Formation Of Metal Particles Research Articles

Innovative Design of anode materials for Li-ion batteries: Bismuth oxide/sodium bismuth molybdate nanocomposites

Novel bismuth oxide/sodium bismuth molybdate nanocomposites (NCs), Bi2O3@NaBi(MoO4)2, were developed successfully via simple methods. Advanced analyses revealed that the NCs were composed of Bi2O3 and NaBi(MoO4)2 particles at the nanoscale, below 10 nm, in a combination of amorphous and crystalline forms. In this work, these NCs were utilized as lithium-ion battery anode materials for the first time, demonstrating exceptional electrochemical performances, including high capacity, superior capacity retention, high coulombic efficiency, excellent rate capacity, and pseudo-capacitance behavior. For instance, Bi2O3@NaBi(MoO4)2 NCs prepared at 1 h and 3 h of reaction time delivered a reversible charge capacity of 1052 and 1034 mAh g−1 after 200 cycles at current densities of 0.1 A g−1 with a capacity retention of 110 and 129 %, respectively. Notably, all the NCs anodes exhibited an excellent initial coulombic efficiency of above 80 %. Materials characterizations and electrochemical analysis revealed that the improved electrochemical properties of the NCs were attributed to their unique architectures, which featured nanostructures, molybdate components, and a small amount of amorphous phase. In addition, the significant capacity increase could be due to the electrochemical milling effect, the in situ formation of metallic particles, and the role of Mo metal in the NCs anodes as the catalysts for Li2O decomposition during cycling. It concluded that Bi2O3@NaBi(MoO4)2 NCs have great potential as advanced anodes for Li-ion storages.

Ni-Derived NiO Nanosphere Electrocatalyst for Hydrogen Evolution Reaction: The Effect of Synthesis Variables on Activity and Durability

Transition to a decarbonized society will rely on clean energy resources, in particular on "green” hydrogen—a renewable energy carrier that can be generated via water electrolysis [1]. Unlike proton exchange membrane water electrolyzers (PEMWE), anion exchange membrane water electrolyzers (AEMWEs) enable the use of earth-abundant transition metals in both the cathode and anode [2]. In addition, unlike liquid alkaline water electrolyzers, which use a highly concentrated alkaline media (6 M KOH), AEMWEs can operate with low-concentrated electrolyte, and even pure water [3]. Developing active and durable platinum group metal-free (PGM-free) electrocatalysts is crucial for the large-scale implementation of the AEMWE technology. Ni-based electrocatalysts have shown good activity towards the hydrogen evolution reaction (HER) in alkaline media [4]. Herein, carbon supported Ni-derived NiO nanosphere electrocatalysts are synthetized via a sol-gel method followed by thermal treatment under reducing atmosphere. We explored several synthesis parameters, i.e., Ni-to-carbon ratio, annealing temperature, and annealing time. We also investigated the impact of these synthesis variables on the HER activity in alkaline electrolyte. The catalysts were characterized by XRD, SEM, and EDS. The formation of Ni metal particles with a thin oxygen-rich layer on the surface was demonstrated by microscopy and crystallographic characterization. Following optimization, the HER overpotential of the best performing electrocatalyst at a current density of 10 mA cm−2 was reduced to ca. 130 mV. The catalyst durability was tested over 100 h in KOH solutions at different electrolyte concentrations using various testing protocols such as constant current hold and potential cycling. The catalyst showed higher HER activity (100 mV lower HER overpotential) and better durability behavior (0.15 mV/h lower degradation rate) compared to a commercial Ni supported Vulcan XC-72 electrocatalyst.

Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO2 Nano‐Islands

AbstractCeO2‐supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO2‐Al2O3 support. The preferential location of Pd on CeO2 islands leads to a high local surface noble metal concentration and promotes the in situ formation of small Pd clusters at a rather low noble metal loading (0.5 wt %), which are shown to be the active species for CO conversion at low temperatures. As elucidated by complementary in situ/operando techniques, the spatial separation of CeO2 islands on Al2O3 confines the mobility of Pd, preventing the full redispersion or the formation of larger noble metal particles and maintaining a high CO oxidation activity at low temperatures. In a broader perspective, this approach to more efficiently use the noble metal can be transferred to further systems and reactions in heterogeneous catalysis.

Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO2 Nano-Islands.

CeO2-supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO2-Al2O3 support. The preferential location of Pd on CeO2 islands leads to a high local surface noble metal concentration and promotes the in situ formation of small Pd clusters at a rather low noble metal loading (0.5 wt %), which are shown to be the active species for CO conversion at low temperatures. As elucidated by complementary in situ/operando techniques, the spatial separation of CeO2 islands on Al2O3 confines the mobility of Pd, preventing the full redispersion or the formation of larger noble metal particles and maintaining a high CO oxidation activity at low temperatures. In a broader perspective, this approach to more efficiently use the noble metal can be transferred to further systems and reactions in heterogeneous catalysis.

Mechanism behind the Controlled Generation of Liquid Metal Nanoparticles by Mechanical Agitation.

The size-controlled synthesis of liquid metal nanoparticles is necessary in a variety of applications. Sonication is a common method for breaking down bulk liquid metals into small particles, yet the influence of critical factors such as liquid metal composition has remained elusive. Our study employs high-speed imaging to unravel the mechanism of liquid metal particle formation during mechanical agitation. Gallium-based liquid metals, with and without secondary metals of bismuth, indium, and tin, are analyzed to observe the effect of cavitation and surface eruption during sonication and particle release. The impact of the secondary metal inclusion is investigated on liquid metals' surface tension, solution turbidity, and size distribution of the generated particles. Our work evidences that there is an inverse relationship between the surface tension and the ability of liquid metals to be broken down by sonication. We show that even for 0.22 at. % of bismuth in gallium, the surface tension is significantly decreased from 558 to 417 mN/m (measured in Milli-Q water), resulting in an enhanced particle generation rate: 3.6 times increase in turbidity and ∼43% reduction in the size of particles for bismuth in gallium liquid alloy compared to liquid gallium for the same sonication duration. The effect of particles' size on the photocatalysis of the annealed particles is also presented to show the applicability of the process in a proof-of-concept demonstration. This work contributes to a broader understanding of the synthesis of nanoparticles, with controlled size and characteristics, via mechanical agitation of liquid metals for diverse applications.

Ex situ and in situ studies on structural features of Pt/Ce0.75Zr0.25O2 catalyst for water gas shift reaction

Pt/Ce1-xZrxO2 catalysts have shown high activity in water gas shift (WGS) reaction, but their structural organization has been studied insufficiently. This work represents a detailed structural study on the supported Pt species and the metal/support interface in a 5 wt% Pt/Ce0.75Zr0.25O2 catalyst in the initial state, after reductive activation, and after WGS reaction in H2-enriched reformate-simulating mixture. A wide range of methods was used: ex situ and in situ X-ray diffraction (XRD) studies, high resolution transmission electron microscopy (HRTEM), X-ray atomic pair distribution function (PDF) method, pseudo in situ X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR). The Ce0.75Zr0.25O2 mixed oxide was shown to provide a highly dispersed state of Pt species. XPS revealed that the initial catalyst contains Pt2+species. PDF analysis allowed us to propose the structure of ultrafine PtO particles and to elucidate the metal-support interaction with fixation of Pt ions on the support surface. In situ XRD, pseudo in situ XPS, and H2-TPR studies revealed the reduction of ultrafine PtO particles in H2 atmosphere at low temperatures (20–90°С) with the formation of metallic Pt0 particles and simultaneous partial reduction of the support surface due to the hydrogen spillover. Catalytic tests of the as-prepared and poisoned with chlorine 5wt% Pt/Ce0.75Zr0.25O2 catalysts in the WGS reaction showed an important role of the oxygen vacancies in the oxide support as active sites. These findings contribute to the understanding catalytic performance of Pt/Ce1-xZrxO2 systems.

Gold mineralisation by pyrite recrystallisation and arsenopyrite sequestration in the Jiaochong Au deposit, Tongling ore district, eastern China: Implications for the formation of stratabound ore deposits

The Middle–Lower Yangtze River Valley metallogenetic belt (MLYRB) is a large and economically valuable porphyry–skarn Cu–Au ore belt in China with a total reserve of >600 tonnes of gold. Orebodies in the MLYRB are commonly stratabound and extend for several tens of metres in length and locally for more than 1000 m. However, the origin of the stratabound orebodies is uncertain, with proposals including a magmatic or sedimentary genesis, and the specific processes by which these gold deposits were formed are also unclear. Here we report a study of the representative stratabound Jiaochong Au deposit in the Tongling ore district, where stratified gold orebodies are hosted at the Triassic -Permian strata boundary. A detailed field survey, petrologic observations, in situ sulfur isotopic analysis, and major and trace element compositional analysis of gold and sulfide grains were carried out to determine how the gold was enriched. Field survey shows that precipitated sulphides exhibit obvious mineral and textural zonation from wall-rock to orebody centres as follows: Zone 1, colloform pyrite (Py1) ± sphalerite ± chalcopyrite → Zone 2, euhedral pyrite (Py2) ± pyrrhotite + arsenopyrite ± colloform pyrite (Py1) → Zone 3, pyrrhotite + arsenopyrite. From zone 1 to zone 3, the sulphides were progressively phase-transformed, with the earlier Py1 being gradually consumed and converted into Py2, which finally became pyrrhotite. The gold deposition occurs in Zones 2 and 3 and forms two generations of gold grains, one group being completely enclosed within euhedral Py2 with low As contents (<0.1 wt%) and another group infilling fractures between arsenopyrite and pyrrhotite or occurring as inclusions within arsenopyrite with high As contents (0.4 to 1.4 wt%). The comparable S-isotope compositions of the ore sulfides to those of Mesozoic intermediate-felsic intrusions and the veining characteristics of colloform pyrite in the Tongling ore district suggest that Mesozoic magmatic-hydrothermal fluids, rather than Carboniferous sedimentary rocks as usually thought, provided the principal ore-forming materials. The gold precipitation in this study followed two continuous processes: recrystallisation and arsenopyrite sequestration; in the first process, Au is remobilised from the pyrite structure at higher temperatures up to recrystallisation of fine-grained, colloform morphologies into euhedral crystals and formation of Au-bearing metallic particles (Au1); with the ongoing recrystallisation more As is released and accumulated into the equilibrated fluids, forming As-rich pyrite or arsenopyrite and a second period of gold deposition (Au2). The continuous sulphide zonation texture and phase transformation, similar to Jiaochong, have been observed in other gold deposits in the MLYRB, and our gold enrichment processes may also give an explanation for the formation of these stratabound gold deposits.

Determination of tetracycline in honey by flow-injection amperometry on an electrode modified with gold and palladium particles, and reduced graphene oxide

A method of immobilizing Au–Pd binary system on a glassy carbon (GC) electrode surface covered by reduced graphene oxide (GOred) was developed. Using GOred as a matrix for inclusion of Au–Pd binary system resulted in significant increase of its catalytic activity in tetracycline (TC) electro-oxidation process due to increased dispersion of the deposit and formation of nano-sized metal particles (average diameter of particles was around 50 nm). Optimal conditions of immobilizing Au–Pd binary system for achieving maximum electrocatalytic effect were determined. A possibility of amperometric detection of TC on GC modified with Au–Pd and GOred composite (Au–Pd–GOred–GC) by flow injection analysis (FIA) was demonstrated. The method demonstrated high sensitivity (the lowest detection limit of 5 nM), rapidity and efficiency (about 60 samples per hour). The flow injection amperometric method for TC determination hereby developed was tested in analyzing flower honey samples from different Volga Region districts.

Simulation of noble metal particle growth and removal in the molten salt fast reactor

In the Molten Salt Fast Reactor (MSFR), fuel is dissolved in a liquid salt, causing the formation and decay of fission products, such as noble metals, to be inside the salt. Noble metals have very low solubility and do not dissolve in the salt. They are known to agglomorate into particles which, in turn, diffuse, drift or sediment to interfaces such as walls, free surfaces and bubbles, where they deposit. Leveraging this in the MSFR, online or offline helium bubbling is foreseen to act as a means to extract noble metal particles from the salt. This can potentially limit strong deposition of particles onto walls (i.e., plating), preventing dangerous decay heat hotspots in the heat exchangers or other primary circuit components. In this paper, we investigate the efficiency of particle removal by helium bubbles in the MSFR using Computational Fluid Dynamics (CFD). Theoretical estimates of equilibrium particle size distributions are used as initial condition, based on previous work. CFD calculations are performed in a simplified MSFR geometry. Bubble expansion, turbulent bubble coalescence and turbulent break-up are accounted for using the poly-disperse Log-normal Method of Moments (LogMoM) model, embedded in the two-fluid framework in OpenFOAM. The CFD analyses presented in this paper, in conjunction with the developed theory of noble metal particle formation, growth and capture, will help in the understanding and optimization of the fuel cycle in the MSFR or any other molten salt reactor design. The precise knowledge of how noble metal particle populations in the salt can be controlled, and how plating of noble metal particles onto primary circuit reactor components can be reduced, contributes to safe molten salt reactor operation.

Transformation of Iron (III) Nitrate from an Aerosol by Ultrasonic Spray Pyrolysis and Hydrogen Reduction

Due to their unique properties, iron nanoparticles find diverse applications across various fields, including catalysis, electronics, wastewater treatment, and energy storage. Nano-iron particles are mostly sub-micrometer particles that are highly reactive to both air (oxygen) and water, and in nanoparticles (size below 100 nm), it is even more rapid than the bulk material. This characteristic limits its use in inert environments. Iron nanoparticles are not toxic and are mostly used for wastewater treatment. Understanding the hydrogen reduction mechanisms and conditions that lead to the formation of metallic iron particles from iron (III)-nitrate from an aerosol is crucial for enabling their effective utilization. In this work, we studied the hydrogen reduction behavior of Fe2O3 in the absence and presence of additives (SiO2 or Pt). The particles were prepared via ultrasonic spray pyrolysis and hydrogen reduction. The characterization was performed with a scanning electron microscope, energy-dispersive X-ray spectroscopy, and X-ray diffraction. In the absence of additives, the oxygen content of iron oxide particles decreased with increasing temperature from 700 to 950 °C but significantly increased with the doping of 10 mL (40 wt.%) of SiO2. The inhibitory effect of Si on the hydrogen reduction of Fe2O3 formed was more pronounced at 950 °C than at 700 °C. In contrast, the doping of only 5 mL (15 wt.%) of Pt significantly decreased the oxygen concentration in the synthesized particles by catalyzing the reduction reaction of iron oxides at 700 °C. The metallic iron (Fe) product, obtained in the undoped iron oxides run at only 950 °C, was also formed at 700 °C in the Pt-doped Fe2O3 run.

Upcycling plastic polymers into single-walled carbon nanotubes from a magnesia supported iron catalyst

Plastic waste has posed an ever-growing environmental threat to the United Nations’ sustainable development goals. Converting plastic polymers into high value chemicals like carbon nanotubes is a promising approach for recycling without carbon dioxide emission. Using a two-stage pyrolysis-catalytic reactor, we herein report the transformation of five types of plastic polymers into high-quality single-walled carbon nanotubes (SWNTs) with the assistance of a rationally designed heterogeneous catalyst, i.e., an iron metal catalyst supported by porous magnesia. Because of the high metal dispersion and the large carbon solubility of the active component, the heterogeneous catalyst affords the formation of uniform metal particles which can sustain high carbon fluxes, resulting in the synthesis of high quality SWNTs. More importantly, the approach is also demonstrated with mixtures of plastic polymers. This work helps gain deep insights into the mechanisms of plastic polymer conversion to SWNTs, accelerating the progress toward a sustainable plastic economy.

Preparation of Nanoparticles and Diffusion Behavior of Metal Ions in Ionic Liquids

Ionic liquids (ILs) have attracted much attention as tunable liquids because of their unique structures and properties. However, the mechanisms of chemical reactions and solute diffusion in ionic liquids are still unknown. This article summarizes our previous studies and recent results on the mechanisms of metal particle formation and solute diffusion in ionic liquids, focusing on the local structure of ionic liquids. It was found that the shape and size of metal particles formed in ionic liquids using electron beams or X-rays are strongly influenced by the local structure. In the study of the diffusion behavior of metal ions in ionic liquids, we proposed a hopping-like diffusion model and proposed that this behavior could be strongly influenced by local structures such as hole concentration and/or domain structures.

Interlayer Ag+ and In Situ Ag Metal Particles Synergistically Strengthening MnO2 Cathode Performance for Aqueous Zinc-Ion Batteries

Layered manganese oxide has rich active sites, amounts of variable valence states, and economic feasibility, so it has attracted wide attention. In aqueous zinc ion batteries, its poor conductivity and easy solubility in water limit its performance as an electrode. Therefore, we used a simple one-step hydrothermal method to prepare Ag+ intercalated MnO2 for aqueous zinc-ion batteries’ cathode. An in-depth exploration of the electrochemical phenomenon of Ag–MnO2 found that interlayer Ag+ regulates the electronic structure of MnO2 and reduces the Jahn–Teller effect, and the desolvation of Ag–MnO2 is easier, which promotes the embedding of Zn2+. In addition, the migration of Ag+ and the in situ formation of Ag metal particles also enhance the conductivity of the electrode. As a result of the Ag+-Ag0 synergistic effect, Ag–MnO2 has obtained high rate performance (275.6 mA·h·g–1 at 200 mA·g–1) and excellent cycle stability (98.8% capacity retention over 600 cycles at 1000 mA·g–1). This provides insights for the pre-inserted Ag+ to improve the electrochemical performance of MnO2.

Synthesis of Graphite-Encapsulated Ni Micro- and Nanoparticles Using Liquid-Phase Arc Discharge

In this work, the synthesis of nickel particles encapsulated in a few-layer graphene shell was carried out using the method of electric arc discharge in the liquid phase, in various media: deionized water, alcohol, and toluene. Nickel and graphite were used as electrodes. The study was carried out to analyze how various liquids, acting as a cooling medium and a source of carbon, affect the formation of a protective shell around metal particles. Raman studies, analysis of X-ray diffraction data, and scanning electron microscopy confirmed the formation of spherical encapsulated nickel particles in all types of liquid media. It was found out that the use of toluene as a cooling medium increased the number of particles with a graphite shell and allowed obtaining micro- and nanoparticles covered with monolayer graphene. The absence of oxygen in the composition of toluene, in contrast with alcohol and especially water, prevents the oxidation of nickel particles during the synthesis. This fact, along with the initial basic hexagonal carbon structure of toluene, makes it a good medium for the formation of metal particles covered with a protecting graphite shell as a result of arc discharge in the liquid phase.

Visualizing Structural and Chemical Transformations of an Industrial Cu/ZnO/Al2O3 Pre‐catalyst during Activation and CO2 Reduction

AbstractThe typical industrial catalyst used for methanol synthesis is a multi‐component catalyst based on Cu/ZnO/Al2O3. The synergies between various phases of this catalyst play a vital role in defining the overall catalytic function and performance. To gain insights into the role and interaction between the relevant components and phases, ex situ and in situ transmission electron microscopy (TEM) was deployed to investigate the structures and phases of an industrial Cu/ZnO/Al2O3 in its precursor, activated and reaction states. High structural inhomogeneity in this material is revealed, i. e. the presence of various phases with different morphologies and compositions. It is shown how structural and compositional changes occur during hydrogen treatment and how compositional inhomogeneity in the starting material translates into differences in the local composition of the activated and working catalyst. The formation of defective metallic copper particles (stacking faults and twins) that are in an intimate contact with zinc oxide (poorly crystalline, partially reduced ZnOx and crystalline ZnO), alumina, Zn−Al oxide and carbon‐zinc‐oxygen containing phases (such as zinc formate) is observed. It is also uncovered that alumina plays a potentially important role in stabilizing cationic zinc species. This work provides atomic‐level insight into the relevant state of an industrial methanol synthesis catalyst and the associated synergistic interplay between the involved phases in reactive atmosphere.

Atomically Isolated Nickel–Nitrogen–Carbon Electrocatalysts Derived by the Utilization of Mg2+ ions as Spacers in Bimetallic Ni/Mg–Metal–Organic Framework Precursors for Boosting the Electroreduction of CO2

Electrochemical CO2 reduction (CO2R) is a promising avenue for the conversion of CO2 into fuels and beneficial chemicals. Significant efforts have been devoted to the development of active and selective electrocatalysts for CO2R. Atomically dispersed transition metal electrocatalysts have recently attracted consideration for CO2R due to their unique electronic and structural properties that can impart good catalytic performance and high active metal utilization. Among different precursors used for preparing these catalysts, metal–organic frameworks (MOFs) have been utilized as templates for generating atomically dispersed transition metal active sites as they provide well-defined structures that contain transition metals isolated from each other by organic ligands, along with high surface areas. However, maintaining the isolation of the transition metal species, achieving high surface concentrations of active sites, and imparting porosity during the high-temperature heat treatment of MOFs used during synthesis remain a challenge. In this report, Mg2+ ions have been employed as spacers in a bimetallic metal–organic framework (NiMg-MOF-74) to assist in preventing the coalescence of the Ni atoms into Ni-based particles during heat treatment, which combined with the use of urea as a nitrogen source resulted in the formation of isolated Ni–Nx/C active sites. Our findings demonstrated that Mg2+ ions play a crucial role in extending the distance between the adjacent Ni sites in the precursor structure and generating atomically isolated Ni sites. On the contrary, the utilization of Mg-free Ni-MOF-74 led to the formation of metallic Ni particles embedded in a carbon nanotube-based structure. Furthermore, we investigated the impact of pyrolysis temperature on the produced catalyst morphology. The generation of isolated Ni–Nx/C sites was promoted at higher pyrolysis temperatures (900 °C), while Ni-based particles were predominantly formed at a lower temperature (700 °C). The optimized atomically dispersed Ni–N–C catalyst exhibited excellent selectivity toward CO with a Faradaic efficiency of ∼90% and a current density of −4.2 mA/cm2 at −0.76 V vs a reversible hydrogen electrode.

Nickel nanoparticles embedded in porous carbon-coated honeycomb ceramics: A potential monolithic catalyst for continuous hydrogenation reaction

The preparation method of porous carbon coated honeycomb ceramic monolithic catalysts is limited to traditional ideas. The porous carbon and the active metal particles are formed step by step. We have designed a novel preparation method and constructed a series of nickel-embedded porous carbon-coated (Ni@C) monolithic catalysts with different carbonization temperatures. Through the synchronous formation of porous carbon and active metal particles, the relationship between porous carbon and metal is changed from “supported” to “embedded”. The “embedded” structure between nickel particles and porous carbon formed at suitable carbonization temperature is an inseparable whole. Correlation characterization results show that the “embedded” structure has not changed the physical-chemical properties of porous carbon. However, the effect on the physical-chemical properties of nickel particles is very significant. Compared with conventional supported nickel-based monolithic catalysts (NiO/C), embedded nickel particles in the Ni@C monolithic catalyst have four characteristics. They are more uniform particle dispersion, smaller average particle size, more difficult to migrate and stable in metallic Ni0 form in air. Based on these advantages, Ni@C monolithic catalysts show better catalytic activity, stability and convenience in the continuous catalytic hydrogenation of aromatic nitro compounds.

Radiation-Induced Long-Lived Transients and Metal Particle Formation in Solid KCl–MgCl2 Mixtures

Radiation-Induced Long-Lived Transients and Metal Particle Formation in Solid KCl–MgCl₂ Mixtures

Applying metal coatings to dielectric materials by photochemical processes

Abstract Photochemical processes in thin surface layers of solutions of compounds of the copper subgroup elements leading to the formation of dispersed metal particles on the surface of dielectrics are investigated. It is shown that dispersed particles of elemental gold are formed on dielectrics moistened with AuCl3 solution and exposed to sunlight. At the same time, there is no need to use any chemical reducing agents. On cotton fabrics moistened with solutions of AgNO3, CuBr2, when exposed to sunlight, silver and copper monohalides are formed, respectively. These processes take place with the participation of terminal cellulose molecules and also do not require the use of chemical reducing agents. In addition, it was found that copper monohalides can be converted into elemental copper particles by a photochemical reaction involving ascorbic acid. Examples of metallization of a number of dielectrics using photochemical activation using sunlight are given.

Noble metals Pt, Au, and Ag as nucleating agents in BaO/SrO/ZnO/SiO2 glasses: formation of alloys and core\u2013shell structures

Noble metals such as Ag can be used as nucleation agents in glass ceramics. In glasses, it is incorporated predominantly as AgI. At temperatures slightly above the glass transition temperature, Tg, AgI reacts with SbIII to SbV and metallic Ag. Usually, face-centered cubic Ag particles are nearly spherical and get facetted during crystal growth. By contrast, in the case of BaO/SrO/ZnO/SiO2 glasses, silver has, in comparison to other noble metals, another significant, yet different effect. It forms metallic particles (hexagonal phase) with plate-like morphology during thermal treatment at 675 °C. In the second step of thermal treatment at 760 °C, this phase most probably expels some metallic Sb, which is oxidized by SbV (present in the surrounding glass phase) to SbIII. As a result, the plate-like morphology is maintained and a crystalline shell around the metallic core is formed, mainly consisting of ZnO with some SiO2 and antimony oxide, as proved by scanning transmission electron microscopy combined with energy-dispersive X-ray spectroscopy. This shell triggers the volume crystallization of Ba0.5Sr0.5Zn2Si2O7, a phase with low thermal expansion. By comparison, alloying of Au with Sb does not occur according to the phase diagram. Instead, a thermal treatment at temperatures slightly above Tg leads to nanocrystalline, spherical Au particles. Hence, alloying and subsequent decomposition of the alloy is a prerequisite for the formation of plate-like noble metal particles.