Au Seeds Research Articles

Expanding Chemical Space in the Synthesis of Gold Bipyramids.

Gold bipyramids (AuBPs), despite having superior properties compared to their spectroscopically similar counterparts, gold nanorods, have found comparatively limited applications. This discrepancy is primarily due to the lack of protocols to tailor their dimensions. Typically, the concentration of Au seeds is virtually the sole factor that determines the aspect ratio and thus, the optical properties of AuBPs. As a result, varying the volumes of AuBPs while incurring minimal changes to their optical spectra remains a synthetically non-trivial task. Here, the chemical space in the seeded growth of AuBPs, is expanded by exploiting the interplay between bromide, silver ions, and seed concentration for tuning the final dimensions and optical properties of AuBPs. Specifically, a 6 fold change in volumes of AuBPs is achieved while maintaining the fixed plasmon band position. Further overgrowth of as-prepared bipyramids broadens the realizable dimensions without compromising quality and initial morphology. Overall, the results expand the chemical toolbox in the wet-chemistry synthesis of anisotropic gold nanoparticles, which is relevant for health, colorimetric sensors, and energy applications.

Carbon dots based AuAg@AuNPs with oxidase-like activity for SERS dual-readouts detection of D-penicillamine.

An oxidase (OXD)-like AuAg@AuNPs nanozyme was prepared by Au seeds growth using dopamine carbon dots as reducing and capping agents. The AuAg@AuNPs show excellent OXD-like and surface-enhanced Raman spectroscopy (SERS) activities and can oxidize the non-Raman-active leucomalachite green (LMG) into the Raman-active malachite green (MG). The research displays that D-penicillamine (D-PA) can effectively inhibit the OXD-like activity of Au@AgNPs and enhance the SERS signals as substrate. It is attributed to the formation of S-Au bond due to thiol (-SH) in D-PA. Therefore, a highly sensitive and specific SERS dual-readout sensing platform was proposed to assay D-PA with alimit of detection of 0.1μg/mL (direct SERS mode) and 6.64μg/L (indirect SERS mode). This approach was successfully used to determine D-PA in actual pharmaceutical formulations.

Selenium-Doped Seeded Growth of Truncated Octahedral Gold Nanocrystals with Surface Concavities for Surface-Enhanced Raman Spectroscopy.

Concave nanocrystals stand out as a testament to the importance of the nanoscale morphology in dictating the functional properties of materials. In this report, we introduce a facile synthesis method for producing gold (Au) nanocrystals with a truncated octahedral morphology that features surface concavities (Au CNTOs). The incorporation of selenium (Se) doping into the truncated octahedral Au seeds was essential for their enlargement and the formation of concave structures. By simply adjusting the quantity of seeds, we could control the size of the nanocrystals while maintaining their distinctive morphology and surface concavity. The formation mechanism suggests that Se doping likely passivates the side faces, thereby slowing growth and promoting atomic deposition at the edges and corners. The resulting Se-doped Au CNTOs exhibited strong localized surface plasmon resonance (LSPR) absorptions in the visible spectrum and the SERS performance of their assemblies was demonstrated through crystal violet detection, reaching enhancement factors around 105. This study presents an innovative approach to synthesizing concave Au nanocrystals through the incorporation of selenium during a seeded growth process, offering insights into the strategic design of plasmonic nanostructures.

Seed-Mediated Electrodeposition of Silver Nanowires and Nanorods.

Here, we compare the amount and morphology of silver (Ag) nanostructures electrodeposited at varied potentials and times in the presence of cetyltrimethylammonium bromide (CTAB) onto glass/indium tin oxide (glass/ITO) electrodes functionalized with mercaptopropyltrimethoxysilane (MPTMS) and coated or not coated with 4 nm average diameter Au nanoparticle (Au NP) seeds. There is a significantly larger amount of Ag deposited on the seeded electrode surface compared to that in the nonseeded electrode at potentials of -150 to -300 mV (vs Ag/AgCl) since the Au NP seeds act as catalysts for Ag deposition. At more negative overpotentials of -400 to -500 mV, the amount of Ag deposited on both electrodes is similar because the deposition kinetics are fast enough on glass/ITO that the Au seed catalyst does not make as big of a difference. Ag nanorods (NRs) and nanowires (NWs) form on the seeded surfaces, especially at more positive potentials, where deposition primarily occurs on the Au seed catalysts. Deposition of Ag onto the Au seeds appears as a separate peak in the voltammetry. This procedure mimics the seed-mediated growth of Ag NRs observed in solution in the presence of CTAB using ascorbic acid as a reducing agent. The yield, length, and aspect ratio of the Ag NRs/NWs depend on the deposition time and potential with the average length ranging from 300 nm to 3 μm for times of 30-120 min and potentials of -150 to -200 mV. The electrochemical seed-mediated growth of Ag NRs/NWs across electrode gaps could find use for resistive and surface-enhanced Raman-based sensing and molecular electronic applications.

Tuning the Geometry and Optical Chirality of Pentatwinned Au Nanoparticles with 5-Fold Rotational Symmetry.

Chirality transfer from chiral molecules to chiral nanomaterials represents an important topic for exploring the origin of chirality in many natural and artificial systems. Moreover, developing a promising class of chiral nanomaterials holds great significance for various applications, including sensing, photonics, catalysis, and biomedicine. Here we demonstrate the geometric control and tunable optical chirality of chiral pentatwinned Au nanoparticles with 5-fold rotational symmetry using the seed-mediated chiral growth method. A distinctive growth pathway and optical chirality are observed using pentatwinned decahedra as seeds, in comparison with the single-crystal Au seeds. By employing different peptides as chiral inducers, pentatwinned Au nanoparticles with two distinct geometric chirality (pentagonal nanostars and pentagonal prisms) are obtained. The intriguing formation and evolution of geometric chirality with the twinned structure are analyzed from a crystallographic perspective upon maneuvering the interplay of chiral molecules, surfactants, and reducing agents. Moreover, the interesting effects of the molecular structure of peptides on tuning the geometric chirality of pentatwinned Au nanoparticles are also explored. Finally, we theoretically and experimentally investigate the far-field and near-field optical properties of chiral pentatwinned Au nanoparticles through numerical simulations and single-particle chiroptical measurements. The ability to tune the geometric chirality in a controlled manner represents an important step toward the development of chiral nanomaterials with increasing architectural complexity for chiroptical applications.

Aqueous Synthesis of Plasmonic Gold-Tin Alloy Nanoparticles.

This protocol describes the synthesis of Au nanoparticle seeds and the subsequent formation of Au-Sn bimetallic nanoparticles. These nanoparticles have potential applications in catalysis, optoelectronics, imaging, and drug delivery. Previously, methods for producing alloy nanoparticles have been time-consuming, require complex reaction conditions, and can have inconsistent results. The outlined protocol first describes the synthesis of approximately 13 nm Au nanoparticle seeds using the Turkevich method. The protocol next describes the reduction of Sn and its incorporation into the Au seeds to generate Au-Sn alloy nanoparticles. The optical and structural characterization of these nanoparticles is described. Optically, prominent localized surface plasmon resonances (LSPRs) are apparent using UV-visible spectroscopy. Structurally, powder X-ray diffraction (XRD) reflects all particles to be less than 20 nm and shows patterns for Au, Sn, and multiple Au-Sn intermetallic phases. Spherical morphology and size distribution are obtained from transmission electron microscopy (TEM) imaging. TEM reveals that after Sn incorporation, the nanoparticles grow to approximately 15 nm in diameter.

Facile sulfur-assisted synthesis of GaAs nanowires /si heterojunctions for broadband self-powered photodetector

Nanowires (NWs)-based heterojunction photodetectors (PDs) have been widely applied in the fields of remote sensing, night vision, environmental monitoring, and optical communications with high light absorption coefficient and photoelectric conversion efficiency. Here, S-GaAs NWs/Si heterojunction was developed to form a broadband self-powered PDs by growing GaAs NWs on Si substrate through the sulfur-catalyzed assisted chemical vapor deposition (CVD) technology. Compared with the pure GaAs NWs, the sulfur-assisted catalysts could not only inhibit Ostwald ripening of Au seeds to improve the crystalline quality of NWs but also form a thin Ga–S bond passivation layer to reduce surface defects and enhance the optoelectronic performance of the PDs. The fabricated GaAs NWs/Si heterojunction PDs exhibit excellent performances with the large responsivity of 10.3 mA W−1 and high detectivity of 9.59 × 1012 cm Hz1/2 W−1. Additionally, the designed PDs have the broadband wavelength photoresponse from visible to near infrared and fast response speed (rise/fall time of 3.8/21.8 ms). Importantly, the develop strategy of hybrid heterojunction PDs can be extended to other semiconductor materials for facilitating the practical application of high-performance optoelectronic devices.

Plasma-assisted synthesis of gold-silver core-shell nanoparticles and their enhanced catalytic dye degradation and surface enhanced Raman spectroscopy performance

The plasma-liquid interaction (PLI) technique has been employed as a green approach for the synthesis of gold-silver core-shell nanoparticles (Au@AgNPs) using a two-step method. In the first step, the Au seed particles were grown by the PLI technique. Subsequently, the formation of Ag shell was achieved by adding AgNO3 to the solution containing Au seeds and placing it under the atmospheric pressure plasma. The growth of Ag shell on Au seeds was optimized and secondary nucleation was avoided by tuning the discharge current, precursor concentration, and stabilizer (d-fructose) concentration. The shell thickness of Ag was also changed by changing the concentration of AgNO3 in the solution. UV-Vis spectroscopy, scanning electron microscopy, and energy-dispersive x-ray spectroscopy were used to analyze the synthesized nanoparticles. Furthermore, the particles were employed for catalysis and surface enhanced Raman spectroscopy (SERS)-based molecular trace detection. The catalytic efficiency of the NPs was investigated for the reduction of four molecules, i.e., 4-nitrophenol, methyl orange, Congo red, and rhodamine B. The SERS-based trace detection was studied for rhodamine 6G using the substrates of synthesized NPs. In both cases, core-shell nanoparticles showed far superior performance compared to the seed Au nanoparticles.

Ferromagnetic resonance-based heat dissipation in dumbbell-like Au–Fe3O4 nanoparticles

Ferromagnetic resonance (FMR) holds promise for heating magnetic nanoparticles (MNPs) in cancer therapy, especially for rapidly heating MNPs. This study aims to enhance the FMR-based heating efficiency of multifunctional hybrid gold and iron oxide nanoparticles (Au-Fe3O4 NPs) as theranostic agents. We experimentally investigate the FMR-based heating properties of newly developed dumbbell-like Au-Fe3O4 NPs, which feature ∼5 nm gold and 15 nm iron oxide components, in comparison to our previously developed Au-coated Fe3O4 NPs (Fe3O4 core ∼5.2 nm, Au shell thickness ∼0.5 nm). For comparison, we also synthesize pure Fe3O4 NPs (∼11 nm) under the same experimental conditions as the dumbbell-like Au-Fe3O4 NPs but without 5 nm Au seeds. Temperature measurements are taken at various DC fields (HDC = 0‒1600 Oe) under a radiofrequency (RF) field (fAC = 4 GHz, HAC = 1.265 Oe) for ∼13s. The results reveal a rapid temperature rise during RF field ON, followed by a decline upon RF field OFF. Remarkably, dumbbell-like Au-Fe3O4 NPs achieve a peak temperature increase of 23.4 °C, corresponding to a heating rate of 1.73 °C/s at HDC = 400 Oe, surpassing the combined values of ∼11 nm Fe3O4 NPs (11.0 °C, i.e., 0.83 °C/s at HDC = 1000 Oe) and ∼5 nm Au NPs (3.5 °C). Comparing these results to our previously developed Au-coated Fe3O4 NPs, which achieved a heating rate of 1.29 °C/s (temperature rise 16.9 °C) under HDC = 1200 Oe with an RF field at fAC = 4 GHz and a significantly higher HAC = 4 Oe (i.e. for HAC = 1.265 Oe, the estimated heating rate was 0.129 °C/s with a temperature rise of 1.69 °C), the dumbbell-shaped Au-Fe3O4 NPs demonstrate a substantially higher temperature increase by 13.4 times. These findings highlight the exceptional potential of dumbbell-shaped Au-Fe3O4 NPs for application in magnetic hyperthermia.

Urchin-like covalent organic frameworks templated Au@Ag composites for SERS detection of emerging contaminants.

Au@Ag core-shell composites were successfully fabricated on urchin-like covalent organic frameworks (COFs), providing a platform with numerous hot spots for the detection of two categories of emerging contaminants: sulfonamide antibiotics and nanoplastics, using surface-enhanced Raman spectroscopy (SERS). Au seeds (∼10 nm) were generated on the COFs, leveraging the reducing properties of the vinyl and imino groups within the framework. This ensured the growth of dense and uniformly distributed Ag nanoparticles. The COFs exceptionally large surface area (2324 m2 g-1) and high adsorption capacity, significantly contributed to the enrichment and detection of trace pollutants. As a result, using a portable Raman spectrometer, limits of detection of 0.008 μmol L-1 for sulfamethoxazole and 0.029 mg L-1 for polystyrene nanoplastics were achieved.

Homochiral Nanopropeller via Chiral Active Surface Growth.

Under the control of chiral ligand glutathione and in the presence of hexadecyltrimethylammonium bromide, Au deposition on Au seeds is known to give chiral nanostructures. We have previously shown that the protruding chiral patterns, as opposed to flat facets, are likely caused by active surface growth, where nonuniform ligand coverage could be responsible for the focused growth at a few active sites. By pushing the limit of such a growth mode, here, we use decahedral seeds to prepare homochiral nanopropellers with intricate patterns of deep valleys and protruding ridges. Control experiments show that the focused growth depends on the rates of Au deposition by changing either the seed concentration or the reductant concentration, consistent with the proposed mechanism. The dynamic growth competition between the ligand-deficient active sites and the ligand-rich surfaces gradually focuses the growth onto a few active sites, causing the expansion of grooves, squeezing of steep ridges, and a surprising 36° rotation of the pentagonal outline. The imbalanced deposition on the prochiral slopes is responsible for the tilted grooves, the twisted walls, and thus the well-separated and distorted blades, which become the origin of the chiroptical responses.

Separation of Nanoparticle Seed Pseudoisomers via Amplification of Their Crystallographic Differences.

Seed-mediated syntheses rely on small nanoparticle (NP) precursors that act as templates for growth but are often inhomogeneous with respect to their internal twinning structures (e.g., single crystalline, multiply twinned), leading to nonuniform product morphologies. To address this, we developed a method for separating seed NPs of the same approximate size (∼ 10 nm) but with different interior twinning (i.e., NP "pseudoisomers") by exaggerating their crystallographic differences through heteroexpitaxial metal overgrowth. Specifically, single crystalline and pentatwinned Au seeds that are natively inseparable via traditional methods exhibit drastically different Ag shell morphologies that allow for their selective precipitation through colloidal depletion forces. Oxidation of the Ag shell from separated particles results in seeds that are both size uniform and crystallographically pure (>99%), allowing for the controlled synthesis of a library of Oh- and D5h-symmetric gold NPs bearing {111}, {110}, {730}, {310}, {720}, and {100} facets, several of which have no precedent in the literature. These results lay the foundation for precision nanosynthesis by establishing a new paradigm for the purification of NP precursors.

Chiral Gold Nanorods with Five‐Fold Rotational Symmetry and Orientation‐Dependent Chiroptical Properties of Their Monomers and Dimers

AbstractChiral plasmonic nanoparticles have attracted much attention because of their strong chiroptical responses and broad scientific applications. However, the types of chiral plasmonic nanoparticles have remained limited. Herein we report on a new type of chiral nanoparticle, chiral Au nanorod (NR) with five‐fold rotational symmetry, which is synthesized using chiral molecules. Three different types of Au seeds (Au elongated nanodecahedrons, nanodecahedrons, and nanobipyramids) are used to study the growth behaviors. Different synthesis parameters, including the chiral molecules, surfactant, reductant, seeds, and Au precursor, are systematically varied to optimize the chiroptical responses of the chiral Au NRs. The chiral scattering measurements on the individual chiral Au NRs and their dimers are performed. Intriguingly, the chiroptical signals of the individual chiral Au NRs and their end‐to‐end dimers are similar, while those of the side‐by‐side dimers are largely reduced. Theoretical calculations and numerical simulations reveal that the different chiroptical responses of the chiral NR dimers are originated from the coupling effect between the plasmon resonance modes. Our study enriches chiral plasmonic nanoparticles and provides valuable insight for the design of plasmonic nanostructures with desired chiroptical properties.

Chiral Gold Nanorods with Five-Fold Rotational Symmetry and Orientation-Dependent Chiroptical Properties of Their Monomers and Dimers.

Chiral plasmonic nanoparticles have attracted much attention because of their strong chiroptical responses and broad scientific applications. However, the types of chiral plasmonic nanoparticles have remained limited. Herein we report on a new type of chiral nanoparticle, chiral Au nanorod (NR) with five-fold rotational symmetry, which is synthesized using chiral molecules. Three different types of Au seeds (Au elongated nanodecahedrons, nanodecahedrons, and nanobipyramids) are used to study the growth behaviors. Different synthesis parameters, including the chiral molecules, surfactant, reductant, seeds, and Au precursor, are systematically varied to optimize the chiroptical responses of the chiral Au NRs. The chiral scattering measurements on the individual chiral Au NRs and their dimers are performed. Intriguingly, the chiroptical signals of the individual chiral Au NRs and their end-to-end dimers are similar, while those of the side-by-side dimers are largely reduced. Theoretical calculations and numerical simulations reveal that the different chiroptical responses of the chiral NR dimers are originated from the coupling effect between the plasmon resonance modes. Our study enriches chiral plasmonic nanoparticles and provides valuable insight for the design of plasmonic nanostructures with desired chiroptical properties.

Interrelated Roles of Multiple Key Structure-Directing Agents in Seed-Mediated Growth of Monodisperse and Multibranched Au Nanoparticles.

Detailed mechanistic investigations of the interrelated roles of multiple key structure-directing agents in the growth solution of Au nanoparticles (AuNPs) is required for the optimization of synthetic protocols. Here, we report a robust seed-mediated growth strategy for synthesizing multibranched NPs (MB-AuNPs) with monodispersed size distribution, and investigate the roles of Ag ions and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid (HEPES) based on an overgrowth synthesis approach. The intertwining roles of Ag+, surface-capping stabilizers, and reducing agents were elucidated, and used to control the morphology of MB-AuNPs. The overgrowth of MB-AuNPs involves two distinct underlying pathways, namely, directional and anisotropic growth of Au branches on specific facets of Au seeds as well as an aggregation and growth mechanism governed by HEPES. In addition to Ag ions and HEPES, morphology tunability can also be achieved by pre-modification of the Au seeds with molecular probes. Optimized probe-containing MB-AuNPs prove to be excellent surface-enhanced Raman scattering (SERS) substrates and nanozymes. Taken together, the results of this work reveal the mechanistic evolution of nanocrystal growth which should stimulate the development of new synthetic strategies, improve the capabilities of tuning the optical, catalytic, and electronic properties of NPs, and further advance their applications in biolabeling, imaging, biosensing, and therapy.

Elucidating the role of seed structure in the heterometallic seeded growth of copper-based nanocrystals

Seed-mediated synthesis is a versatile method to prepare multimetallic nanocrystals for diverse applications. However, many fundamental questions remain on how the structural and chemical properties of nanocrystal seeds control the reaction pathways, especially for nonaqueous synthesis at elevated temperatures. Herein, we elucidate the role of surface ligands and crystallinity of Au nanocrystal seeds on the heterometallic seeded growth of Cu-based nanocrystals. We found that weakly coordinating ligands are critical to facilitate the diffusion between Au and Cu, which enables subsequent one-dimensional growth of Cu. Replacing multiple-twinned Au seeds with single-crystalline ones switched the growth pathway to produce heterostructured nanocrystals. Our work illustrates the importance of precise control of seed characteristics for the predictive synthesis of structurally complex multimetallic nanocrystals.

Seed-assisted electrodeposition of multilayer Au nanoparticles-assembled films for sensitive surface-enhanced Raman scattering detection

Surface-enhanced Raman scattering (SERS) spectroscopy can be used to realize sensitive rapid detection of molecules. Three-dimensional (3D) SERS substrates can provide more hotspots within the excitation laser beam when compared with the corresponding two-dimensional (2D) SERS substrates. Most of the methods for fabrication of 3D SERS substrates involve complex processes. Therefore, it is significant to develop a simple and effective method for fabrication of 3D SERS substrates. Here, a seed-assisted electrodeposition approach is developed for fabrication of a 3D SERS substrate composed of multilayer Au nanoparticles. Interestingly, it is demonstrated that a uniform film composed of multilayer Au nanoparticles that can serve as a 3D SERS substrate can be achieved directly by one-step electrodeposition on a conductive surface coated with monolayer Au seeds. It is found that a diffusion-controlled growth during electrodeposition narrows the nanoparticle size distribution and results monosized Au nanoparticles. The as-prepared multilayer Au nanoparticles-assembled film shows high SERS sensitivity and good spectral uniformity. For SERS detection of rhodamine 6G, a limit of detection as low as 3.4×10−12 M has been achieved. Moreover, good spectral uniformity (relative standard deviation ∼7.8%) and high substrate-to-substrate reproducibility (relative standard deviation ∼8.6%) have also been demonstrated. The as-prepared multilayer Au nanoparticles-assembled film is used to detect organic pollutants such as dye molecule crystal violet (CV) and methylene blue (MB). Calibration curves with a linear correlation between the logarithmic SERS intensity and logarithmic concentration of CV and MB have been obtained. Limit of detections for CV and MB are 1.2×10−8 M and 9.8×10−10 M, respectively. Therefore, the fabricated 3D SERS substrate has good application prospects in sensitive detection of organic molecules.

Au-wrapped CuS-Interlaced Chain Structure for Ultrafast Response and High Sensitive Non-Enzymatic Glucose Sensor

We report the fabrication and testing of ultrafast response nonenzymatic glucose sensor based on the use of interlaced chain structure Au@CuS nanomaterial. The new Au@CuS nanomaterial was synthesized by a facile solvothermal method from L-cysteine、Cu(NO3)2·3H2O and Au Seeds without using additional surfactants or templates. The combination of Au and CuS solves the problems of poor electrical conductivity of CuS and the susceptibility of Au to toxicity, while the interlaced chain structure exposes more active sites to facilitate the diffusion of glucose molecules with a low resistance to increase the inter-electron transfer rate. The non-enzymatic Au@CuS-based glucose sensor showed a wide linear range with excellent sensitivity (5817.37 and 3629.78 μA mM−1cm−2), ultrafast response time (<0.1 s), excellent selectivity and outstanding long-term stability. Further, the designed glucose sensor was used to determine glucose in human blood serum sample with satisfactory result.

Intermetallic Au3LixM1-x (M = Fe, Ni or Co) nanoalloys: Effect of synthetic conditions on the composition and order-disorder transition

Nanoalloys combining magnetic and plasmonic properties are interesting systems for catalysis and photo-catalysis, magneto-optics, nanomagnetism and fundamental studies. Nevertheless, their synthesis is challenging due to the immiscibility of Au and 3d magnetic metals at mild temperatures in equilibrium conditions. In this work we prepared through colloidal chemistry synthesis Au3LixM1-x (M = Fe, Ni or Co) nanoalloys and studied the synthetic conditions that affect the transition between a disordered and an ordered L12 intermetallic alloy crystal phase. We found that Au seeds act as templates for the formation of the intermetallic nanoalloys, and that lithium (coming from the Butyllithium reducing agent injected after the seeds formation) plays a fundamental role in the stabilization of the intermetallic phase. By tuning the synthetic parameters, we were able to tune the Fe content in Au3LixFe1-x intermetallic nanoalloys from 0.6 to 2.6 %, also tuning the magnetic moment of the nanoalloys. All the synthesized nanoalloys were able to sustain a plasmonic resonance in the visible range, which is blue shifted and broadened with respect to Au NPs. Our results can open colloidal synthesis to novel crystal phases and nanomaterials combining plasmonic and magnetic functionalities at the nanoscale.

Geometrical design of top-to-bottom magnesiophilicity-gradient host for reversible Mg-metal batteries

Magnesium-metal batteries (MMBs) are promising candidates for large-scale energy-storage systems owing to their high volumetric capacity, low cost, and high level of safety. However, the problems of dendritic Mg deposition and its poor adhesion to a substrate remain unresolved. Herein, we first propose a unique geometrical design of a top-to-bottom magnesiophilicity-gradient 3D host for reversible MMBs. By systematically stacking three mesh layers with different Mg affinities, the 3D-Mg affinity controlled architecture (3D-MACA) can be simply fabricated. The bottom layer was designed to contain numerous nanofibers decorated with magnesiophilic Au seeds, which effectively guided the bottom-oriented Mg nucleation. In addition, the electrically insulated top layer could minimize the undesirable top-plating of Mg. As a result, 3D-MACA showed the lowest nucleation overpotential and highest cycle retention among the potential candidates. For evidence of bottom-oriented growth, ex-situ observation analysis of 3D-MACA was performed, and the geometrical effect was further investigated and explained by the theoretical 3D simulation. The proposed strategy may provide insight for future studies aimed at solving the prevailing issues for MMBs; in addition, the unique design can be extended to other metal battery systems.