H. Vrielinck

Development of porous organic polymers as metal free photocatalysts for the aromatization of N-heterocycles

M. Debruyne, N. Raeymackers, H. Vrielinck, S. Radhakrishnan, E. Breynaert, M. Delaey, A. Laemont, K. Leus, J. Everaert, H. Rijckaert, D. Poelman, R. Morent, N. De Geyter, P. Van der Voort, V. Van Speybroeck, C. Stevens, T.S.A Heugebaert
ChemCatChem
2024
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Abstract 

Porous organic polymers (POPs), and especially covalent triazine frameworks (CTFs), are being developed as the next generation of metal-free heterogeneous photocatalysts. However, many of the current synthetic routes to obtain these photoactive POPs require expensive monomers and rely on precious metal catalysts, thus hindering their widespread implementation. In this work, a range of POPs was synthesized from simple unfunctionalized aromatic building blocks, through Lewis acidcatalyzed polymerization. The obtained materials were applied, for the first time, as heterogeneous photocatalysts for the aromatization of N-heterocycles. With the use of the most active material, denoted as CTF-Pyr, which consists of photoactive pyrene and triazine moieties, a wide range of pyridines, dihydroquinoline-5-ones, tetrahydroacridine-1,8-diones and pyrazoles were obtained in excellent yields (70-99%). Moreover, these reactions were carried out under very mild conditions using air and at room temperature, highlighting the potential of these materials as catalysts for green transformations.

Engineering of Phenylpyridine- and Bipyridine-Based Covalent Organic Frameworks for Photocatalytic Tandem Aerobic Oxidation/Povarov Cyclization

M. Debruyne, S. Borgmans, S. Radhakrishnan, E. Breynaert, H. Vrielinck, K. Leus, A. Laemont, J. De Vos, K. S. Rawat, S. Vanlommel, H. Rijckaert, H. Salemi, J. Everaert, F. Vanden Bussche, D. Poelman, R. Morent, N. De Geyter, P. Van der Voort, V. Van Speybroeck, C.V. Stevens
ACS Applied Materials & Interfaces
15, 29, 35092–35106
2023
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Abstract 

Covalent organic frameworks (COFs) are emerging as a new class of photoactive organic semiconductors, which possess crystalline ordered structures and high surface areas. COFs can be tailor-made toward specific (photocatalytic) applications, and the size and position of their band gaps can be tuned by the choice of building blocks and linkages. However, many types of building blocks are still unexplored as photocatalytic moieties and the scope of reactions photocatalyzed by COFs remains quite limited. In this work, we report the synthesis and application of two bipyridine- or phenylpyridine-based COFs: TpBpyCOF and TpPpyCOF. Due to their good photocatalytic properties, both materials were applied as metal-free photocatalysts for the tandem aerobic oxidation/Povarov cyclization and α-oxidation of N-aryl glycine derivatives, with the bipyridine-based TpBpyCOF exhibiting the highest activity. By expanding the range of reactions that can be photocatalyzed by COFs, this work paves the way toward the more widespread application of COFs as metal-free heterogeneous photocatalysts as a convenient alternative for commonly used homogeneous (metal-based) photocatalysts.

Open Access version available at UGent repository

Pyrene-Based Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production

J. Sun, H. S. Jena, C. Krishnaraj, K. S. Rawat, S. Abednatanzi, J. Chakraborty, A. Laemont, W. Liu, H. Chen, Y.-Y. Liu, K. Leus, H. Vrielinck, V. Van Speybroeck, P. Van der Voort
Angewandte Chemie int. Ed.
Volume: 62; Issue: 19
2023
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Abstract 

Four highly porous covalent organic frameworks (COFs) containing pyrene units were prepared and explored for photocatalytic H2O2 production. The experimental studies are complemented by density functional theory calculations, proving that the pyrene unit is more active for H2O2 production than the bipyridine and (diarylamino)benzene units reported previously. H2O2 decomposition experiments verified that the distribution of pyrene units over a large surface area of COFs plays an important role in catalytic performance. The Py-Py-COF, though contains more pyrene units than other COFs, induces a high H2O2 decomposition due to a dense concentration of pyrene in small proximity over a limited surface area. Therefore, a two-phase reaction system (water-benzyl alcohol) was employed to inhibit H2O2 decomposition. This is the first report on applying pyrene-based COFs in a two-phase system for photocatalytic H2O2 generation.

Identification of vanadium dopant sites in the metal–organic framework DUT-5(Al)

K. Maes, L.I.D.J. Martin, S. Khelifi, A.E.J. Hoffman, K. Leus, P. Van der Voort, E. Goovaerts, P.F. Smet, V. Van Speybroeck, F. Callens, H. Vrielinck
Physical Chemistry Chemical Physics (PCCP)
23, 7088-7100
2021
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Abstract 

Studying the structural environment of the VIV ions doped in the metal–organic framework (MOF) DUT-5(Al) ((AlIIIOH)BPDC) with electron paramagnetic resonance (EPR) reveals four different vanadium-related spectral components. The spin-Hamiltonian parameters are derived by analysis of X-, Q- and W-band powder EPR spectra. Complementary Q-band Electron Nuclear DOuble Resonance (ENDOR) experiments, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray spectroscopy (EDX), X-Ray Diffraction (XRD) and Fourier Transform InfraRed (FTIR) measurements are performed to investigate the origin of these spectral components. Two spectral components with well resolved 51V hyperfine structure are visible, one corresponding to VIV=O substitution in a large (or open) pore and one to a narrow (or closed) pore variant of this MOF. Furthermore, a broad structureless Lorentzian line assigned to interacting vanadyl centers in each other's close neighborhood grows with increasing V-concentration. The last spectral component is best visible at low V-concentrations. We tentatively attribute it to (VIV=O)2+ linked with DMF or dimethylamine in the pores of the MOF. Simulations using these four spectral components convincingly reproduce the experimental spectra and allow to estimate the contribution of each vanadyl species as a function of V-concentration.

Elucidating the promotional effect of a covalent triazine framework in aerobic oxidation

S. Abednatanzi, P. Gohari Derakhshandeh, P. Tack, F. Muniz-Miranda, Y-Y Liu, J. Everaert, M. Meledina, F. Vanden Bussche, L. Vincze, C. Stevens, V. Van Speybroeck, H. Vrielinck, F. Callens, K. Leus, P. Van der Voort
Applied Catalysis B: Environmental
269, 118769
2020
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Elucidating the Vibrational Fingerprint of the Flexible Metal-Organic Framework MIL-53(Al) Using a Combined Experimental/Computational Approach

A.E.J. Hoffman, L. Vanduyfhuys, I. Nevjestic, J. Wieme, S.M.J. Rogge, H. Depauw, P. Van der Voort, H. Vrielinck, V. Van Speybroeck
Journal of Physical Chemistry C
122, 5, 2734-2746
2018
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Abstract 

In this work mid-infrared (mid-IR), far-IR, and Raman spectra are presented for the distinct (meta)stable phases of the flexible metal-organic framework MIL-53(Al). Static density functional theory (DFT) simulations are performed allowing for the identification of all IR active modes, which is unprecedented in the low-frequency region. A unique vibrational fingerprint is revealed, resulting from aluminum-oxide backbone stretching modes, which can be used to clearly distinguish the IR spectra of the closed- and large-pore phases. Furthermore, molecular dynamics simulations based on a DFT description of the potential energy surface enable to determine the theoretical Raman spectrum of the closed- and large-pore phases for the first time. An excellent correspondence between theory and experiment is observed. Both the low-frequency IR and Raman spectra show major differences in vibrational modes between the closed- and large-pore phases indicating changes in lattice dynamics between the two structures. In addition, several collective modes related to the breathing mechanism in MIL-53(Al) are identified. In particular, we rationalize the importance of the trampoline-like motion of the linker for the phase transition.

Open Access version available at UGent repository
Gold Open Access

Systematic study of the chemical and hydrothermal stability of selected "stable" Metal Organic Frameworks

K. Leus, T. Bogaerts, J. De Decker, H. Depauw, K. Hendrickx, H. Vrielinck, V. Van Speybroeck, P. Van der Voort
Microporous and Mesoporous Materials
226, 110-116
2016
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Abstract 

In this work, the hydrothermal and chemical stability towards acids, bases, air, water and peroxides of Metal Organic Frameworks, that are commonly considered to be stable, is presented. As a proof of stability both the crystallinity and porosity are measured before and after exposure to the stress test. The major part of the MOFs examined in this study showed a good hydrothermal stability except for the UiO-67, NH2-MIL-101 (Al) and CuBTC material. The chemical stability towards acids and bases show a similar tendency and an ordering can be proposed as: MIL-101(Cr)>NH2-UiO-66>UiO-66>UiO-67>NH2-MIL-53>MIL-53(Al)>ZIF-8>CuBTC>NH2-MIL-101(Al). In the tests with the H2O2 solution most materials behaved poorly, only the UiO-66 and NH2-UiO-66 framework showed a good stability.

Dominant stable radicals in irradiated sucrose: g tensors and contribution to the powder electron paramagnetic resonance spectrum

H. De Cooman, J. Keysabyl, J. Kusakovskij, A. Van Yperen-De Deyne, M. Waroquier, F. Callens, H. Vrielinck
Journal of Physical Chemistry B
117 (24), 7169–7178
2013
A1

Abstract 

Ionizing radiation induces a composite, multiline electron paramagnetic resonance (EPR) spectrum in sucrose, that is stable at room temperature and whose intensity is indicative of the radiation dose. Recently, the three radicals which dominate this spectrum were identified and their proton hyperfine tensors were accurately determined. Understanding the powder EPR spectrum of irradiated sucrose, however, also requires an accurate knowledge of the g tensors of these radicals. We extracted these tensors from angular dependent electron nuclear double resonance-induced EPR measurements at 110 K and 34 GHz. Powder spectrum simulations using this completed set of spin Hamiltonian parameters are in good agreement with experimentally recorded spectra in a wide temperature and frequency range. However, as-yet nonidentified radicals also contribute to the EPR spectra of irradiated sucrose in a non-negligible way.

Ti-functionalized NH2-MIL-47: an effective and stable epoxidation catalyst

K. Leus, G. Vanhaelewyn, T. Bogaerts, Y-Y Liu, F. Esquivel, F. Callens, G.B. Marin, V. Van Speybroeck, H. Vrielinck, P. Van der Voort
Catalysis Today
208, 97-105
2013
A1

Abstract 

In this paper, we describe the post-functionalization of a V-containing Metal-organic framework with TiO(acac)2 to create a bimetallic oxidation catalyst. The catalytic performance of this V/Ti-MOF was examined for the oxidation of cyclohexene using molecular oxygen as oxidant in combination with cyclohexanecarboxaldehyde as co-oxidant. A significantly higher cyclohexene conversion was observed for the bimetallic catalyst compared to the non-functionalized material. Moreover, the catalyst could be recycled at least 3 times without loss of activity and stability. No detectable leaching of V or Ti was noted. Electron paramagnetic resonance measurements were performed to monitor the fraction of V-ions in the catalyst in the +IV valence state. A reduction of this fraction by ∼17% after oxidation catalysis is observed, in agreement with the generally accepted mechanism for this type of reaction.

Room Temperature Radiation Products in Trehalose Single Crystals: EMR and DFT analysis

H. De Cooman, M. Tarpan, H. Vrielinck, M. Waroquier, F. Callens
Radiation Research
179 (3), 313-322
2013
A1

Abstract 

Radicals generated in trehalose single crystals by X radiation at room temperature were investigated by electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR) and ENDOR-induced EPR measurements, together with periodic density functional theory calculations. In the first days after irradiation, three radical species (I1, I2 and I3) were detected, two of which (I1 and I2) dominate the EPR spectrum and could be identified as H-abstracted species centered at C3′ (I1) and C2 (I2), the latter with additional formation of a carbonyl group at C3. Annealing the sample at 40°C for 3 days or storing it in ambient conditions for three months resulted in another, more stable EPR spectrum. Two major species could be characterized in this stage (S1 and S2), only one of which was tentatively identified as an H-abstracted, C2-centered species (S1). Our findings disagree with a previous EPR study [Gräslund and Löfroth (23)] on several accounts. This work stresses the need for caution when interpreting composite EPR spectra and thermally induced spectral changes of radiation-induced species, even in these relatively simple carbohydrates. It also provides further evidence that the pathways for radiation damage critically depend on the specific conformation of a molecule and its environment, but also that carbonyl group formation is a common process in the radiation chemistry of sugars and related compounds.

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