Search NASA⌕ Search

Engineering topics

Xing, Xianran

Publications and source records attributed to Xing, Xianran.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Highly efficient semi-hydrogenation in strained ultrathin PdCu shell and the atomic deciphering for the unlocking of activity-selectivity

Excellent ethylene selectivity in acetylene semi-hydrogenation is often obtained at the expense of activity. To break the activity-selectivity trade-off, precise control and in-depth understanding of the three-dimensional atomic structure of surfacial active sites are crucial. Here, we designed a novel Au@PdCu core–shell nanocatalyst featuring diluted and stretched Pd sites on the ultrathin shell (1.6 nm), which showed excellent reactivity and selectivity, with 100% acetylene conversion and 92.4% ethylene selectivity at 122 °C, and the corresponding activity was 3.3 times higher than that of the PdCu alloy. The atomic three-dimensional decoding for the activity-selectivity balance was revealed by combining pair distribution function (PDF) and reverse Monte Carlo simulation (RMC). The results demonstrate that a large number of active sites with a low coordination number of Pd–Pd pairs and an average 3.25% tensile strain are distributed on the surface of the nanocatalyst, which perform a pivotal function in the simultaneous improvement of hydrogenation activity and ethylene selectivity. Our work not only develops a novel strategy for unlocking the linear scaling relation in heterogeneous catalysis but also provides a paradigm for atomic 3D understanding of lattice strain in core–shell nanocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

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 Pd 34 Cu 66 nanocatalysts, outperforming most of the reported advanced catalysts. Further, t he quantitative deciphering shows a large number of active sites with a Pd-Pd coordination number of 3 distributed on the surface of Pd 34 Cu 66 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.

36 MATERIALS SCIENCE↗
DOE OSTI2024

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 (α l = 1.10 × 10 -6 K -1 , 260–310 K) in the natural heterogeneous LaFe 54 Co 3.5 Si 3.35 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.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Atomic Three-Dimensional Investigations of Pd Nanocatalysts for Acetylene Semi-hydrogenation

Deciphering the three-dimensional (3D) insight into nanocatalyst surfaces at the atomic level is crucial to understanding catalytic reaction mechanisms and developing high-performance catalysts. Nevertheless, better understanding the inherent insufficiency of a long-range ordered lattice in nanocatalysts is a big challenge. Here, in this work, we report the local structure of Pd nanocatalysts, which is beneficial for demonstrating the shape-structure-adsorption relationship in acetylene hydrogenation. The 5.27 nm spherical Pd catalyst (Pd sph ) shows an ethylene selectivity of 88% at complete acetylene conversion, which is much higher than those of the Pd octahedron and Pd cube and superior to other reported monometallic Pd nanocatalysts so far. By virtue of the local structure revelation combined with the atomic pair distribution function (PDF) and reverse Monte Carlo (RMC) simulation, the atomic surface distribution of the unique compressed strain of Pd-Pd pairs in Pd sph was revealed. Density functional theory calculations verified the obvious weakening of the ethylene adsorption energy on account of the surface strain of Pd sph . It is the main factor to avoid the over-hydrogenation of acetylene. The present work, entailing shape-induced surface strain manipulation and atomic 3D insight, opens a new path to understand and optimize chemical activity and selectivity in the heterogeneous catalysis process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Interplanar Ferromagnetism Enhanced Ultrawide Zero Thermal Expansion in Kagome Cubic Intermetallic (Zr,Nb)Fe 2

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)Fe 2 . A remarkably isotropic ZTE is achieved with a negligible coefficient of thermal expansion (+0.47 x 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. Finally, this work presents a promising ZTE in kagome metallic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Giant uniaxial negative thermal expansion in FeZr 2 alloy over a wide temperature range

Negative thermal expansion (NTE) alloys possess great practical merit as thermal offsets for positive thermal expansion due to its metallic properties. However, achieving a large NTE with a wide temperature range remains a great challenge. Herein, a metallic framework-like material FeZr 2 is found to exhibit a giant uniaxial (1D) NTE with a wide temperature range (93-1078 K, $\overline{α}_{l}$=–34.01×10 –6 K –1 ). Such uniaxial NTE is the strongest in all metal-based NTE materials. The direct experimental evidence and DFT calculations reveal that the origin of giant NTE is the couple with phonons, flexible framework-like structure, and soft bonds. Interestingly, the present metallic FeZr 2 excites giant 1D NTE mainly driven by high-frequency optical branches. It is unlike the NTE in traditional framework materials, which are generally dominated by low energy acoustic branches. In the present study, a giant uniaxial NTE alloy is reported, and the complex mechanism has been revealed. It is of great significance for understanding the nature of thermal expansion and guiding the regulation of thermal expansion.

36 MATERIALS SCIENCE↗
DOE OSTI2023

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 ErFe 10 phase reacts with the migrated boron and transforms into the target Er 2 Fe 14 B (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.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Annealing in Argon Universally Upgrades the Na‐Storage Performance of Mn‐Based Layered Oxide Cathodes by Creating Bulk Oxygen Vacancies

Abstract Manganese‐rich layered oxide cathodes of sodium‐ion batteries (SIBs) are extremely promising for large‐scale energy storage owing to their high capacities and cost effectiveness, while the Jahn–Teller (J–T) distortion and low operating potential of Mn redox largely hinder their practical applications. Herein, we reveal that annealing in argon rather than conventional air is a universal strategy to comprehensively upgrade the Na‐storage performance of Mn‐based oxide cathodes. Bulk oxygen vacancies are introduced via this method, leading to reduced Mn valence, lowered Mn 3 d‐ orbital energy level, and formation of the new‐concept Mn domains. As a result, the energy density of the model P2‐Na 0.75 Mg 0.25 Mn 0.75 O 2 cathode increases by ≈50 % benefiting from the improved specific capacity and operating potential of Mn redox. The Mn domains can disrupt the cooperative J–T distortion, greatly promoting the cycling stability. This exciting finding opens a new avenue towards high‐performance Mn‐based oxide cathodes for SIBs.

Chemistry↗
DOE OSTI2023

Zero thermal expansion in non-stoichiometric and single-phase (Hf,Nb)Fe 2.5 alloy

Zero thermal expansion (ZTE) alloys are dimensionally stable under the influence of heat, which is critical in high-precision components but remains rare among single phase materials. This work reports a single phase and nearly isotropic ZTE alloy (Hf 0.8 Nb 0.2 )Fe 2.5 over a wide temperature range of 5–460 K ($α_l ≈ 1.07 × 10^{–6} K^{–1}$) via non-stoichiometric regulation. The introduction of excess Fe breaks the dual-phase nature of parent alloy, extends the magnetic ordering temperature, and induces a spin reorientation. Further, the evolution of magnetic structure versus temperature gives rise to the ZTE behavior. The design concept of changing the internal magnetic interaction through non-stoichiometric regulation provides support for the discovery of novel ZTE materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Emergence of high piezoelectricity from competing local polar order-disorder in relaxor ferroelectrics

Relaxor ferroelectrics are known for outstanding piezoelectric properties, finding a broad range of applications in advanced electromechanical devices. Decoding the origins of the enhanced properties, however, have long been complicated by the heterogeneous local structures. Here, we employ the advanced big-box refinement method by fitting neutron-, X-ray-based total scattering, and X-ray absorption spectrum simultaneously, to extract local atomic polar displacements and construct 3D polar configurations in the classical relaxor ferroelectric Pb(Mg 1/3 Nb 2/3 )O 3 –PbTiO 3 . Our results demonstrate that prevailing order-disorder character accompanied by the continuous rotation of local polar displacements commands the composition-driven global structure evolution. The omnidirectional local polar disordering appears as an indication of macroscopic relaxor characteristics. Combined with phase-field simulations, it demonstrates that the competing local polar order-disorder between different states with balanced local polar length and direction randomness leads to a flattening free-energy profile over a wide polar length, thus giving rise to high piezoelectricity. Our work clarifies that the critical structural feature required for high piezoelectricity is the competition states of local polar rather than relaxor.

42 ENGINEERING↗
DOE OSTI2023

Chemical heterogeneity modulated zero thermal expansion alloy over super-wide temperature range

Chemical heterogeneity is usually avoided in solution chemistry, but it may still occur with sometimes dramatic effects on target materials and their properties. Here, we propose chemical heterogeneity as a counterintuitive strategy to design high-performance zero thermal expansion (ZTE) alloys. We apply this approach in a Hf-Ti-Fe alloy with excess Fe in the Hf/Ti sublattice and produce Hf/Ti concentration alternations at the micro level. Such chemical heterogeneity regulates local magnetic interactions in alloy and triggers a dispersed magnetic phase transition that modulates the thermal expansions at the micro level and hence results in a remarkable ZTE behavior over a super-wide temperature window from 10 to 480 K. This mechanism is supported by comprehensive studies on morphological microstructures, crystal and magnetic structures, and theoretical calculations. The strategy of local chemical heterogeneity opens up an avenue to design ZTE and the related functional materials directly via microstructure engineering.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Ferroelectric Ordering in Nanosized PbTiO 3

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. Here, in this paper, a neutron pair distribution function (nPDF) was utilized to analyze the spontaneous polarization distribution of zero-dimensional PbTiO 3 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.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Chemical order-disorder nanodomains in Fe 3 Pt 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 Fe 3 Pt 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 Fe 3 Pt 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.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Plastic and low-cost axial zero thermal expansion alloy by a natural dual-phase composite

Zero thermal expansion (ZTE) alloys possess unique dimensional stability, high thermal and electrical conductivities. Their practical application under heat and stress is however limited by their inherent brittleness because ZTE and plasticity are generally exclusive in a single-phase material. Besides, the performance of ZTE alloys is highly sensitive to change of compositions, so conventional synthesis methods such as alloying or the design of multiphase to improve its thermal and mechanical properties are usually inapplicable. In this study, by adopting a one-step eutectic reaction method, we overcome this challenge. A natural dual-phase composite with ZTE and plasticity was synthesized by melting 4 atom% holmium with pure iron. The dual-phase alloy shows moderate plasticity and strength, axial zero thermal expansion, and stable thermal cycling performance as well as low cost. By using synchrotron X-ray diffraction, in-situ neutron diffraction and microscopy, the critical mechanism of dual-phase synergy on both thermal expansion regulation and mechanical property enhancement is revealed. These results demonstrate that eutectic reaction is likely to be a universal and effective method for the design of high-performance intermetallic-compound-based ZTE alloys.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

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. Furthermore, these findings pave the way for exploiting thermal-expansion-control engineering and related functional materials.

36 MATERIALS SCIENCE↗