AVS2014 Session AP+AS+EN+NS+SS-ThA: APT and FIM Analysis of Catalysts and Nanomaterials
Time Period ThA Sessions | Abstract Timeline | Topic AP Sessions | Time Periods | Topics | AVS2014 Schedule
Start | Invited? | Item |
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2:20 PM | Invited |
AP+AS+EN+NS+SS-ThA-1 In Situ Study of Gas - Solid Reactions via Environmental APT
Krishna Rajan (Iowa State University) In this presentation we describe the design and examples of applications of the use of an environmental cell integrated into a LEAP atom probe. The use of such a cell helps to open up the field of in-situ gas-solid reactions by permitting one to study surface and near surface reactions which are closer to ambient conditions than is possible in traditional surfaces science studies. The implications for this experimental approach in the context of the study of catalysts and nanomaterials are discussed. |
3:00 PM |
AP+AS+EN+NS+SS-ThA-3 Propagation of Chemical Waves: A Field Emission Microscopy Study
Cédric Barroo, Yannick De Decker, Norbert Kruse, Thierry Visart de Bocarmé (Université Libre de Bruxelles, Belgium) Thecatalytic hydrogenation of NO2 over platinum field emitter tips has been investigated by means of field emission techniques. Field emission microscopy (FEM), as well as field ion microscopy (FIM), has been proved to be an efficient method to study the dynamics of catalytic reactions occurring at the surface of a nanosized metal tip, which represents a good model of a single catalytic nanoparticle. These studies are performed during the ongoing reaction which is imaged in real time and space. Nanoscale resolution allows for a local indication of the instantaneous surface composition. The presence of adsorbates modifies the value of the local work function. These variations are expressed by modulations of the brightness of field emission patterns. A qualitative investigation of the local surface composition is then possible as function of time. The microscope is run as an open nanoreactor, ensuring that the system is kept far from thermodynamic equilibrium. Under these conditions, chemical reactions can induce time and space symmetry breaking of the composition of a system, for which periodic oscillations and target patterns are well-known examples. Self-sustained periodic oscillations have been reported for the NO2 reduction. By increasing the time resolution of the system, it is now possible to study the emergence of these oscillations and to observe the propagation of chemical waves at the nanoscale, on a single facet of a nanocrystal. The velocity of wave propagation is estimated to be in the μm/s range, which is in accordance with previous studies of catalytic reaction at the mesoscale. |
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3:20 PM |
AP+AS+EN+NS+SS-ThA-4 3D Nanoscale Chemical/Structure Analysis in Mineral Carbon Sequestration Study using Atom Probe Tomography
Jia Liu, Daniel Perea, Robert Colby, Libor Kovarik, Bruce Arey, Odeta Qafoku, Andrew Felmy (Pacific Northwest National Laboratory) Mineral carbon sequestration is one of the important means to store CO2 in order to mitigate the environmental concern regarding ever-growing anthropogenic CO2 emissions. Olivines, X2SiO4 where X = Mg and Fe, hold promise as potential media to sequester carbon due to its broad availability in basalt deposits and reactivity to form stable metal carbonates. Site-specific reactivity of olivine with supercritical CO2 is of great interest in understanding the fundamental elementary reaction mechanisms, where the presence of impurities within the bulk mineral may affect reaction kinetics. A combination of atom probe tomography (APT) and scanning transmission electron microscopy (STEM) is being used to map the complex composition and nanoscale structure across various site-specific regions. APT analysis of unreacted natural fayalite indicates the presence of 2-3-nm-thick hydrated iron oxide layers. In addition, Na impurities were found to concentrate within the hydrated layers while Mg and Mn were depleted from these regions. With the ability of APT to detect the chemical/structural heterogeneity at nanometer-scale, we find that APT will provide a means to correlate with ongoing experimental reaction studies and also provide guidance into models of the heterogeneous phase formation and reaction rates at precisely defined interfaces within minerals. |
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3:40 PM | BREAK | |
4:00 PM | Invited |
AP+AS+EN+NS+SS-ThA-6 Catalyst Nanomaterials Analysis via Atom Probe Tomography
Paul Bagot (Oxford University, UK); Qifeng Yang (University of Oxford, UK); Karen Kruska (Pacific Northwest National Laboratory); Daniel Haley (University of Oxford, UK); Eric Marceau, Xavier Carrier (Université Pierre et Marie Curie, France); Michael Moody (University of Oxford, UK) Heterogeneous catalytic materials play an increasingly critical, yet largely unnoticed, role underpinning countless modern technologies. Their active components are generally transition group metals, each of which offers different catalytic properties in terms of selectivity, yield and stability under demanding operating conditions. The need to develop more efficient catalysts that meet industrial demands and comply with environmental legislation targets requires better understanding how different catalysts may alter at the atomic scale in terms of structure or surface composition under their respective operating environments. Further, many catalysts take the form of nanoparticles, the performance of which can be strongly correlated to size, shape, chemistry and structure. However, discerning the nature of nanoparticles scale poses significant challenges to conventional microscopy. Recently, atom probe tomography (APT) techniques have been developed to provide unique insight into the behaviour of catalyst alloys subject to conditions like those experienced in service [1–3]. This study is aimed at more accurate and insightful analyses comprising unique 3D atomistic descriptions of the evolving alloy nanostructure which can then be correlated to catalyst performance. Here, APT results are presented for characterization of oxidation-induced segregation in a Pt-Pd-Rh gauze and Fe-Ni alloy catalysts. Progress in the development of new approaches for the analysis of nanoparticles via APT is also presented. [1] T. Li et al., Atomic engineering of platinum alloy surfaces. Ultramicroscopy 132, 205 (2013). [2] T. Li et al., Atomic Imaging of Carbon-Supported Pt, Pt/Co, and Ir@Pt Nanocatalysts by Atom-Probe Tomography. ACS Catalysis 4, 695 (2014). [3] P. Felfer et al, Long-Chain Terminal Alcohols through Catalytic CO Hydrogenation. Journal of the American Chemical Society 135, 7114 (2013). |