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Xiao, Haiyan

Publications and source records attributed to Xiao, Haiyan.

10 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Electrostatic Asymmetry of Wurtzite Nanocrystals and Resulting Photocatalytic Properties

Efficient light absorption and high energy of charge carriers of zinc cadmium sulfide (ZCS) make this semiconductor attractive for many photocatalytic reactions. Despite marked successes in shape-controlled synthesis of ZCS central to their photocatalytic performance, recombination of charge carriers as they migrate through the nanoscale particles results in losses of excitation energy, markedly reducing the photocatalytic activity of ZCS and other heterogeneous photocatalysts. Here, in this study, we show that the electrostatic asymmetry of nanostructures, previously discovered for nearly spherical nanoparticles, also manifests in wurtzite ZCS with planar geometry. The electrostatic asymmetry assists charge separation and substantially increases the yield of photocatalytic reactions in monocrystalline ZCS. The synthesized ZCS nanorods and nanoplates with identical chemical composition were found to have markedly different photocatalytic activity for evolution of hydrogen in water. Despite much smaller specific surface areas, the ~500 nm wide nanoplates displayed a hydrogen evolution rate 12 times higher than the ~35 nm long nanorods, also outperforming other ZCS photocatalysts. Experimental and computational data indicate that the homo- and heterojunction-free ZCS nanoplates with continuous wurtzite lattice behave essentially as nanoscale dipoles with intrinsic dipole moment as high as 48.39 D per unit cell. Electric-field-directed migration of charge carriers stimulates their localization on opposite parts of the nanoplates. Direct imaging of the intraparticle electrical field using off-axis electron holography confirmed their electrostatic asymmetry. Polarization-enhanced charge separation provides a new pathway to efficient and stable photocatalysts for sustainable energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Atomistic Conversion Reaction Mechanism of WO 3 in Secondary Ion Batteries of Li, Na, and Ca

Abstract Intercalation and conversion are two fundamental chemical processes for battery materials in response to ion insertion. The interplay between these two chemical processes has never been directly seen and understood at atomic scale. Here, using in situ HRTEM, we captured the atomistic conversion reaction processes during Li, Na, Ca insertion into a WO 3 single crystal model electrode. An intercalation step prior to conversion is explicitly revealed at atomic scale for the first time for Li, Na, Ca. Nanoscale diffraction and ab initio molecular dynamic simulations revealed that after intercalation, the inserted ion–oxygen bond formation destabilizes the transition‐metal framework which gradually shrinks, distorts and finally collapses to an amorphous W and M x O (M=Li, Na, Ca) composite structure. This study provides a full atomistic picture of the transition from intercalation to conversion, which is of essential importance for both secondary ion batteries and electrochromic devices.

He, Yang↗
DOE OSTI2016

Atomistic Conversion Reaction Mechanism of WO 3 in Secondary Ion Batteries of Li, Na, and Ca

Abstract Intercalation and conversion are two fundamental chemical processes for battery materials in response to ion insertion. The interplay between these two chemical processes has never been directly seen and understood at atomic scale. Here, using in situ HRTEM, we captured the atomistic conversion reaction processes during Li, Na, Ca insertion into a WO 3 single crystal model electrode. An intercalation step prior to conversion is explicitly revealed at atomic scale for the first time for Li, Na, Ca. Nanoscale diffraction and ab initio molecular dynamic simulations revealed that after intercalation, the inserted ion–oxygen bond formation destabilizes the transition‐metal framework which gradually shrinks, distorts and finally collapses to an amorphous W and M x O (M=Li, Na, Ca) composite structure. This study provides a full atomistic picture of the transition from intercalation to conversion, which is of essential importance for both secondary ion batteries and electrochromic devices.

He, Yang↗
DOE OSTI2014

Investigation of oxygen point defects in cubic ZrO 2 by density functional theory

The energetics of formation and migration of the oxygen vacancy and interstitial in cubic ZrO 2 are investigated by density functional theory calculations. In an O-rich environment, the negatively charged oxygen interstitial is the most dominant defect whereas, the positively charged oxygen vacancy is the most dominant defect under O-poor conditions. Oxygen interstitial migration occurs by the interstitialcy and the direct interstitial mechanisms, with calculated migration energy barriers of 2.94 eV and 2.15 eV, respectively. For the oxygen vacancy, diffusion is preferred along the <100> direction, and the calculated energy barriers are 0.26 eV for V 2+ O , 0.27 eV for V 1+ O and 0.54 eV for V 0 O . Furthermore, these results indicate that oxygen diffusivity is higher through the vacancy-migration mechanism.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Coexistence of epitaxial lattice rotation and twinning tilt induced by surface symmetry mismatch

Combined x-ray diffraction and first-principles studies of various epitaxial rutile-type metal dioxide films on Al{sub 2}O{sub 3}(0001) substrates reveal an unexpected rectangle-on-parallelogram heteroepitaxy. Unique matching of particular lattice spacings and crystal angles between the oxygen sublattices of Al{sub 2}O{sub 3}(0001) and the film(100) result in coexisted crystal rotation and lattice twinning inside the film. We demonstrate that, besides symmetry and lattice mismatch, angular mismatch along a specific crystal direction is also an important factor determining epitaxy. A generalized theorem has been proposed to explain epitaxial behaviors for tetragonal metal dioxides on Al{sub 2}O{sub 3}(0001).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Effects of boron-nitride substrates on Stone-Wales defect formation in graphene: An ab initio molecular dynamics study

Ab initio molecular dynamics simulations are performed to investigate the effects of a boron nitride (BN) substrate on Stone-Wales (SW) defect formation and recovery in graphene. It is found that SW defects can be created by an off-plane recoil atom that interacts with the BN substrate. A mechanism with complete bond breakage for formation of SW defects in suspended graphene is also revealed for recoils at large displacement angles. In addition, further irradiation can result in recovery of the SW defects through a bond rotation mechanism in both graphene and graphene/BN, and the substrate has little effect on the recovery process. This study indicates that the BN substrate enhances the irradiation resistance of graphene.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

First-principles study of the stability and migration of Kr, I and Xe in ZrO2

The stability and migration of Kr, I and Xe in bulk ZrO2 and on the ZrO2 (1 1 1) surface have been studied by standard density functional theory (DFT) and the DFT-D2 method that corrects for the van der Waals interaction. Both methods show that Kr and Xe prefer to incorporate in the bulk phase rather than adsorb on the surface, and Xe is very mobile in the bulk state. For Kr and Xe adsorption on the surface, van der Waals interaction dominates, causing the weak interaction between the adsorbate and substrate. Iodine is found to have comparable stability in both phases and forms I O bonds with strong covalency. It exhibits higher mobility on the surface than in the bulk ZrO2, and diffusion from bulk-like state to surface state is an exothermic process. The fission product behavior in ZrO2 is shown to be a complicated synergetic effect of fission product atomic size, electron negativity, occupation site and phase structure of the host.

Xiao, Haiyan↗
DOE OSTI2014

Nonlinear luminescence response of CaF{sub 2}:Eu and YAlO{sub 3}:Ce to single-ion excitation

Understanding scintillation physics and nonproportionality is essential to accelerate materials discovery that has been restricted due to the difficulties inherent to large crystal growth and complex nature of gamma-solid interaction. Taking advantage of less restrictive growth and deposition techniques for smaller crystal sizes or thin films and better fundamental understanding of ion-solid interactions, a unique ion approach is demonstrated to effectively screen candidate scintillators with relatively small size and evaluate their nonlinear scintillation response. Response of CaF{sub 2}:Eu and YAlO{sub 3}:Ce scintillators to single ions of H{sup +}, He{sup +}, and O{sup 3+} are measured by the corresponding pulse height over a continuous energy range using a time-of-flight–scintillator–photoelectric multiplier tube apparatus. Nonlinear response of the scintillators under ionizing ion irradiation is quantitatively evaluated by considering the energy partitioning process. In a differential energy deposition region with negligible displacement damage, the low, medium and high excitation energy deposition density (D{sub exci}) can be produced by energetic H{sup +}, He{sup +} and O{sup 3+} ions, respectively, and significantly different impacts on the response characteristics of these two benchmark scintillators are observed. For CaF{sub 2}:Eu, the scintillation efficiency under ion irradiation monotonically decreases with increasing excitation-energy density. In contrast, the response efficiency of YAlO{sub 3}:Ce scintillation initially increases with excitation-energy density at low excitation-energy densities, goes through a maximum, and then decreases with further increasing excitation-energy density. The fundamental mechanism causing these different response behaviours in the scintillators is based on the competition between the scintillation response and the nonradiative quenching process under different excitation densities, which is also the main origin of the nonlinear response of the scintillators to irradiation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Composition dependent intrinsic defect structures in SrTiO3

Intrinsic point defect complexes in SrTiO3 under different chemical conditions are studied using density functional theory. The Schottky defect complex consisting of nominally charged Sr, Ti and O vacancies is predicted to be the most stable defect structure in stoichiometric SrTiO3, with a relatively low formation energy of 1.64 eV/defect. In addition, the mechanisms of defect complex formation in nonstoichiometric SrTiO3 are investigated. Excess SrO leads to the formation of the oxygen vacancies and a strontium-titanium antisite defect, while a strontium vacancy together with an oxygen vacancy and the titanium-strontium antisite defect are produced in an excess TiO2 environment. Since point defects, such as oxygen vacancies and cation antisite defects, are intimately related to the functionality of SrTiO3, these results provide guidelines for controlling the formation of intrinsic point defects and optimizing the functionality of SrTiO3 by controlling nonstoichiometric chemical compositions of SrO and TiO2 in experiments.

defects↗