Tag Archive: Materials Science

Mar 30

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(2015): 4.509
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.


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.

Dec 13

MRS seminar: Topological Insulators

Bart Sorée receives a commemorative frame of the event. Foto courtesy of Rajesh Ramaneti.

Today I have the pleasure of chairing the last symposium of the year of the MRS chapter at UHasselt. During this invited lecture, Bart Sorée (Professor at UAntwerp and KULeuven, and alumnus of my own Alma Mater) will introduce us into the topic of topological insulators.

This topic became unexpectedly a hot topic as it is part of the 2016 Nobel Prize in Physics, awarded last Saturday.

This year’s Nobel prize in physics went to: David J. Thouless (1/2), F. Duncan M. Haldane (1/4) and J. Michael Kosterlitz (1/4) who received it

“for theoretical discoveries of topological phase transitions and topological phases of matter.”

On the Nobel Prize website you can find this document which gives some background on this work and explains what it is. Beware that the explanation is rather technical and at an abstract level. They start with introducing the concept of an order parameter. You may have heard of this in the context of dynamical systems (as I did) or in the context of phase transitions. In the latter context, order parameters are generally zero in one phase, and non-zero in the other. In overly simplified terms, one could say an order parameter is a kind of hidden variable (not to be mistaken for a hidden variable in QM) which becomes visible upon symmetry breaking. An example to explain this concept.

Example: Magnetization of a ferromagnet.

In a ferromagnetic material, the atoms have what is called a spin (imagine it as a small magnetic needle pointing in a specific direction, or a small arrow). At high temperature these spins point randomly in all possible directions, leading to a net zero magnetization (the sum of all the small arrows just lets you run in circles going nowhere). This magnetization is the order parameter. At the high temperature, as there is no preferred direction, the system is invariant under rotation and translations (i.e. if you shift it a bit or you rotate it, or both you will not see a difference) When the temperature is lower, you will cross what is called a critical temperature. Below this temperature all spins will start to align themselves parallel, giving rise to a non-zero magnetization (if all arrows point in the same direction, their sum is a long arrow in that direction). At this point, the system has lost the rotational invariance (because all spins point in  direction, you will know when someone rotated the system) and the symmetry is said to have broken.

Within the context of phase transitions, order parameters are often temperature dependent. In case of topological materials this is not the case. A topological material has a topological order, which means both phases are present at absolute zero (or the temperature you will never reach in any experiment no matter how hard you try) or maybe better without the presence of temperature (this is more the realm of computational materials science, calculations at 0 Kelvin actually mean without temperature as a parameter). So the order parameter in a topological material will not be temperature dependent.

Topological insulators

To complicate things, topological insulators are materials which have a topological order which is not as the one defined above 😯 —yup why would we make it easy 🙄 . It gets even worse, a topological insulator is conducting.

OK, before you run away or loose what is remaining of your sanity. A topological insulator is an insulating material which has surface states which are conducting. In this it is not that different from many other “normal” insulators. What makes it different, is that these surface states are, what is called, symmetry protected. What does this mean?

In a topological insulator with 2 conducting surface states, one will be linked to spin up and one will be linked to spin down (remember the ferromagnetism story of before, now the small arrows belong to the separate electrons and exist only in 2 types: pointing up=spin up, and pointing down=spin down). Each of these surface states will be populated with electrons. One state with electrons having spin up, the other with electrons having spin down. Next, you need to know that these states also have a real-space path let the electrons run around the edge of material. Imagine them as one-way streets for the electrons. Due to symmetry the two states are mirror images of one-another. As such, if electrons in the up-spin state more left, then the ones in the down-spin state move right. We are almost there, no worries there is a clue. Now, where in a normal insulator with surface states the electrons can scatter (bounce and make a U-turn) this is not possible in a topological insulator. But there are roads in two directions you say? Yes, but these are restricted. And up-spin electron cannot be in the down-spin lane and vice versa. As a result, a current going in such a surface state will show extremely little scattering, as it would need to change the spin of the electron as well as it’s spatial motion. This is why it is called symmetry protected.

If there are more states, things get more complicated. But for everyone’s sanity, we will leave it at this.  😎

Sep 08

Colloquium on Porous Frameworks: Day 2

Program Porous Frameworks ColloquiumOn Monday, we had the second day of our colloquium on Porous Frameworks, containing no less than 4 full sessions, covering all types of frameworks. We started the day with the invited presentation of Prof. Dirk De Vos of the KU Leuven, who discussed the breathing behavior in Zr and Ti containing MOFs, including the work on the COK-69 in which I was involved myself. In the MOFs presented, the breathing behavior was shown to originate from the folding of the linkers, in contrast to breathing due to the hinging motion of the chains in MIL-47/53 MOFs.

After the transition metals, things were stepped up even further by Dr. Stefania Tanase who talked about the use of lanthanide ions in MOFs. These lanthanides give rise to coordinated water molecules which appear to be crucial to their luminescence. Prof. Donglin Jiang, of JAIST in Japan, changed the subject to the realm of COFs, consisting of 2D porous sheets which, through Van Der Waals interactions form 3D structures (similar to graphite). The tunability of these materials would make them well suited for photoconductors and photoenergy conversion (i.e. solar cells).

With Prof. Rochus Schmid of the University of Bochum we delved into the nitty-gritty details of developing Force-Fields for MOFs. He noted that such force-fields can provide good first approximations for structure determination of new MOFs, and if structure related terms are missing in the force-field these will pop up as missing phonon-frequencies.

Prof. Monique Van der Veen showed us how non-polar guest molecules can make a MOF polar, while Agnes Szecsenyi bravely tackled the activity in Iron based MIL-53 MOFs from the DFT point of view. The row of 3 TU Delft contributions was closed by the invited presentation of Prof. Jorge Gascon who provided an overview of the work in his group and discussed how the active sites in MOFs can be improved through cooperative effects.

Prof. Jaroslaw Handzlik provided the last invited contribution, with a comparative theoretical study of Cr-adsorption on various silicate based materials (from amorphous silicate to zeolites). The final session was then closed by the presentations of Dr. Katrine Svane (Bath University) who discussed the effect of defects in UiO-66 MOFs in further detail and Marcus Rose presenting his findings on hyper-crosslinked Polymers, a type of COFs with an amorphous structure and a wide distribution in different pore sizes.

This brought us to a happy end of a successful colloquium, which was celebrated with a drink in the city center of Groningen. Tuesday we traveled back home, such that Wednesday Sylvia could start at the third part of the conference-holiday roller coaster by leaving for Saltzburg.

Sep 04

Colloquium on Porous Frameworks: Day 1

Program Porous Frameworks ColloquiumToday the CMD26 conference started in Groningen, and with its kick-off also our own 2-day colloquium on porous frameworks (aka MOFs, COFs and Zeolites) was launched. During the two sessions of the day, the focus mainly went out to the Zeolites, with Prof. Emiel Hensen of the Technical university of Eindhoven introducing us to the subject and discussing how new zeolites could be designed in a more rational way. He showed us how the template used during synthesis plays a crucial role in the final growth and structure. Dr. Nakato explained how alkali-metal nanoclusters can undergo insulator to metal transitions when incorporated in zeolites (it is due to the competition between electron-electron repulsion and electron-phonon coupling), while Dr. De Wijs informed us on how Al T-sites need to be ordered and assigned in zeolites to allow for the prediction of NMR parameters.

After the coffee break Dr. Palcic, from the Rudjer Boskovic Institute in Croatia, taught us about the role of heteroatoms in zeolites. She told us that even though more than 2 million theoretical structures exist, only 231 have officially been recognized as having been synthesized, so there is a lot more work to be done. She also showed that to get stable zeolites with pores larger than 7-8 Angstrom one needs to have 3 and 4-membered rings in the structure, since these lead to more rigid configurations. Unfortunately these rings are themselves less stable, and need to be stabilized by different atoms at the T-sites.

Dr. Vandichel, still blushing from his tight traveling scheme, changed the subject from zeolites to MOFs, in providing new understanding in the role of defects in MOFs on their catalytic performance. Dr. Liu changed the subject even further with the introduction of COFs and showing us how Hydrogen atoms migrate through these materials. Using the wisdom of Bruce Lee :

You must be shapeless, formless, like water. When you pour water in a cup, it becomes the cup. When you pour water in a bottle, it becomes the bottle. When you pour water in a teapot, it becomes the teapot.

he clarified how water behaves inside these porous materials. Our first colloquium day was closed by Ir. Rohling, who took us back to the zeolite scene (although he was comparing the zeolites to enzymes). He discussed how reactivity in zeolites can be tweaked by the confinement of the reacting agents, and how this can be used for molecule identification. More importantly he showed how multiple active site collaborate, making chemical reactions much easier than one would expect from single active site models.

After all was said and done, it was time to relax a little during the conference welcome reception. And now time to prepare for tomorrow, day 2 of our colloquium on porous frameworks.


Aug 31

Holiday-Conference roller coaster

Visit to Stockholm. The knight at the Medeltidsmuseet (top left), brown bear in Skansen (top right), visiting the Royal palace (bottom left) and local entertainment in the old city center (bottom right).

Visit to Stockholm. The knight at the Medeltidsmuseet (top left), brown bear in Skansen (top right), visiting the Royal palace (bottom left) and local entertainment in the old city center (bottom right).

Summertime is a time of rest for most people. For our little academic family, last summer was a bit of a roller coaster; alternating holidays with hard work which had been postponed too much. The last vestige of my start of a new chapter (moving the remaining stuff from the apartment to our house) was finally bested. Now the conference roller coaster has started with Sylvia’s plenary lecture on conceptual spaces in Stockholm.

As neither of us ever visited Sweden before, we decided to turn it into a semi-family-holiday as well. Our 4-year-old son enjoyed his first ever plane flight (he wasn’t really convinced something impressive was going on). And while Sylvia was of to the conference, the two of us went to explore Stockholm: Finding the knight in the Medeltidsmuseet (at the left in the back of this beautiful museum 🙂 ) and searching for the king and queen at their palace (they weren’t there 🙁 ). Or visiting one of the oldest open-air musea; Skansen (similar to Bokrijk in Belgium) where we saw old professions at work (making cheese for example) and native Scandinavian farm and wild animals (from peacocks to brown bears).

Next weekend starts the next episode of the conference roller-coaster with me hosting a 2-day colloquium on porous frameworks together with Bartek Szyja and Ionut Tranca at the CMD-26 conference in Groningen. We have a nicely packed colloquium with about 20 presentations (8 invited and 12 contributed) covering the whole realm of porous materials from zeolites to COFs and MOFs. The program of the colloquium can be downloaded below:Program Porous Frameworks Colloquium

Jun 30

I have a Question: about thermal expansion

“I have a question”(ik heb een vraag). This is the name of a Belgian (Flemisch) website aimed at bringing Flemisch scientists and the general public together through scientific or science related questions. The basic idea is rather simple. Someone has a scientific question and poses it on this website, and a scientist will provide an answer. It is an excellent opportunity for the latter to hone his/her own science communication skills (and do some outreach) and for the former to get an good answer to his/her question.

All questions and answers are collected in a searchable database, which currently contains about fifteen thousand questions answered by a (growing) group of nearly one thousand scientists. This is rather impressive for a region of about 6.5 Million people. I recently joined the group of scientists providing answers.

An interesting materials-related question was posed by Denis (my translation of his question and context):

What is the relation between the density of a material and its thermal expansion?

I was wondering if there exists a relation between the density of a material and the thermal expansion (at the same temperature)? In general, gasses expand more than solids, so can I extend this to the following: Materials with a small density will expand more because the particles are separated more and thus experience a small cohesive force. If this statement is true, then this would imply that a volume of alcohol should expand more than the same volume of air, which I think is puzzling. Can you explain this to me?

Answer (a bit more expanded than the Dutch one):

Unfortunately there exists no simple relation between the density of a material and its thermal expansion coefficient.

Let us first correct something in the example given: the density of alcohol (or ethanol) is 46.07 g/mol (methanol would be 32.04 g/mol) which is significantly more than the density of air which is 28.96 g/mol. So following the suggested assumption, air should expand more. If we look at liquids, it is better to compare ethanol (0.789 g/cm3) to compare water (1 g/cm3) as liquid air (0.87 g/cm3) needs to be cooled below  -196 °C (77K). The thermal expansion coefficients of wtare and ethanol are 207×10-6/°C and 750×10-6/°C, respectively. So in this case, we see that alcohol will expand more than water (at 20°C). Supporting Denis’ statement.

Unfortunately, these are just two simple materials at a very specific temperature for which this statement is true. In reality, there are many interesting aspects complicating life. A few things to keep in mind are:

  • A gas (in contrast to a liquid or solid) has no own boundary. So if you do not put it in any type of a container, then it will just keep expanding. The change in volume observed when a gas is heated is due to an increase in pressure (the higher kinetic energy of the gas molecules makes them bounce harder of the walls of your container, which can make a piston move or a balloon grow). In a liquid or a solid on the other hand, the expansion is rather a stretching of the material itself.
  • Furthermore, the density does not play a role at all, in case of the expansion of an ideal gas, since p*V=n*R*T. From this it follows that 1 mole of H2 gas, at 20°C and a pressure of 1 atmosphere, has the exact same volume as 1 mole of O2 gas, at 20°C and a pressure of 1 atmosphere, even though the latter has a density which is 16 times higher.
  • There are quite a lot of materials which show a negative thermal expansion in a certain temperature region (i.e. they shrink when you increase the temperature). One well-known example is water. The density of liquid water at 0 °C is lower than that of water at 4 °C. This is the reason why there remains some liquid water at the bottom of a pond when it is frozen over.
  • There are also materials which show “breathing” behavior (this are reversible volume changes in solids which made the originators of the term think of human breathing: inhaling expands our lungs and chest, while exhaling contracts it again.) One specific class of these materials are breathing Metal-Organic Frameworks (MOFs). Some of these look like wine-racks (see figure here) which can open and close due to temperature variations. These volume variations can be 50% or more! 😯

The way a material expands due to temperature variations is a rather complex combination of different aspects. It depends on how thermal vibrations (or phonons) propagate through the material, but also on the possible presence of phase-transitions. In some materials there are even phase-transitions between solid phases with a different crystal structure. These, just like solid/liquid phase transitions can lead to very sudden jumps in volume during heating or cooling. These different crystal phases can also have very different physical properties. During the middle-ages, tin pest was a large source of worries for organ-builders. At a temperature below 13°C β-tin is more stable α-tin, which is what was used in organ pipes. However, the high activation energy prevents the phase-transformation from α-tin to β-tin to happen too readily. At temperatures of -30 °C and lower this barrier is more easily overcome.This phase-transition gives rise to a volume reduction of 27%. In addition, β-tin is also a brittle material, which easily disintegrates. During the middle ages this lead to the rapid deterioration and collapse of organ-pipes in church organs during strong winters. It is also said to have caused the buttons of the clothing of Napoleon’s troops to disintegrate during his Russian campaign. As a result, the troops’ clothing fell apart during the cold Russian winter, letting many of them freeze to death.



Apr 12

Call for Abstracts: Condensed Matter Science in Porous Frameworks: On Zeolites, Metal- and Covalent-Organic Frameworks

Flyer for the Colloquium on Porous Frameworks at the CMD26Together with Ionut Tranca (TU Eindhoven, The Netherlands) and Bartłomiej Szyja (Wrocław University of Technology, Poland) I am organizing a colloquium “Condensed Matter Science in Porous Frameworks: On Zeolites, Metal- and Covalent-Organic Frameworks” which will take place during the 26th biannual Conference & Exhibition CMD26 – Condensed Matter in Groningen (September 4th – 9th, 2016). During our colloquium, we hope to bring together experimental and theoretical researchers working in the field of porous frameworks, providing them the opportunity to present and discuss their latest work and discoveries.

Zeolites, Metal-Organic Frameworks, and Covalent-Organic Frameworks are an interesting class of hybrid materials. They are situated at the boundary of research fields, with properties akin to both molecules and solids. In addition, their porosity puts them at the boundary between surfaces and bulk materials, while their modular nature provides a wealthy playground for materials design.

We invite you to submit your abstract for oral or poster contributions to our colloquium. Poster contributions participate in a Best Poster Prize competition.

The deadline for abstract submission is April 30th, 2016.

The extended deadline for abstract submission is May 14th, 2016.


CMD26 – Condensed Matter in Groningen is an international conference, organized by the Condensed Matter Division of the European Physical Society, covering all aspects of condensed matter physics, including soft condensed matter, biophysics, materials science, quantum physics and quantum simulators, low temperature physics, quantum fluids, strongly correlated materials, semiconductor physics, magnetism, surface and interface physics, electronic, optical and structural properties of materials. The scientific programme will consist of a series of plenary and semi-plenary talks and Mini-colloquia. Within each Mini-colloquium, there will be invited lectures, oral contributions and posters.


Feel free to distribute this call for abstracts and our flyer and we hope to see you in Groningen!

Mar 09


SBDD XXI logoToday was the first day of the three-day long diamond conference at the university of Hasselt. And although this sounds as-if it is a mere small-scale local conference, it is actually one of the two main international conferences in the field. The Surface and Bulk Defects in Diamond (SBDD) workshop grew in twenty years from a small event with only a few dozen participants to the current event with over 200 participants. As such, it is the place to be, for one as me, who is dipping into a new field of materials.

One thing that already became quite clear today, is the fact that there are many opportunities in this field for the computational materials scientist, as the large majority of the researchers are experimentalists. Of the >120 posters presented, I have only discovered about 5 theoretical ones. Having had very nice chats with their presenters I already learned a lot of what I will have to keep in mind when studying diamond. But so far, I have not come across any issues that are impossible to resolve, which is good news :-).

Mar 01

Helium flash: the beginning of a new chapter.

During the past two and a half years, part of being a delocalized physicist has meant for me that I had to work at one end of the country while my girlfriend and son lived at the other. Today this situation drastically changed, as I moved with my FWO-postdoctoral project from my alma mater to the University of Hasselt, where I started in the Wide Band Gap Materials group of Prof. Ken Haenen.

My delocalization will now take the form of Metal-Organic Frameworks on the one side and Diamond based materials on the other. As the sole computational solid state physicist in an otherwise entirely experimental group (and even institute) I seem to have returned to a well known configuration (At Ghent university I was initially the house-theoretician of the SCRiPTS group). Also the idea of performing calculations on diamond brings back memories, since this allotrope of carbon lives two levels above the germanium on which Pt nanowires grow. All-in-all I look forward to an exciting time. But first things first: getting my HPC credentials and data safely transported from the one end of the country to the other.

Feb 11

First-Principles Study of Antisite Defect Configurations in ZnGa2O4:Cr Persistent Phosphors

Authors: Arthur De Vos, Kurt Lejaeghere, Danny E. P. Vanpoucke, Jonas J. Joos, Philippe F. Smet, and Karen Hemelsoet
Journal: Inorg. Chem. 55(5), 2402-2412 (2016)
doi: 10.1021/acs.inorgchem.5b02805
IF(2015): 4.820
export: bibtex
pdf: <Inorg.Chem>
Graphical Abstract: (left) Ball-and-stick model of zinc gallate (right) density of states of Cr doped zinc gallate.
Graphical Abstract: First-principles simulations on zinc gallate solid phosphors (ZGO) containing a chromium dopant and antisite defects (left) rationalize the attractive interactions between the various elements. A large number of antisite pair configurations is investigated and compared with isolated antisite defects. Defect energies point out the stability of the antisite defects in ZGO. Local structural distortions are reported, and charge transfer mechanisms are analyzed based on theoretical density of states (right) and Hirshfeld-I charges.


Zinc gallate doped with chromium is a recently developed near-infrared emitting persistent phosphor, which is now extensively studied for in vivo bioimaging and security applications. The precise mechanism of this persistent luminescence relies on defects, in particular, on antisite defects and antisite pairs. A theoretical model combining the solid host, the dopant, and/or antisite defects is constructed to elucidate the mutual interactions in these complex materials. Energies of formation as well as dopant, and defect energies are calculated through density-functional theory simulations of large periodic supercells. The calculations support the chromium substitution on the slightly distorted octahedrally coordinated gallium site, and additional energy levels are introduced in the band gap of the host. Antisite pairs are found to be energetically favored over isolated antisites due to significant charge compensation as shown by calculated Hirshfeld-I charges. Significant structural distortions are found around all antisite defects. The local Cr surrounding is mainly distorted due to a ZnGa antisite. The stability analysis reveals that the distance between both antisites dominates the overall stability picture of the material containing the Cr dopant and an antisite pair. The findings are further rationalized using calculated densities of states and Hirshfeld-I charges.

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