Ultrafast Carrier-Lattice Interactions and Interlayer Modulations of Bi2Se3 by X-ray Free-Electron Laser Diffraction.

As a 3D topological insulator, bismuth selenide (Bi2Se3) has potential applications for electrically and optically controllable magnetic and optoelectronic devices. Understanding the coupling with its topological phase requires studying the interactions of carriers with the lattice on time scales down to the subpicosecond regime. Here, we investigate the ultrafast carrier-induced lattice contractions and interlayer modulations in Bi2Se3 thin films by time-resolved diffraction using an X-ray free-electron laser. The lattice contraction depends on the carrier concentration and is followed by an interlayer expansion accompanied by oscillations. Using density functional theory and the Lifshitz model, the initial contraction can be explained by van der Waals force modulation of the confined free carrier layers. Our theoretical calculations suggest that the band inversion, related to a topological phase transition, is modulated by the expansion of the interlayer distance. These results provide insights into the topological phase control by light-induced structural change on ultrafast time scales.

In Situ Strain Evolution on Pt Nanoparticles during Hydrogen Peroxide Decomposition.

Fundamental understanding of structural changes during catalytic reactions is crucial to understanding the underlying mechanisms and optimizing efficiencies. Surface energy and related catalytic mechanisms are widely studied. However, the catalyst lattice deformation induced by catalytic processes is not well understood. Here, we study the strain in an individual platinum (Pt) nanoparticle (NP) using Bragg coherent diffraction imaging under in situ oxidation and reduction reactions. When Pt NPs are exposed to H2O2, a typical oxidizer and an intermediate during the oxygen reduction reaction process, alternating overall strain distribution near the surface and inside the NP is observed at the (111) Bragg reflection. In contrast, relatively insignificant changes appear in the (200) reflection. Density functional theory calculations are employed to rationalize the anisotropic lattice strain in terms of induced stress by H2O2 adsorption and decomposition on the Pt NP surface. Our study provides deeper insight into the activity-structure relationship in this system.

Defect Dynamics at a Single Pt Nanoparticle during Catalytic Oxidation.

Defects can affect all aspects of a material by altering its electronic properties and controlling its chemical reactivity. At defect sites, preferential adsorption of reactants and/or formation of chemical species at active sites are observed in heterogeneous catalysis. Understanding the structural response at defect sites during catalytic reactions provides a unique opportunity to exploit defect control of nanoparticle-based catalysts. However, it remains difficult to characterize the strain and defect evolution for a single nanocrystal catalyst in situ. Here, we report Bragg coherent X-ray diffraction imaging of defect dynamics in an individual Pt nanoparticle during catalytic methane oxidation. We observed that the initially tensile strained regions of the crystal became seed points for the development of further strain and subsequent disappearance of diffraction density during oxidation reactions. Our detailed understanding of the catalytically induced deformation at the defect sites and observed reversibility during the relevant steps of the catalytic oxidation process provide important insights of defect control and engineering of heterogeneous catalysts.

Strain Development of Selective Adsorption of Hydrocarbons in a Cu-ZSM-5 Crystal.

Zeolites are 3D aluminosilicate materials having subnanometer pore channels. The Lewis basic pores have charge-balancing cations, easily tuned to metallic ions as more chemically active sites. Among the ion-exchanged zeolites, Cu2+ ion-exchanged ZSM-5 (Cu-ZSM-5) is one of the most active zeolites with chemical interactions of Lewis basic compounds. Even though the chemical interactions of hydrocarbons with Cu2+ sites in Cu-ZSM-5 have been tremendously studied in the category of zeolite catalysts, it is not yet thoroughly investigated how such interactions affect the structural lattice of the zeolite. Hydrocarbons with different chemical properties and their relative size can induce lattice strain by different chemical adsorption effects on the Cu2+ sites. In this work, we investigate the internal deformation of the Cu-ZSM-5 crystal using Bragg coherent X-ray diffraction imaging during the adsorption of four hydrocarbons depending on the alkyl chain length, the existence of a double bond in the molecule, linear structure versus benzene ring structure, and so forth. In the three-carbon system (propane and propene), relatively weak chemical adsorption occurred at room temperature and 100 °C, whereas strong adsorption was observed over 150 °C. For the six-carbon system (n-hexane and benzene), strong strains evolved in the crystal by active chemical adsorption from 150 °C. The observations suggest that propene and propane adsorb at the Cu2+ sites from the outer shell to the center with increasing temperature. In comparison, n-hexane and benzene adsorb at both parts at the same temperature. The results provide the internal structural information for the lattice with the chemical interactions of hydrocarbons in the Cu-ZSM-5 zeolite and help to understand zeolite-based chemisorption or catalysis research.

Time-resolved in situ visualization of the structural response of zeolites during catalysis.

Zeolites are three-dimensional aluminosilicates having unique properties from the size and connectivity of their sub-nanometer pores, the Si/Al ratio of the anionic framework, and the charge-balancing cations. The inhomogeneous distribution of the cations affects their catalytic performances because it influences the intra-crystalline diffusion rates of the reactants and products. However, the structural deformation regarding inhomogeneous active regions during the catalysis is not yet observed by conventional analytical tools. Here we employ in situ X-ray free electron laser-based time-resolved coherent X-ray diffraction imaging to investigate the internal deformations originating from the inhomogeneous Cu ion distributions in Cu-exchanged ZSM-5 zeolite crystals during the deoxygenation of nitrogen oxides with propene. We show that the interactions between the reactants and the active sites lead to an unusual strain distribution, confirmed by density functional theory simulations. These observations provide insights into the role of structural inhomogeneity in zeolites during catalysis and will assist the future design of zeolites for their applications.

Coherence and pulse duration characterization of the PAL-XFEL in the hard X-ray regime.

We characterize the spatial and temporal coherence properties of hard X-ray pulses from the Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL, Pohang, Korea). The measurement of the single-shot speckle contrast, together with the introduction of corrections considering experimental conditions, allows obtaining an intrinsic degree of transverse coherence of 0.85 ± 0.06. In the Self-Amplified Spontaneous Emission regime, the analysis of the intensity distribution of X-ray pulses also provides an estimate for the number of longitudinal modes. For monochromatic and pink (i.e. natural bandwidth provided by the first harmonic of the undulator) beams, we observe that the number of temporal modes is 6.0 ± 0.4 and 90.0 ± 7.2, respectively. Assuming a coherence time of 2.06 fs and 0.14 fs for the monochromatic and pink beam respectively, we estimate an average X-ray pulse duration of 12.6 ± 1.0 fs.

Active site localization of methane oxidation on Pt nanocrystals.

High catalytic efficiency in metal nanocatalysts is attributed to large surface area to volume ratios and an abundance of under-coordinated atoms that can decrease kinetic barriers. Although overall shape or size changes of nanocatalysts have been observed as a result of catalytic processes, structural changes at low-coordination sites such as edges, remain poorly understood. Here, we report high-lattice distortion at edges of Pt nanocrystals during heterogeneous catalytic methane oxidation based on in situ 3D Bragg coherent X-ray diffraction imaging. We directly observe contraction at edges owing to adsorption of oxygen. This strain increases during methane oxidation and it returns to the original state after completing the reaction process. The results are in good agreement with finite element models that incorporate forces, as determined by reactive molecular dynamics simulations. Reaction mechanisms obtained from in situ strain imaging thus provide important insights for improving catalysts and designing future nanostructured catalytic materials.