The origin of exceptionally large ductility in molybdenum alloys dispersed with irregular-shaped La2O3 nano-particles.

Molybdenum and its alloys are known for their superior strength among body-centered cubic materials. However, their widespread application is hindered by a significant decrease in ductility at lower temperatures. In this study, we demonstrate the achievement of exceptional ductility in a Mo alloy containing rare-earth La2O3 nanoparticles through rotary-swaging, a rarity in Mo-based materials. Our analysis reveals that the large ductility originates from substantial variations in the electronic density of states, a characteristic intrinsic to rare-earth elements. This characteristic can accelerate the generation of oxygen vacancies, facilitating the amorphization of the oxide-matrix interface. This process promotes vacancy absorption and modification of dislocation configurations. Furthermore, by inducing irregular shapes in the La2O3 nanoparticles through rotary-swaging, incoming dislocations interact with them, creating multiple dislocation sources near the interface. These dislocation sources act as potent initiators at even reduced temperatures, fostering diverse dislocation types and intricate networks, ultimately enhancing dislocation plasticity.

Realizing Outstanding Energy Storage Performance in KBT-Based Lead-Free Ceramics via Suppressing Space Charge Accumulation.

The great potential of K1/2Bi1/2TiO3 (KBT) for dielectric energy storage ceramics is impeded by its low dielectric breakdown strength, thereby limiting its utilization of high polarization. This study develops a novel composition, 0.83KBT-0.095Na1/2Bi1/2ZrO3-0.075 Bi0.85Nd0.15FeO3 (KNBNTF) ceramics, demonstrating outstanding energy storage performance under high electric fields up to 425 kV cm-1: a remarkable recoverable energy density of 7.03 J cm-3, and a high efficiency of 86.0%. The analysis reveals that the superior dielectric breakdown resistance arises from effective mitigation of space charge accumulation at the interface, influenced by differential dielectric and conductance behaviors between grains and grain boundaries. Electric impedance spectra confirm the significant suppression of space charge accumulation in KNBNTF, attributable to the co-introduction of Na1/2Bi1/2ZrO3 and Bi0.85Nd0.15FeO3. Phase-field simulations reveal the emergence of a trans-granular breakdown mode in KNBNTF resulting from the mitigated interfacial polarization, impeding breakdown propagation and increasing dielectric breakdown resistance. Furthermore, KNBNTF exhibits a complex local polarization and enhances the relaxor features, facilitating high field-induced polarization and establishing favorable conditions for exceptional energy storage performance. Therefore, the proposed strategy is a promising design pathway for tailoring dielectric ceramics in energy storage applications.

Enhancing Ni/Co Activity by Neighboring Pt Atoms in NiCoP/MXene Electrocatalyst for Alkaline Hydrogen Evolution.

Density functional theory (DFT) calculations demonstrate neighboring Pt atoms can enhance the metal activity of NiCoP for hydrogen evolution reaction (HER). However, it remains a great challenge to link Pt and NiCoP. Herein, we introduced curvature of bowl-like structure to construct Pt/NiCoP interface by adding a minimal 1 ‰-molar-ratio Pt. The as-prepared sample only requires an overpotential of 26.5 and 181.6 mV to accordingly achieve the current density of 10 and 500 mA cm-2 in 1 M KOH. The water dissociation energy barrier (Ea) has a ~43 % decrease compared with NiCoP counterpart. It also shows an ultrahigh stability with a small degradation rate of 10.6 µV h-1 at harsh conditions (500 mA cm-2 and 50 °C) after 3000 hrs. X-ray photoelectron spectroscopy (XPS), soft X-ray absorption spectroscopy (sXAS), and X-ray absorption fine structure (XAFS) verify the interface electron transfer lowers the valence state of Co/Ni and activates them. DFT calculations also confirm the catalytic transition step of NiCoP can change from Heyrovsky (2.71 eV) to Tafel step (0.51 eV) in the neighborhood of Pt, in accord with the result of the improved Hads at the interface disclosed by in situ electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) tests.

Corrosion Dynamics of Carbon-Supported Platinum Electrocatalysts with Metal-Carbon Interactions Revealed by In Situ Liquid Transmission Electron Microscopy.

Carbon support is essential for electrocatalysis, but limitations remain, as carbon corrosion can lead to electrocatalyst degradation and affect the long-term durability of electrocatalysts. Here, we studied the corrosion dynamics of carbon nanotubes (CNTs) and Vulcan carbon (VC) together with platinum (Pt) nanoparticles in real time by liquid cell (LC) transmission electron microscopy (TEM). The results showed that CNTs with a high degree of graphitization exhibited higher corrosion resistance compared to VC. Furthermore, we observed that the main degradation path of Pt nanoparticles in Pt/CNTs was ripening, while in Pt/VC, it was aggregation and coalescence, which was dominated by the interactions between Pt nanoparticles and different hybridization of carbon supports. Finally, we performed an ex situ CV stability test to confirm the conclusions obtained from in situ experiments. This work provides deep insights into the corrosion mechanism of carbon-supported electrocatalysts to optimize the design of electrocatalysts with a higher durability.

Engineering Strategy for Enhancing the Co Loading of Co-N4-C Single-Atomic Catalysts Based on the ZIF-67@Yeast Construction.

The Co-N4-C single-atom catalysts (SACs) have attracted great research interest in the energy storage and conversion fields owing to 100% atom utilization. However, enhancing the Co loading for higher electrocatalytic performance is still challenging. In this context, we propose an engineering strategy to fabricate the high Co atomic loading Co-N4-C SACs based on the zeolitic imidazolate framework-67 (ZIF-67)@yeast construction. The rich amino groups provide the possibility for Co2+ ion anchorage and ZIF-67@yeast construction via the biomineralization of yeast cells. The functional design induces the formation of Co-N4-C sites and regulates the porosity for exposure of such Co-N4-C sites. As a result, the Co-N4-C sites were anchored on spherical micrometer flower carbonaceous materials through our novel strategy. The as-obtained optimal sample exhibited a Co atomic loading of 12.18 wt % and a specific surface area of 403.26 m2 g-1. High Co atomic loading and large specific surface area delivered excellent electrocatalytic kinetics as well as a high discharge voltage of 1.08 V at 10 mA cm-2 for more than 100 h in Zn-air batteries. This work represents a promising strategy for fabricating high-loading SACs with high activity and good durability.

PtNi-W/C with Atomically Dispersed Tungsten Sites Toward Boosted ORR in Proton Exchange Membrane Fuel Cell Devices.

The performance of proton exchange membrane fuel cells is heavily dependent on the microstructure of electrode catalyst especially at low catalyst loadings. This work shows a hybrid electrocatalyst consisting of PtNi-W alloy nanocrystals loaded on carbon surface with atomically dispersed W sites by a two-step straightforward method. Single-atomic W can be found on the carbon surface, which can form protonic acid sites and establish an extended proton transport network at the catalyst surface. When implemented in membrane electrode assembly as cathode at ultra-low loading of 0.05 mgPt cm-2, the peak power density of the cell is enhanced by 64.4% compared to that with the commercial Pt/C catalyst. The theoretical calculation suggests that the single-atomic W possesses a favorable energetics toward the formation of *OOH whereby the intermediates can be efficiently converted and further reduced to water, revealing a interfacial cascade catalysis facilitated by the single-atomic W. This work highlights a novel functional hybrid electrocatalyst design from the atomic level that enables to solve the bottle-neck issues at device level.

Parallel Aluminum-Cobalt Oxide Nanosheet Arrays with High-Temperature Ferromagnetism.

Parallel nanomaterials possess unique properties and show potential applications in industry. Whereas, vertically aligned 2D nanomaterials have plane orientations that are generally chaotic. Simultaneous control of their growth direction and spatial orientation for parallel nanosheets remains a big challenge. Here, a facile preparation of vertically aligned parallel nanosheet arrays of aluminum-cobalt oxide is reported via a collaborative dealloying and hydrothermal method. The parallel growth of nanosheets is attributed to the lattice-matching among the nanosheets, the buffer layer, and the substrate, which is verified by a careful transmission electron microscopy study. Furthermore, the aluminum-cobalt oxide nanosheets exhibit high-temperature ferromagnetism with a 919 K Curie temperature and a 5.22 emu g-1 saturation magnetization at 300 K, implying the potential applications in high-temperature ferromagnetic fields.

Unconventional Giant "Magnetoresistance" in Bosonic Semiconducting Diamond Nanorings.

The emergence of superconductivity in doped insulators such as cuprates and pnictides coincides with their doping-driven insulator-metal transitions. Above the critical doping threshold, a metallic state sets in at high temperatures, while superconductivity sets in at low temperatures. An unanswered question is whether the formation of Cooper pairsin a well-established metal will inevitably transform the host material into a superconductor, as manifested by a resistance drop. Here, this question is addressed by investigating the electrical transport in nanoscale rings (full loops) and half loops manufactured from heavily boron-doped diamond. It is shown that in contrast to the diamond half-loops (DHLs) exhibiting a metal-superconductor transition, the diamond nanorings (DNRs) demonstrate a sharp resistance increase up to 430% and a giant negative "magnetoresistance" below the superconducting transition temperature of the starting material. The finding of the unconventional giant negative "magnetoresistance", as distinct from existing categories of magnetoresistance, that is, the conventional giant magnetoresistance in magnetic multilayers, the colossal magnetoresistance in perovskites, and the geometric magnetoresistance in semiconductor-metal hybrids, reveals the transformation of the DNRs from metals to bosonic semiconductors upon the formation of Cooper pairs. DNRs like these could be used to manipulate Cooper pairs in superconducting quantum devices.

Tensile-Strained Platinum-Cobalt Alloy Surface on Palladium Octahedra as a Highly Durable Oxygen Reduction Catalyst.

Designing shape-controlled Pt-based core-shell nanocrystals is a prospective strategy to maximize the utilization of Pt while maintaining high activity for oxygen reduction reaction (ORR). However, the core-shell structures with ultrathin Pt shell exhibit limited electrochemical durability. Therefore, a thicker shell is proposed to successfully improve the durability of the core-shell structures by preventing the core from dissolution. Nevertheless, the deposition of Pt tends to switch to the Stranski-Krastanov (S-K) growth mode with the increase of the number of layer, resulting in the absence of a conformal morphology. Herein, we realize the deposition of three-to-five-layer epitaxial Pt-Co layers on Pd octahedral seeds by introducing tensile strain in the epitaxial layer to impede the S-K growth. The as-obtained Pd@Pt-Co octahedra with four layers exhibit enhanced mass activity (0.69 A/mgPt) and specific activity (1.00 mA/cm2) for ORR, which are 4.93 and 5 times that of the commercial Pt/C, respectively. Furthermore, it shows only 17% decay for specific activity after a 30,000-cycle durability test. This work is expected to enlighten the design and synthesis of related core-shell nanocrystals with facetted multicomponent shells, offering a promising strategy for designing cost-effective and efficient catalysts.

Engineering Platinum Catalysts via a Site-Isolation Strategy with Enhanced Chlorine Resistance for the Elimination of Multicomponent VOCs.

Pt-based catalysts can be poisoned by the chlorine formed during the oxidation of multicomponent volatile organic compounds (VOCs) containing chlorinated VOCs. Improving the low-temperature chlorine resistance of catalysts is important for industrial applications, although it is yet challenging. We hereby demonstrate the essential catalytic roles of a bifunctional catalyst with an atomic-scale metal/oxide interface constructed by an intermetallic compound nanocrystal. Introducing trichloroethylene (TCE) exhibits a less negative effect on the catalytic activity of the bimetallic catalyst for o-xylene oxidation, and the partial deactivation caused by TCE addition is reversible, suggesting that the bimetallic, HCl-etched Pt3Sn(E)/CeO2 catalyst possesses much stronger chlorine resistance than the conventional Pt/CeO2 catalyst. On the site-isolated Pt-Sn catalyst, the presence of aromatic hydrocarbon significantly inhibits the adsorption strength of TCE, resulting in excellent catalytic stability in the oxidation of the VOC mixture. Furthermore, the large amount of surface-adsorbed oxygen species generated on the electronegative Pt is highly effective for low-temperature C-Cl bond dissociation. The adjacent promoter (Sn-O) possesses the functionality of acid sites to provide sufficient protons for HCl formation over the bifunctional catalyst, which is considered critical to maintaining the reactivity of Pt by removing Cl and decreasing the polychlorinated byproducts.

Direct Synthesis of Stable 1T-MoS2 Doped with Ni Single Atoms for Water Splitting in Alkaline Media.

Metallic MoS2 (i.e., 1T-MoS2 ) is considered as the most promising precious-metal-free electrocatalyst with outstanding hydrogen evolution reaction (HER) performance in acidic media comparable to Pt. However, sluggish kinematics of HER in alkaline media and its inability for the oxygen evolution reaction (OER), hamper its development as bifunctional catalysts. The instability of 1T-MoS2 further impedes its applications for scaling up, calling an urgent need for simple synthesis to produce stable 1T-MoS2 . In this work, the challenge of 1T-MoS2 synthesis is first addressed using a direct one-step hydrothermal method by adopting ascorbic acid. 1T-MoS2 with flower-like morphology is obtained, and transition metals (Ni, Co, Fe) are simultaneously doped into 1T-MoS2 . Ni-1T-MoS2 achieves an enhanced bifunctional catalytic activity for both HER and OER in alkaline media, where the key role of Ni doping as single atom is proved to be essential for boosting HER/OER activity. Finally, a Ni-1T-MoS2 ||Ni-1T-MoS2 electrolyzer is fabricated, reaching a current density of 10 mA cm-2 at an applied cell voltage of only 1.54 V for overall water splitting.

Recent Progress on Revealing 3D Structure of Electrocatalysts Using Advanced 3D Electron Tomography: A Mini Review.

Electrocatalysis plays a key role in clean energy innovation. In order to design more efficient, durable and selective electrocatalysts, a thorough understanding of the unique link between 3D structures and properties is essential yet challenging. Advanced 3D electron tomography offers an effective approach to reveal 3D structures by transmission electron microscopy. This mini-review summarizes recent progress on revealing 3D structures of electrocatalysts using 3D electron tomography. 3D electron tomography at nanoscale and atomic scale are discussed, respectively, where morphology, composition, porous structure, surface crystallography and atomic distribution can be revealed and correlated to the performance of electrocatalysts. (Quasi) in-situ 3D electron tomography is further discussed with particular focus on its impact on electrocatalysts' durability investigation and post-treatment. Finally, perspectives on future developments of 3D electron tomography for eletrocatalysis is discussed.

Mesoporous Single-Crystal Lithium Titanate Enabling Fast-Charging Li-Ion Batteries.

There remain significant challenges in developing fast-charging materials for lithium-ion batteries (LIBs) due to sluggish ion diffusion kinetics and unfavorable electrolyte mass transportation in battery electrodes. In this work, a mesoporous single-crystalline lithium titanate (MSC-LTO) microrod that can realize exceptional fast charge/discharge performance and excellent long-term stability in LIBs is reported. The MSC-LTO microrods are featured with a single-crystalline structure and interconnected pores inside the entire single-crystalline body. These features not only shorten the lithium-ion diffusion distance but also allow for the penetration of electrolytes into the single-crystalline interior during battery cycling. Hence, the MSC-LTO microrods exhibit unprecedentedly high rate capability, achieving a specific discharge capacity of ≈174 mAh g-1 at 10 C, which is very close to its theoretical capacity, and ≈169 mAh g-1 at 50 C. More importantly, the porous single-crystalline microrods greatly mitigate the structure degradation during a long-term cycling test, offering ≈92% of the initial capacity after 10 000 cycles at 20 C. This work presents a novel strategy to engineer porous single-crystalline materials and paves a new venue for developing fast-charging materials for LIBs.

Moiré Fringe Method via Scanning Transmission Electron Microscopy.

Moiré fringe, originated from the beating of two sets of lattices, is a commonly observed phenomenon in physics, optics, and materials science. Recently, a new method of creating moiré fringe via scanning transmission electron microscopy (STEM) has been developed to image materials' structures at a large field of view. Moreover, this method shows great advantages in studying atomic structures of beam sensitive materials by significantly reduced electron dose. Here, the development of the STEM moiré fringe (STEM-MF) method is reviewed. The authors first introduce the theory of STEM-MF and then discuss the advances of this technique in combination with geometric phase analysis, annular bright field imaging, energy dispersive X-ray spectroscopy, and electron energy loss spectroscopy. Applications of STEM-MF on strain, defects, 2D materials, and beam-sensitive materials are further summarized. Finally, the authors' perspectives on the future directions of STEM-MF are presented.

Atomically Dispersed Platinum Modulated by Sulfide as an Efficient Electrocatalyst for Hydrogen Evolution Reaction.

Catalytically active metals atomically dispersed on supports presents the ultimate atom utilization efficiency and cost-effective pathway for electrocatalyst design. Optimizing the coordination nature of metal atoms represents the advanced strategy for enhancing the catalytic activity and the selectivity of single-atom catalysts (SACs). Here, we designed a transition-metal based sulfide-Ni3S2 with abundant exposed Ni vacancies created by the interaction between chloride ions and the functional groups on the surface of Ni3S2 for the anchoring of atomically dispersed Pt (PtSA-Ni3S2). The theoretical calculation reveals that unique Pt-Ni3S2 support interaction increases the d orbital electron occupation at the Fermi level and leads to a shift-down of the d -band center, which energetically enhances H2O adsorption and provides the optimum H binding sites. Introducing Pt into Ni position in Ni3S2 system can efficiently enhance electronic field distribution and construct a metallic-state feature on the Pt sites by the orbital hybridization between S-3p and Pt-5d for improved reaction kinetics. Finally, the fabricated PtSA-Ni3S2 SAC is supported by Ag nanowires network to construct a seamless conductive three-dimensional (3D) nanostructure (PtSA-Ni3S2@Ag NWs), and the developed catalyst shows an extremely great mass activity of 7.6 A mg-1 with 27-time higher than the commercial Pt/C HER catalyst.

Platinum single-atom catalyst coupled with transition metal/metal oxide heterostructure for accelerating alkaline hydrogen evolution reaction.

Single-atom catalysts provide an effective approach to reduce the amount of precious metals meanwhile maintain their catalytic activity. However, the sluggish activity of the catalysts for alkaline water dissociation has hampered advances in highly efficient hydrogen production. Herein, we develop a single-atom platinum immobilized NiO/Ni heterostructure (PtSA-NiO/Ni) as an alkaline hydrogen evolution catalyst. It is found that Pt single atom coupled with NiO/Ni heterostructure enables the tunable binding abilities of hydroxyl ions (OH*) and hydrogen (H*), which efficiently tailors the water dissociation energy and promotes the H* conversion for accelerating alkaline hydrogen evolution reaction. A further enhancement is achieved by constructing PtSA-NiO/Ni nanosheets on Ag nanowires to form a hierarchical three-dimensional morphology. Consequently, the fabricated PtSA-NiO/Ni catalyst displays high alkaline hydrogen evolution performances with a quite high mass activity of 20.6 A mg-1 for Pt at the overpotential of 100 mV, significantly outperforming the reported catalysts.

Two-Dimensional Palladium-Copper Alloy Nanodendrites for Highly Stable and Selective Electrochemical Formate Production.

Pd is the only metal that can catalyze electrochemical CO2 reduction to formate at close-to-zero overpotential. It is unfortunately subjected to severe poisoning by trace CO as the side product and suffers from deteriorating stability and selectivity with increasing overpotential. Here, we demonstrate that alloying Pd with Cu in the form of two-dimensional nanodendrites could enable highly stable and selective formate production. Such unique bimetallic nanostructures are formed as a result of the rapid in-plane growth and suppressed out-of-plane growth by carefully controlling a set of experimental parameters. Thanks to the combined electronic effect and nanostructuring effect, our alloy product catalyzes CO2 reduction to formate with remarkable stability and selectivity under the working potential as cathodic as -0.4 V. Our results are rationalized by computational simulations, evidencing that Cu atoms weaken the *CO adsorption and stabilize the *OCHO adsorption on neighboring Pd atoms.

Glass crystallization making red phosphor for high-power warm white lighting.

Rapid development of solid-state lighting technology requires new materials with highly efficient and stable luminescence, and especially relies on blue light pumped red phosphors for improved light quality. Herein, we discovered an unprecedented red-emitting Mg2Al4Si5O18:Eu2+ composite phosphor (λex = 450 nm, λem = 620 nm) via the crystallization of MgO-Al2O3-SiO2 aluminosilicate glass. Combined experimental measurement and first-principles calculations verify that Eu2+ dopants insert at the vacant channel of Mg2Al4Si5O18 crystal with six-fold coordination responsible for the peculiar red emission. Importantly, the resulting phosphor exhibits high internal/external quantum efficiency of 94.5/70.6%, and stable emission against thermal quenching, which reaches industry production. The maximum luminous flux and luminous efficiency of the constructed laser driven red emitting device reaches as high as 274 lm and 54 lm W-1, respectively. The combinations of extraordinary optical properties coupled with economically favorable and innovative preparation method indicate, that the Mg2Al4Si5O18:Eu2+ composite phosphor will provide a significant step towards the development of high-power solid-state lighting.

Facet-Dependent Cobalt Ion Distribution on the Co3O4 Nanocatalyst Surface.

Co3O4 is an important catalyst widely used for CO oxidation or electrochemical water oxidation near room temperature and was also recently used as support for single-atom catalysts (SACs). Co3O4 with a spinel structure hosts dual oxidation states of Co2+ and Co3+ in the lattice, leading to the complexity of its surface structure as the exposure of Co2+ and Co3+ has a significant impact on the performance of the catalysts. Although it is acknowledged that different facets exhibit varied catalytic activities and different abilities in hosting single atoms to provide active centers in SACs, the Co3O4 surface structure remains under-investigated. In this study, major facets of {111}, {110}, and {100} were studied down to subangstrom scale using advanced electron microscopy. We noticed that each facet has its own most stable surface configuration. The distribution of Co2+ and Co3+ on each facet was quantified, revealing a facet-dependent distribution of Co2+ and Co3+. Co3+ was found to be preferentially exposed on {100} and {110} as well as surface steps. Surface reconstruction was revealed, where a subangstrom scale shift of Co2+ was confirmed on facets of {111} and {100} due to polarity compensation and oxygen deficiency on the surface. This work not only improves our fundamental understanding of the Co3O4 surface structure but also may promote the design of Co3O4-based catalysts with tunable activity and stability.

Microstructural Study of Two-Dimensional Organic-Inorganic Hybrid Perovskite Nanosheet Degradation under Illumination.

Two-dimensional (2D) organic-inorganic hybrid perovskite materials have received substantial attention because of their exceptional optoelectronic properties. Although the applications of 2D perovskite nanosheets are promising in various optoelectronic devices, which all face harsh working conditions of light exposure, little is known about the photo-stability and degradation mechanisms of these 2D perovskite nanosheets. In this work, degradation of (C4H9NH3)2PbBr4 (BA2PbBr4) nanosheets when exposed to ultraviolet (UV) light and white light is explored. The morphology, optical properties, and microstructure of the nanosheets, under different conditions of light exposure, was studied in detail. UV light is more destructive compared to white light, which both led to a nanosheet breakdown. A combination of transmission electron microscopy (TEM) imaging and electron diffraction revealed that the organic moieties are most sensitive to light exposure and partial disorder toward complete disorder takes place during light exposure. Moreover, excessive light exposure further causes a [PbBr6]4- octahedron tilt and re-ordering within the perovskite structure. This study could enrich the understanding of 2D perovskite nanosheets and their photostability, offer a new perspective in interpreting the light-perovskite interaction, and further help the design of robust and light-tunable 2D perovskite-based optoelectronic devices.