Violet light excited white light emitting diodes (LEDs) have attracted widespread attention due to their advantages of tunable color temperature and visual comfort. However, high-performance phosphors suitable for violet light excitation (400-420 nm) have not yet been widely applied on a large scale. One of the key factors regarding the commercial utilizations is the stability. Unfortunately, there still lacks research on this issue. In this study, three rare-earth phosphors suitable for violet light excitation in LEDs were synthesized via a solid-state reaction method, namely K2CaPO4F:Eu2+, K1.3Al11O17+δ:Eu2+ and Ca2YHf2Al3O12:Ce3+,Tb3+. The stability experiments were then conducted under conditions of high temperature and humidity, water immersion, and long-term violet light irradiation from LED chips. The luminescent properties, failure mechanisms, and environmental stability were analyzed. Finally, a white LED device was prepared by combining the as-synthesized three phosphors onto a 400 nm violet light chip. Results demonstrate that the as-synthesized phosphors exhibit not only optimized luminescence performance compared to phosphors prepared in former works, but also a more comprehensive evaluation of environmental stability across different conditions. The white LED device achieves a color rendering index of 93.6, a correlated color temperature of 5151 K and a color coordinate of (0.34, 0.36), showcasing excellent white light illumination performance. Furthermore, the environmental stability of the white LED device is improved compared to individual phosphors. By taking lead in investigating the environmental stability of violet light excited LED phosphors, this work provides valuable insights and guidance for advancing their applications.
As an essential candidate for environment-friendly luminescent quantum dots (QDs), CuInS-based QDs have attracted more attention in recent years. However, several drawbacks still hamper their industrial applications, such as lower photoluminescence quantum yield (PLQY), complex synthetic pathways, uncontrollable emission spectra, and insufficient photostability. In this study, CuInZnS@ZnS core/shell QDs was prepared via a one-pot/three-step synthetic scheme with accurate and tunable control of PL spectra. Then their ensemble spectroscopic properties during nucleation formation, alloying, and ZnS shell growth processes were systematically investigated. PL peaks of these QDs can be precisely manipulated from 530 to 850 nm by controlling the stoichiometric ratio of Cu/In, Zn2+ doping and ZnS shell growth. In particular, CuInZnS@ZnS QDs possess a significantly long emission lifetime (up to 750 ns), high PLQY (up to 85%), and excellent crystallinity. Their spectroscopic evolution is well validated by Cu-deficient related intragap emission model. By controlling the stoichiometric ratio of Cu/In, two distinct Cu-deficient related emission pathways are established based on the differing oxidation states of Cu defects. Therefore, this work provides deeper insights for fabricating high luminescent ternary or quaternary-alloyed QDs.
Ultra-high temperature ceramic (UHTC) structural materials have emerged as critical candidates in the fields of aerospace, defense equipment, energy and power sectors due to their outstanding oxidation/ablation resistance, high-temperature strength retention, and thermal shock resistance in oxidative environments exceeding 1600 ℃. In recent years, extensive research has been achieved in both fundamental research and technological applications focusing on compositional control, structural design, fabrication techniques, and performance optimization of these materials. UHTC systems, characterized by carbides, borides and nitrides, are currently facing increasingly stringent demands for enhanced thermal performance in more complex environments. To further advance development of UHTC structural materials for such conditions, this paper systematically reviews the latest research progress in this field. Firstly, synthesis techniques of UHTC powders are elaborated. Subsequently, systems, densification methods and structural regulation strategies of UHTCs are presented. Furthermore, fabrication techniques and performance enhancement strategies of UHTC matrix composites (UHTCMCs), UHTCs modified carbon/carbon composites (UHTCs-C/C), and UHTC coatings are examined, with particular emphasis on the latest breakthroughs in oxidation/ablation resistance. Additionally, primary technical challenges related to the long-term stability and reliability of UHTC structural materials under extreme conditions are identified, and a forward-looking perspective on future development trends is provided.
Perovskite quantum dots have unique advantages in display. However, their long-term stability at high brightness is still a huge challenge. Therefore, this article focuses on the progress of the regulation of perovskite quantum dots and their luminescent film morphology, explains the influence of long-range ordered perovskite quantum dot films on their electroluminescent properties, and looks forward to the development prospects in improving the electroluminescent stability of perovskite quantum dots.
To further expand the application of advanced ceramic materials in helicopters, this paper reviews their application in helicopter structures both domestically and internationally. It emphasizes the technical maturity and development trends of various ceramic materials in helicopter specific structural applications, such as energy impact protection parts, energy conversion components, and corrosion protection areas. By comparing the gaps between domestic and international use of advanced ceramic materials in helicopter specific structures, the paper provides suggestions for the future development. Recommendations include the use of reaction-sintered contoured integrated opaque armor ceramics and polycrystalline transparent armor ceramics for the high-speed dynamic impact energy protection parts, cermet composite coatings compatible with epoxy resin composite substrates for the low-energy impact protection parts, and hybrid ceramic matrix composite/polymer matrix composite (HCMC-PMC) materials for the thermal shock protection parts. Additionally, multifunctional composite materials, such as high-performance miniature piezoelectric ceramic thin film functional devices and flexible hybrid electronic structures based on micro-piezoelectric ceramic materials, should be developed for the mechanical and electrical energy conversion components. Microwave-absorbing ceramic composites derived from polymer-derived ceramics that are compatible with epoxy resin composite substrates are recommended for the electromagnetic and thermal energy conversion components. Furthermore, high-performance abrasion-resistant and corrosion-resistant Sol-Gel coatings are suggested for the corrosion protection areas. It is also essential to establish a high-speed dynamic energy impact protection mechanism for helicopters, optimize the ballistic performance of protective materials, and develop advanced ceramic materials digital testing and verification technologies, represented by multi-functional composite materials for helicopter specific structures. These efforts will greatly shorten the application cycle of advanced ceramic materials and reduce the verification cost.
Bentonite is an abundant, cheap and readily available natural clay mineral, with montmorillonite (MMT) as its main mineral composition. MMT possesses excellent ion exchange, adsorption and ion transport properties due to its unique two-dimensional layered nanostructure, abundant pore structure, and high specific surface area. Moreover, it also possesses excellent thermal, chemical and mechanical stabilities. In recent years, MMT has attracted extensive attention in the field of electrochemical energy storage owing to the above excellent characteristics, especially the inherent fast ion (Li+, Na+, Zn2+, etc.) transport properties. Thus, the bentonite-based functional materials have been widely applied to the key components (i.e., electrodes, polymer electrolytes, and separators) of electrochemical energy storage devices and show good application prospects. In this review, the structure and physicochemical properties of bentonite are firstly introduced, and then the research progress of bentonite-based functional materials in the field of electrochemical energy storage, mainly including metal anodes, lithium-sulfur battery cathodes, solid/gel polymer electrolytes, and polymer separators, is comprehensively summarized. On the basis of these facts, the ion transport promotion mechanism of bentonite-based functional materials during the process of electrochemical energy storage is elaborated. Finally, the current problems and challenges faced by application of bentonite-based materials in electrochemical energy storage devices are pondered, and the possible future research directions are prospected. This review provides useful guidance for the design and development of bentonite-based electrochemical energy storage functional materials.
Nowadays, we are facing increasingly serious energy and environmental problems, which urgently need more efficient chemical industry technologies to meet the requirements of low cost, high yield and sustainability. Developing efficient catalysts is of great significance for improving production efficiency, expanding economic benefits, optimizing energy structure, and ameliorating industrial structure. Single-atom catalysts (SACs), featuring unique properties arising from their single-atom dispersion on support surface, have demonstrated exceptional activity, selectivity and stability in energy catalysis, environmental catalysis and organic catalysis. Therefore, preparation methods and catalytic mechanisms of SACs have become a hot research topic on the international catalytic community. This review describes three strategies for preparing SACs: bottom-up synthesis, top-down synthesis and quantum dots cross-linking/self-assembly. Specifically, methods such as co-precipitation, immersion, atomic layer deposition, high-temperature atom thermal transfer, and high-temperature pyrolysis are presented in detail. These approaches precisely control the location and distribution of metal atoms, maximizing their utilization and catalytic efficiency. In addition, the challenges and development prospects faced by SACs related to stability, integrated control and industrial scalability are also summarized.
Carbide ultra-high temperature ceramics (UHTCs) have emerged as ideal coating materials for the thermal protection systems of hypersonic vehicles due to their high melting point (>3000 ℃), high hardness, low thermal conductivity, excellent heat resistance, and good chemical stability. This review provides a comprehensive overview of structure and properties of carbide UHTCs, namely TiC, ZrC, HfC, NbC, and TaC. Furthermore, it summarizes recent developments in preparation of carbide UHTC coatings using various methods, including chemical vapor deposition, plasma spraying, and solid-phase reaction. Effects of coating microstructure, composition, structural design, and heat flux on the ablation behavior are analyzed. Data from recent literature corroborate that the added second phase can facilitate formation of complex oxides, generate an oxidation layer during ablation to undergo moderate sintering, protect structural integrity, and enhance oxygen barrier properties. Multi-layer structural designs utilize gradient layering and multi-functional structures, which effectively alleviate thermal stress within the coating, suppress crack propagation, and facilitate synergistic enhancing effects among different layers. Finally, the challenges and opportunities in development of carbide UHTC anti-ablation coatings are prospected.
Inorganic non-metallic biomaterial is one of main types of biomaterials, which is widely used in biomedical fields such as tissue repair, tumor therapy, and drug delivery., making an important contribution to national life and health. Research on inorganic non-metallic biomaterials in China is flourishing, but their production and application are still in the stage of overcoming difficulties. To realize the high-quality development of China's inorganic non-metallic biomaterials and improve their hard power to protect national life and health, this paper analyzes hotspots and difficult problems in research and application of China's inorganic non-metallic biomaterials by means of strategic study. Based on current development opportunities and challenges, some suggestions are proposed for the development of inorganic non-metallic biomaterials, such as material design for unique performance, research on materiobiology, exploration of new principles and mechanisms mediated by materials, customization by intelligent personalization, design through big data screening and artificial intelligence, and standardization based evaluation/regulation. This aims to provide guidance for development of inorganic non-metallic biomedical products and push forward scientific research while accumulating talent resources.
SiC ceramics exhibit high strength and thermal stability, rendering them highly suitable for applications in space and thermal components. However, the growing demand for large-sized and complex-shaped SiC ceramics necessitates advanced manufacturing techniques. In comparison to traditional reduction and equal material manufacturing methods, 3D printing technology offers significant advantages in various aspects, such as manufacturing cycle, effective cost, and reliability. There are many 3D printing methods, each with distinct characteristics. Stereolithography (SLA) is capable of achieving high precision and superior surface quality. However, its practical applications often necessitate special design of support structures. Additionally, issues such as residual stress and low solid content significantly hinder its further development. Selective laser sintering (SLS) exhibits strong material compatibility, which is suitable for a wide range of materials, including polymers, metals and ceramics. This technology enables large-scale rapid prototyping at low manufacturing costs. But its surface quality of the formed billet is typically insufficient, which needs additional post-processing. Fused deposition modeling (FDM) though facilitates the preparation of SiC ceramics via reaction sintering, proves unsuitable for constructing large components which restricts its applicability in actual production contexts, due to its inadequate interlayer bonding strength coupled with pronounced surface striations and slower forming speeds. This paper reviews the latest research progresses of 3D-printed SiC ceramics and analyzes the subsequent high-temperature densification treatments of green bodies, along with their fundamental physical properties. Finally, it proposes some prospects of 3D printing of SiC ceramic materials, and strengthens integration of new 3D printing technologies and various printing methods for fine regulation of ceramics’ macro- and micro-structures.
Compared with traditional lithium-ion batteries, sodium-ion batteries are an ideal alternative due to their cost advantages and sustainable resource supply. At present, the cathode materials for sodium-ion batteries mainly include transition metal oxides, polyanionic compounds and Prussian blue analogues. However, irreversible phase conversion, Jahn-Teller effect and interface instability of cathode materials seriously affect the cycling stability of sodium-ion batteries. In this paper, the research progress and industrialization process of strategies for improving cyclic stability of cathode materials for sodium-ion batteries are systematically introduced. Firstly, the structure as well as advantages and disadvantages of cathode materials is analyzed in detail, and the structural stability, cost and cycling performance are compared. Secondly, the latest research progress of structure optimization and chemical element doping strategies in improving the cycling stability of cathode materials is elaborated in detail, and the interaction between structural stability, electronic conductivity, ion intercalation/deintercalation of cathode materials and electrochemical performance is revealed. Then, the development process and industrialization progress of sodium-ion batteries are summarized. Finally, the significant problems that still need to be addressed for cathode materials and systems for sodium-ion batteries are sorted out and their future developments are prospected, aiming to propel the steady and healthy development of sodium-ion battery industry.
High-entropy carbide (HEC) ceramics are distinguished by their high hardness, oxidation resistance, corrosion resistance, wear resistance, and high thermal conductivity, positioning them as promising candidates for application in extreme environments. However, inherent brittleness of these high-entropy ceramics limits their further application. In order to enhance the toughness of HEC ceramics, polycarbosilane (PCS), a precursor of silicon carbide (SiC), was added into the precursor of (Zr, Hf, Nb, Ta, W)C high-entropy ceramic. The in-situ formed SiC (SiCi) by pyrolysis of PCS can serve as reinforcement for HEC ceramics. The results demonstrate that the volume fraction of SiC in the ceramics obtained from the pyrolysis of PCS is 23.38%. The SiC phases, with an average grain size of 1.19 μm, are evenly distributed in the high-entropy ceramic matrix. The pyrolysis process of ceramic precursors was investigated, revealing that the pyrolysis products of PCS exit as amorphous Ox-Si-Cy at low pyrolysis temperature, while a crystalline SiC phase emerges when the pyrolysis temperature exceeds 1500 ℃. Bulk (Zr, Hf, Nb, Ta, W)C-SiCi ceramic was prepared by hot-pressing of precursor-derived ceramic powders obtained through pyrolysis at 1600 ℃. Mechanical properties of (Zr, Hf, Nb, Ta, W)C-SiCi ceramic bulk were investigated, and composite ceramic bulks toughened by commercial silicon carbide nanopowders or silicon carbide whiskers were also prepared for comparison. Compared with (Zr, Hf, Nb, Ta, W)C ceramic, all composite ceramic bulks exhibit enhanced flexural strength and toughness. Notably, the in-situ generated SiCi via precursor-derived method shows the most significant toughening effect. Flexural strength and fracture toughness of (Zr, Hf, Nb, Ta, W)C-SiCi ceramic are (698±9) MPa and (7.9±0.6) MPa·m1/2, respectively, representing improvements of 17.71% and 41.07% compared to that of (Zr, Hf, Nb, Ta, W)C ceramic bulk. Taking all above data into comprehensive account, the improvement is mainly due to the small grain size and uniform distribution of SiC in the composite ceramics prepared via precursor-derived method, which enhance energy consumption and hinder crack propagation under external stress.
Development of novel artificial synaptic devices, which make up the majority of neural networks, has emerged as a pivotal path to hardware realization of neuromorphic computing. An electrochemical ion synapse, also known as a three-terminal synaptic device based on electrochemical transistors, is a device that may efficiently use ions in the electrolyte layer to modify channel conductivity. By electrochemical doping and recovering ions in channel materials exhibiting redox activity, this device mimics biological synaptic properties. The advantages of the electrochemical ion synapse, which uses proton (H+) as the doping particle, are lower energy consumption, faster operation, and a longer cycle life among the ions that alter the channel material's conductance. This article reviews the recent research progress on proton-regulated electrochemical ion synapses, summarizes the material systems used for the channel layer and electrolyte layer of proton-regulated electrochemical ion synapses, analyzes the challenges faced by proton-regulated electrochemical ion synapses, and points out directions on their future development.
Li1.3Al0.3Ti1.7(PO4)3 (LATP), one of the NASICON-type solid-state electrolytes, possesses a high ionic conductivity, excellent chemical stability, and high shear modulus (40-60 GPa). However, the tetravalent titanium ion in LATP is particularly prone to undergo reduction reaction with lithium metal during cycling, leading to the structure degradation and electron introduction in LATP electrolyte. In order to maintain the chemical and electrochemical stability of LATP, this work modified the surface of LATP solid electrolyte with a Prussian blue (PB) interfacial layer to optimize the contact between electrolyte and anode. Using PB with abundant open-frame lithium ion diffusion channels as the mixed conductive modification layer has several advantages. (1) Intrinsic conductivity of PB layer is enhanced after lithiation, accelerating homogenized transmission of electrons from the interfacial layer to the negative electrode. (2) Lithiation process is accompanied by enhancing lithium affinity of PB intermediate layer, which enables the interface contact between LATP and lithium metal to be closer during the electrochemical process. (3) Lithiated PB still maintains a three-dimensional skeleton structure, which is conducive to the homogenization effect of lithium ion flux at interface, thereby promoting stabilization of lithium deposition/stripping process. (4) The PB with metal-organic framework (MOF) structure is conducive to ensuring the mechanical stability of interface during cycling and reducing volume change of lithium negative electrode. (5) The PB structure does not collapse after lithiation, not easy to cause phase separation and additional phase boundaries or phase gaps, which is conducive to the integration of lithium ion flow and electron flow. (6) More uniquely, redox potential of PB is higher than those of lithium metal and LATP on both sides of the PB interface, conducive to the formation of an electron transport barrier between Li and LATP, and prevents the reduction and degradation of LATP. The improved solid-state battery has good cycling stability and kinetic performance. At a current density of 0.025 mA·cm-2, the PB-modified Li/Li symmetric solid-state cell can achieve a stable cycle of 800 h. After 160 cycles at a current density of 0.025 mA·cm-2, the capacity of PB-modified Li/LiFePO4 solid-state battery is still close to 200 mAh·g-1. The modified Li/FeF3 solid-state battery can be operated at 0.025 mA·cm-2 with the preservation of a high Coulombic efficiency, indicating that the PB modification has good tolerance to the volume change generated during electrochemical cycling.
Inorganic nanoparticles have demonstrated significant applications in biomedicine field, whose biomedical functions and physicochemical properties are greatly influenced by their size and morphology. However, it still remains challenging to achieve high batch-to-batch reproducibility in the synthesis of inorganic nanoparticles with traditional batch synthesis methods. Meanwhile, microfluidic technology offers an advanced strategy that provides high controllability and repeatability for the synthesis of inorganic nanoparticles. Additionally, it facilitates rapid mass and heat transfer, while offering the advantages of small reaction volumes and low energy consumption, rendering it an ideal approach for the synthesis of inorganic nano-biomaterials. This article reviews the research and application progress of microfluidic technology in preparation of inorganic nano-biomaterials. Firstly, flow regimes and principles of mixing in the microfluidic devices are introduced. Subsequently, structural features and fluid mixing efficiency of five widely studied and applied microfluidic devices are presented. Importantly, applications of these microfluidic devices in synthesis and surface modification of inorganic nanoparticles are comprehensively summarized. Finally, this article briefly outlines challenges and potential opportunities for future developments in microfluidic-based synthesis and application of inorganic nano-biomaterials.
With upgrading of communication technology and driving of 5G communication applications, the explosive number of filters required by various smart devices promoted prosperity of the filter market. However, the demanded performance also becomes increasingly stringent, including broad bandwidth, high frequency, high power capacity, miniaturization, integration, and low cost, in both academia and industry. To meet these strict requirements, the thin film bulk acoustic resonator (FBAR) filters have emerged as one of the most promising types of filters with commercial success. But currently they are still facing difficulties such as insufficient performance, complex fabrication process, relatively higher cost, and technological constraints. This paper reviews the relevant issues and key technologies in FBAR filters in three aspects: theoretical research on devices and structural optimization, preparation and optimization of high-performance piezoelectric materials, and development of novel processes and technological integration. The purpose of this paper is to delineate the trajectory of technological advancements and iterations in FBAR filters for scholars in the research field, with the expectation of providing several considerations for future research directions and pathways.
Control and removal of volatile organic compounds (VOCs) have always been critical issues in the environmental field. Catalytic oxidation has emerged as one of the most promising technologies for VOCs removal due to its low operational temperature, high efficiency, and non-toxic by-products. Perovskite oxides (ABO3) are recognized as efficient and stable catalysts for the catalytic oxidation of VOCs. To enhance the catalytic efficiency of perovskite-based catalysts, it is necessary to systematically analyze and optimize the design of perovskite oxides to meet the specific requirements for the removal of different VOCs. This paper comprehensively reviews recent advances in the catalytic oxidation of VOCs using perovskite oxides. Firstly, various design strategies for perovskite oxides in the catalytic oxidation of VOCs, including morphology control, A-site and B-site substitution, defect engineering, and supported perovskite catalysts, are introduced, giving a close link between the catalytic performance of perovskite oxides and their material composition, morphology, surface properties (oxygen species, defects), and intrinsic properties (oxygen vacancy concentration, lattice structure). The reaction mechanisms and degradation pathways involved in the catalytic oxidation of VOCs are analyzed, and the prospects and challenges in the rational design of perovskite oxide catalysts and the exploration of reaction mechanisms are outlined.
Piezoelectric materials, which serve as converters between mechanical energy and electric energy, are important functional materials. Recently, the technology for textured piezoelectric ceramics has become an important technical approach for developing the next generation of high-performance piezoelectric materials. By tailoring grain orientation, textured piezoelectric ceramics exhibit properties akin to single crystals, exhibiting enhanced piezoelectric and electromechanical properties, as well as improved thermal stability. Furthermore, as polycrystalline ceramics, textured ceramics inherit the advantages of traditional ceramic materials, including ease of fabrication, favorable mechanical properties, and suitability of special-shape and syntype. This paper provides a brief introduction to texturing technique, development of perovskite templates for textured ceramics, and research results related to lead titanate (PbTiO3, PT) based textured piezoelectric ceramics. It systemizes the development and status of the piezoelectric textured ceramics while summarizing their technical advantages. Additionally, the existing scientific problems and future challenges of PT-based textured piezoelectric ceramics are analyzed, focusing on the suitability of templates and matrix via theoretical prediction, the relationship between microstructure and macroscopic properties of textured ceramics, and piezoelectric devices based on textured piezoelectric ceramics. By reviewing the PT-based textured piezoelectric ceramics, this paper aims to provide an in-depth introduction to texturing techniques and theories, seeks to enhance understanding of textured piezoelectric ceramics, and promotes the development of high- performance piezoelectric materials. This work is expected to benefit the breakthrough innovation and leap forward development of next generation high-end piezoelectric devices.
Volatile organic compounds (VOCs) pose significant risks to environmental quality and human health. To enhance adsorption performance of adsorbents for VOCs, further improvement of the unsaturated metal centers becomes a key factor based on the principle that metal ions can be replaced in metal organic frameworks (MOFs). Here, a one-step solvothermal synthesis system was utilized to dope abundant, cost-effective, and environment friendly Al3+ ions into MIL-101(Cr) for preparing Al-MIL-101(Cr). Morphologies and structures of MIL-101(Cr) and Al-MIL-101(Cr) samples, alongside the static adsorption performance for toluene, n-hexane, oil and p-xylene, were analyzed. Static adsorption capacities of toluene, n-hexane, oil, and p-xylene of MIL-101(Cr) were 0.676, 0.621, 0.451 and 0.812 g·g-1, respectively. When Al3+ doping amount reached 0.75 mmol, Al-0.75-MIL-101(Cr) displayed maximum VOCs adsorption capacities (0.911 g·g-1 for toluene, 0.755 g·g-1 for n-hexane, 0.713 g·g-1 for oil, and 0.875 g·g-1 for p-xylene). The dynamic toluene adsorption behavior was assessed through single-component breakthrough curves. Both dynamic and static adsorption results demonstrate that Al-MIL-101(Cr) possesses excellent VOCs removal capabilities, which are attributed to the extensive specific surface area and augmented unsaturated metal sites.
The research of sodium-ion batteries (SIBs) is of great significance for development of new energy and energy storage methods. As cathode material, P2-type layered oxide material Na2/3Ni1/3Mn2/3O2 has attracted wide attention due to its excellent capacity and high working voltage. However, it suffers from undesired P2-O2 phase transition, which leads to a drastic change in volume and rapid capacity decay. Here, a P2-Na0.67Ni0.18Cu0.10Mg0.05Mn0.67O2 (NCMM-10-05) cathode was synthesized through solid-state method with synergetic substitution of Cu and Mg. The results indicated that the incorporation of Cu and Mg suppressed irreversible P2-O2 phase transition when charging to high voltage and initialized OP4 phase formation, which improved reversible stability of structure. Thus the as-obtained material exhibited excellent electrochemical performance, which delivered an initial discharge capacity of 113 mAh·g-1 in the voltage range of 2.00-4.35 V (vs. Na+/Na), a reversible capacity of 64.1 mAh·g-1 at 8C (1C=100 mA·g-1), and a capacity retention of 88.9% after 200 cycles at 1C. The effect of Cu and Mg synergetic substitution on the structure and electrochemical properties of P2-type layered oxides was explored, and the specific roles played by Cu and Mg in the structural evolution were further investigated by in situ X-ray diffraction (XRD) analysis and density functional theory (DFT) calculations. This work provides a new insight into the rational design of highly stable cathode materials with rapid Na+ transport capability for SIBs.
Metal phosphides have been studied as prospective anode materials for sodium-ion batteries (SIBs) due to their higher specific capacity compared to other anode materials. However, rapid capacity decay and limited cycle life caused by volume expansion and low electrical conductivity of phosphides in SIBs remain still unsolved. To address these issues, GeP3 was first prepared by high-energy ball milling, and then Ketjen black (KB) was introduced to synthesize composite GeP3/KB anode materials under controlled milling speed and time by a secondary ball milling process. During the ball milling process, GeP3 and KB form strong chemical bonds, resulting in a closely bonded composite. Consequently, the GeP3/KB anodes was demonstrated excellent sodium storage performance, achieving a high reversible capacity of 933.41 mAh·g-1 at a current density of 0.05 A·g-1 for a special formula of GeP3/KB-600-40 sample prepared at ball milling speed of 600 r/min for 40 h. Even at a high current density of 2 A·g-1 over 200 cycles, the capacity remains 314.52 mAh·g-1 with a retention rate of 66.6%. In conclusion, this work successfully prepares GeP3/KB anode-carbon composite for electrodes by high-energy ball milling, which can restrict electrode volume expansion, enhance capacity, and improve cycle stability of SIBs.
Currently, the carbothermal reduction-nitridation (CRN) process is the predominant method for preparing aluminum nitride (AlN) powder. Although AlN powder prepared by CRN process exhibits high purity and excellent sintering activity, it also presents challenges such as the necessity for high reaction temperatures and difficulties in achieving uniform mixing of its raw materials. This study presents a comprehensive investigation into preparation process of AlN nanopowders using a combination of hydrothermal synthesis and CRN. In the hydrothermal reaction, a homogeneous composite precursor consisting of carbon and boehmite (γ-AlOOH) is synthesized at 200 ℃ using aluminum nitrate as the aluminum source, sucrose as the carbon source, and urea as the precipitant. During the hydrothermal process, the precursor develops a core-shell structure, with boehmite tightly coated with carbon (γ-AlOOH@C) due to electrostatic attraction. Compared with conventional precursor, the hydrothermal hybrid offers many advantages, such as ultrafine particles, uniform particle size distribution, good dispersion, high reactivity, and environmental friendliness. The carbon shell enhances thermodynamic stability of γ-Al2O3 compared to the corundum phase (α-Al2O3) by preventing the loss of the surface area in alumina. This stability enables γ-Al2O3 to maintain high reactivity during CRN process, which initiates at 1300 ℃, and concludes at 1400 ℃. The underlying mechanisms are substantiated through experiments and thermodynamic calculations. This research provides a robust theoretical and experimental foundation for the hydrothermal combined carbothermal preparation of non-oxide ceramic nanopowders.
With the rapid development of new aerospace vehicles, there are increasing demands for higher structural reliability and wideband microwave stealth requirements for the components operating under high-temperature condition. SiBCN based metastable ceramics exhibit good resistance to high temperature, thermal shock, ablation, long-term oxidation, and creep, showcasing great potential in the field of high-temperature structural microwave absorption. However, their ability to absorb electromagnetic waves is limited by low dielectric loss. In this study, the SiBCN-rGO ceramic fibers with good mechanical and microwave-absorbing properties were prepared using the wet spinning technology. Results showed that the as-prepared SiBCN-rGO ceramic fibers possessed porous structure, with porosity increasing with the increase of reduced graphene oxide (rGO) content. Additionally, both high rGO content and high fiber specific surface area promoted the crystallization of SiC within the amorphous matrix. The introduction of rGO significantly enhanced the tensile properties of the resulting ceramic fibers. As the mass fraction of rGO increased from 0 to 4%, the fibers’ elongation at break increased from 8.05% to 18.05%, and the tensile strength increased from 1.62 cN/dtex (0.324 GPa) to 2.32 cN/dtex (0.464 GPa). The increase of rGO content also reduced the electrical resistivity of the ceramic fibers. Moreover, as the rGO mass fraction increased from 0 to 4%, both the real and imaginary parts of the fibers’ dielectric constant decreased, while the loss tangent gradually increased. The SiBCN-rGO ceramic fibers with those containing 6% (mass fraction) rGO exhibited excellent wave-absorption performance, showing the minimum reflection coefficient of -50.90 dB at 9.20 GHz and an effective absorption bandwidth of 2.3 GHz, indicating promising applications in wave-absorbing ceramic matrix composites.
Microwave dielectric ceramics are the key basic materials of 5G/6G communication technology, with particular emphasis on the materials that exhibit a high quality factor (Q×f), low dielectric constant (εr) and near-zero temperature coefficient of resonant frequency (τf). However, most low-εr materials tend to have a significantly negative τf value. This study provides a systematic overview of the classical ionic polarizability dilution mechanism and phase transition mechanism, along with the structural factors affecting τf, such as unit cell volume mechanism, oxygen polyhedron distortion, bond energy, bond ionicity, and bond valence. Subsequently, the anomalous changes in τf in the cubic normal and inverse garnet systems without phase transition are described in detail. The “Rattling” effect is introduced as a novel mechanism affecting the τf of microwave dielectric ceramics. Cations involved in “Rattling”, characterized by high coordination and weak chemical bonds, are the primary factors affecting the overall microwave dielectric polarization and loss of the material. This phenomenon results in an increase in ionic polarizability and εr, a forward shift in τf and a reduction in Q×f value, which has been verified and applied in many different material systems. Furthermore, the introduction of a weighted function for total ion polarization deviation serves to evaluate the impact of the entire molecule's “Rattling” and “Compressed” effects on εr. A novel concept of temperature coefficient of ionic polarizability (ταm) is also proposed, allowing for quantitative calculation. This simplifies the factors that affect the positive and negative of dielectric constant temperature coefficient (τε), by relating it to εr, ταm and linear expansion coefficient αL.
Pb(Zr,Ti)O3 (PZT) ceramics play a crucial role in fields such as national defense, healthcare, communication, and energy conversion due to their excellent piezoelectric, ferroelectric, and pyroelectric properties. However, the sintering temperature of PZT ceramics usually exceeds 1200 ℃, resulting in high energy consumption and a large amount of PbO volatilization. This volatilization disrupts the stoichiometric balance of PZT ceramics, thereby adversely affecting their electrical properties. Moreover, the rapid development of piezoelectric multilayer devices further requires PZT ceramics to be co-sintered with low-cost metal electrodes at low temperatures. To address these challenges, researchers have extensively investigated the low-temperature sintering of PZT piezoelectric ceramics, successfully reducing the sintering temperature of PZT ceramics to below 1000 ℃, which has attracted widespread attention. Starting from the structural characteristics and physical properties of PZT ceramics, this article reviews the current research status of low-temperature sintering technology in the field of PZT ceramics. It mainly introduces the current status of low-temperature sintering techniques, including spark plasma sintering, hot-pressing sintering, cold sintering, as well as the use of sintering aids such as forming solid solutions, liquid-phase sintering, and transient liquid-phase sintering. The influence of these sintering techniques on the microstructure and electrical properties of PZT piezoelectric ceramics is systematically summarized. The issue of electrical performance degradation caused by sintering aids and possible solutions are analyzed. At last, future development trends of low-temperature sintering technologies for PZT ceramic are explored.
Pb(Zr,Ti)O3-Pb(Zn1/3Nb2/3)O3 (PZT-PZN) based ceramics, as important piezoelectric materials, have a wide range of applications in fields such as sensors and actuators, thus the optimization of their piezoelectric properties has been a hot research topic. This study investigated the effects of phase boundary engineering and domain engineering on (1-x)[0.8Pb(Zr0.5Ti0.5)O3-0.2Pb(Zn1/3Nb2/3)O3]-xBi(Zn0.5Ti0.5)O3 ((1-x)(0.8PZT-0.2PZN)- xBZT) ceramic to obtain excellent piezoelectric properties. The crystal phase structure and microstructure of ceramic samples were characterized. The results showed that all samples had a pure perovskite structure, and the addition of BZT gradually increased the grain size. The addition of BZT caused a phase transition in ceramic samples from the morphotropic phase boundary (MPB) towards the tetragonal phase region, which is crucial for optimizing piezoelectric properties. By adjusting content of BZT and precisely controlling position of the phase boundary, the piezoelectric performance can be optimized. Domain structure is one of the key factors affecting piezoelectric performance. By using domain engineering techniques to optimize grain size and domain size, piezoelectric properties of ceramic samples have been significantly improved. Specifically, excellent piezoelectric properties (piezoelectric constant d33=320 pC/N, electromechanical coupling factor kp=0.44) were obtained simultaneously for x=0.08. Based on experimental results and theoretical analysis, influence mechanisms of phase boundary engineering and domain engineering on piezoelectric properties were explored. The study shows that addition of BZT not only promotes grain growth, but also optimizes the domain structure, enabling the polarization reversal process easier, thereby improving piezoelectric properties. These research results not only provide new ideas for the design of high-performance piezoelectric ceramics, but also lay a theoretical foundation for development of related electronic devices.
Methane pyrolysis is a technology that utilizes fossil energy to produce high added value carbon materials and hydrogen. However, traditional methods, such as chemical vapor deposition (CVD) and molten metal catalysis, face challenges in the production of graphene, including catalyst deactivation, difficulty in separating graphene from the catalyst, and high reaction temperatures (≥1100 ℃), which limit their industrial applications. This study proposes an innovative approach to produce graphene by catalyzing methane pyrolysis using Cu and metal oxides-KCl molten medium. By adding metal oxides (Al2O3, TiO2, ZrO2, MgO, SiO2) as dispersants, the dispersion of active Cu sites is enhanced. Notably, Cu/ZrO2 with a Cu content of 50% (in volume) and Cu/MgO with a Cu content of 75% (in volume) catalysts enable the efficient production of few-layer graphene. Cu/ZrO2 catalyst with a Cu content of 50% (in volume) exhibits the highest activity, achieving a methane conversion rate of 22%, a hydrogen production yield of 21.5 mmol/h, and formation of large-area and smooth few-layer graphene. This study provides a new technical route for co-production of graphene and hydrogen via methane pyrolysis, offering potential for large-scale graphene production in the future.
Ortho to para hydrogen conversion catalyst (O-P catalyst) is integral for large-scale hydrogen liquefaction projects. However, factors that influence catalyst performance remain preliminary and unclear. In the mean time, the mechanical strength of the O-P catalyst is crucial for its efficacy and longevity, yet most related research has paid sufficient attention to the catalytic activity. In this work, an iron-based O-P catalyst was synthesized using a straightforward precipitation method. And effects of catalyst activation method, drying temperature, particle size, concentration ratio, and doping element on catalytic activity and mechanical strength were studied. Furthermore, the catalytic performance and structural characterization of the prepared catalyst and commercial catalyst were compared. The prepared catalyst achieved a para hydrogen (p-H2) content of 46.49% post-conversion at 77 K with a hydrogen flow rate of 1200 mL/min, surpassing the commercial catalyst by 2.9%. The maximum single particle crushing force of the prepared catalyst reached 4.75 N. Therefore, a preliminary mechanism for enhancing catalytic activity optimization was elucidated, offering valuable insights into ortho to para hydrogen conversion, and this study provides foundational data supporting the scaled production of domestic catalysts.
Volatile organic compounds (VOCs) and NOx are important precursors of PM2.5 and O3, and their excessive emissions have significant negative impacts on environmental quality and human health. Compared with ordinary VOCs, nitrogen-containing volatile organic compounds (N-VOCs) need more complex environmental control strategies due to their nitrogen heteroatoms. Therefore, development and application of control technologies for N-VOCs have become a current research hotspot. In order to achieve the two key objectives of low-temperature high catalytic activity and high N2 selectivity in catalytic oxidation system of N-VOCs, there is an urgent need to design efficient and low-cost catalysts. This paper systematically summarizes the research progress of mineral materials, metal materials, single atom catalysts (SACs) and molecular sieves in catalytic oxidation of common N-VOCs (N,N-dimethylformamide, acrylonitrile, acetonitrile, n-butylamine, triethylamine, etc.), and describes the sources and hazards of N-VOCs. The key factors affecting catalytic oxidation of amines, nitriles and other typical N-VOCs are summarized, including catalytic activity, catalyst physicochemical properties, catalytic constitutive relationship and reaction mechanism. It is proposed that secondary pollutants should be avoided from deep oxidation of intermediate products in catalytic oxidation of N-VOCs. Finally, the prospects and challenges on catalytic oxidation of N-VOCs are discussed, aiming to provide theoretical guidance and practical cases for clearing N-VOCs in the future.
SiC/SiC composites have emerged as essential thermal structure materials for development of hypersonic vehicles and high thrust-to-weight ratio aero-engines. Design and utilization of boron-containing ceramic precursors as impregnation agents for precursor infiltration and pyrolysis (PIP) to introduce self-healing components into matrix represent a key strategy for enhancing the antioxidant properties of SiC/SiC composites. Here, borane pyridine or borane triethylamine were utilized as boron sources and subsequently mixed with a solid polycarbosilane (PCS) xylene solution to prepare different boron-modified PCS solutions. These solutions were used as PIP impregnation agents to fabricate various boron-modified SiC/PyC (pyrolytic carbon)/SiC composites. The physicochemical properties of boron-modified PCS-derived ceramics, along with the physical and mechanical properties of SiC/PyC/SiC composites before and after matrix boron modification, were investigated. Results demonstrated that addition of appropriate amounts of borane pyridine and borane triethylamine as boron sources in solid PCS solutions effectively introduced boron as a heterogeneous element into the derived SiC ceramics. Compared to PCS, the boron-modified PCS solutions (BP-1 and BP-2) exhibited increased ceramic yields. The derived ceramics exhibited a semi-crystalline β-SiC structure, with boron element contents of 1.7% and 2.2% (in mass), respectively. In contrast to unmodified composite, the boron-modified SiC/SiC composites exhibited negligible changes in density, apparent porosity, and fracture toughness. However, the flexural modulus increased from 116 GPa to 132 GPa. Furthermore, the flexural strength of the modified composite using borane pyridine alone as boron source was 658 MPa, comparable to the unmodified composite's strength of 643 MPa, but with a reduced dispersion coefficient. All above data demonstrate that borane pyridine can be used as boron source for preparation of boron-modified SiC/SiC composites, providing valuable insights for developing high-performance SiC/SiC composite hot-end components.
Silicon-carbide-fiber-reinforced silicon-carbide-ceramic-based matrix (SiC/SiC) composites possess excellent properties such as low density, high strength and high temperature resistance, showing a potential application for structural components in the aerospace field, but their oxidation behavior remains largely unknown. In this study, Yb2Si2O7 modified SiC/SiC (SiC/SiC-Yb2Si2O7) mini-composites were prepared by introducing Yb2Si2O7 as anti-oxidation phase into SiC fiber bundles via Sol-Gel and depositing SiC matrix by chemical vapor deposition (CVD). Influence of Yb2Si2O7 on microstructure, mechanical property and oxidation behavior of SiC/SiC mini-composites was investigated. The results showed that after oxidation in air at 1200 and 1400 ℃ for 50 h, the tensile strength retentions of SiC/SiC mini-composites were 77% and 69%, respectively, and the fracture morphology exhibited flat. The Yb2Si2O7 introduced by Sol-Gel partially distributed in layers, contributing to the toughening of the material. On the fracture surface, there was interlayer debonding, which extended energy dissipation mechanism of SiC/SiC mini-composites. Tensile strength of SiC/SiC-Yb2Si2O7 mini-composites at room temperature was 484 MPa. After oxidation in air at 1200 and 1400 ℃ for 50 h, the tensile strengths decreased to 425 and 374 MPa, resulting in retention rates of 88% and 77%, respectively. It displayed typical non-brittle fracture characteristics. The interface oxygen content of SiC/SiC mini-composites at the fracture surface was higher than that of SiC/SiC-Yb2Si2O7 mini-composites, indicating that introduction of Yb2Si2O7 could alleviate oxygen diffusion towards the interface, and therefore improve the oxidation resistance of SiC/SiC-Yb2Si2O7 mini-composites.
SiC fiber-bonded ceramics (FBCs), representing a novel class of SiC materials, synthesized via direct sintering of SiC fibers and characterized by lack of a matrix phase, porosity below 3% and fiber volume fraction exceeding 90%, exhibit remarkable properties, including high-temperature resistance, high strength, and robust resistance to oxidation and irradiation. Consequently, they are a promising contender for future aero-engine and advanced nuclear energy applications. Herein, SiC(Al) FBCs were prepared by pre-treating the fibers to form in-situ graphite (iG) layers on their surface, followed by direct sintering the fibers using a hot-press sintering process. Then, macroscopic/microscopic structures, mechanical properties and oxidative properties of the fibers and bulk ceramics were characterized. The results show that pre-treatment of SiC(Al) fibers leads to forming a 300-400 nm thick carbon layer, adhering well to the fibers. Density of the hot-press sintered iG/SiC(Al) FBCs is 3.15 g/cm3, with a porosity of only 0.52%. Meanwhile, the matrix is completely dense, the fibers are deformed in a new form of hexagonal prisms, and the well-defined interfaces are present between the fibers. Furthermore, bending strength, fracture toughness, and work of fracture of the bulk ceramics are 320 MPa, 9.5 MPa·m1/2 and 1169 J·m-2, respectively. After oxidation at 1500 and 1600 ℃ for 100 h in air, the retention rates of the flexural strength remain as high as 86% and 72%, respectively, while maintaining a quasi-plastic fracture mode.
The accepted doping ion in Ti4+-site of PbZryTi1-yO3 (PZT)-based piezoelectric ceramics is a well-known method to increase mechanical quality factor (Qm), since the acceptor coupled by oxygen vacancy becomes defect dipole, which prevents the domain rotation. In this field, a serious problem is that generally, Qm decreases as the temperature (T) increases, since the oxygen vacancies are decoupled from the defect dipoles. In this work, Qm of Pb0.95Sr0.05(Zr0.53Ti0.47)O3 (PSZT) ceramics doped by 0.40% Fe2O3 (in mole) abnormally increases as T increases, of which the Qm and piezoelectric coefficient (d33) at room temperature and Curie temperature (TC) are 507, 292 pC/N, and 345 ℃, respectively. The maximum Qm of 824 was achieved in the range of 120-160 ℃, which is 62.52% higher than that at room temperature, while the dynamic piezoelectric constant (d31) was just slightly decreased by 3.85%. X-ray diffraction (XRD) and piezoresponse force microscopy results show that the interplanar spacing and the fine domains form as temperature increases, and the thermally stimulated depolarization current shows that the defect dipoles are stable even the temperature up to 240 ℃. It can be deduced that the aggregation of oxygen vacancies near the fine domains and defect dipole can be stable up to 240 ℃, which pins domain rotation, resulting in the enhanced Qm with the increasing temperature. These results give a potential path to design high Qm at high temperature.
The rapid development of communication technology has put forward increasingly stringent requirements on dielectric ceramic filters. Efficient design of novel dielectric materials to facilitate their progression is of great significance. The relationship between structure and performance of materials is crucial for the synthesis and design of microwave dielectric ceramics. The P-V-L bond theory aims to provide crystal structure parameters and basic chemical bond characteristics through calculations, such as the bond ionicity, bond covalency, bond sensitivity, lattice energy, and bond energy. These parameters provide a theoretical basis and guidance for modification design of microwave dielectric ceramics. In recent years, researchers have been committed to applying the P-V-L bond theory to a large number of ceramic systems to explain the relationship between structure and performance of microwave dielectric ceramics. Based on this theory, new modification strategies have been proposed to obtain excellent microwave dielectric properties. This review provides a comprehensive overview of the fundamental concepts of the P-V-L bond theory and the binary bonding formula of complex polycrystals, and outlines the methods of calculating chemical bond parameters and chemical bond characteristics in the field of microwave dielectric ceramics. Meanwhile, the application of the P-V-L bond theory in several common microwave dielectric ceramic systems in recent years is analyzed. Data from literatures show that the P-V-L bond theory analysis can provide the bond characteristics in ion-doped modified systems, as well as the structural evolution and dielectric properties. This understanding is highly significant for guiding development and application direction of microwave dielectric ceramics.
Early diagnosis of tumor is a key factor for efficient diagnosis and treatment of cancer. Fluorescence imaging technology, particularly utilizing near-infrared (NIR) light, has shown promising potential in the biomedical field, specifically in the early detection of cancer. NIR light has minimal absorption and scattering in biological tissues, allowing for high-quality imaging with high resolution and signal-to-noise ratio. Realization of high-quality NIR fluorescence imaging relies on excellent fluorescent probes. Upconversion nanoparticles (UCNPs), excited by NIR light, have soared in fluorescence imaging due to their favorable characteristics such as low toxicity, narrow-band emission, tunable emission, long fluorescence lifetime, good stability, and high quantum yield. This article summarizes the basic principles, synthesis methods, and modification/decoration techniques of upconversion fluorescent probes, mainly expounds on several typical imaging modes of rare earth doped upconversion fluorescent probes and their latest research progress in tumor visualization, and prospects the further application research on the integration of diagnosis and treatment.
Nano-hydroxyapatite (nHAP) possesses both biocompatibility and environmental friendliness, and holds the potential to become a novel ultraviolet (UV) absorbent material following iron doping modification. This study employed co-precipitation and hydrothermal methods to prepare iron-doped nano-hydroxyapatite (Fe-nHAP). Influence of the preparation process on UV absorption performance was investigated by adjusting reaction time, temperature, and iron doping ratio. The results indicate that with the increase of temperature from 37 ℃ to 150 ℃ or the extension of reaction time from 0.5 h to 3 h, both the crystallinity and the peak of UV absorption improve. It can be inferred that there is a certain positive correlation between the UV absorption performance and crystallinity of Fe-nHAP. Additionally, the UV absorption capacity is closely correlated to the iron doping ratio. As the iron doping molar ratio increases from 0 to 10%, the UV absorption capacity is gradually enhanced, with the maximum absorption value rising from 0.03 to 1.35. This phenomenon is attributed to the reduction in optical bandgap caused by iron doping. However, a high iron doping ratio leads to excessive reduction in material crystallinity, resulting in weakened enhancement of UV absorption performance. The safety assessment indicates that Fe-nHAP with an iron doping molar ratio of 7% does not demonstrate cytotoxicity, phototoxicity and skin irritation. In summary, Fe-nHAP has a suitable UV absorption performance. With its favorable biosecurity, it is anticipated to emerge as a new type of UV absorption material.
Rare-earth zirconates (REZs) have attracted attention in the field of thermal barrier materials because they are more resistant to calcium-magnesium-aluminum-silicon oxide (CMAS) corrosion than yttria stabilized zirconia (YSZ). High-entropy design of zirconates is an effective method to enhance CMAS corrosion resistance, but currently the ability of its corrosion resistance still does not meet the growing requirement. In this work, a solid-state reaction technique was used to synthesize high-entropy rare-earth zirconate (HE-REZ) (Y0.2Gd0.2Er0.2Yb0.2Lu0.2)2Zr2O7 powder with a single-phased defect fluorite structure, and pressureless sintering (PLS) combined with cold isostatic pressing (CIP) technique was used to efficiently prepare bulk samples. The phase composition, microstructure, element distribution, thermal and mechanical properties were studied, focusing on the CMAS corrosion resistance. According to the results, under the same CMAS corrosion environment at 1300 ℃, the corrosion depth of HE-REZ with a relative density of 98.6% is only 2.6% of 7YSZ and 22.6% of Gd2Zr2O7 (GZO). The synergistic effect of zirconates' chemical inertness and high-entropy materials' sluggish diffusion accounts for this exceptional corrosion resistance. The obtained HE-REZ shows higher hardness and Young's modulus, larger coefficient of linear expansion, and lower thermal conductivity than ever, making its mechanical and thermal properties superior to GZO. All these outcomes demonstrate the good application potential of (Y0.2Gd0.2Er0.2Yb0.2Lu0.2)2Zr2O7 in the field of thermal barrier materials.
Pt3Co catalyst is the most active catalyst for oxygen reduction reaction (ORR) in Pt based alloys, in which synthesis of Pt3Co high-index facets (HIFs) is an effective strategy to improve its catalytic performance. However, HIFs possessing the highest ORR activity have not yet been clarified, and at present, there is a lack of a systematic study on the ORR of Pt3Co HIFs. In this study, six different Pt3Co HIFs were constructed, and their stability was proved through ab initio molecular dynamics (AIMD) calculations. Binding energies (BE) of *O, *OH and *OOH intermediates for the six Pt3Co HIFs during ORR process were calculated by density functional theory (DFT), and d-band center (εd), Bader charge and coordination number (CN) were used to explain the different binding energies at terrace and edge sites. Relationship between CN of adsorbed atoms and εd was also analyzed. Overpotential (η) during ORR was analyzed through ORR free energy step diagram, and it revealed that the magnitude of η was mainly related to *OH binding energy (BE-*OH). The Pt3Co(211) facet has the smallest η, which at the Pt3Co(211) terrace site reaches 0.294 eV. Therefore, this work provides a sound theoretical basis for the development of high ORR activity HIFs catalysts.
BaTiO3 multi-layer ceramic capacitors (MLCCs) are meeting the growing performance demands in consumer electronics, aerospace and defense research. Distribution and segregation of elements during complex fabrication process of MLCCs significantly affect the phase composition, microstructures and hence the performance, which necessitates an effective analytical means capable of accurately resolving elements of MLCCs at microscopic scales. Elemental analysis techniques integrated with modern transmission electron microscope (TEM) have unique advantages due to their ultra-high spatial resolution, reaching the sub-angström scale. Among them, energy dispersive X-ray spectroscopy (EDS) provides a simple and fast way for qualitative analysis of metallic elements. However, their limitations, such as low sensitivity for detecting the light element O, and more critically, low energy resolution (~130 eV), which results in the severe overlap of spectral peaks of Ba and Ti elements, hinder accurate quantitative analysis of BaTiO3. In contrast, electron energy-loss spectroscopy (EELS) possesses ultra-high energy resolution (<1.0 eV), and can provide additional information regarding chemical valence, thus demonstrating enhanced potentials and advantages in the micro-scale elemental analysis of MLCC. In this work, EELS is employed to address the limitation of EDS in distinguishing between Ba and Ti elements due to the overlap of spectral peaks. In addition, EELS reveals that proportion of Ti3+ ions is higher in smaller BaTiO3 grains. Meanwhile, EELS line-scan analysis of individual grains indicates that Ba element diffuses more easily than Ti during sintering process of ceramics. Given its high spatial resolution, EELS offers more accurate and comprehensive information on the elements and valence states, thereby providing potential support for the process improvement and performance optimization of MLCC.
Compared with single-phase Y2O3 ceramics, Y2O3-MgO nanocomposite ceramics exhibit superior mechanical strength, hardness, thermal conductivity, and excellent infrared band transparency, endowing them a good infrared window material. However, harsh mechanical and thermal operating conditions impose stringent requirements on the optical and mechanical properties of infrared window materials. In this study, high-purity Y2O3-MgO nanocomposite powder was used as raw material, and Y2O3-MgO nanocomposite powders with different ZrO2 contents, in which Zr4+ ions accounted for the percentage of Y3+ ions at 1%, 3% and 5%, were prepared by adding zirconium nitrate aqueous solution during ball milling. ZrO2:Y2O3-MgO nanocomposite ceramics were fabricated by hot pressing sintering at 1350 ℃ and 35 MPa for 30 min. The influence of ZrO2 content on the phase, microstructure, infrared transmittance, hardness, and bending strength of nanocomposite ceramics was systematically studied. The results showed that doping ZrO2 dissolved and uniformly distributed in the Y2O3 lattice changed microstructure of Y2O3-MgO nanocomposite ceramics and caused lattice distortion, which had a significant impact on the optical and mechanical properties of Y2O3-MgO nanocomposite ceramics. The microstructures of ZrO2:Y2O3-MgO nanocomposite ceramics reveal that increasing ZrO2 content can hinder ceramic densification, resulting in obvious pores in 5%ZrO2:Y2O3-MgO nanocomposite ceramic. Meanwhile, doping ZrO2 can enhance the hardness and bending strength of Y2O3-MgO nanocomposite ceramics, which can be attributed to lattice distortion suppressing the dislocations’ motion. 3%ZrO2:Y2O3-MgO nanocomposite ceramic has a dense microstructure, with a transmittance of ~82% in the range of 3-5 μm, while exhibiting a hardness of 11.43 GPa and a bending strength of 276.67 MPa.