). Polycarboxylates facilitate pronounced, kinetic bicarbonate entrapment in the DLP. Since bicarbonate is destabilized in the solid state, DLP dehydration towards solid ACC necessitates the formation of locally calcium deficient sites, thereby inhibiting nucleation. Magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy of poly-aspartate-stabilized ACC reveals the presence of two distinct environments. The first contains immobile calcium and carbonate ions and structural water molecules, undergoing restricted, anisotropic motion. In the second environment, water molecules undergo slow, but isotropic motion. Indeed, conductive atomic force microscopy (C-AFM) reveals that ACC conducts electrical current, strongly suggesting that the mobile environment pervades the bulk of ACC, with dissolved hydroxide ions constituting the charge carriers. We propose that the distinct environments arise from colloidally stabilized interfaces of DLP nanodroplets, consistent with the pre-nucleation cluster (PNC) pathway.

Ammonia-free synthesis of lithium manganese iron phosphate cathodes via a co-precipitation reaction

A novel precursor phase (Mn, Fe)5(PO4)2(HPO4)2·4H2O is introduced with a co-precipitation reaction, enabling a low-cost, sustainable, scalable production of LMFP cathodes exhibiting excellent cycling stability with good tap density.

Synergistic inhibition of green rust crystallization by co-existing arsenic and silica.

Arsenic and silica are known inhibitors of the crystallization of iron minerals from poorly ordered precursor phases. However, little is known about the effects of co-existing As and Si on the crystallization and long-term stability of mixed-valence Fe minerals such as green rust (GR). GR usually forms in anoxic, Fe2+-rich, near-neutral pH environments, where they influence the speciation and mobility of trace elements, nutrients and contaminants. In this work, the Fe2+-induced transformation of As- and/or Si-bearing ferrihydrite (FHY) was monitored at pH 8 ([As]initial = 100 μM, Si/As = 10) over 720 h. Our results showed that in the presence of As(III) + Si or As(V) + Si, GR sulfate (GRSO4) formation from FHY was up to four times slower compared to single species system containing only As(III), As(V) or Si. Co-existing As(III) + Si and As(V) + Si also inhibited GRSO4 transformation to magnetite, contrary to systems with only Si or As(V). Overall, our findings demonstrate the synergistic inhibitory effect of co-existing Si on the crystallization and solid-phase stability of As-bearing GRSO4, establishing an inhibitory effect ladder: As(III) + Si > As(V) + Si > As(III) > Si > As(V). This further highlights the importance of GR in potentially controlling the fate and mobility of As in ferruginous, Si-rich groundwater and sediments such as those in South and Southeast Asia.