Decoupled phononic-electronic transport in multi-phase n-type half-Heusler nanocomposites enabling efficient high temperature power generation

Strongly coupled electronic and thermal transport behavior in thermoelectric (TE) materials has limited their figure of merit (zT). Here we provide breakthrough in decoupling TE parameters in n-type (Hf_0.6Zr_0.4)NiSn_0.99Sb_0.01 half-Heusler (hH) alloys through multi-scale nanocomposite architecture comprising of tungsten nanoinclusions. The tungsten nanoparticles not only assist electron injection, thereby improving electrical conductivity, but also enhance the Seebeck coefficient through energy filtering effect. The microstructure comprises of disordered phases with varying size of microstructural features, which assists in effective scattering of heat-carrying phonons over diverse mean-free-path ranges. Cumulatively, these effects are shown to result in outstanding thermoelectric performance of zT_max ∼ 1.4 at 773 K and zT_avg ∼ 0.93 between 300 and 973 K. Using this material, a TE generator is demonstrated, which exhibits high power density of 13.93 W cm⁻² and conversion efficiency of 10.7% under ΔT = 674 K. The fundamental material design principle for TE nanocomposites demonstrated here can be generalized and extended to other TE systems.     

Phase‐Controlled Synthesis of Monolayer W1−xRexS2 Alloy with Improved Photoresponse Performance

Tuning bandgap and phases in the ternary 2D transition metal dichalcogenides (TMDs) alloys has opened up unexpected opportunities to engineer optoelectronic properties and explore potential applications. In this work, a salt‐assisted chemical deposition vapor (CVD) growth strategy is reported for the creation of high‐quality monolayer W_1?xRe_xS₂ alloys to fulfill a readily phase control from 1H to DT by changing the ratio of Re and W precursors. The structures and chemical compositions of doping alloys are confirmed by combining atomic resolution scanning transmission electron microscopy‐annular dark field imaging with energy dispersive X‐ray spectroscopy (EDS) and X‐ray photoelectron spectroscopy, matching well with the calculated results. The field‐effect transistors (FETs) devices fabricated based on 1H‐W_0.9Re_0.1S₂ monolayer exhibit a n‐type semiconducting behavior with the mobility of 0.4 cm² V^?1 s^?1. More importantly, the FETs show high‐performance responsivity with a value of 17 µA W^?1 in air, which is superior to that of monolayer CVD‐grown WS₂. This work paves the way toward synthesizing monolayer ternary alloys with controlled phases for potential optoelectronic applications.     

Realizing zT of 2.3 in Ge1−x−ySbxInyTe via Reducing the Phase‐Transition Temperature and Introducing Resonant Energy Doping

GeTe with rhombohedral‐to‐cubic phase transition is a promising lead‐free thermoelectric candidate. Herein, theoretical studies reveal that cubic GeTe has superior thermoelectric behavior, which is linked to (1) the two valence bands to enhance the electronic transport coefficients and (2) stronger enharmonic phonon–phonon interactions to ensure a lower intrinsic thermal conductivity. Experimentally, based on Ge_1?xSb_xTe with optimized carrier concentration, a record‐high figure‐of‐merit of 2.3 is achieved via further doping with In, which induces the distortion of the density of states near the Fermi level. Moreover, Sb and In codoping reduces the phase‐transition temperature to extend the better thermoelectric behavior of cubic GeTe to low temperature. Additionally, electronic microscopy characterization demonstrates grain boundaries, a high‐density of stacking faults, and nanoscale precipitates, which together with the inevitable point defects result in a dramatically decreased thermal conductivity. The fundamental investigation and experimental demonstration provide an important direction for the development of high‐performance Pb‐free thermoelectric materials.     

Synthesis of Large‐Size 1T′ ReS2xSe2(1−x) Alloy Monolayer with Tunable Bandgap and Carrier Type

Chemical vapor deposition growth of 1T′ ReS_2x Se_{2(1?x )} alloy monolayers is reported for the first time. The composition and the corresponding bandgap of the alloy can be continuously tuned from ReSe₂ (1.32 eV) to ReS₂ (1.62 eV) by precisely controlling the growth conditions. Atomic‐resolution scanning transmission electron microscopy reveals an interesting local atomic distribution in ReS_2x Se_{2(1?x )} alloy, where S and Se atoms are selectively occupied at different X sites in each Re‐X₆ octahedral unit cell with perfect matching between their atomic radius and space size of each X site. This structure is much attractive as it can induce the generation of highly desired localized electronic states in the 2D surface. The carrier type, threshold voltage, and carrier mobility of the alloy‐based field effect transistors can be systematically modulated by tuning the alloy composition. Especially, for the first time the fully tunable conductivity of ReS_2x Se_{2(1?x )} alloys from n‐type to bipolar and p‐type is realized. Owing to the 1T′ structure of ReS_2x Se_{2(1?x )} alloys, they exhibit strong anisotropic optical, electrical, and photoelectric properties. The controllable growth of monolayer ReS_2x Se_{2(1?x )} alloy with tunable bandgaps and electrical properties as well as superior anisotropic feature provides the feasibility for designing multifunctional 2D optoelectronic devices.     

A Simple and Scalable Route to Synthesize CoxCu1−xCo2O4@CoyCu1−yCo2O4 Yolk–Shell Microspheres,A High‐Performance Catalyst to Hydrolyze Ammonia Borane for Hydrogen Production

Yolk–shell structured micro/nano‐sized materials have broad and important applications in different areas due to their unique spatial configurations. In this study, yolk–shell structured Co₃O₄@Co₃O₄ is prepared using a simple and scalable hydrothermal reaction, followed by a calcination process. Then, Co_xCu_1?xCo₂O₄@Co_yCu_1?yCo₂O₄ microspheres are synthesized via adsorption and calcination processes using the as‐prepared Co₃O₄@Co₃O₄ as the precursor. A possible formation mechanism of the yolk–shell structures is proposed based on the characterization results, which is different from those of yolk–shell structures in previous study. For the first time, the catalytic activity of yolk–shell structured catalysts in ammonia borane (AB) hydrolysis is studied. It is discovered that the yolk–shell structured Co_xCu_1?xCo₂O₄@Co_yCu_1?yCo₂O₄ microspheres exhibit high performance with a turnover frequency (TOF) of 81.8 mol_hydrogen min^?1 mol_cat^?1. This is one of the highest TOF values reported for a noble‐metal‐free catalyst in the literature. Additionally, the yolk–shell structured Co_xCu_1?xCo₂O₄@Co_yCu_1?yCo₂O₄ microspheres are highly stable and reusable. These yolk–shell structured Co_xCu_1?xCo₂O₄@Co_yCu_1?yCo₂O₄ microsphere is a promising catalyst candidate in AB hydrolysis considering the excellent catalytic behavior and low cost.     

2D Antimony–Arsenic Alloys

Alloying in group V 2D materials and heterostructures is an effective degree of freedom to tailor and enhance their physical properties. Up to date, black arsenic‐phosphorus is the only 2D group V alloy that has been experimentally achieved by exfoliation, leaving all other possible alloys in the realm of theoretical predictions. Herein, the existence of an additional alloy consisting of 2D antimony arsenide (2D‐As_xSb_1?x) grown by molecular beam epitaxy on group IV semiconductor substrates and graphene is demonstrated. The atomic mixing of As and Sb in the lattice of the grown 2D layers is confirmed by low‐energy electron diffraction, Raman spectroscopy, and X‐ray photoelectron spectroscopy. The As content in 2D‐As_xSb_1?x is shown to depend linearly on the As₄/Sb₄ deposition rate ratio and As concentrations up to 15 at% are reached. The grown 2D alloys are found to be stable in ambient conditions in a timescale of weeks but to oxidize after longer exposure to air. This study lays the groundwork for a better control of the growth and alloying of group V 2D materials, which is critical to study their basic physical properties and integrate them in novel applications.     

Ti‐Substituted NaNi0.5Mn0.5‐xTixO2 Cathodes with Reversible O3−P3 Phase Transition for High‐Performance Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) have been considered as potential candidates for stationary energy storage because of the low cost and wide availability of Na sources. O3‐type layered oxides have been considered as one of the most promising cathodes for SIBs. However, they commonly show inevitable complicated phase transitions and sluggish kinetics, incurring rapid capacity decline and poor rate capability. Here, a series of sodium‐sufficient O3‐type NaNi_0.5Mn_{0.5‐ x} Ti _x O₂ (0 ≤ x ≤ 0.5) cathodes for SIBs is reported and the mechanisms behind their excellent electrochemical performance are studied in comparison to those of their respective end‐members. The combined analysis of in situ X‐ray diffraction, ex situ X‐ray absorption spectroscopy, and scanning transmission electron microscopy for NaNi_0.5Mn_0.2Ti_0.3O₂ reveals that the O3‐type phase transforms reversibly into a P3‐type phase upon Na+ deintercalation/intercalation. The substitution of Ti for Mn enlarges interslab distance and could restrain the unfavorable and irreversible multiphase transformation in the high voltage regions that is usually observed in O3‐type NaNi_0.5Mn_0.5O₂, resulting in improved Na cell performance. This integration of macroscale and atomicscale engineering strategy might open up the modulation of the chemical and physical properties in layered oxides and grasp new insight into the optimal design of high‐performance cathode materials for SIBs.     

Tunable Color Temperatures and Efficient White Emission from Cs2Ag1−xNaxIn1−yBiyCl6 Double Perovskite Nanocrystals

Recently, Bi‐doped Cs₂Ag_0.6Na_0.4InCl₆ lead‐free double perovskites demonstrating efficient warm‐white emission have been reported. To enable the solution processing and enrich the application fields of this promising material, here a colloidal synthesis of Cs₂Ag_1?xNa_xIn_1?yBi_yCl₆ nanocrystals is further developed. Different from its bulk states, the emission color temperatures of the nanocrystal can be tuned from 9759.7 to 4429.2 K by Na⁺ and Bi³⁺ incorporation. Furthermore, the newly developed nanocrystals can break the wavefunction symmetry of the self‐trapped excitons by partial replacement of Ag⁺ ions with Na⁺ ions and consequently allow radiative recombination. Assisted with Bi³⁺ ions doping and ligand passivation, the photoluminescence quantum yield of the Cs₂Ag_0.17Na_0.83In_0.88Bi_0.12Cl₆ nanocrystals is further promoted to 64%, which is the highest value for lead‐free perovskite nanocrystals at present. The new colloidal nanocrystals with tunable color temperature and efficient photoluminescence are expected to greatly advance the research progress of lead‐free perovskites in single‐emitter‐based white emitting materials and devices.     

Microstructure and Mechanical Properties of Al25 − xCr25 + 0.5xFe25Ni25 + 0.5x (x = 19, 17, 15 at%) Multi‐Component Alloys

A series of Al_{25 ? x}Cr_{25 + 0.5x}Fe₂₅Ni_{25 + 0.5x} (x = 19, 17, 15 at%) multi‐component alloys are prepared by arc‐melting and rapid solidification of copper molds. The technique of thermal‐mechanical processing is further applied to the master alloys to improve their mechanical properties. These alloys consist of face‐centered cubic (FCC) and body‐centered cubic (BCC) structure. The volume fraction of the BCC phase increases as Al content increase and Cr and Ni contents decrease, accompanied with a microstructural evolution from dendritic structure to lamella‐like structure. Due to the increase of volume fraction of BCC phase, the master alloys exhibit an increased strength and a declined ductility as Al content increases. The rapid solidified alloys have more BCC phase compared with the master alloys, which enhances the strength and decreases the ductility. After homogenization, hot‐rolling, and annealing at 1000 °C, the Al₈Cr_33.5Fe₂₅Ni_33.5 alloy displays excellent combination of strength (yield strength is ～635 MPa and fracture strength is ～1155 MPa) and ductility (tension strain is ～11%).

     

Defect‐Induced Pt–Co–Se Coordinated Sites with Highly Asymmetrical Electronic Distribution for Boosting Oxygen‐Involving Electrocatalysis

Rational design and synthesis of hetero‐coordinated moieties at the atomic scale can significantly raise the performance of the catalyst and obtain mechanistic insight into the oxygen‐involving electrocatalysis. Here, a facile plasma‐photochemical strategy is applied to construct atomically coordinated Pt–Co–Se moieties in defective CoSe₂ (CoSe_2?x) through filling the plasma‐created Se vacancies in CoSe_2?x with single Pt atomic species (CoSe_2?x‐Pt) under ultraviolet irradiation. The filling of single Pt can remarkably enhance the oxygen evolution reaction (OER) activity of CoSe₂. Optimal OER specific activity is achieved with a Pt content of 2.25 wt% in CoSe_2?x‐Pt, exceeding that of CoSe_2?x by a factor of 9. CoSe_2?x‐Pt shows much better OER performance than CoSe_2?x filled with single Ni and even Ru atomic species (CoSe_2?x‐Ni and CoSe_2?x‐Ru). Noticeably, it is general that Pt is not a good OER catalyst but Ru is; thus the design of active sites for electrocatalysis at an atomic level should follow a different intrinsic mechanism. Mechanism studies unravel that the single Pt can induce much higher electronic distribution asymmetry degree than both single Ni and Ru, and benefit the interaction between the Co sites and adsorbates (OH*, O*, and OOH*) during the OER process, leading to a better OER activity.     

Anionic Se‐Substitution toward High‐Performance CuS1−xSex Nanosheet Cathode for Rechargeable Magnesium Batteries

Rechargeable magnesium batteries (rMBs) are promising as the most ideal further energy storage systems but lack competent cathode materials due to sluggish redox reaction kinetics. Herein, developed is an anionic Se‐substitution strategy to improve the rate capability and the cycling stability of 2D CuS_1?xSe_x nanosheet cathodes through an efficient microwave‐induced heating method. The optimized CuS_1?xSe_x (X = 0.2) nanosheet cathode can exhibit high reversible capacity of 268.5 mAh g^?1 at 20 mA g^?1 and good cycling stability (140.4 mAh g^?1 at 300 mA g^?1 upon 100 cycles). Moreover, the CuS_1?xSe_x (X = 0.2) nanosheet cathode can deliver remarkable rate capability with a reversible capacity of 119.2 mAh g^?1 at 500 mA g^?1, much higher than the 21.7 mAh g^?1 of pristine CuS nanosheets. The superior electrochemical performance can be ascribed to the enhanced reaction kinetics, enriched cation storage active sites, and shortened ion diffusion pathway of the CuS_1?xSe_x nanosheet. Therefore, tuning anionic chemical composition demonstrates an effective strategy to develop novel cathode materials for rMBs.     

Band Structure Perfection and Superconductivity in Type‐II Dirac Semimetal Ir1−xPtxTe2

The discovery of a new type‐II Dirac semimetal in Ir_1?xPt_xTe₂ with optimized band structure is described. Pt dopants protect the crystal structure holding the Dirac cones and tune the Fermi level close to the Dirac point. The type‐II Dirac dispersion in Ir_1?xPt_xTe₂ is confirmed by angle‐resolved photoemission spectroscopy and first‐principles calculations. Superconductivity is also observed and persists when the Fermi level aligns with the Dirac points. Ir_1?xPt_xTe₂ is an ideal platform for further studies on the exotic properties and potential applications of type‐II DSMs, and opens up a new route for the investigation of the possible topological superconductivity and Majorana physics.     

Y3−xErxAl5O12 Aluminate Ceramics: Preparation,Thermal Properties and Theoretical Model of Thermal Conductivity

Rare‐earth aluminate ceramics for thermal‐barrier coatings (TBCs) are synthesized. The Young's modulus and thermal properties decrease with erbium additive increasing. The Y_3?xEr_xAl₅O₁₂ ceramics (x = 1, 3) possess a much‐lower thermal conductivity compared with 8YSZ. The lower Young's modulus and thermal‐expansion coefficient are due to the larger atomic weight of the Er substitutional atom. Additional phonon‐scattering effects also contribute to the lower thermal conductivity. The results indicate that Y_3?xEr_xAl₅O₁₂ can be explored as a candidate material for TBC systems. A theoretical model that describes the influence of point defects on the thermal conductivity is discussed.     

New rutile solid solutions,Ti1−4xLixM3xO2: M = Nb,Ta, Sb

Three extensive new rutile solid solution series have been prepared in which Ti⁴⁺ is replaced by a combination of Li⁺ and a pentavalent cation: Nb⁵⁺, Ta⁵⁺, Sb⁵⁺. The formulae are Ti_1?4xLi_xM_3xO₂: 0 < x ? 0.15, M = Ta; 0 < x ? 0.17, M = Nb; 0 < x ? 0.12, M = Sb. The solid solutions were characterised by X-ray powder diffraction and density measurements. In addition to the rutile solid solutions, LiNb₃O₈ forms a limited range of solid solutions, Li_1?yNb_3?3yTi_4yO₈: 0 < y ? 0.06.     

Unique 1D Cd1−xZnxS@O‐MoS2/NiOx Nanohybrids: Highly Efficient Visible‐Light‐Driven Photocatalytic Hydrogen Evolution via Integrated Structural Regulation

Development of noble‐metal‐free photocatalysts for highly efficient sunlight‐driven water splitting is of great interest. Nevertheless, for the photocatalytic H₂ evolution reaction (HER), the integrated regulation study on morphology, electronic band structures, and surface active sites of catalyst is still minimal up to now. Herein, well‐defined 1D Cd_1?xZn_xS@O‐MoS₂/NiO_x hybrid nanostructures with enhanced activity and stability for photocatalytic HER are prepared. Interestingly, the band alignments, exposure of active sites, and interfacial charge separation of Cd_1?xZn_xS@O‐MoS₂/NiO_x are optimized by tuning the Zn‐doping content as well as the growth of defect‐rich O‐MoS₂ layer and NiO_x nanoparticles, which endow the hybrids with excellent HER performances. Specifically, the visible‐light‐driven (>420 nm) HER activity of Cd_1?xZn_xS@O‐MoS₂/NiO_x with 15% Zn‐doping and 0.2 wt% O‐MoS₂ (CZ_0.15S‐0.2M‐NiO_x) in lactic acid solution (66.08 mmol h^?1 g^?1) is about 25 times that of Pt loaded CZ_0.15S, which is further increased to 223.17 mmol h^?1 g^?1 when using Na₂S/Na₂SO₃ as the sacrificial agent. Meanwhile, in Na₂S/Na₂SO₃ solution, the CZ_0.15S‐0.2M‐NiO_x sample demonstrates an apparent quantum yield of 64.1% at 420 nm and a good stability for HER under long‐time illumination. The results presented in this work can be valuable inspirations for the exploitation of advanced materials for energy‐related applications.     

Au Nanoclusters Sensitized Black TiO2−x Nanotubes for Enhanced Photodynamic Therapy Driven by Near‐Infrared Light

The low reactive oxygen species production capability and the shallow tissue penetration of excited light (UV) are still two barriers in photodynamic therapy (PDT). Here, Au cluster anchored black anatase TiO_2?x nanotubes (abbreviated as Au₂₅/B‐TiO_2?x NTs) are synthesized by gaseous reduction of anatase TiO₂ NTs and subsequent deposition of noble metal. The Au₂₅/B‐TiO_2?x NTs with thickness of about 2 nm exhibit excellent PDT performance. The reduction process increased the density of Ti³⁺ on the surface of TiO₂, which effectively depresses the recombination of electron and hole. Furthermore, after modification of Au₂₅ nanoclusters, the PDT efficiency is further enhanced owing to the changed electrical distribution in the composite, which forms a shallow potential well on the metal–TiO₂ interface to further hamper the recombination of electron and hole. Especially, the reduction of anatase TiO₂ can expend the light response range (UV) of TiO₂ to the visible and even near infrared (NIR) light region with high tissue penetration depth. When excited by NIR light, the nanoplatform shows markedly improved therapeutic efficacy attributed to the photocatalytic synergistic effect, and promotes separation or restrained recombination of electron and hole, which is verified by experimental results in vitro and in vivo.     

Structure‐Property Relationships of a High Strength Superelastic NiTi–1Hf Alloy

The authors report on a relatively new alloy, Ni₅₄Ti₄₅Hf₁, that exhibits strengths more than 40% greater than those of conventional NiTi‐based shape memory alloys ? 2.5 GPa in compression and 1.9 GPa in torsion ? and retains those strengths during cycling. Furthermore, the superelastic hysteresis is very small and stable with cycling. Aging treatments are used to induce a very high density of Ni₄Ti₃ precipitates, which impede plasticity during cycling yet do not impart substantial dissipation to the reversibility of the phase transformation. Pairing compression testing with high‐energy synchrotron X‐ray diffraction and aberration‐corrected electron microscopy provides an in‐depth look at the structure‐property relationships of this alloy. Specifically, it is found that a combination of small, untwinned retained martensite laths, and dislocations on the austenite‐martensite interfaces primarily strengthen the alloy as opposed to dislocation networks. Furthermore, some combination of nanoprecipitation and interface dislocations is responsible for the remarkably low mechanical hysteresis exhibited by this material.

     

Ternary Sn–Ti–O Based Nanostructures as Anodes for Lithium Ion Batteries

SnO_x (x = 0, 1, 2) and TiO₂ are widely considered to be potential anode candidates for next generation lithium ion batteries. In terms of the lithium storage mechanisms, TiO₂ anodes operate on the base of the Li ion intercalation–deintercalation, and they typically display long cycling life and high rate capability, arising from the negligible cell volume change during the discharge–charge process, while their performance is limited by low specific capacity and low electronic conductivity. SnO_x anodes rely on the alloying–dealloying reaction with Li ions, and typically exhibit large specific capacity but poor cycling performance, originating from the extremely large volume change and thus the resultant pulverization problems. Making use of their advantages and minimizing the disadvantages, numerous strategies have been developed in the recent years to design composite nanostructured Sn–Ti–O ternary systems. This Review aims to provide rational understanding on their design and the improvement of electrochemical properties of such systems, including SnO_x–TiO₂ nanocomposites mixing at nanoscale and nanostructured Sn_xTi_1‐xO₂ solid solutions doped at the atomic level, as well as their combinations with carbon‐based nanomaterials.     

Hierarchical α‐MnO2 Nanowires@Ni1‐xMnxOy Nanoflakes Core–Shell Nanostructures for Supercapacitors

A facile two‐step solution‐phase method has been developed for the preparation of hierarchical α‐MnO₂ nanowires@Ni_1‐xMn_xO_y nanoflakes core–shell nanostructures. Ultralong α‐MnO₂ nanowires were synthesized by a hydrothermal method in the first step. Subsequently, Ni_1‐xMn_xO_y nanoflakes were grown on α‐MnO₂ nanowires to form core–shell nanostructures using chemical bath deposition followed by thermal annealing. Both solution‐phase methods can be easily scaled up for mass production. We have evaluated their application in supercapacitors. The ultralong one‐dimensional (1D) α‐MnO₂ nanowires in hierarchical core–shell nanostructures offer a stable and efficient backbone for charge transport; while the two‐dimensional (2D) Ni_1‐xMn_xO_y nanoflakes on α‐MnO₂ nanowires provide high accessible surface to ions in the electrolyte. These beneficial features enable the electrode with high capacitance and reliable stability. The capacitance of the core–shell α‐MnO₂@Ni_1‐xMn_xO_y nanostructures (x = 0.75) is as high as 657 F g^?1 at a current density of 250 mA g^?1, and stable charging‐discharging cycling over 1000 times at a current density of 2000 mA g^?1 has been realized.     

Regulating Surface and Grain‐Boundary Structures of Ni‐Rich Layered Cathodes for Ultrahigh Cycle Stability

The wide applications of Ni‐rich LiNi_1‐x‐yCo_xMn_yO₂ cathodes are severely limited by capacity fading and voltage fading during the cycling process resulting from the pulverization of particles, interfacial side reactions, and phase transformation. The canonical surface modification approach can improve the stability to a certain extent; however, it fails to resolve the key bottlenecks. The preparation of Li(Ni_0.4Co_0.2Mn_0.4)_1‐xTi_xO₂ on the surface of LiNi_0.8Co_0.1Mn_0.1O₂ particles with a coprecipitation method is reported. After sintering, Ti diffuses into the interior and mainly distributes along surface and grain boundaries. A strong surface and grain boundary strengthening are simultaneously achieved. The pristine particles are fully pulverized into first particles due to mechanical instability and high strains, which results in serious capacity fading. In contrast, the strong surface and the grain boundary strengthening can maintain the structural integrity, and therefore significantly improve the cycle stability. A general and simple strategy for the design of high‐performance Ni‐rich LiNi_1‐x‐yCo_xMn_yO₂ cathode is provided and is applicable to surface modification and grain‐boundary regulation of other advanced cathodes for batteries.