Amorphous Precursor Research Articles

Amine-grafted H-MFI zeolite precursors as acidic-basic catalysts for deacetalization-Knoevenagel condensation

Amorphous and semi-crystalline precursors of zeolites have a large number of silanols that can be used to anchor organic functionalities, like silane-based amines, resulting in formation of basic sites. This work describes the use of amorphous and semi-crystalline precursors of H-MFI zeolite reacting with aminopropyltrimethoxysilane (APTMS) to produce bifunctional acidic-basic catalysts for the deacetalization-Knoevenagel condensation. The effect of precursors crystallinity on the catalytic performance is explained by the formation of Brønsted acidic sites, which catalyze the deacetalization step, and on the propylamine anchoring capacity, controlled by the amount of external silanols present in the aluminosilicate. It is shown that the aluminosilicates with lower crystallinity provide a higher yield of the end product ethyl trans-α-cyanocinnamate due to the greater number of grafted propylamine groups. These results provide new insights into the preparation of acidic-basic catalysts for converting bulky molecules.

Biomineralization and Properties of Guanine Crystals.

Guanine crystals with unique optical properties in organisms have been extensively studied and the biomineralization principles of guanine are being established. This review summarizes the fundamental physicochemical properties (solubility, tautomers, bands, and refractivity), polymorphs, morphology of biological and synthetic forms, and the reported biomineralization principles of guanine (selective recrystallization of amorphous precursor, preassembled scaffolds, additives, twinning, hypoxanthine doping, fluorescence, and assembly). The biomineralization principles of guanine will be helpful for the synthesis of guanine crystals with excellent properties and the design of functional organic materials for drugs, dyes, organic semiconductors, etc.

Systematic synthesis of (Gd1−xLax)2O2SO4:Tb3+ and (Gd1−xLax)2O2S:Tb3+ nanophosphors for remarkably enhanced luminescence

AbstractCoprecipitation with rare‐earth nitrate, ammonium sulfate, and ammonium hydroxide produced hydroxide‐type amorphous precursors incorporating sulfate and carbonate anions, from which [(Gd1−xLax)0.99Tb0.01]2O2SO4 and [(Gd1−xLax)0.99Tb0.01]2O2S (x = 0, 0.15, 0.3, 0.5, 0.65, 0.8, and 1) were obtained as two series of nanophosphors by calcination at 950°C in air and hydrogen, respectively. The detailed characterization by X‐ray diffractometer, scanning electron microscopy/transmission electron microscopy, Brunauer–Emmett–Teller, and particle sizing confirmed that solid solutions were directly formed and that the products have small crystallite size, unimodal size distribution, and high specific surface area, revealing the advantages of the synthesis method. Photoluminescence study revealed that La3+ admixture may significantly improve the 545 nm main emission of Tb3+ for both the phosphor series. Furthermore, the 545 nm main emission of [(Gd1−xLax)0.99Tb0.01]2O2SO4 was identified to have an excellent thermal stability, which retained over 90% of its room‐temperature intensity at 150°C (no quenching for Gd2O2SO4:Tb3+). The two series of phosphors were comparatively studied for their excitation and luminescence performances, as a function of temperature and La3+ content, and the results were rationalized by considering bandgap, crystal structure, UV absorption, and the character of chemical bonds.

Wafer-Scale Synthesis of 2D Materials by an Amorphous Phase-Mediated Crystallization Approach.

The interest in the wafer-scale growth of two-dimensional (2D) materials, including transition metal dichalcogenides (TMDCs), has been rising for transitioning from lab-scale devices to commercial-scale systems. Among various synthesis techniques, physical vapor deposition, such as pulsed laser deposition (PLD), has shown promise for the wafer-scale growth of 2D materials. However, due to the high volatility of chalcogen atoms (e.g., S and Se), films deposited by PLD usually suffer from a lack of stoichiometry and chalcogen deficiency. To mitigate this issue, excess chalcogen is necessary during the deposition, which results in problems like uniformity or not being repeatable. This study demonstrates a condensed-phase or amorphous phase-mediated crystallization (APMC) approach for the wafer-scale synthesis of 2D materials. This method uses a room-temperature PLD process for the deposition and formation of amorphous precursors with controlled thicknesses, followed by a post-deposition crystallization process to convert the amorphous materials to crystalline structures. This approach maintains the stoichiometry of the deposited materials throughout the deposition and crystallization process and enables the large-scale synthesis of crystalline 2D materials (e.g., MoS2 and WSe2) on Si/SiO2 substrates, which is critical for future wafer-scale electronics. We show that the thickness of the layers can be digitally controlled by the number of laser pulses during the PLD phase. Optical spectroscopy is used to monitor the crystallization dynamics of amorphous layers as a function of annealing temperature. The crystalline quality, domain sizes, and the number of layers were explored using nanoscale and atomistic characterization (e.g., AFM, STEM, and EDS) along with electrical characterization to explore process-structure-performance relationships. This growth technique is a promising method that could potentially be adopted in conventional semiconductor industries for wafer-scale manufacturing of next-generation electronic and optoelectronic devices.

Mechanisms and kinetics of C-S-H nucleation approaching the spinodal line: Insights into the role of organics additives

Wet chemistry C-S-H precipitation experiments were performed under controlled conditions of solution supersaturation in the presence and absence of gluconate and three hexitol molecules. Characterization of the precipitates with SAXS and cryo-TEM experiments confirmed the presence of a multi-step nucleation pathway. Induction times for the formation of the amorphous C-S-H spheroids were determined from light transmittance. Analysis of those data with the classical nucleation theory revealed a significant increase of the kinetic prefactor in the same order as the complexation constants of calcium and silicate with each of the organics. Finally, two distinct precipitation regimes of the C-S-H amorphous precursor were identified: i) a nucleation regime at low saturation indexes (SI) and ii) a spinodal nucleation regime at high SI where the free energy barrier to the phase transition is found to be of the order of the kinetic energy or less.

Dual clumped (Δ47-Δ48) isotope data for amorphous carbonates and transformation products reveal a novel mechanism for disequilibrium clumped isotope effects

Amorphous precursors to minerals have been observed in laboratory materials and in nature, including across diverse phyla. These metastable phases allow for the incorporation of cations at higher concentrations than classical crystallization pathways, thus, their chemistry and behavior have implications in an array of disciplines. Currently, little is known about the isotopic composition of the anion in amorphous carbonates and how isotopic values evolve during transformation into a mineral. Here, we examined the evolution of isotopic values in amorphous carbonates and mineral transformation products to identify the potential origins of disequilibrium isotopic compositions in carbonate minerals that form from an amorphous precursor. We measured dual carbonate clumped isotopes (13C18O16O - Δ47; 12C18O18O - Δ48), bulk stable isotope ratios (δ13C, δ18O), and chemical and structural data throughout the transformation of amorphous calcium magnesium carbonate (ACMC) into high Mg-calcite (HMC) over 1 year, with crystallization occurring in solutions from 10 to 60 °C. The Δ47, Δ48, and δ18O values evolved significantly during transformation, indicating dissolution of ACMC and reprecipitation of HMC. After crystallization, the Δ47 and Δ48 values achieved a disequilibrium steady state, while δ18O values continued to evolve. For the fully crystallized HMC samples, the low temperature samples formed at 10 °C had the greatest extent of oxygen isotope disequilibrium (measured value – equilibrium value = −39‰); conversely; the greatest clumped isotope disequilibrium was observed in high temperature samples formed at 40 and 60 °C (0.068‰ for Δ47, 0.072‰ for Δ48). These results are consistent with a new potential mechanism of disequilibrium clumped isotope values in carbonate minerals. Specifically, the dissolution of ACMC during transformation causes disequilibrium oxygen and clumped isotope values in the dissolved inorganic carbon (DIC) pool. The extent of isotopic disequilibrium in DIC during transformation is temperature dependent, and is recorded by the forming mineral. Isotopic results may also reflect mixing effects, as scanning electron microscopy (SEM) showed ACMC and HMC existing simultaneously during transformation, indicating that ACMC likely progressively dissolves and reprecipitates as the DIC pool isotopically evolves. This may result in heterogeneous isotopic values in HMC. In total, these data suggest a highly dynamic localized environment could exist in biomineralizing organisms and abiotic systems that utilize amorphous precursors to form carbonate minerals, potentially resulting in isotopic values that are not representative of formation temperature.

Engineering hollow covalent organic framework particle through self‐templated crystallization

AbstractNano/microparticles with hollow structures have many applications in various fields. However, engineering hollow covalent organic framework (COF) particles in a simple and efficient manner remains a significant challenge. In this study, we propose a self‐template crystallization method to prepare imine‐based COF microparticles with tailored shell thickness and high crystallinity. This method involves the post‐transformation of amorphous microparticles in a highly reversible reaction system containing monofunctional competitors. The amorphous precursors with high‐Gibbs free energy decompose and reconstruct to form highly crystalline COFs in situ on the particle surface. This process allows for the preparation of various Schiff‐base COF particles with good crystallinity and tailored hollow structures, with diameters ranging from 120 to 680 nm and shell thicknesses of 27–96 nm. These COF particles have well‐defined micropore sizes centered between 1.0 and 4.0 nm and a high‐specific surface area of up to 543 m2 g−1. The resulted COF particles could be used to support ethylene oligomerization catalysts for improving their activity and selectivity, that is, the mass fraction of α‐olefins above C10 increased from almost zero to 52.7% after COF supporting. Our method thus provides an efficient way to precisely tailor the microstructure and morphology of COF materials for advanced applications.

The response of coral skeletal nano structure and hardness to ocean acidification conditions.

Ocean acidification typically reduces coral calcification rates and can fundamentally alter skeletal morphology. We use atomic force microscopy (AFM) and microindentation to determine how seawater pCO2 affects skeletal structure and Vickers hardness in a Porites lutea coral. At 400 µatm, the skeletal fasciculi are composed of tightly packed bundles of acicular crystals composed of quadrilateral nanograins, approximately 80-300 nm in dimensions. We interpret high adhesion at the nanograin edges as an organic coating. At 750 µatm the crystals are less regular in width and orientation and composed of either smaller/more rounded nanograins than observed at 400 µatm or of larger areas with little variation in adhesion. Coral aragonite may form via ion-by-ion attachment to the existing skeleton or via conversion of amorphous calcium carbonate precursors. Changes in nanoparticle morphology could reflect variations in the sizes of nanoparticles produced by each crystallization pathway or in the contributions of each pathway to biomineralization. We observe no significant variation in Vickers hardness between skeletons cultured at different seawater pCO2. Either the nanograin size does not affect skeletal hardness or the effect is offset by other changes in the skeleton, e.g. increases in skeletal organic material as reported in previous studies.

Large lattice mismatch of nanocomposite coating: In-situ establishment of MoS2 by precursor and desulfurization reaction

Constructing large lattice mismatch interfaces, especially two-dimensional materials such as MoS2, is the key to reaching the structural lubricity of heterogeneous structures. Large lattice mismatch prevents the nucleation of reinforcement of composite material, such as in situ synthesized MoS2 during the PEO process, thus affecting the mechanical performance. In this work, a precursor reaction, which can form an amorphous MoS3/TiO2 mixtures, is proposed, and the MoS2/TiO2 noncoherent interface with large mismatch is obtained through solid-state in situ desulfurization of suspended S with the action of reheat. Meanwhile, the precursor reaction is strongly dependent on the sulfur source concentration, which can form the interface with a large number of interfacial dislocations by regulating the concentration of sulfur source. Such edge pining noncoherent interface enables more dislocation and distortion near interface during scratch, which reduces the twist-angle dependence thus further improving the tribological properties. Additionally, these results render the herein presented amorphous precursor reaction strategy generally applicable for exhibiting broad application of in situ synthesis of reinforcement.

Understanding Hierarchical Structure Construction Strategies and Biomimetic Design Principles: A Review

Organisms use gene and cell engineering to tailor the mineralization process and synthesize structure composites with special functions and favorable properties. This spurs scientists to design functional materials based on learning from nature. Herein, a systematic review of the biomimetic synthesis and hierarchical structure design of calcium carbonate–based minerals is presented. First, biomimetic synthesis strategies, including additive‐induced, template‐oriented, and gel‐mediated routes to direct the construction of the hierarchical structure, are reviewed. The molecular‐recognition technique and directional assembly pathway are then summarized to precisely describe the interactions between inorganic minerals and organic matter, and direct the mineral growth. Next, the underlying mineralization mechanisms governing the evolution of the complex morphology and structure are discussed. Nonclassical pathways that control mineral growth, including the theories of the amorphous phase, oriented attachment, mesocrystal formation, and liquid precursor, are concluded. Finally, herein, the applications of calcium carbonate–based minerals are discussed. Unique hierarchical structure endows minerals with special functions, including optical performance, biomedical applications, and environmental and ecological restoration. Overall, in this report, the biomimetic synthesis of calcium carbonate–based minerals is reviewed, covering the fundamental principles, construction of the hierarchical structure, underlying mechanisms of mineral growth, and functional designs.

Ultra-fine microstructure and exceptional low coercivity developed in a high-Bs Fe-Si-B-P alloy by co-alloying Ni, Mo, and Cu

Designing soft magnetic alloys with high saturation magnetic induction (Bs) is of great importance for improving the power density of electric and electronic devices. For high-Bs nanocrystalline alloys, the main problem is the grain coarsening effect induced by high Fe content (>80 at.%), which deteriorates the soft magnetic properties. In present work, we designed new Fe-based nanocrystalline alloys by microalloying a Fe-Si-B-P alloy. The co-alloying of Ni, Mo, and Cu effectively refines the microstructure of nanocrystalline alloys from 28.5 nm to 13.1 nm and increased the stability of soft magnetic properties. Even though there are 28-nm-large surface crystallites in the amorphous precursors, an exceptional low coercivity of 1–2 A/m with a high Bs of 1.81 T was developed after nanocrystallization. These excellent magnetic properties could be maintained within a wide annealing temperature window of 50 K and an annealing time window up to 600 s for high heating rate annealing.

Room temperature magnetron sputtering and laser annealing of ultrathin amorphous sulfur-rich MoSx films

Room temperature magnetron sputtering of an ultra-thin transition-metal dichalcogenide amorphous precursor and subsequent laser annealing-induced phase transformations were investigated for the synthesis of polycrystalline 2H-MoS2 semiconducting thin films. Radio frequency magnetron sputtering of a MoS3.6 target was used to produce amorphous precursors with S to Mo ratios greater than 2:1 on thermally annealed SiO2 substrates, glass, indium tin oxide coated glass, and amorphous boron-oxy-nitride. The influence of working pressure on the MoS2 and MoS3 interatomic bonding arrangements in amorphous MoSx films was explored with x-ray photoelectron spectroscopy. A 248 nm pulsed laser was used for annealing 1 cm2 sized areas of the amorphous precursor in an ambient atmosphere at fluences of 100–450 mJ for 1, 5, and 10 pulses to form a crystalline 2H-MoS2 phase. The role of laser fluence and substrate choice on phase transformation from the amorphous precursor to the 2H phase, as well as the competition between oxidation, elemental sulfur segregation, and ablation is discussed. Hall effect measurements confirmed p-type behavior of the produced semiconducting films and established mobility and charge carrier density characteristics of the laser-annealed films. The feasibility of scalable processing by combining sputtering from sulfur-rich targets and laser annealing for production of p-type 2H-MoS2 ultrathin films on various substrates is presented.

Nucleation and Crystallization of Ferrous Phosphate Hydrate via an Amorphous Intermediate.

The fundamental processes of nucleation and crystallization are widely observed in systems relevant to material synthesis and biomineralization; yet most often, their mechanism remains unclear. In this study, we unravel the discrete stages of nucleation and crystallization of Fe3(PO4)2·8H2O (vivianite). We experimentally monitored the formation and transformation from ions to solid products by employing correlated, time-resolved in situ and ex situ approaches. We show that vivianite crystallization occurs in distinct stages via a transient amorphous precursor phase. The metastable amorphous ferrous phosphate (AFEP) intermediate could be isolated and stabilized. We resolved the differences in bonding environments, structure, and symmetric changes of the Fe site during the transformation of AFEP to crystalline vivianite through synchrotron X-ray absorption spectroscopy at the Fe K-edge. This intermediate AFEP phase has a lower water content and less distorted local symmetry, compared to the crystalline end product vivianite. Our combined results indicate that a nonclassical, hydration-induced nucleation and transformation driven by the incorporation and rearrangement of water molecules and ions (Fe2+ and PO43-) within the AFEP is the dominating mechanism of vivianite formation at moderately high to low vivianite supersaturations (saturation index ≤ 10.19). We offer fundamental insights into the aqueous, amorphous-to-crystalline transformations in the Fe2+-PO4 system and highlight the different attributes of the AFEP, compared to its crystalline counterpart.

Reduced lattice thermal conductivity through tailoring of the crystallization behavior of NbCoSn by V addition

Nanostructuring is a key approach for reducing lattice thermal conductivity. Amorphous precursors can be used to obtain complex nanostructures, as their crystallization behavior can be controlled by varying their composition, temperature, and annealing time. Herein, we investigated the effects of V alloying on the crystallization behavior and resulting lattice thermal conductivity of amorphous NbCoSn alloys. After heat treatment at 783 K for 2 h, the V-containing alloy showed a significantly finer grain size (100 ± 30 nm) than the alloy without V (870 ± 360 nm) owing to the different crystallization kinetics. We revealed that Sn-rich nanoprecipitates with a diameter of 10 nm acted as heterogeneous nucleation sites for crystallization, resulting in a finer grain size in the V-containing alloy. As a result, the V-containing alloy exhibited a lower lattice thermal conductivity (2.6 ± 0.2 W m−1 K−1) than the alloy without V (3.3 ± 0.2 W m−1 K−1) at room temperature owing to increased phonon scattering at the grain boundary, point defects, and nanoprecipitates.

Formation and growth of anatase TiO2 nanocrystals under hydrothermal conditions

This work is devoted to the study of the processes of formation and growth of TiO2 nanoparticles under hydrothermal conditions. TiO2 nanocrystals were obtained during the dehydration of hydrated titanium dioxide by varying the temperature and duration of hydrothermal treatment, as well as the method of precipitation of the synthesis precursor. The study of various characteristics of the synthesized TiO2 nanoparticles by PXRD, SEM, TEM, and low-temperature nitrogen sorption made it possible to propose mechanisms for the formation of crystalline titanium dioxide from an X-ray amorphous precursor and the growth of titanium dioxide nanocrystals with an anatase structure under hydrothermal conditions. Within the scope of the chosen model of oriented attachment, the dependence of the sizes of TiO2 crystallites on the parameters of hydrothermal synthesis is mathematically described. It was concluded that the direct precipitation of the synthesis precursor from titanium tetrachloride is superior to the reverse. It is shown that the temperature of hydrothermal treatment largely determines the size and morphology of the formed crystallites and TiO2 nanoparticles, the rate of the crystallization process, and the preferred mechanisms of nanocrystal growth, while the duration of synthesis affects the agglomeration processes and the specific surface area of titanium dioxide powders.

Affable thermal treatment process to overcome the trade-off relation via interface engineering in an Fe-based amorphous film

As pre-eminent soft magnetic materials, Fe-based amorphous alloys have been extensively studied due to adjustable composition, low cost, and low iron core loss. The soft magnetic properties could be further improved after thermal annealing, which achieve a low coercive force (Hc) due to the low magnetic anisotropy and a high saturation magnetic flux density (Bs) on account of the precipitation of soft magnetic nanocrystalline phases. However, it is a key difficulty to control the nucleation and growth procedures of nanocrystals during annealing, resulting in rapid deterioration of Hc. Here, a soft magnetic Fe76Si8B13Nb3 film with ultra-fine amorphous/crystalline (a/c) core–shell structure is achieved from an amorphous precursor with the nanoscale phase separation. The pre-existing nanoscale phase separation provides vast nucleation sites and interphase boundaries, which could generate high concentration of nanocrystals and depresses the subsequent coarsening behavior even for long-time heat treatment. In consequence, the a/c core–shell soft magnetic film breaks the general trade-off relation in the soft magnetic material family with the highest Bs and lowest Hc simultaneously. This work provides a new perspective to design a/c alloys by amorphous precursor with dual phase structure, and importantly, it supplies effortless thermal treatment requirement to conveniently regulate the microstructures and soft magnetic properties of metallic glasses.

Enhanced thermoelectric properties of NbCoSn half-Heuslers through in-situ nanocrystallization of amorphous precursors during the consolidation process

Tailoring nanostructures is a general approach used to obtain enhanced thermoelectric properties for half-Heusler compounds because the wide areas of grain and phase boundaries could be scattering centers that lower lattice thermal conductivity. However, a common fabrication method based on the sintering of crystalline precursors crushed from as-cast alloy ingots has limitations in obtaining a homogeneous microstructure without microsized impurity phases, owing to residual elemental segregation from casting. In this study, we used amorphous NbCoSn alloys as a precursor for the sintered specimen to obtain a homogeneous NbCoSn bulk specimen without microsized impurity phases and segregation, which led to the enhanced Seebeck coefficient due to the high purity of the half-Heusler phase after crystallization. Moreover, superplasticity originating from amorphous features enabled the powders to be largely deformed during the sintering process, even at a low sintering temperature (953 K). This resulted in less oxidation at both, the grain boundary and the interior, as the O diffusion pathway was blocked during the sintering process. As a result, the NbCoSn0.95Sb0.05 specimen using an amorphous precursor exhibited an enhanced zT of 0.7, due to the increase in the power factor and a decrease in lattice thermal conductivity compared to the specimen using a crystalline precursor.

Low-Temperature Fabrication of Bulk-Type All-Solid-State Lithium-Ion Battery Utilizing Nanosized Garnet Solid Electrolytes.

Garnet-type Li7 La3 Zr2 O12 (LLZ) materials are attracting attention as solid electrolytes (SEs) in oxide-based all-solid-state batteries (ASSBs) owing to their high ionic conductivity. Although the electrochemical stability of LLZ against Li metal is demonstrated with possible high energy density, high-temperature sintering above 1000 °C, which is required to achieve high Li-ion conductivity, results in the formation of insulating impurities at the electrode-electrolyte interfaces. Here, nanosized fine-particle samples of Ta-substituted Li6.5 La3 Zr1.5 Ta0.5 O12 (LLZT) are successfully prepared at a remarkably low temperature of 400 °C utilizing an amorphous precursor oxide. The dense LLZT SE sintered by hot pressing at 500 °C shows room-temperature Li-ion conductivity of 1.03 × 10-4 S cm-1 without any additives. In addition, the bulk-type NCM-graphite full battery cell fabricated with the LLZT fine particles through a hot-pressing sintering method at 550 °C exhibits a good charge-discharge performance at room temperature with the bulk-type areal discharge capacity of 0.831 mAh cm-2 . The nanosized garnet SE strategy demonstrated in this study paves the way for the formation of oxide-based ASSBs by low-temperature sintering.

Low-temperature graphitization of lignin via Co-assisted electrolysis in molten salt

The ever-growing energy demand and environmental issues have stimulated the development of sustainable energy technologies. Herein, an efficient and environmentally friendly electrochemical transformation technology was proposed to prepare highly graphitized carbon materials from an abundant natural resource - lignin (LG). The preparation process mainly includes pyrolytic carbonization of raw LG material and electrochemical conversion of amorphous carbon precursor. Interestingly, with the assistance of Co catalyst, the graphitization degree of the products was significantly improved, in which the mechanism was the removal of heteroatoms in LG and the rearrangement of carbon atoms into graphite lattice. Furthermore, tunable microstructures (nanoflakes) under catalytic effects could also be observed by controlling the electrolytic parameters. Compared with the products CN1 (without catalyst) and CN5 (with 10% catalyst), the specific surface area are 158.957 and 202.246 m2 g−1, respectively. When used as the electrode material for lithium-ion batteries, CN5 delivered a competitive specific capacity of ∼350 mAh g−1 (0.5 C) compared with commercial graphite. The strategy proposed in this work provides an effective way to extract value-added graphite materials from lignin and can be extended to the graphitization conversion of any other amorphous carbon precursor materials.

Molecular Modification of Zeolites with Cold Atmospheric-Pressure Plasma Jet: A Green and Facile Strategy

Widespread applications of zeolites demand the optimization of crystal size and morphology. Crystal growth modifiers (CGMs) have been proved effective for zeolite rational design, but the additional chemicals raise environmental and safety concerns. Herein, the industry-ready technique of cold atmospheric-pressure plasma jet (CAPPJ) was employed to induce reactive plasma species as green and eco-friendly CGMs. The synthesis mixtures of three aluminosilicate zeolites with assorted Si/Al ratios (SAR), channel dimensionalities, and pore apertures (i.e., MFI, LTA, and LTL framework types) were first subjected to Ar-CAPPJ treatment for up to 30 min during the aging period. Apparent size and shape modifications were successfully achieved for the resulting crystals with the emergence of rounded surfaces implying surface roughening at the molecular level. For the silicoaluminophosphate SAPO-34 (CHA type), the introduction of plasma CGMs was found to propel a phase transformation, promoting the crystallization of SAPO-18 (AEI type) impurity with reduced framework density. Experimental observations seem to suggest that the classical model of CGMs attaching to selected crystal surfaces is less likely to happen. Whereas, the investigation of zeolite L dispersions revealed enhanced concentrations and altered physicochemical properties of soluble species and amorphous precursors, alluding to the potential functional mechanism (s) of plasma CGMs. As a plausible technique to generate green and versatile CGMs, the impacts of CAPPJ on zeolite crystallization are systematically investigated for the first time, promoting the understanding of classical and nonclassical crystallization phenomena during zeolite synthesis.