Heterostructured Nanoparticles Research Articles

Layered Ferrihydrite and BN Nanoparticle Heterostructures Doped with Ag for CO2 Hydrogenation

Layered Ferrihydrite and BN Nanoparticle Heterostructures Doped with Ag for CO₂ Hydrogenation

Nanocage confined nitrogen-rich MOF-derived Co/CoN heterostructure for overall water splitting

Of great significance is the study towards replacing precious metal electrocatalysts with transition metal electrocatalysts for the electrocatalytic hydrogen evolution from water, regarding clean energy utilization. The precise design and engineering of catalysts at the nanoscale, with a focus on their structural and functional attributes, have garnered significant attention and research interest as pivotal approaches to optimizing their catalytic performance. Among those strategies, fabricating transition metals and their corresponding nitrides has lately gained extensive attentions for electrocatalytic water decomposition, because of their adjustable distribution of electrons. In this study, ZIF-67@MAT-6 precursor was formed by coating ZIF-67 with triazole ligand (MAT-6) based on ligand exchange strategy, followed by confining Co/CoN heterostructure nanoparticles in nitrogen-doped carbon nanocages upon heat treatment under nitrogen flow. The resulting electrocatalyst exhibited outstanding electrocatalytic performance for hydrogen and oxygen evolution reactions in alkaline media, with overpotentials of 115 mV and 290 mV to reach 10 mA·cm−2 in 1 M KOH electrolyte, respectively. In addition, the electrocatalyst showed great durability with only 2.16 % current decay during 24 h potentiostatic electrolysis for water decomposition. The density functional theory (DFT) theoretically supported that the accelerated interfacial charge transfer and promoted electrical conductivity were responsible for the remarkable electrocatalytic performance, caused by the synergic effect between the heterogeneous Co and CoN.

Colloidal Synthesis of (PbBr2)2(AMTP)2PbBr4 a Periodic Perovskite "Heterostructured" Nanocrystal.

Heterostructures in nanoparticles challenge our common understanding of interfaces due to quantum confinement and size effects, giving rise to synergistic properties. An alternating heterostructure in which multiple and reoccurring interfaces appear in a single nanocrystal is hypothesized to accentuate such properties. We present a colloidal synthesis for perovskite layered heterostructure nanoparticles with a (PbBr2)2(AMTP)2PbBr4 composition. By varying the synthetic parameters, such as synthesis temperature, solvent, and selection of precursors, we control particle size, shape, and product priority. The structures are validated by X-ray and electron diffraction techniques. The heterostructure nanoparticles' main optical feature is a broad emission peak, showing the same range of wavelengths compared to the bulk sample.

NiSe2/CoSe2 heterostructure nanoparticles anchoring on graphene for enhanced Li-ions storage

Selenide anodes have been extensively studied due to their exceptional electrochemical performance in lithium-ion batteries (LIBs). However, selenides suffer from inadequate specific capacity and high mechanical stress/strain resulting from significant volume changes during cycling. This leads to a rapid reduction in capacity and reversibility, which limits their practical application. Nanoscale bimetallic heterostructure selenides can effectively reduce the lattice vibration induced by lithiation/delithiation and improve the lithium storage capacity and cycle life. This study describes the preparation of NiSe2 and CoSe2 nanoparticles anchored on graphene (NiSe2/CoSe2/Graphene) using freeze-drying and thermal selenization methods. The graphene, selenide particles, and electric field between heterostructure interfaces significantly enhance electrical conductivity, provide active species storage sites, and improve lithium-ion adsorption ability, resulting in high storage capacity and excellent cycling stability. The NiSe2/CoSe2/Graphene composite exhibited a specific capacity of 929.6 mAh g−1 after 320 cycles at a current density of 100 mA g−1. Even at a high current density of 1000 mA g−1, the composite was stably cycled for 1250 cycles with a continuous increase in specific capacity. This study provides valuable insights into the use of bimetallic selenides for improved lithium storage.

Construction of nickel phosphide/iron oxyhydroxide heterostructure nanoparticles for oxygen evolution

Active and stable oxygen evolution electrocatalysts are essential in increasing the efficiency of water electrolyzers. The Ni2P/Fe(O)OH heterostructure nanoparticles are prepared via solvothermal phosphidization of Ni metal-organic frameworks (MOF) followed by immersing in Fe3+ aqueous solution. Characterizations reveal that the Ni2P/Fe(O)OH heterostructure nanoparticles are 12.83 nm in size averagely, and the heterointerface induces electron interactions between the Ni2P and Fe(O)OH phases. When used to catalyze OER in alkaline solutions, the Ni2P/Fe(O)OH-40/nickel foam (NF) is the most active and exhibits 240 mV overpotential to reach 10 mA cm−2 oxygen evolution (OER) current densities, which is significantly better than the Ni2P/NF. Lower apparent activation energy, charge transfer resistance, and Tafel slope, along with higher electron rate constant are observed at Ni2P/Fe(O)OH-40/NF, which suggests that the OER kinetics is more facile at the surface of heterostructure nanoparticles. The OER mechanistic pathways of both Ni2P/Fe(O)OH-40/NF and Ni2P/NF involve decoupled electron and proton transfer processes, and higher degree of lattice oxygen oxidation mechanism (LOM) participation is observed at Ni2P/Fe(O)OH-40/NF, which results from the increased acidity of the Ni sites. Density functional theory calculations prove that the formation of heterostructure with Fe(O)OH alters the band structure and the adsorption energies of OER intermediates, which leads to lower energy barrier in the rate-determining step. The Ni2P/Fe(O)OH-40/NF is also stable towards OER in alkaline solutions.

Three-phase Sn-based heterostructure nanoparticles anchored on N-doped graphene as a promising anode for lithium/sodium storage

Microstructure modulation by phase engineering induces electrode materials to exhibit excellent energy storage performance due to their adjustable surface/ interface and electronic characteristics. For tin dioxide (SnO2), effective strategies for adjusting their microstructure properties are still lacking. Herein, 2D flexibleN-doped graphene (NG) is rationally integrated with SnO2/SnS/Sn heterostructure via hydrothermal and subsequent partial in-situ vulcanization, in which the SnO2/SnS/Snnanoparticles are tightly anchored on NG network (SnO2/SnS/Sn@NG). The unique SnO2/SnS/Snheterostructures with modulated electronic properties can induce accelerated charge transfer kinetics and enhanced ionsdiffusion/adsorption capacities. The hierarchical structure with a large surface area along with nanocomponents can offer better permeability, more available charge storage sites of active material, and a stable electrochemical framework. As expected, the SnO2/SnS/Sn@NG heterostructure as an anode for lithium-ion battery exhibits an excellent charge capacity of 748 mAh g−1at 0.2 A g−1, long-term cyclic stability of 507 mAh g−1 at 1Ag−1for 800 cycles, and high-rate capability with of 476 mAh g−1 at 5Ag−1. Moreover, the anode for sodium-ion battery also shows excellent cyclic stability and rate capability.

Enhancing energy storage performance of PVDF-based composites through semiconducting AZO-BT heterostructure

Commercially available flexible dielectric capacitors with high energy density (Ud) still present a significant challenge due to the inherent trade-off between breakdown strength (Eb) and dielectric constant (εr). In this context, a novel strategy is proposed to synchronously improve the Eb and εr of PVDF-based polymer capacitors by incorporating AZO-BT heterostructure nanoparticles, forming AZO-BT/PVDF composite films. Initially, the tightly polarized AZO affixed to the surface of BT particles create a localized electric field that enhances and sustains the polarization intensity of BT. Additionally, the heterojunction electric field generated inhibits the migration of the injected electron. Furthermore, the semiconducting AZO with high electron affinity effectively captures and traps the injected and excited electrons. Notably, the existed oxygen vacancies in AZO significantly enhances Eb and polarization reverse. Consequently, the AZO-BT/PVDF composite film achieves the highest Ud of 9.10 J·cm−3 at 460 MV·m−1. The innovative approach of constructing a semiconducting-ferroelectric heterostructure offers a promising avenue for designing and fabricating high energy density polymer capacitors.

Heterostructure MnO/MnSe nanoparticles encapsulated in a nitrogen-doped carbon shell for high-performance lithium/sodium-ion batteries

Heterostructure MnO/MnSe nanoparticles, encapsulated in a nitrogen-doped carbon shell (MnO/MnSe@NC), were synthesized as anode materials using a hydrothermal approach followed situ calcination and selenization process. The NC shell, possessing high electronic conductivity, can function as a substrate to prevent nanoparticle agglomeration and mitigate volume variations. The porous nanostructures can shorten the ion diffusion path and increase active sites, thereby accelerating ion migration and ultimately enhancing battery capacity. Moreover, the MnO/MnSe heterostructure can facilitate Li+/Na+ diffusion, leading to improved rate performance. Benefiting from the structural advantage of MnO/MnSe heterostructure nanoparticles encapsulated within a nitrogen doped carbon shell, this electrode demonstrates exceptional electrochemical performance as an anode for LIBs, including a high discharge capacity (1740 mAh g−1 at 0.1 A g−1), remarking rate capability (849.9 mAh g−1 at 15.0 A g−1), and superior cycling stability (802 mAh g−1 over 1500 cycles at 5.0 A g−1). Meanwhile, the MnO/MnSe@NC serves as an anode material in SIBs, demonstrating a remarkable reversible specific capacity of 902.8 mAh g−1 at 0.1 A g−1 and excellent rate capability (681.6 mAh g−1 at 15.0 A g−1). The present study presents a straightforward approach for fabricating the anode electrode of high-performance lithium/sodium ion batteries.

FeNiCo|MnGaOx Heterostructure Nanoparticles as Bifunctional Electrocatalyst for Zn-Air Batteries.

Driven by the pressing demand for stable energy systems, zinc-air batteries (ZABs) have emerged as crucial energy storage solutions. However, the quest for cost-effective catalysts to enhance vital oxygen evolution and reduction reactions remains challenging. FeNiCo|MnGaOx heterostructure nanoparticles on carbon nanotubes (CNTs) are synthesized using liquid-phase reduction and H2 calcination approach. Compared to its component, such FeNiCo|MnGaOx /CNT shows a high synergistic effect, low impedance, and modulated electronic structure, leading to a superior bifunctional catalytic performance with an overpotential of 255mV at 10mAcm-2 and half-wave potential of 0.824V (ω=1600rpm and 0.1m KOH electrolyte). Moreover, ZABs based on FeNiCo|MnGaOx /CNT demonstrate notable features, including a peak power density of 136.1mWcm-2 , a high specific capacity of 808.3mAhgZn -1 , and outstanding stability throughout >158h of uninterrupted charge-discharge cycling. Theoretical calculations reveal that the non-homogeneous interface can introduce more carriers and altered electronic structures to refine intermediate adsorption reactions, especially promoting O* formation, thereby enhancing electrocatalytic performance. This work demonstrates the importance of heterostructure interfacial modulation of electronic structure and enhancement of adsorption capacity in promoting the implementation of OER/ORR, ZABs, and related applications.

Oxygen-Independent Synchronized ROS Generation and Hypoxia Prodrug Activation with Z-Scheme Heterostructure Sonosensitizer.

Combination therapy has emerged as a promising approach for effective tumor treatment. However, the combination of sonodynamic therapy (SDT) and hypoxia-activated prodrugs (HAPs) has not been explored due to the contradictory requirement of oxygen (O2 ) for reactive oxygen species (ROS) generation and the necessity to avoid O2 for the activation of HAPs. In this study, this challenge is addressed by developing BiOCl-Au-Ag2 S Z-scheme heterostructure nanoparticles loaded with tirapazamine (TPZ) to achieve O2 -independent therapy. These nanoparticles demonstrate efficient electron-hole separation under ultrasound irradiation while maintaining a high redox potential. The generated holes react with water to efficiently produce hydroxyl radicals, while the electrons autonomously activate TPZ, negating the need for O2 . In vitro and in vivo assessments validate the effective tumor elimination by these Z-scheme nanoparticles without disrupting the hypoxic environment. This innovative design overcomes the limitations associated with O2 requirement in SDT and introduces a novel strategy for HAP activation and synergistic therapy between ROS and HAPs-based therapy.

Co3Fe7/CoCx nanoparticles encapsulated in nitrogen-doped carbon nanotubes synergistically promote the oxygen reduction reaction in Zn-air batteries

Efficient and stable non-precious metal catalysts (NPMCs) for the oxygen reduction reaction (ORR) are crucial for the advancement of Zn-air batteries. Herein, we report a supramolecular self-scarifying template and confinement pyrolysis strategy to obtain an efficient ORR catalyst of well-dispersed Co3Fe7/CoCx heterostructure nanoparticles encapsulated by nitrogen-doped carbon nanotubes (Co3Fe7/CoCx@N-CNT). The as-synthesized Co3Fe7/CoCx@N-CNT catalyst exhibited outstanding ORR activity, with a half-wave potential of 0.88 V versus a reversible hydrogen electrode, and good stability. The Zn-air battery based on the Co3Fe7/CoCx@N-CNT cathode achieved a peak power density of 265 mW cm−2 and a durability of over 200 h, which is superior to most reported NPMCs and even the Pt/C counterpart. The physical characterization and electrochemical poisoning experiments revealed that the Co3Fe7/CoCx nanoparticles in the core along with pyridine N and Fe–Nx hosted in the carbon nanotube all acted as active sites for the ORR. Further theoretical calculations showed that the charge redistribution between the Co3Fe7/CoCx nanoparticles and the Fe–Nx carbon overlayers downshifted the d-band center of Fe and optimized the adsorption ability, which boosted the ORR kinetics. This work provides an effective strategy to synthesize non-precious metal ORR catalysts with multiple active sites and highlights the synergistic role of encapsulated nanoparticles and carbon support.

Procedural Promotion of Multiple Stages in the Wound Healing Process by Graphene-Spiky Silica Heterostructured Nanoparticles.

Multiple stages including hemostasis, inflammation, proliferation, and remodeling were involved in the wound healing process. The increase in nanomaterials in recent years has extended the scope of tools for wound healing; however, it is still difficult to achieve the four multistage procedures simultaneously. In this study, graphene-spiky silica heterostructured nanoparticles (GS) were synthesized for the procedural acceleration of the multistage in wound healing process. The nanobridge effect of GS was analyzed through the adhesion of two skins, the antibacterial effect was assessed in Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) bacteria, cell proliferation and migration were investigated in mouse embryonic fibroblast (NIH-3T3) cells, and the in vivo wound healing effect was examined in female BALB/c mice with a cutting wound and E. coli or S. aureus bacteria infection on the back. First, GS has a strong nanobridge effect on the rapid closure of wounds because the spiky architecture on the surface of GS facilitates the adhesion of skins, promoting the hemostasis stage. Second, graphene exhibits antimicrobial activities both in chemical and physical interactions, especially under simulated sunlight irradiation. Third, graphene plays an important role in scaffolding function, together with the spiky topographical architecture of GS, accelerating the proliferation and maturation stages. By periodically promoting every stage of wound healing, GS combined with simulated sunlight irradiation could significantly accelerate wound healing. With a simple composition and compact structure but multiple functions, this strategy will be the guideline for the development of ideal wound-healing nanomaterials.

Thermally Induced Domain Migration and Interfacial Restructuring in Cation Exchanged ZnS-Cu1.8S Heterostructured Nanorods.

Partial cation exchange reactions can be used to rationally design and synthesize heterostructured nanoparticles that are useful targets for applications in photocatalysis, nanophotonics, thermoelectrics, and medicine. Such reactions introduce intraparticle frameworks that define the spatial arrangements of different materials within a heterostructured nanoparticle, as well as the orientations and locations of their interfaces. Here, we show that upon heating to temperatures relevant to their synthesis and applications, the ZnS regions and Cu1.8S/ZnS interfaces of heterostructured ZnS-Cu1.8S nanorods migrate and restructure. We first use partial cation exchange reactions to synthesize a library of seven distinct samples containing various patches, bands, and tips of ZnS embedded within Cu1.8S nanorods. Upon annealing in solution or in air, ex situ TEM analysis shows evidence that the ZnS domains migrate in different ways, depending upon their sizes and locations. Using differential scanning calorimetry, we correlate the threshold temperature for ZnS migration to the superionic transition temperature of Cu1.8S, which facilitates rapid diffusion throughout the nanorods. We then use in situ thermal TEM to study the evolution of individual ZnS-Cu1.8S nanorods upon heating. We find that ZnS domain migration occurs through a ripening process that minimizes small patches with higher-energy interfaces in favor of larger bands and tips having lower-energy interfaces, as well as through restructuring of higher-energy Cu1.8S/ZnS interfaces. Notably, Cu1.8S nanorods containing multiple patches of ZnS thermally transform into ZnS-Cu1.8S heterostructured nanorods having ZnS tips and/or central bands, which provides mechanistic insights into how these commonly observed products form during synthesis.

Crucial Role of Self‐Exsolved Heterostructured Cermet Nanoparticles in Highly Active Spinel Electrodes for CO2/H2O Co‐Electrolysis

AbstractThe versatility of the spinel (AB2O4) oxides means they are of great interest for a variety of catalysis and energy conversion applications, involving gas reactions and reforming. CuFe2O4 spinel is identified as a highly efficient fuel electrode for CO2/H2O co‐electrolysis due to its promising electrocatalytic activity. To identify the actual active sites, the electrochemical characteristics, composition, chemical state, and microstructure are systematically investigated while optimizing the electrolysis performance by varying the feed gas composition. Markedly enhanced electrolysis current density is achieved under a CO2‐enriched composition of 50%CO2/10%H2O‐Ar. This promising performance is attributed to the in situ exsolution of heterostructural “Cu/Fe3O4” nanoparticles on the parent CuFe2O4 surface during co‐electrolysis. Interestingly, a strong correlation of the electrolysis performance with the amount of the formed heterostructural cermet is observed. The exsolved cermet heterostructure plays a crucial role in CO2/H2O electroreduction, as also confirmed by density‐functional‐theory studies. The self‐exsolved Cu/Fe3O4 nanoparticles present exceptional strength due to a strong interaction between the formed metallic Cu and Fe3O4, enabling the electrode to remain active and stable under such high electrical polarization. The excellent durability and stability of the self‐exsolved heterostructural nanoparticles are clearly confirmed by long‐term operation at high‐working voltage with an outstanding Faradaic efficiency (nearly 100%).

Heterostructured Cobalt Silicide Nanocrystals: Synthesis in Molten Salts, Ferromagnetism, and Electrocatalysis.

Nanoscale heterostructures of covalent intermetallics should give birth to a wide range of interface-driven physical and chemical properties. Such a level of design however remains unattainable for most of these compounds, due to the difficulty to reach a crystalline order of covalent bonds at the moderate temperatures required for colloidal chemistry. Herein, we design heterostructured cobalt silicide nanoparticles to trigger magnetic and catalytic properties in silicon-based materials. Our strategy consists in controlling the diffusion of cobalt atoms into silicon nanoparticles, by reacting these particles in molten salts. By adjusting the temperature, we tune the conversion of the initial silicon particles toward homogeneous CoSi nanoparticles and core-shell nanoparticles made of a CoSi shell and a silicon-rich core. The increased interface-to-volume ratio of the CoSi component in the core-shell particles yields distinct properties compared to the bulk and homogeneous nanoparticles. First, the core-shell particles exhibit increased ferromagnetism, despite the bulk diamagnetic properties of cobalt monosilicide. Second, the core-shell nanoparticles act as efficient precatalysts for alkaline water oxidation, where the nanostructure is converted in situ into a layered cobalt silicon oxide/(oxy)hydroxide with high and stable oxygen evolution reaction (OER) electrocatalytic activity. This work demonstrates a route to design heterostructured nanocrystals of covalent intermetallic compounds and shows that these new structures exhibit very rich, yet poorly explored, interface-based physical properties and reactivity.

Embedding Co6Mo6C2-Mo2C heterostructure nanoparticles in carbon nanofibers as highly efficient electrocatalysts for overall water splitting

In this study, carbon nanofibers (CNFs) embedding molybdenum carbide (Mo2C)/cobalt (Co)-molybdenum (Mo) bimetallic carbide heterostructure electrocatalysts (denoted as A-B/CNFs) were prepared via electrospinning and high-temperature carbonization. Owing to the synergistic interaction between Co6Mo6C2 and Mo2C components, the catalyst activity is improved. Furthermore, the rich mesoporous structure and electrical conductivity of CNFs, accelerate the reaction kinetics. As a result, the optimized Co6Mo6C2-Mo2C/CNFs-1 has excellent bifunctional electrocatalytic activity. With the current density of 10 mA cm−2, the hydrogen evolution reaction (HER) overpotential is only 94 mV, and the oxygen evolution reaction (OER) overpotential is 295 mV in an alkaline electrolyte. Building an alkaline electrolyzer with Co6Mo6C2-Mo2C/CNFs-1 as the anode and cathode electrodes requires a low cell voltage of only 1.66 V to achieve the current density of 10 mA cm−2, while maintaining ideal durability. This research offers a versatile and effective approach to creating bimetallic-based monolithic hydrolysis electrocatalysts.

Composition-optimized manganese phosphide nanoparticles anchored on porous carbon network for efficiently electrocatalytic hydrogen evolution

Electrocatalytic water splitting is an efficient method for producing high purity hydrogen and has the advantage of emitting zero waste. Manganese phosphides are considered to be promising electrocatalysts for the hydrogen evolution reaction (HER) with their electrocatalytic properties being composition-dependent. In this work, we achieved the targeted synthesis of manganese-rich Mn2P, phosphorus-rich MnP, and their heterostructure Mn2P-MnP nanoparticles dispersed uniformly on a P, N-doped carbon network (Mn2P-MnP/PNC) through a facile strategy involving the use of phosphate resin derived with potassium hydroxide. Systematic studies were conducted on formation mechanism of Mn2P-MnP/PNC. Density functional theory (DFT) calculations indicate that Mn2P-MnP has an optimized electronic structure and Gibbs free energy of H adsorption, with that of Mn2P-MnP (0.057 eV) being closest to zero compared to Mn2P (-0.306 eV) and MnP (0.325 eV). The Mn2P-MnP/PNC only requires small overpotentials of 63 and 98 mV to achieve 10 mA cm−2 for HER in H2SO4 and KOH solution, respectively. Furthermore, Mn2P-MnP/PNC exhibits ultrahigh stability for HER in both acid and alkaline solutions, retaining a current rate of 98.18% and 97.57% after 96 and 120 h chronoamperometry tests, respectively.

Enhanced electron beam and X-ray beam therapy by applying nanoparticle heterojunctions: A Monte Carlo simulation

Cancer has become one of the major diseases that seriously threaten human health. In order to improve the therapeutic gain ratio (TGF) of conventional X-ray and electron beams, we studied the dose enhancement effect and secondary electrons emission of Au–Fe nanoparticle heterostructures by Monte Carlo method. Under the irradiation of 6 MeV photon and 6 MeV electron beams, the Au–Fe mixture has a dose enhancement effect. For this reason, we explored the secondary electrons production that leads to dose enhancement. For 6 MeV electron beam irradiation, Au–Fe nanoparticle heterojunctions have an higher electrons emission than Au and Fe nanoparticles. When cubic, spherical and cylindrical heterogeneous structures are considered, the electron emission of the columnar Au–Fe nanoparticles is the highest, with a maximum value of 0.00024. For 6 MV X-ray beam irradiation, Au nanoparticle and Au–Fe nanoparticle heterojunction have similar electrons emission, while Fe nanoparticle has the lowest one. When cubic, spherical and cylindrical heterogeneous structures are considered, the electron emission of the columnar Au–Fe nanoparticles is the highest, with a maximum value of 0.000118. This study contributes to improve the tumor-killing effect of conventional X-ray radiotherapy treatment and has guiding significance for the research of new nanoparticles.

Spiky surface topography of heterostructured nanoparticles for programmable acceleration of multistage wound healing

Wound healing is a complex and orchestrated physiological process that involves multiple stages, including hemostasis, inflammation, proliferation, and remodeling stages. Various nanomaterials have been developed to improve the wound healing; however, most of them can only promote an individual stage of this intricate process, lacking hierarchical acceleration for multiple stages. In the present study, spiky gold-palladium heterostructured nanoparticles (AuPd SHs) were designed to possess topographical architectures on the surface of nanoparticles, capable of promoting multistage wound healing in a programmable manner. First, the spiky surface topography of AuPd SHs exhibited the potent nanobridge effect for rapid wound closure, promoting the hemostasis stage. Second, the heterostructures of AuPd SHs realized visible-light-mediated hot electron excitation and electron–hole spatial separation between Au cores and Pd spikes to efficiently generate reactive oxygen species, beneficial for the inflammation stage. Third, the spiky surface topography of AuPd SHs triggered macrophage polarization from M1 to M2 phenotype, promoting the proliferation and maturation stages. Spiky AuPd SHs with simple composition and compact structures exhibit hierarchical acceleration on multiple stages of wound healing.

Insights into the Synthesis Mechanisms of Ag-Cu3P-GaP Multicomponent Nanoparticles

Metal-semiconductor nanoparticle heterostructures are exciting materials for photocatalytic applications. Phase and facet engineering are critical for designing highly efficient catalysts. Therefore, understanding processes occurring during the nanostructure synthesis is crucial to gain control over properties such as the surface and interface facets' orientations, morphology, and crystal structure. However, the characterization of nanostructures after the synthesis makes clarifying their formation mechanisms nontrivial and sometimes even impossible. In this study, we used an environmental transmission electron microscope with an integrated metal-organic chemical vapor deposition system to enlighten fundamental dynamic processes during the Ag-Cu3P-GaP nanoparticle synthesis using Ag-Cu3P seed particles. Our results reveal that the GaP phase nucleated at the Cu3P surface, and growth proceeded via a topotactic reaction involving counter-diffusion of Cu+ and Ga3+ cations. After the initial GaP growth steps, the Ag and Cu3P phases formed specific interfaces with the GaP growth front. GaP growth proceeded by a similar mechanism observed for the nucleation involving the diffusion of Cu atoms through/along the Ag phase toward other regions, followed by the redeposition of Cu3P at a specific Cu3P crystal facet, not in contact with the GaP phase. The Ag phase was essential for this process by acting as a medium enabling the efficient transport of Cu atoms away from and, simultaneously, Ga atoms toward the GaP-Cu3P interface. This study shows that enlightening fundamental processes is critical for progress in synthesizing phase- and facet-engineered multicomponent nanoparticles with tailored properties for specific applications, including catalysis.