Category: publications

Jan 23 2020

Investigation of structural, electronic and magnetic properties of breathing metal–organic framework MIL-47(Mn): a first principles approach

Authors: Mohammadreza Hosseini, Danny E. P. Vanpoucke, Paolo Giannozzi, Masoud Berahman  and Nasser Hadipour
Journal: RSC Adv. 10, 4786-4794 (2020)
doi: 10.1039/C9RA09196C
IF(2019): 3.119
export: bibtex
pdf: <RSC Adv.> (Open Access)

 

Graphical abstract: MIL-47(Mn) paper
Graphical Abstract: The breathing MIL-47(Mn) Metal-Organic Framework. Upon breathing, the electronic structure of this MOF undergoes a transition from an anti-ferromagnetic semiconductor, to a ferromagnetic semi-metal.

Abstract

The structural, electronic and magnetic properties of the MIL-47(Mn) metal–organic framework are investigated using first principles calculations. We find that the large-pore structure is the ground state of this material. We show that upon transition from the large-pore to the narrow-pore structure, the magnetic ground-state configuration changes from antiferromagnetic to ferromagnetic, consistent with the computed values of the intra-chain coupling constant. Furthermore, the antiferromagnetic and ferromagnetic configuration phases have intrinsically different electronic behavior: the former is semiconducting, the latter is a metal or half-metal. The change of electronic properties during breathing posits MIL-47(Mn) as a good candidate for sensing and other applications. Our calculated electronic band structure for MIL-47(Mn) presents a combination of flat dispersionless and strongly dispersive regions in the valence and conduction bands, indicative of quasi-1D electronic behavior. The spin coupling constants are obtained by mapping the total energies onto a spin Hamiltonian. The inter-chain coupling is found to be at least one order of magnitude smaller than the intra-chain coupling for both large and narrow pores. Interestingly, the intra-chain coupling changes sign and becomes five times stronger going from the large pore to the narrow pore structure. As such MIL-47(Mn) could provide unique opportunities for tunable low-dimensional magnetism in transition metal oxide systems.

Mar 29 2019

Can Europium Atoms form Luminescent Centres in Diamond: A combined Theoretical-Experimental Study

Authors: Danny E. P. Vanpoucke, Shannon S. Nicley, Jorne Raymakers, Wouter Maes, and Ken Haenen
Journal: Diam. Relat. Mater 94, 233-241 (2019)
doi: 10.1016/j.diamond.2019.02.024
IF(2019): 2.650
export: bibtex
pdf: <DiamRelatMater>

 

Spin polarization around the various Eu-defect models in diamond. Blue and red represent the up and down spin channels respectively
Graphical Abstract: Spin polarization around the various Eu-defect models in diamond. Blue and red represent the up and down spin channels respectively.

Abstract

The incorporation of Eu into the diamond lattice is investigated in a combined theoretical-experimental study. The large size of the Eu ion induces a strain on the host lattice, which is minimal for the Eu-vacancy complex. The oxidation state of Eu is calculated to be 3+ for all defect models considered. In contrast, the total charge of the defect-complexes is shown to be negative: -1.5 to -2.3 electron. Hybrid-functional electronic-band-structures show the luminescence of the Eu defect to be strongly dependent on the local defect geometry. The 4-coordinated Eu substitutional dopant is the most promising candidate to present the typical Eu3+ luminescence, while the 6-coordinated Eu-vacancy complex is expected not to present any luminescent behaviour. Preliminary experimental results on the treatment of diamond films with Eu-containing precursor indicate the possible incorporation of Eu into diamond films treated by drop-casting. Changes in the PL spectrum, with the main luminescent peak shifting from approximately 614 nm to 611 nm after the growth plasma exposure, and the appearance of a shoulder peak at 625 nm indicate the potential incorporation. Drop-casting treatment with an electronegative polymer material was shown not to be necessary to observe the Eu signature following the plasma exposure, and increased the background
luminescence.

Nov 20 2018

Synthesis, characterization and thermodynamic stability of nanostructured ε-iron carbonitride powder prepared by a solid-state mechanochemical route

Authors: Seyyed Amin Rounaghi, Danny E. P. Vanpoucke, Elaheh Esmaeili, Sergio Scudino, and Jürgen Eckert
Journal: J. Alloys Compd. 778, 327-336 (2019)
doi: 10.1016/j.jallcom.2018.11.007
IF(2019): 4.650
export: bibtex
pdf: <JAlloysCompd>

Abstract

Nanostructured epsilon iron carbonitride (ε-Fe3CxN1-x, x ∼ 0.05) powder with high purity (>97 wt%) was synthesized through a simple mechanochemical reaction between metallic iron and melamine. Various characterization techniques were employed to investigate the chemical and physical characteristics of the milling intermediates and the final products. The thermodynamic stability of the different phases in the Fe-C-N ternary system, including nitrogen and carbon doped structures were studied through density functional theory (DFT) calculations. A Boltzmann-distribution model was developed to qualitatively assess the stability and the proportion of the different milling products vs. milling energy. The theoretical and experimental results revealed that the milling products mainly comprise the ε-Fe3CxN1-xphase with a mean crystallite size of around 15 nm and a trace of amorphous carbonmaterial. The thermal stability and magnetic properties of the milling products were thoroughly investigated. The synthesized ε-Fe3CxN1-x exhibited thermal stabilities up to 473 K and 673 K in air and argon atmospheres, respectively, and soft magnetic properties with a saturation magnetization of around 125 emu/g.

Nov 13 2018

Predicting Partial Atomic Charges in Siliceous Zeolites

Authors: Jarod J. Wolffis, Danny E. P. Vanpoucke, Amit Sharma, Keith V. Lawler, and Paul M. Forster
Journal: Microporous Mesoporous Mater. 277, 184-196 (2019)
doi: 10.1016/j.micromeso.2018.10.028
IF(2019): 4.551
export: bibtex
pdf: <MicroporousMesoporousMater>

 

Partial charges in zeolites for force fields.
Graphical Abstract: Partial charges in zeolites for force fields.

Abstract

Partial atomic charge, which determines the magnitude of the Coulombic non-bonding interaction, represents a critical parameter in molecular mechanics simulations. Partial charges may also be used as a measure of physical properties of the system, i.e. covalency, acidic/catalytic sites, etc. A range of methods, both empirical and ab initio, exist for calculating partial charges in a given solid, and several of them are compared here for siliceous (pure silica) zeolites. The relationships between structure and the predicted partial charge are examined. The predicted partial charges from different methods are also compared with related experimental observations, showing that a few of the methods offer some guidance towards identifying the T-sites most likely to undergo substitution or for proton localization in acidic framework forms. Finally, we show that assigning unique calculated charges to crystallographically unique framework atoms makes an appreciable difference in simulating predicting N2 and O2 adsorption with common dispersion-repulsion parameterizations.

Jul 27 2018

Book chapter: Computational Chemistry Experiment Possibilities

Authors: Bartłomiej M. Szyja and Danny Vanpoucke
Book: Zeolites and Metal-Organic Frameworks, (2018)
Chapter Ch 9, p 235-264
Title Computational Chemistry Experiment Possibilities
ISBN: 978-94-629-8556-8
export: bibtex
pdf: <Amsterdam University Press>
<Open Access>

 

Zeolites and Metal-Organic Frameworks (the hard-copy)

Abstract

Thanks to a rapid increase in the computational power of modern CPUs, computational methods have become a standard tool for the investigation of physico-chemical phenomena in many areas of chemistry and technology. The area of porous frameworks, such as zeolites, metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs), is not different. Computer simulations make it possible, not only to verify the results of the experiments, but even to predict previously inexistent materials that will present the desired experimental properties. Furthermore, computational research of materials provides the tools necessary to obtain fundamental insight into details that are often not accessible to physical experiments.

The methodology used in these simulations is quite specific because of the special character of the materials themselves. However, within the field of porous frameworks, density functional theory (DFT) and force fields (FF)
are the main actors. These methods form the basis of most computational studies, since they allow the evaluation of the potential energy surface (PES) of the system.

Related:

Newsflash: here

Oct 26 2017

Audioslides tryout.

One of the new features provided by Elsevier upon publication is the creation of audioslides. This is a kind of short presentation of the publication by one of the authors. I have been itching to try this since our publication on the neutral C-vancancy was published. The interface is quite intuitive, although the adobe flash tend to have a hard time finding the microphone. However, once it succeeds, things go quite smoothly. The resolution of the slides is a bit low, which is unfortunate (but this is only for the small-scale version, the large-scale version is quite nice as you can see in the link below). Maybe I’ll make a high resolution version video and put it on Youtube, later.

The result is available here (since the embedding doesn’t play nicely with WP).

And a video version can be found here.
 

Sep 23 2017

Revisiting the Neutral C-Vacancy in Diamond: Localization of Electrons through DFT+U

Authors: Danny E. P. Vanpoucke and Ken Haenen
Journal: Diam. Relat. Mater 79, 60-69 (2017)
doi: 10.1016/j.diamond.2017.08.009
IF(2017): 2.232
export: bibtex
pdf: <DiamRelatMater>

 

Combining a scan over possible values for U and J with reference electronic structures obtained using the hybrid functional HSE06, DFT+U can be fit to provide hybrid functional quality electronic structures at the cost of DFT calculations.
Graphical Abstract: Combining a scan over possible values for U and J with reference electronic structures obtained using the hybrid functional HSE06, DFT+U can be fit to provide hybrid functional quality electronic structures at the cost of DFT calculations.

Abstract

The neutral C-vacancy is investigated using density functional theory calculations. We show that local functionals, such as PBE, can predict the correct stability order of the different spin states, and that the success of this prediction is related to the accurate description of the local magnetic configuration. Despite the correct prediction of the stability order, the PBE functional still fails predicting the defect states correctly. Introduction of a fraction of exact exchange, as is done in hybrid functionals such as HSE06, remedies this failure, but at a steep computational cost. Since the defect states are strongly localized, the introduction of additional on site Coulomb and exchange interactions, through the DFT+U method, is shown to resolve the failure as well, but at a much lower computational cost. In this work, we present optimized U and J parameters for DFT+U calculations, allowing for the accurate prediction of defect states in defective
diamond. Using the PBE optimized atomic structure and the HSE06 optimized electronic structure as reference, a pair of on-site Coulomb and exchange parameters (U,J) are fitted for DFT+U studies of defects in diamond.

Related:

Poster-presentation: here

DFT+U series (varying J) for a specific spin state of the C-vacancy defect.

DFT+U series (varying J) for a specific spin state of the C-vacancy defect.

Sep 23 2017

A combined experimental and theoretical investigation of the Al-Melamine reactive milling system: a mechanistic study towards AlN-based ceramics

Authors: Seyyed Amin Rounaghi, Danny E.P. Vanpoucke, Hossein Eshghi, Sergio Scudino, Elaheh Esmaeili, Steffen Oswald and Jürgen Eckert
Journal: J. Alloys Compd. 729, 240-248 (2017)
doi: 10.1016/j.jallcom.2017.09.168
IF(2017): 3.779
export: bibtex
pdf: <J.Alloys Compd.>

 

Graphical Abstract: Evolution of the end products as function of Al and N content during ball-milling synthesis of AlN.
Graphical Abstract: Evolution of the end products as function of Al and N content during ball-milling synthesis of AlN.

Abstract

A versatile ball milling process was employed for the synthesis of hexagonal aluminum nitride (h-AlN) through the reaction of metallic aluminum with melamine. A combined experimental and theoretical study was carried out to evaluate the synthesized products. Milling intermediates and products were fully characterized via various techniques including XRD, FTIR, XPS, Raman and TEM. Moreover, a Boltzmann distribution model was proposed to investigate the effect of milling energy and reactant ratios on the thermodynamic stability and the proportion of different milling products. According to the results, the reaction mechanism and milling products were significantly influenced by the reactant ratio. The optimized condition for AlN synthesis was found to be at Al/M molar ratio of 6, where the final products were consisted of nanostructured AlN with average crystallite size of 11 nm and non-crystalline heterogeneous carbon.

Apr 28 2017

Mechanochemical synthesis of nanostructured metal nitrides, carbonitrides and carbon nitride: A combined theoretical and experimental study

Authors: Seyyed Amin Rounaghi, Danny E.P. Vanpoucke, Hossein Eshghi, Sergio Scudino, Elaheh Esmaeili, Steffen Oswald and Jürgen Eckert
Journal: Phys. Chem. Chem. Phys. 19, 12414-12424 (2017)
doi: 10.1039/C7CP00998D
IF(2017): 3.906
export: bibtex
pdf: <Phys.Chem.Chem.Phys.>

Abstract

Nowadays, the development of highly efficient routes for the low cost synthesis of nitrides is greatly growing. Mechanochemical synthesis is one of those promising techniques which is conventionally employed for the synthesis of nitrides by long term milling of metallic elements under pressurized N2 or NH3 atmosphere (A. Calka and J. I. Nikolov, Nanostruct. Mater., 1995, 6, 409-412). In the present study, we describe a versatile, room-temperature and low cost mechanochemical process for the synthesis of nanostructured metal nitrides (MNs), carbonitrides (MCNs) and carbon nitride (CNx). Based on this technique, melamine as a solid nitrogen-containing organic compound (SNCOC) is ball milled with four different metal powders (Al, Ti, Cr and V) to produce nanostructured AlN, TiCxN1-x, CrCxN1-x, and VCxN1-x (x~0.05). Both theoretical and experimental techniques are implemented to determine the reaction intermediates, products, by-products and finally, the mechanism underling this synthetic route. According to the results, melamine is polymerized in the presence of metallic elements at intermediate stages of the milling process, leading to the formation of a carbon nitride network. The CNx phase subsequently reacts with the metallic precursors to form MN, MCN or even MCN-CNx nano-composites depending on the defect formation energy and thermodynamic stability of the corresponding metal nitride, carbide and C/N co-doped structures.

Mar 30 2017

Linker Functionalization in MIL-47(V)-R Metal–Organic Frameworks: Understanding the Electronic Structure

Authors: Danny E. P. Vanpoucke
Journal: J. Phys. Chem. C 121(14), 8014-8022 (2017)
doi: 10.1021/acs.jpcc.7b01491
IF(2017): 4.484
export: bibtex
pdf: <J.Phys.Chem.C>
Graphical Abstract: Evolution of the electronic band structure of MIL-47(V) upon OH-functionalization of the BDC linker.
Graphical Abstract: Evolution of the electronic band structure of MIL-47(V) upon OH-functionalization of the BDC linker. The π-orbital of the BDC linker splits upon functionalisation, and the split-off π-band moves up into the band gap, effectively reducing the latter.

Abstract

Metal–organic frameworks (MOFs) have gained much interest due to their intrinsic tunable nature. In this work, we study how linker functionalization modifies the electronic structure of the host MOF, more specifically, the MIL-47(V)-R (R = −F, −Cl, −Br, −OH, −CH3, −CF3, and −OCH3). It is shown that the presence of a functional group leads to a splitting of the π orbital on the linker. Moreover, the upward shift of the split-off π-band correlates well with the electron-withdrawing/donating nature of the functional groups. For halide functional groups the presence of lone-pair back-donation is corroborated by calculated Hirshfeld-I charges. In the case of the ferromagnetic configuration of the host MIL-47(V+IV) material a half-metal to insulator transition is noted for the −Br, −OCH3, and −OH functional groups, while for the antiferromagnetic configuration only the hydroxy group results in an effective reduction of the band gap.