Crystal Nucleation Research Articles

Electrochemically Assisted Single Crystal Growth of Reduced Preyssler Polyoxometalates Decorated with M2+ (M = Co, Ni) and Cubane-Like Ni4O4 Units.

Polyoxometalates (POMs) are of great interest to the scientific community, and their reduction and nucleation have been well-established by multi-step techniques. The present study develops an electrochemical approach for simultaneous reduction and nucleation of polyoxometalate-containing solids. Herein we report crystal growth of reduced Preyssler polyoxotungstate-based (anionic formula [NaP5W30O110]14-) new crystalline solids made of Preyssler anions interlinked by Co2+ and Ni2+ ions. Crystal nucleation and in situ reduction were achieved at room temperature using a two silver wire electrode setup in various aqueous solutions under constant applied potentials. The POM material was deposited on the cathode, and its structure was characterized by X-ray diffraction techniques. The primary structure type observed involves POMs decorated by disordered Co2+/Ni2+ octahedra and fused into 1-D pillars by additional Co2+/Ni2+ octahedra. A secondary phase was observed in the Ni-based reactions, where reduced Preyssler anions are decorated by Ni4O4 cubane-like units. To understand the electrochemical process, polarization curves of the electrolyte solutions are presented, suggesting an applied potential best suited for crystal growth. The work highlights the effectiveness of an electrochemical pathway where nucleation and simultaneous reduction of POMs can make novel reduced POM solids.

Epitaxial Growth of Two-Dimensional Organic Crystals with In-Plane Heterostructured Domain Regulation.

Complex organic lateral heterostructures (OLHs) with spatial distribution of two or more chemical components are crucial for designing and realizing unique structure-dependent optoelectronic applications. However, the precise design of well-defined OLHs with flexible domain regulation remains a considerable challenge. Herein, we present a stepwise solution self-assembly method to synthesize two-dimensional (2D) OLHs with a central rhombus domain and a lateral region featuring tunable blue and green emission based on the sequential nucleation and growth of 2D crystals. By controlling the initial crystallization time of 2,6-diphenylanthracene, the rhombic length ratio (α) of the multicolor-emissive part of the 2D OLHs is precisely modified. Furthermore, a third lateral layer is constructed on the resulting OLHs, demonstrating scalable lateral regulation. Significantly, these prepared 2D OLHs exhibit great excitation position-dependent waveguide characteristics and enable a 0.06 dB/μm low-loss waveguiding, which are conducive to photon transport and conversion for photonic integrated circuits. This work provides a stepwise strategy for the accurate fabrication of 2D OLHs, fabricating the developments of next-generation optoelectronics devices.

Sand improvement by microbial-induced carbonate precipitation with casein micelles

This study explores the incorporation of casein micelles to improve the conventional microbial-induced carbonate precipitation technique used for soil improvement. With a single application of the proposed biocementing agent containing casein micelles, a mixed slurry of natural sand solidified to self-sustaining strength within 48 h at 37°C was obtained. The stress–strain curves of the biocemented specimens obtained from a consolidated drained triaxial compression test exhibited sharp peaks at less than 1% strain. Under effective confining pressures of 30, 50 and 100 kPa, the peak deviatoric stress registered 415, 479 and 536 kPa, respectively – representing 1·8–4·1 times the maximum strength of the original sand. Vaterite calcium carbonate crystals formed by the biocementing agent ensured bridging between sand particles, resulting in the improved cohesion. The cohesion-derived residual strength tended to increase at the critical state in biocemented sand under the lowest confining stress. The localised shear band formed by the crystals may control the movement of sand particles, resulting in a change in volumetric strain behaviour. The formation of casein micelles induced the nucleation and growth of spherical crystals, acting as a casein-mediated vaterite. This formation likely contributed to the improved cohesion of sand observed in this study.

The rise and fall of adenine clusters in the gas phase: a glimpse into crystal growth and nucleation.

The emergence of a crystal nucleus from disordered states is a critical and challenging aspect of the crystallization process, primarily due to the extremely short length and timescales involved. Methods such as liquid-cell or low-dose focal-series transmission electron microscopy (TEM) are often employed to probe these events. In this study, we demonstrate that ion mobility spectrometry-mass spectrometry (IMS-MS) offers a complementary and insightful perspective on the nucleation process by examining the sizes and shapes of small clusters, specifically those ranging from n = 2 to 40. Our findings reveal the significant role of sulfate ions in the growth of adeninediium sulfate clusters, which are the precursors to the formation of single crystals. Specifically, sulfate ions stabilize adenine clusters at the 1:1 ratio. In contrast, guanine sulfate forms smaller clusters with varied ratios, which become stable as they approach the 1:2 ratio. The nucleation size is predicted to be between n = 8 and 14, correlating well with the unit cell dimensions of adenine crystals. This correlation suggests that IMS-MS can identify critical nucleation sizes and provide valuable structural information consistent with established crystallographic data. We also discuss the strengths and limitations of IMS-MS in this context. IMS-MS offers rapid and robust experimental protocols, making it a valuable tool for studying the effects of various additives on the assembly of small molecules. Additionally, it aids in elucidating nucleation processes and the growth of different crystal polymorphs.

Two-step crystallization in a supersaturated solution with application to protein crystal growth: Theory and analytical solutions

A theory of two-step nucleation and evolution of crystals with allowance for their diffusion in the space of particle radii is developed. The theory is based on a two-step growth law of crystals appearing in dense liquid precursors, initially evolving within them with a diffusion-limited growth law, and then leaving them and evolving with another growth law. This two-step crystal growth law influences the integrodifferential system of kinetic and balance equations for the crystal-size distribution function and liquid supersaturation. The system of integrodifferential equations for the evolution of polydisperse ensemble of crystals is solved using the integral Laplace transform and saddle-point methods for the Weber–Volmer–Frenkel–Zel’dovich and Meirs kinetic mechanisms. A complete analytical solution to this non-linear system has been constructed in a parametric form. Namely, the particle-size distribution function, liquid supersaturation and time have been found as the functions of decision variable — the maximum size of crystals. The theory is in agreement with the experimental data on the growth of beta-lactoglobulin and insulin crystals.

Investigation of the effect of Tideglusib on the hydroxyapatite formation, crystallinity and elasticity of conditioned resin-dentin interfaces

To investigate the effect of dentin infiltration with polymeric nanoparticles (NPs) doped with tideglusib (TDg) (TDg-NPs) on hydroxyapatite formation, crystallinity and elasticity of conditioned resin-dentin interfaces. Dentin conditioned surfaces were infiltrated with NPs or TDg-NPs. Bonded interfaces were created, stored for 24 h and submitted to mechanical and thermal challenging. Resin-dentin interfaces were evaluated through nanoindentation to determine the modulus of elasticity, X-ray diffraction and transmission electron microscopy through selected area diffraction and bright-filed imaging. TDg-NPs provoked peaks narrowing after the diffraction-intensity analysis that corresponded with high crystallinity, with an increased modulus of Young after load cycling in comparison with the samples treated with undoped NPs. New minerals, in the group of TDg-NPs, showed the greatest both deviation of line profile from perfect crystal diffraction and dimension of the lattice strain, i.e., crystallite, grain size and microstrain and 002 plane-texture. The new minerals generated after TDg-NPs application and mechanical loading followed a well defined lineation. Undoped NPs mostly produced small hydroxyapatite crystallites, non crystalline or amorphous in nature with poor maturity. Tideglusib promoted the precipitation of hydroxyapatite, as a major crystalline phase, at the intrafibrillar compartment of the collagen fibrils, enabling functional mineralization. TDg-NPs facilitated nucleation of crystals randomly oriented, showing less structural variation in angles and distances that improved crystallographic relative order of atoms and maturity. Nanocrystals inducted by TDg-NPs were hexagonal prisms of submicron size. Thermal challenging of dentin treated with TDg-NPs have provoked a decrease of functional mineralization and crystallinity, associated to immature hydroxyapatite. New polycrystalline lattice formation generated after TDg-NPs infiltration may become correlated with high mechanical performance. This association can be inferred from the superior crystallinity that was obtained in presence of tideglusib. Immature crystallites formed in dentin treated with undoped NPs will account for a high remineralizing activity.

Simple and sustainable synthesis of loosely stacked nano-H-ZSM-5 aggregates from kaolin and catalytic studies

The conversion of natural clay to crystalline zeolites has been the subject of considerable interest from both academic and industrial circles. We present an effective strategy for converting kaolin to ZSM-5 zeolite, addressing the issue of reduced mesopore formation in conventional nano-ZSM-5 aggregates due to close-packing. This strategy utilizes kaolin as the sole source of silicon and aluminum, and by decoupling the nucleation and growth of ZSM-5 crystals, loosely stacked nano-H-ZSM-5 aggregates with high crystallinity crystals can be synthesized in a solid-like system by employing a tiny amount of TPAOH (TPAOH/SiO2 = 0.064). The resulting nano-H-ZSM-5 aggregates exhibited high specific surface area (405.66 m2/g), high mesopore volume (0.64 cm3/g), and superior catalytic activity. This strategy offers a novel approach to the cost-effective synthesis of nano-H-ZSM-5 aggregates suitable for industrial applications.

Influence of micromixing and shear on precipitation process in the jet-flow high shear reactors

Micromixing and fluid shear stress significantly affect the nucleation and growth of crystals during the precipitation process. The jet-flow high shear reactor (JFHSR) has strong shear rate and high localized energy dissipation rate, making it promising for applications where the size and the morphology of crystals need to be modified. In this paper, the micromixing properties of JFHSR were first investigated using Villermaux/Dushman method, and the intrinsic correlation among micromixing, shear, and BaSO4 crystals was explored. The results show that the stator, the increased Re and θ, the reduced feed tube diameter and the closer the feed position to the rotor promote micromixing. Excellent micromixing promotes burst nucleation by generating uniform supersaturation, while shear is more likely to provide an environment dominated by the secondary nucleation of fluid shear stress. The correlations of XS, tm (about 10−4 s) and d43,P are obtained, providing guidelines for JFHSR design and application

Construction of tree-ring mimetic 3D networks in polyvinyl alcohol/boron nitride composites for enhanced thermal management and mechanical properties

Constructing a three-dimensional (3D) filler network in polymer thermal interface materials (TIMs) is crucial for enhancing thermal conductivity and mechanical properties. However, the discontinuous and loose network of fillers are one of the main reasons hindering the joint improvement of thermal conductivity and mechanical properties. The construction of a regular and dense 3D continuous filler network remains a significant challenge. In this study, an innovative bidirectional freezing technique was designed to create a polyvinyl alcohol (PVA)/boron nitride (BN) composite with a tree-ring-like 3D network. This technique promotes the formation of 3D network consisting of long-range lamellar BN layers with a tree-ring-like structure by controlling the nucleation and growth of ice crystals along the bidirectional temperature gradient induced by a polytetrafluoroethylene (PTFE) cone. The resulting PVA/BN composite exhibits high thermal conductivity (6.25 W/m·K) due to the lower interfacial thermal resistance between fillers (1.271 × 10−7 K m2/W), and an enhanced tensile strength of 41.71 MPa, which is attributed to the regular and dense BN network. This study presents a feasible strategy for constructing a 3D continuous network structure in polymer-based TIMs, paving the way for advancements in thermal management solutions.

The interactions of protein-calcium oxalate in crystallization process

Understanding the pathogenic crystallization of calcium oxalate (CaOx), a major constituent of kidney stones, is crucial in developing effective treatment strategies. In this work, the interactions between lysozyme and CaOx during crystallization have been investigated. Further investigations into the crystal morphology, size, quantity, and nucleation time of the lysozyme have been designed. The results reveal that CaCl2 could act as an effective precipitant for lysozyme crystallization. The formation process and structure of the distinctive composite CaOx-lysozyme crystal has been investigated. The addition of lysozyme promoted the formation of individual CaOx crystals by preventing the crystal aggregation in the solution. The presence of lysozyme induced a transformation in the CaOx crystals from calcium oxalate monohydrate to calcium oxalate dihydrate. These findings contribute to a better understanding of protein-CaOx interactions and their implications in kidney stone pathogenesis.

Templated Nucleation of Clotrimazole and Ketoprofen on Polymer Substrates.

The use of different template surfaces in crystallization experiments can directly influence the nucleation kinetics, crystal growth, and morphology of active pharmaceutical ingredients (APIs). Consequently, templated nucleation is an attractive approach to enhance crystal nucleation kinetics and preferentially nucleate desired crystal polymorphs for solid-form drug molecules, particularly large and flexible molecules that are difficult to crystallize. Herein, we investigate the effect of polymer templates on the crystal nucleation of clotrimazole and ketoprofen with both experiments and computational methods. Crystallization was carried out in toluene solvent for both APIs with a template library consisting of 12 different polymers. In complement to the experimental studies, we developed a computational workflow based on molecular dynamics (MD) and derived descriptors from the simulations to score and rank API-polymer interactions. The descriptors were used to measure the energy of interaction (EOI), hydrogen bonding, and rugosity (surface roughness) similarity between the APIs and polymer templates. We used a variety of machine learning models (14 in total) along with these descriptors to predict the crystallization outcome of the polymer templates. We found that simply rank-ordering the polymers by their API-polymer interaction energy descriptors yielded 92% accuracy in predicting the experimental outcome for clotrimazole and ketoprofen. The most accurate machine learning model for both APIs was found to be a random forest model. Using these models, we were able to predict the crystallization outcomes for all polymers. Additionally, we have performed a feature importance analysis using the trained models and found that the most predictive features are the energy descriptors. These results demonstrate that API-polymer interaction energies are correlated with heterogeneous crystallization outcomes.

Simulating Crystallization in a Colloidal System Using State Predictive Information Bottleneck Based Enhanced Sampling.

We investigate crystal nucleation in supersaturated colloid suspensions using enhanced molecular dynamics simulations augmented with machine learning techniques. The simulations reveal that crystallization in the model colloidal system studied here, with particles interacting through a repulsive screened Coulomb Yukawa potential, proceeds from vapor to dense liquid droplet to crystalline phases across multiple high barriers. Employing a one-dimensional reaction coordinate derived from the State Predictive Information Bottleneck framework, our simulations capture back-and-forth phase transitions across multiple barriers effectively in biased metadynamics simulations. We obtain relative free energy differences between different phases and also quantify the roles of different molecular level features in driving the phase changes.

Identifying crystal nucleation mechanisms in a synthetic trachybasalt: a multimodal approach

To develop new criteria to distinguish different crystal nucleation mechanisms in silicate melts, we performed crystallization experiments using a synthetic hydrous (2 wt% H2O) trachybasalt and combined three-dimensional information from synchrotron X-ray computed microtomography with two-dimensional mapping of crystallographic orientation relationships (CORs) using electron backscatter diffraction. Crystallization experiments were performed at 400 MPa by cooling the melt from 1300 °C to resting temperatures of 1150 and 1100 °C and maintaining isothermal conditions for 30 min and 8 h. Three distinct titanomagnetite (Tmt) populations formed: (1) skeletal crystals, isolated or partially embedded in clinopyroxene (Cpx); (2) anhedral crystals, always attached to Cpx; (3) flattened needle-shaped crystals, embedded in Cpx. These morphologically different Tmt populations formed in response to one cooling event, with varying nucleation mechanisms and at different undercooling conditions. The clustered three-dimensional distribution of population 2 and 3 Tmt grains and the high proportion of Tmt-Cpx interfaces sharing CORs indicate that these Tmt grains heterogeneously nucleated on Cpx. The near-random three-dimensional distribution of (often isolated) population 1 Tmt grains, together with the low proportion of Tmt-Cpx interfaces sharing CORs, imply their isolated, possibly homogeneous nucleation, potentially followed by heterogeneous nucleation of Cpx on population 1 Tmt. Heterogeneous nucleation in slightly to moderately undercooled magmas should affect the sequence of crystallization as well as morphology and clustering of crystals, which may actively contribute to the variation of rheological parameters like viscosity. Finally, observed intra- and inter-sample variations in Tmt-Cpx COR frequencies indicate the potential for this parameter to record further petrological information.

Effect of wet grinding carbonation of sintering red mud on the performance of carbon sequestered mortar

The use of alkaline solid waste to CO2 capture is a potential way to upgrade the recycling of solid waste and reduce CO2 emission. In previous work, we proposed a novel wet grinding carbonation technique to achieve rapid carbonation of sintering red mud (SRM). Herein, the effect of wet grinding carbonation of SRM (WGCS) replacement rate (0 %, 5 %, 10 %, 15 %, 20 % and 25 %) on the hydration and hardening of Portland cement was further explored, such as rheology, compressive strength, hydration products and water transfer properties. The plastic viscosity and yield stress of carbon sequestered paste rose together with the WGCS replacement rate, which was due to the decreased D50 of SRM after wet grinding carbonation. When the WGCS replacement rate was 15 %, the 56 d compressive strength of carbon sequestered mortar was increased by 14.1 %. The microscopic characterization showed that the nucleation of calcite crystals and the pozzolanic reaction of silica-rich gels clearly improved the microstructure compactness. The electric flux and porosity of cement mortar was decreased by 25.7 % and 11.4 %, respectively. In terms of environmental and economic benefits, the CO2 sequestration of carbon sequestered mortar reached as high as 24.7 kg/m3 and the CO2 emission was reduced by 30.9 %.

Stereoselective Crystallization of Chiral Pharmaceuticals Aided by Cellulose Derivatives through Helical Pattern Matching.

Stereoselective inhibition aided by "tailor-made" polymeric additives is an efficient approach to obtain enantiopure compounds through conglomerate crystallization. The chemical and configurational match between the side groups of polymers and the molecules of undesired enantiomer is considered to be a necessary condition for successful stereoseparation. Whereas in this contribution, we present an effective resolution of chiral pharmaceuticals by using cellulose acetates as the additives, which stereoselectively reside on the specific crystal faces of one enantiomer and inhibit its crystal nucleation and growth through helical pattern and supramolecular interaction complementarity. An investigation of nimodipine serves as a case study to highlight the novelty of this strategy wherein R-crystals exhibiting an impressive enantiomeric excess value of 97 % can be attained by employing a mere 0.01 wt % cellulose acetate. Guaifenesin and phenyl lactic acid are also well-resolved by utilizing this methodology. Our work not only brings about a brand-new design strategy for "tailor-made" additives, but will also promote the further exploration of the endless potential for utilizing natural biomolecules in chiral recognition and resolution.

Iodine-induced self-depassivation strategy to improve reversible kinetics in Na-Cl2 battery

Rechargeable sodium-chlorine (Na-Cl2) batteries show high theoretical specific energy density and excellent adaptability for extreme environmental applications. However, the reported cycle life is mostly less than 500 cycles, and the understanding of battery failure mechanisms is quite limited. In this work, we demonstrate that the substantially increased voltage polarization plays a critical role in the battery failure. Typically, the passivation on the porous cathode caused by the deposition of insulated sodium chloride (NaCl) is a crucial factor, significantly influencing the three-phase chlorine (NaCl/Na+, Cl-/Cl2) conversion kinetics. Here, a self-depassivation strategy enabled by iodine anion (I-)-tuned NaCl deposition was implemented to enhance the chlorine reversibility. The nucleation and growth of NaCl crystals are well balanced through strong coordination of the NaI deposition-dissolution process, achieving depassivation on the cathode and improving the reoxidation efficiency of solid NaCl. Consequently, the resultant Na-Cl2 battery delivers a super-long cycle life up to 2000 cycles.

Passivation of Lead-Acid Batteries Lead Negative Electrodes by PbSO4 Crystals: Analysis from Modeling Cyclic Voltammetry Responses

Lead-acid batteries (LABs) play a pivotal role in the energy storage sector with applications spanning from starting-ignition-lightning batteries to grid energy storage. Passivation of lead negative electrodes by PbSO4 crystals is a one fundamental mechanism limiting the performance of LAB. In this regard, we developed an electrochemical mathematical model that simulates the nucleation and growth dynamics of PbSO4 crystals on a flat lead electrode, responsible for its passivation. The model considers the electrochemical dissolution of Pb2+ from lead electrode and the ternary transport of lead, bisulfate, and hydrogen ions in H2SO4 electrolyte. We have validated the model with a rich dataset of cyclic voltammetry (CV) responses collected at several scan rates and several concentrations of H2SO4. The model shows remarkable qualitative and quantitative agreement with the experimental data including the onset potential, center, height, and width of the CV peaks, discharge capacity, and particle size. The model is used to give insights on how different physical and operational parameters can influence the electrochemical response of lead negative electrodes. Keywords: lead-acid battery, nucleation and growth, passivation, cyclic voltammetry

The morphology of liquid CO2 hydrate films at different temperatures under saturation pressure

CO2 hydrate film formed on the surface of water droplets in liquid CO2 was studied via digital microscope system and in situ Raman spectrometer. Temperature significantly affects the initial morphology and lateral growth rate of hydrate film. In the temperature range of 273.15–279.15 K under corresponding saturation pressure of liquid CO2, the growth and development process is primarily separated into three stages, that is, rapid lateral growth, rapid thickening, and slow development. However, in the temperature range of 280.15–282.15 K, the growth and evolution of hydrated film is dominated by rapid lateral growth and slow development processes, while the rapid thickening disappears on our experimental scale, caused by the decrease in the driving force. Each of these two temperature ranges has unique characteristics and interesting discoveries during the hydrate film formation and development. For hydrate film formed at 283.15 K, the formation of hydrate is very difficult. It needs to nucleate inside the droplet with the assistance of the hydrate crystal seeds remaining in the water droplet after decomposition, so that the small hydrate crystals can grow in the water phase, and as the crystals get larger, they will eventually emerge on the droplet’s surface and produce a complete hydrate film. Combining the experimental phenomena during the growth and development of hydrate films at various temperatures, the further growth of the hydrate phase during the generation process mainly depends on the mass transfer process of water molecules through the hydrate film. This work provides valuable information on the mechanism of nucleation, growth and decomposition of liquid CO2 hydrate crystals, which is of great significance for applications in seafloor CO2 gas sequestration.

Silk sericin-coated polyamide thin-film composite membranes to simultaneously improve anti-scaling properties, long-term storage, and waste-to-resource recovery

A polyamide thin-film composite (PA-TFC) membrane, which is one of the widely used for desalination and water softening processes, features a lot of carboxyl groups inevitably formed by hydrolysis of unreacted acyl chlorides after interfacial polymerization. However, since carboxyl groups interact with multivalent cations and thereby cause membrane scaling, it is desirable to reduce the density of carboxyl groups on the membrane surface. In this regard, silk sericin (SS) can be an excellent alternative to modifying the surface characteristics to mitigate scaling because it has various hydrophilic amino acids with a much lower density of carboxyl groups per unit mass. Given the properties, we prepared anti-scaling TFC membranes by coating SS on the PA active layer. According to the result, the SS-PA-TFC (16.4% decrease) significantly reduced the flux decline to half of the PA-TFC (36.7% decrease) during the 48-h scaling test under the condition for heterogeneous gypsum crystal nucleation. More importantly, the comparison of operation duration until cleaning obviously revealed the anti-scaling properties of the SS-PA-TFC, which was evidenced by about 7.5 times longer duration than the PA-TFC. Furthermore, the cyclic scaling test in 19 mM CaSO4 showed that the SS-PA-TFC (3.6%) could decrease the irreversible fouling to about one-fifth of the PA-TFC (15.9%). This outstanding anti-scaling performance of the SS-PA-TFC stemmed from the less negatively charged (‐40.8 and ‐28.1 mV for the PA-TFC and SS-PA-TFC, respectively) and much more hydrophilic surface (52.2° and 18.2° for the contact angles of the PA-TFC and SS-PA-TFC, respectively). Suprisingly, the above-mentioned anti-scaling properties of the SS-PA-TFC membrane were achieved without the trade-off between water flux and salt rejection thanks to a very thin SS coating layer (ca. 16 nm). Apart from the anti-scaling properties, SS coating also improved long-term storage and waste-to-resource recovery.

In Situ Visual Observation of Surface Energy-Controlled Heterogeneous Nucleation of Metal Nanocrystals.

Electrochemical growth of metal nanocrystals is pivotal for material synthesis, processing, and resource recovery. Understanding the heterogeneous interface between electrolyte and electrode is crucial for nanocrystal nucleation, but the influence of this interaction is still poorly understood. This study employs advanced in situ measurements to investigate the heterogeneous nucleation of metals on solid surfaces. By observing the copper nanocrystal electrodeposition, an interphase interaction-induced nucleation mechanism highly dependent on substrate surface energy is uncovered. It shows that a high-energy (HE) electrode tended to form a polycrystalline structure, while a low-energy (LE) electrode induced a monocrystalline structure. Raman and electrochemical characterizations confirmed that HE interface enhances the interphase interaction, reducing the nucleation barrier for the sturdy nanostructures. This leads to a 30.92-52.21% reduction in the crystal layer thickness and a 19.18-31.78% increase in the charge transfer capability, promoting the formation of a uniform and compact film. The structural compactness of the early nucleated crystals enhances the deposit stability for long-duration electrodeposition. This research not only inspires comprehension of physicochemical processes correlated with heterogeneous nucleation, but also paves a new avenue for high-quality synthesis and efficient recovery of metallic nanomaterials.