Tag: Materials Science

New Functionalized Metal-Organic Frameworks MIL-47-X (X = -Cl, -Br, -CH3, -CF3, -OH, -OCH3): Synthesis, Characterization and CO2 Adsorption Properties

Authors: Shyam Biswas, Danny E. P. Vanpoucke, Toon Verstraelen, Matthias Vandichel, Sarah Couck, Karen Leus, Ying-Ya Liu, Michel Waroquier, Veronique Van Speybroeck, Joeri F. M. Denayer, and Pascal Van Der Voort
Journal: J. Phys. Chem. C 117(44), 22784-22796 (2013)
doi: 10.1021/jp406835n
IF(2013): 4.835
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pdf: <J.Phys.Chem.C>


Six new functionalized vanadium hydroxo terephthalates [VIII(OH)(BDC-X)]·n(guests) (MIL-47(VIII)-X-AS) (BDC = 1,4-benzenedicarboxylate; X = −Cl, −Br, −CH3, −CF3, −OH, −OCH3; AS = as-synthesized) along with the parent MIL-47 were synthesized under rapid microwave-assisted hydrothermal conditions (170 °C, 30 min, 150 W). The unreacted H2BDC-X and/or occluded solvent molecules can be removed by thermal activation under vacuum, leading to the empty-pore forms of the title compounds (MIL-47(VIV)-X). Except pristine MIL-47 (+III oxidation state), the vanadium atoms in all the evacuated functionalized solids stayed in the +IV oxidation state. The phase purity of the compounds was ascertained by X-ray powder diffraction (XRPD), diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, Raman, thermogravimetric (TG), and elemental analysis. The structural similarity of the filled and empty-pore forms of the functionalized compounds with the respective forms of parent MIL-47 was verified by cell parameter determination from XRPD data. TGA and temperature-dependent XRPD (TDXRPD) experiments in an air atmosphere indicate high thermal stability in the 330–385 °C range. All the thermally activated compounds exhibit significant microporosity (SBET in the 305–897 m2 g–1 range), as verified by the N2 and CO2 sorption analysis. Among the six functionalized compounds, MIL-47(VIV)-OCH3 shows the highest CO2 uptake, demonstrating the determining role of functional groups on the CO2 sorption behavior. For this compound and pristine MIL-47(VIV), Widom particle insertion simulations were performed based on ab initio calculated crystal structures. The theoretical Henry coefficients show a good agreement with the experimental values, and calculated isosurfaces for the local excess chemical potential indicate the enhanced CO2 affinity is due to two effects: (i) the interaction between the methoxy group and CO2 and (ii) the collapse of the MIL-47(VIV)-OCH3 framework.

Tuning of CeO2 buffer layers for coated superconductors through doping

Authors: Danny E. P. Vanpoucke, Stefaan Cottenier, Veronique Van Speybroeck, Patrick Bultinck, and Isabel Van Driessche,
Journal: Appl. Surf. Sci. 260, 32-35 (2012)
doi: 10.1016/j.apsusc.2012.01.032
IF(2012): 2.112
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pdf: <Appl.Surf.Sci.> <arXiv>


The appearance of microcracks in cerium oxide (CeO2) buffer layers, as used in buffer layer architectures for coated superconductors, indicates the presence of stress between this buffer layer and the substrate. This stress can originate from the differences in thermal expansion or differences in lattice parameters between the CeO2 buffer layer and the substrate. In this article, we study, by means of ab initio density functional theory calculations, the influence of group IV doping elements on the lattice parameter and bulk modulus of CeO2. Vegard’s law behavior is found for the lattice parameter in systems without oxygen vacancies, and the Shannon crystal radii for the doping elements are retrieved from the lattice expansions. We show that the lattice parameter of the doped CeO2 can be matched to that of the La2Zr2O7 coated NiW substrate substrate for dopant concentrations of about 5%, and that bulk modulus matching is either not possible or would require extreme doping concentrations.

Models and simulations in material science: two cases without error bars

Authors: Sylvia Wenmackers and Danny E. P. Vanpoucke
Journal: Statistica Neerlandica 66, 339-355 (2012)
doi: 10.1111/j.1467-9574.2011.00519.x
IF(2012): 0.585
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pdf: <Stat.Neer.> <arXiv>


We discuss two research projects in material science in which the results cannot be stated with an estimation of the error: a spectroscopic ellipsometry study aimed at determining the orientation of DNA molecules on diamond and a scanning tunneling microscopy study of platinum-induced nanowires on germanium. To investigate the reliability of the results, we apply ideas from the philosophy of models in science. Even if the studies had reported an error value, the trustworthiness of the result would not depend on that value alone.

Aqueous CSD approach for the growth of novel, lattice-tuned LaxCe1- xOδ epitaxial layers

Authors: Vyshnavi Narayanan, Petra Lommens, Klaartje De Buysser, Danny E.P. Vanpoucke, Ruben Huehne, Leopoldo Molina, Gustaaf Van Tendeloo , Pascal Van Der Voort, Isabel Van Driessche
Journal: J. Mater. Chem. 22, 8476-8483 (2012)
doi: 10.1039/C2JM15752G
IF(2012): 6.101
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pdf: <J.Mater.Chem.>


Lanthanum–cerium oxide (LCO) films were deposited on Ni-5%W substrates by chemical solution deposition (CSD) from water-based precursors. LCO films containing different ratios of lanthanum and cerium ions (from CeO2 to La2Ce2O7) were prepared. The composition of the layers was optimized towards the formation of LCO buffer layers, lattice-matched with the superconducting YBa2Cu3Oy layer, useful for the development of coated conductors. Single, crack-free LCO layers with a thickness of up to 140 nm could be obtained in a single deposition step. The crystallinity and microstructure of these lattice-matched LCO layers were studied by X-ray diffraction techniques, RHEED and SEM. We find that only layers with thickness below 100 nm show a crystalline top surface although both thick and thin layers show good biaxial texture in XRD. On the most promising layers, AFM and (S)TEM were performed to further evaluate their morphology. The overall surface roughness varies between 3.9 and 7.5 nm, while the layers appear much more dense than the frequently used La2Zr2O7 (LZO) systems, showing much smaller nanovoids (1–2 nm) than the latter system. Their effective buffer layer action was studied using XPS. The thin LCO layers supported the growth of superconducting YBCO deposited using PLD methods.

Investigation of tunable buffer layers for coated superconductors:
from solid state physics to quantum chemistry

Authors: Danny E.P. Vanpoucke
Ph.D. Thesis at Ghent University, Belgium
date: October 5th, 2012
Promoters Prof. Dr. Isabel Van Driessche and Prof. Dr. Patrick Bultinck
#pages 218
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pdf: <PhD.Thesis>
research page with more information


High temperature ceramic superconductors can be grown in layered structures on metallic wires to provide the mechanical flexibility required for industrial applications. To prevent the metal atoms of diffusing into the superconductor—destroying its superconductivity—buffer layers are grown between the metal substrate and the superconductor. Recently, cerium oxide has been used as such a buffer layer. However, the layer thickness of these buffer layers is limited by the formation of cracks during deposition. This behaviour has been linked to internal stress due to lattice mismatch and different thermal expansion coefficients of the substrate and the buffer layer. A simple way to reduce these mismatches is through metal doping.

In this work, we study the influence of dopants on the properties of cerium oxide through the use of ab initio calculations. Trends in the stability, lattice parameter, bulk modulus and thermal expansion coefficient of cerium oxide doped with different dopants are investigated. In addition, the influence of charge compensating oxygen vacancies is studied, and their role in the stability of heavily La-doped cerium oxide (La2Ce2O7) is presented. The use of dopants with different valences also leads to a modification of the charge distribution around the dopant sites. A way to have a more quantitative estimate of the charge transfer induced by dopants is via the introduction of the chemical concept of ‘atoms in a molecule’ into solids. This can be considered a first step in the direction of answering the experimental question: What is the charge of a given atom in a certain compound? In this work we present an implementation of this Hirshfeld method for solids, and calculate the atomic charges in doped cerium oxides.

Front cover of the PhD thesis.

Density functional theory study of La2Ce2O7: disordered fluorite vs pyrochlore structure

Authors: Danny E. P. Vanpoucke, Patrick Bultinck, Stefaan Cottenier, Veronique Van Speybroeck and Isabel Van Driessche,
Journal: Phys. Rev. B 84, 054110 (2011)
doi: 10.1103/PhysRevB.84.054110
IF(2011): 3.691
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pdf: <Phys.Rev.B.> <arXiv>


The crystal structure of lanthanum cerium oxide (La2Ce2O7) is investigated using ab initio density functional theory calculations. The relative stability of fluorite- and pyrochlore-like structures is studied through comparison of their formation energies. These formation energies show the pyrochlore structure to be favored over the fluorite structure, apparently contradicting the conclusions based on experimental neutron and x-ray diffraction (XRD).
By calculating and comparing XRD spectra for a set of differently ordered and random structures, we show that the pyrochlore structure is consistent with diffraction experiments. For these reasons, we suggest the pyrochlore structure as the ground-state crystal structure for La2Ce2O7.

Pt Nanowires on Ge(001): Sheep in Wolf’s Clothing?

Authors: Danny E. P. Vanpoucke
Journal: Belgian Physical Society Magazine 3, 11-16 (2011)
(Featured Article for the BΦ)
pdf: <local>


The deposition of small amounts of platinum on a germanium (001) surface gives rise to the formation of monatomic nanowires. These nanowires are defect–and kink-free and their length is only limited by the underlying terrace, to which they are uniquely connected. Using ab initio calculations and simulated scanning tunneling microscopy (STM) images we model these nanowires, and show them to consist of germanium atoms, in contrast to earlier proposed models.

CO adsorption on Pt-induced Ge nanowires

Authors: Danny E. P. Vanpoucke and Geert Brocks
Journal: Phys. Rev. B 81, 235434 (2010)
doi: 10.1103/PhysRevB.81.235434
IF(2010): 3.774
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pdf: <Phys.Rev.B> <arXiv>


Using density-functional theory, we investigate the possible adsorption sites of CO molecules on the recently discovered Pt-induced Ge nanowires (NWs) on Ge(001). Calculated scanning tunneling microscope (STM) images are compared to experimental STM images to identify the experimentally observed adsorption sites. The CO molecules are found to adsorb preferably onto the Pt atoms between the Ge nanowire dimer segments. This adsorption site places the CO molecule in between two nanowire dimers, pushing them outward along the NW direction, blocking the nearest equivalent adsorption sites. This explains the observed long-range repulsive interaction between CO molecules on these Pt-induced nanowires.

Pt-induced nanowires on Ge(001): A density functional theory study

Authors: Danny E. P. Vanpoucke and Geert Brocks
Journal: Phys. Rev. B 81, 085410 (2010)
doi: 10.1103/PhysRevB.81.085410
IF(2010): 3.774
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pdf: <Phys.Rev.B> <arXiv>


We study formation of the nanowires formed after deposition of Pt on a Ge(001) surface. The nanowires form spontaneously after high-temperature annealing. They are thermodynamically stable, only one atom wide and up to a few hundred atoms long. Ab initio density functional theory calculations are performed to identify possible structures of the Pt-Ge(001) surface with nanowires on top. A large number of structures are studied. With nanowires that are formed out of Pt or Ge dimers or mixed Pt-Ge dimers. By comparing simulated scanning tunneling microscopy images (STM) with experimental ones we model the formation of the nanowires and identify the geometries of the different phases in the formation process. We find that the formation of nanowires on a Pt-Ge(001) surface is a complex process based on increasing the Pt density in the top layers of the Ge(001) surface. Most remarkably we find the nanowires to consist of germanium dimers placed in troughs lined by mixed Pt-Ge dimer rows.

Density functional theory study of Pt-induced Ge(001) reconstructions

Authors: Danny E. P. Vanpoucke and Geert Brocks
Journal: Phys. Rev. B 81, 035333 (2010)
doi: 10.1103/PhysRevB.81.035333
IF(2010): 3.774
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pdf: <Phys.Rev.B> <arXiv>


Pt deposited on a Ge(001) surface spontaneously forms nanowire arrays. These nanowires are thermodynamically stable and can be hundreds of atoms long. The nanowires only occur on a reconstructed Pt-Ge-surface where they fill the troughs between the dimer rows on the surface. This unique connection between the nanowires and the underlying substrate make a thorough understanding of the latter necessary for understanding the growth of the nanowires. In this paper we study possible surface reconstructions containing 0.25 and 0.5 of a monolayer of Pt. Comparison of calculated scanning tunneling microscope (STM) images to experimental STM images of the surface reconstruction reveal that the Pt atoms are located in the top layer, creating a structure with rows of alternating Pt-Ge and Ge-Ge dimers in a c(4×2) arrangement. Our results also show that Pt atoms in the second or third layer cannot be responsible for the experimentally observed STM images.