Intrinsic-strain-induced ferroelectric order and ultrafine nanodomains in SrTiO3.

Nano ferroelectrics holds the potential application promise in information storage, electro-mechanical transformation, and novel catalysts but encounters a huge challenge of size limitation and manufacture complexity on the creation of long-range ferroelectric ordering. Herein, as an incipient ferroelectric, nanosized SrTiO3 was indued with polarized ordering at room temperature from the nonpolar cubic structure, driven by the intrinsic three-dimensional (3D) tensile strain. The ferroelectric behavior can be confirmed by piezoelectric force microscopy and the ferroelectric TO1 soft mode was verified with the temperature stability to 500 K. Its structural origin comes from the off-center shift of Ti atom to oxygen octahedron and forms the ultrafine head-to-tail connected 90° nanodomains about 2 to 3 nm, resulting in an overall spontaneous polarization toward the short edges of nanoparticles. According to the density functional theory calculations and phase-field simulations, the 3D strain-related dipole displacement transformed from [001] to [111] and segmentation effect on the ferroelectric domain were further proved. The topological ferroelectric order induced by intrinsic 3D tensile strain shows a unique approach to get over the nanosized limitation in nanodevices and construct the strong strain-polarization coupling, paving the way for the design of high-performance and free-assembled ferroelectric devices.

Decoding Active Sites for Highly Efficient Semihydrogenation of Acetylene in Palladium-Copper Nanoalloys.

Accurately decoding the three-dimensional atomic structure of surface active sites is essential yet challenging for a rational catalyst design. Here, we used comprehensive techniques combining the pair distribution function and reverse Monte Carlo simulation to reveal the surficial distribution of Pd active sites and adjacent coordination environment in palladium-copper nanoalloys. After the fine-tuning of the atomic arrangement, excellent catalytic performance with 98% ethylene selectivity at complete acetylene conversion was obtained in the Pd34Cu66 nanocatalysts, outperforming most of the reported advanced catalysts. The quantitative deciphering shows a large number of active sites with a Pd-Pd coordination number of 3 distributed on the surface of Pd34Cu66 nanoalloys, which play a decisive role in highly efficient semihydrogenation. This finding not only opens the way for guiding the precise design of bimetal nanocatalysts from atomic-level insight but also provides a method to resolve the spatial structure of active sites.

Chemical Diversity for Tailoring Negative Thermal Expansion.

Negative thermal expansion (NTE), referring to the lattice contraction upon heating, has been an attractive topic of solid-state chemistry and functional materials. The response of a lattice to the temperature field is deeply rooted in its structural features and is inseparable from the physical properties. For the past 30 years, great efforts have been made to search for NTE compounds and control NTE performance. The demands of different applications give rise to the prominent development of new NTE systems covering multifarious chemical substances and many preparation routes. Even so, the intelligent design of NTE structures and efficient tailoring for lattice thermal expansion are still challenging. However, the diverse chemical routes to synthesize target compounds with featured structures provide a large number of strategies to achieve the desirable NTE behaviors with related properties. The chemical diversity is reflected in the wide regulating scale, flexible ways of introduction, and abundant structure-function insights. It inspires the rapid growth of new functional NTE compounds and understanding of the physical origins. In this review, we provide a systematic overview of the recent progress of chemical diversity in the tailoring of NTE. The efficient control of lattice and deep structural deciphering are carefully discussed. This comprehensive summary and perspective for chemical diversity are helpful to promote the creation of functional zero-thermal-expansion (ZTE) compounds and the practical utilization of NTE.

The Structure of Terbium in the Ferromagnetic State.

Metals typically crystallize in highly symmetric structures due to their nondirectional and nonsaturated metallic bonds. Here, we report that terbium metal in its ferromagnetic state adopts an unusual low-symmetry orthorhombic structure with a Cmcm space group. A similar structure has been previously observed only in a few actinide metals with bonding 5f electrons at ambient pressure, such as uranium, neptunium, and plutonium, but with different nearest coordination numbers and bond-length variations. The Tb atom occupies the 4c site (0, ∼0.1661, 1/4), building up -[Tb-Tb]- layers stacking along the b-axis. Our first-principles many-body calculations of the crystal field splitting in the correlated Tb 4f-shell demonstrate that the Cmcm structure for ferromagnetic terbium is stabilized by magneto-elastic forces due to a secondary order of quadrupolar moments in the ferromagnetic state. These findings are significant for further understanding of the nature of terbium, including its electron structure, energy bands, phonons, and magnetism.

Interplanar Ferromagnetism Enhanced Ultrawide Zero Thermal Expansion in Kagome Cubic Intermetallic (Zr,Nb)Fe2.

A cubic metal exhibiting zero thermal expansion (ZTE) over a wide temperature window demonstrates significant applications in a broad range of advanced technologies but is extremely rare in nature. Here, enabled by high-temperature synthesis, we realize tunable thermal expansion via magnetic doping in the class of kagome cubic (Fd-3m) intermetallic (Zr,Nb)Fe2. A remarkably isotropic ZTE is achieved with a negligible coefficient of thermal expansion (+0.47 × 10-6 K-1) from 4 to 425 K, almost wider than most ZTE in metals available. A combined in situ magnetization, neutron powder diffraction, and hyperfine Mössbauer spectrum analysis reveals that interplanar ferromagnetic ordering contributes to a large magnetic compensation for normal lattice contraction upon cooling. Trace Fe-doping introduces extra magnetic exchange interactions that distinctly enhance the ferromagnetism and magnetic ordering temperature, thus engendering such an ultrawide ZTE. This work presents a promising ZTE in kagome metallic materials.

Ferroelectric Ordering in Nanosized PbTiO3.

The insight into the three-dimensional configuration of ferroelectric ordering in ferroelectric nanomaterials is motivated by the application of the development of functional nanodevices and the structural designing. However, the atomic deciphering of the spatial distribution of ordered structure remains challenging for the limitation of dimension and probing techniques. In this paper, a neutron pair distribution function (nPDF) was utilized to analyze the spontaneous polarization distribution of zero-dimensional PbTiO3 nanoparticles in three dimensions, via the application of reverse Monte Carlo (RMC) modeling. The comprehensive identification with transmission electron microscopy verified the linear characteristics of polarization along the c-axis in the main body, while electric polarization distribution on the surface was enhanced abnormally. In addition, the correlation of dipole vectors extending to three unit cells below the surface is retained. This work shows an application of the micro/macroscale information to effectively decode the polarization structure of nanoferroelectrics, providing new views of designing nanoferroelectric devices.

Two-Dimensional Negative Thermal Expansion in a Facile and Low-Cost Oxalate-Based Metal-Organic Framework.

Two-dimensional negative thermal expansion (NTE) is achieved in a tetragonal oxalate-based metal-organic framework (MOF), CdZrSr(C2O4)4, within a temperature range from 123 to 398 K [space group I4̅m2, αa = -2.4(7) M K-1, αc = 11.3(3) M K-1, and αV = 6.4(1) M K-1]. By combining variable-temperature X-ray diffraction, a high-resolution synchrotron X-ray pair distribution function, and thermogravimetry-differential scanning calorimetry, we shows that NTE within the ab plane derives from the oriented rotation of an oxalate ligand in zigzag chains (-CdO8-ox-ZrO8-ox-)∞. That is simplified to the Zr atom rotating with an unchanged Zr···Cd distance as the radius, which also gives rise to the deformation of a hingelike connection along the c axis and results in its positive thermal expansion. By virtue of the facile and low-cost oxalate ligand, the present NTE MOF may show application prospects in the future.

Ultrawide Temperature Range Super-Invar Behavior of R_{2}(Fe,Co)_{17} Materials (R = Rare Earth).

Super Invar (SIV), i.e., zero thermal expansion of metallic materials underpinned by magnetic ordering, is of great practical merit for a wide range of high precision engineering. However, the relatively narrow temperature window of SIV in most materials restricts its potential applications in many critical fields. Here, we demonstrate the controlled design of thermal expansion in a family of R_{2}(Fe,Co)_{17} materials (R=rare Earth). We find that adjusting the Fe-Co content tunes the thermal expansion behavior and its optimization leads to a record-wide SIV with good cyclic stability from 3-461 K, almost twice the range of currently known SIV. In situ neutron diffraction, Mössbauer spectra and first-principles calculations reveal the 3d bonding state transition of the Fe-sublattice favors extra lattice stress upon magnetic ordering. On the other hand, Co content induces a dramatic enhancement of the internal molecular field, which can be manipulated to achieve "ultrawide" SIV over broad temperature, composition and magnetic field windows. These findings pave the way for exploiting thermal-expansion-control engineering and related functional materials.

Zero Thermal Expansion and Strong Covalent Binding of VB2 Compound.

Zero thermal expansion (ZTE) is an intriguing phenomenon by virtue of its peculiar lack of expansion and contraction with temperature. The achievement of ZTE in a metallic material is a desired but challenging task. Here we report the ZTE behavior of a single-phase metallic VB2 compound, stacking with the V and B atomic layers along the c direction (αV = 2.18 × 10-6 K-1, 5-150 K). Neutron powder diffraction demonstrates that the ZTE behavior is entangled in the direct blocking of the lattice expansion along all crystallographic directions with temperature. X-ray photoelectron spectroscopy and density functional theory calculations indicate that strong covalent binding adheres the nearest-neighbor B-B and V-B pairs, which is proposed to control the ZTE within both the basal plane and the c direction. An intimate correlation is revealed between the covalent binding and the lattice parameters. Our work indicates the opportunity to design metallic ZTE with strong chemical binding in the future.

Role of "Dumbbell" Pairs of Fe in Spin Alignments and Negative Thermal Expansion of Lu2Fe17-Based Intermetallic Compounds.

Knowledge of negative thermal expansion (NTE) is an interesting issue in the field of materials science and engineering. It has been proposed that the unique dumbbell pairs of Fe (dumbbells) are highly entangled in the NTE behaviors of R2Fe17 (R = rare earth) compounds but still remain controversial. Here, a facile method is employed to explore the role of dumbbells in spin alignments and NTE by the nonstoichiometric design of Lu2-xFe17 compounds. The powder synchrotron X-ray diffraction, magnetometry, and neutron powder diffraction investigations indicate that a decrease of the Lu content can enhance the dumbbell concentration and motivate an incommensurate magnetic structure simultaneously. However, increasing the dumbbell concentration makes little difference in the amplitude of the ordered magnetic moments of Fe sublattices, which reveals an equivalent NTE behavior for Lu2-xFe17 compounds. This work gives insight into the role that dumbbells played in spin alignments and NTE for Lu2Fe17-based compounds, correcting the previously proposed conjecture and probably conducive to adjusting the related magnetic performances of R2Fe17 compounds in the future.

Manipulating Spin Alignments of (Y,Lu)1.7Fe17 Intermetallic Compounds via Unusual Thermal Pressure.

External pressure has been successfully employed to achieve desirable spin alignments in the field of materials science but is seriously restricted by the difficulty of reaching high pressure with conventional methods. The search for simple and effective ways to apply pressure on the lattice is challenging but intriguing. Here we report a new strategy to manipulate the spin alignments of (Y,Lu)1.7Fe17 intermetallic compounds through unusual thermal pressure. The spin alignments of Fe initially lie parallel inside the basal plane and then turn spirally between adjacent layers with a zone axis along the c direction under higher Lu concentration. The synchrotron and neutron powder diffraction investigations clearly reveal that the direction of spin alignments is highly correlated to large lattice contraction induced by negative thermal expansion (NTE), an unusual thermal pressure, along the c direction. The critical lattice parameter c to form spiral spin alignments is determined unambiguously. This work presents a feasible way to adjust spin alignments through NTE, which might be conducive to the future design of particular spin alignments instead of physical pressure for functional magnetic materials.

Neutron Diffraction Study of Unusual Magnetic Behaviors in the Ho2Fe11Al6 Intermetallic Compound.

Knowledge of structure-property relationships is fundamental but significant in the exploitation of magnetic materials. Here we report that the high Al substitution for Fe transformed the crystal structure from a hexagonal Ho2Fe17 compound to a rhombohedral Ho2Fe11Al6 compound. Intriguingly, the latter shows unusual evolution of magnetization around 86 and 220 K compared with the former. Integrated investigations of the detailed structure analysis and magnetic performance on the Ho2Fe11Al6 compound demonstrate that the Ho2Fe11Al6 compound possesses a stable rhombohedral structure (R3̅m) from 5 to 430 K with preferred occupation of Al atoms and ferrimagnetic structure in which the magnetic moments of Ho and Fe lie antiparallel in the basal plane below the Curie temperature. The results of the temperature dependence of moments reveal that the disparate rates of change of the moments for Ho and Fe sublattices give rise to unusual evolution of magnetization around 86 and 220 K and then turn to paramagnetic above 280 K. This work provides clear structure and magnetization information on the Ho2Fe11Al6 compound, which may be beneficial to guiding the future development of magnetic materials.

Adjustable Magnetic Phase Transition Inducing Unusual Zero Thermal Expansion in Cubic RCo2-Based Intermetallic Compounds (R = Rare Earth).

Metallic materials that exhibit negligible thermal expansion or zero thermal expansion (ZTE) have great merit for practical applications, but these materials are rare and their thermal expansions are difficult to control. Here, we successfully tailored the thermal expansion behaviors from strongly but abruptly negative to zero over wide temperature ranges in a series of (Gd,R)(Co,Fe)2 (R = Dy, Ho, Er) intermetallic compounds by tuning the composition to bring the first-order magnetic phase transition to second-order. Interestingly, an unusual isotropic ZTE property with a coefficient of thermal expansion of α l = 0.16(0) × 10-6 K-1 was achieved in cubic Gd0.25Dy0.75Co1.93Fe0.07 (GDCF) in the temperature range of 10-275 K. The short-wavelength neutron powder diffraction, synchrotron X-ray diffraction, and magnetic measurement studies evidence that this ZTE behavior was ascribed to the rare-earth-moment-dominated spontaneous volume magnetostriction, which can be controlled by an adjustable magnetic phase transition. The present work extends the scope of the ZTE family and provides an effective approach to exploring ZTE materials, such as by adjusting the magnetism or ferroelectricity-related phase transition in the family of functional materials.

Structure and Phase Transformation in the Giant Magnetostriction Laves-Phase SmFe2.

As one class of the most important intermetallic compounds, the binary Laves-phase is well-known for its abundant magnetic properties. Samarium-iron alloy system SmFe2 is a prototypical Laves compound that shows strong negative magnetostriction but relatively weak magnetocrystalline anisotropy. SmFe2 has been identified as a cubic Fd3̅m structure at room temperature; however, the cubic symmetry, in principle, does not match the spontaneous magnetization along the [111]cubic direction. Here we studied the crystal structure of SmFe2 by high-resolution synchrotron X-ray powder diffraction, X-ray total scattering, and selected-area electron diffraction methods. SmFe2 is found to adopt a centrosymmetric trigonal R3̅m structure at room temperature, which transforms to an orthorhombic Imma structure at 200 K. This transition is in agreement with the changes of easy magnetization direction from [111]cubic to [110]cubic direction and is further evidenced by the inflection of thermal expansion behavior, the sharp decline of the magnetic susceptibility in the field-cooling-zero field-cooling curve, and the anomaly in the specific heat capacity measurement. The revised structure and phase transformation of SmFe2 could be useful to understand the magnetostriction and related physical properties of other RM2-type pseudocubic Laves-phase intermetallic compounds.

Regulating luminescence thermal enhancement in negative thermal expansion metal-organic frameworks.

Overcoming thermal quenching is generally essential for the practical application of luminescent materials. It has been recently found that frameworks with negative thermal expansion (NTE) could be a promising candidate to engineer unconventional luminescence thermal enhancement. However, the mechanism through which luminescence thermal enhancement can be well tuned remains an open issue. In this work, enabled by altering ligands in a series of UiO-66 derived Eu-based metal-organic frameworks, it was revealed that the changes in the thermal expansion are closely related to luminescence thermal enhancement. The NTE of the aromatic ring part favors luminescence thermal enhancement, while contraction of the carboxylic acid part plays the opposite role. Modulation of functional groups in ligands can change the thermal vibration of aromatic rings and then achieve luminescence thermal enhancement in a wide temperature window. Our findings pave the way to manipulate the NTE and luminescence thermal enhancement based on ligand engineering.

An isotropic zero thermal expansion alloy with super-high toughness.

Zero thermal expansion (ZTE) alloys with high mechanical response are crucial for their practical usage. Yet, unifying the ZTE behavior and mechanical response in one material is a grand obstacle, especially in multicomponent ZTE alloys. Herein, we report a near isotropic zero thermal expansion (αl = 1.10 × 10-6 K-1, 260-310 K) in the natural heterogeneous LaFe54Co3.5Si3.35 alloy, which exhibits a super-high toughness of 277.8 ± 14.7 J cm-3. Chemical partition, in the dual-phase structure, assumes the role of not only modulating thermal expansion through magnetic interaction but also enhancing mechanical properties via interface bonding. The comprehensive analysis reveals that the hierarchically synergistic enhancement among lattice, phase interface, and heterogeneous structure is significant for strong toughness. Our findings pave the way to tailor thermal expansion and obtain prominent mechanical properties in multicomponent alloys, which is essential to ultra-stable functional materials.

One-step synthesis of MoS2/NiS heterostructures with a stable 1T phase for an efficient hydrogen evolution reaction.

Metallic phase (1T) MoS2 has been regarded as an ideal catalytic material for the hydrogen evolution reaction (HER) due to its high active site density and favorable electrical conductivity. However, the preparation of 1T-phase MoS2 samples requires tough reaction conditions and 1T-MoS2 has poor stability under alkaline conditions. In this work, 1T-MoS2/NiS heterostructure catalysts grown in situ on carbon cloth were prepared by a simple one-step hydrothermal method. The obtained MoS2/NiS/CC combines the advantages of high active site density and a self-supporting structure, achieving stable 77% metal phase (1T) MoS2. The combination of NiS and 1T-MoS2 enhances the intrinsic activity of MoS2 while the electrical conductivity is improved. These advantages enable the 1T-MoS2/NiS/CC electrocatalyst to have a low overpotential of 89 mV (@10 mA cm-2) and a small Tafel slope of 75 mV dec-1 under alkaline conditions and provide a synthetic strategy of stable 1T-MoS2-based electrocatalysts for the HER by a heterogeneous structure.

Superior zero thermal expansion dual-phase alloy via boron-migration mediated solid-state reaction.

Rapid progress in modern technologies demands zero thermal expansion (ZTE) materials with multi-property profiles to withstand harsh service conditions. Thus far, the majority of documented ZTE materials have shortcomings in different aspects that limit their practical utilization. Here, we report on a superior isotropic ZTE alloy with collective properties regarding wide operating temperature windows, high strength-stiffness, and cyclic thermal stability. A boron-migration-mediated solid-state reaction (BMSR) constructs a salient "plum pudding" structure in a dual-phase Er-Fe-B alloy, where the precursor ErFe10 phase reacts with the migrated boron and transforms into the target Er2Fe14B (pudding) and α-Fe phases (plum). The formation of such microstructure helps to eliminate apparent crystallographic texture, tailor and form isotropic ZTE, and simultaneously enhance the strength and toughness of the alloy. These findings suggest a promising design paradigm for comprehensive performance ZTE alloys.

The Efficacy of Extended Metacognitive Training on Neurocognitive Function in Schizophrenia: A Randomized Controlled Trial.

The aim of this study was to evaluate the effect of metacognitive training (MCT) on improving the neurocognitive function of Chinese patients with schizophrenia. One hundred inpatients with schizophrenia were selected by regional group randomization and divided into the control (treated as usual, TAU) group (n = 50) and the TAU + MCT group (n = 50). In this study, a 10-module MCT was used and the intervention process lasted 30 days. Cognitive function was assessed blindly using the Repeatable Battery of Neuropsychological Status (RBANS) scale at baseline, 24 h post-treatment, and 12 weeks' post-treatment. The differences between the total RBANS score and baseline (pre-test) for the post-test and 12-week-follow-up tests were used as the primary outcome, and the difference between the RBANS dimension scores and baseline (pre-test) were used as a secondary outcome in this study. The completion rate at follow-up was high in the TAU + MCT group (94%). Intention-to-treat analysis and per-protocol analysis showed a significant increase in total neurocognitive function scores and three-dimensional scores (delayed memory, visual breadth, and attention) in the TAU + MCT group immediately after the intervention and at the 12-week follow-up compared with baseline. This study provides support for the efficacy of 10 module MCT concerning neurocognition.

Chemical order-disorder nanodomains in Fe3Pt bulk alloy.

Chemical ordering is a common phenomenon and highly correlated with the properties of solid materials. By means of the redistribution of atoms and chemical bonds, it invokes an effective lattice adjustment and tailors corresponding physical properties. To date, however, directly probing the 3D interfacial interactions of chemical ordering remains a big challenge. In this work, we deciphered the interlaced distribution of nanosized domains with chemical order/disorder in Fe3Pt bulk alloy. HAADF-STEM images evidence the existence of such nanodomains. The reverse Monte Carlo method with the X-ray pair distribution function data reveal the 3D distribution of local structures and the tensile effect in the disordered domains at the single-atomic level. The chemical bonding around the domain boundary changes the bonding feature in the disordered side and reduces the local magnetic moment of Fe atoms. This results in a suppressed negative thermal expansion and extended temperature range in Fe3Pt bulk alloy with nanodomains. Our study demonstrates a local revelation for the chemical order/disorder nanodomains in bulk alloy. The understanding gained from atomic short-range interactions within the domain boundaries provides useful insights with regard to designing new functional compounds.