V. Van Speybroeck

An embedded interfacial network stabilizes inorganic CsPbI3 perovskite thin films

J.A. Steele, T. Braeckevelt, V. Prakasam, G. Degutis, H. Yuan, H. Jin, E. Solano, P. Puech, S. Basak, M.I. Pintor-Monroy, H. Van Gorp, G. Fleury, R.X. Yang, Z. Lin, H. Huang, E. Debroye, D. Chernyshov, B. Chen, M. Wei, Y. Hou, R. Gehlhaar, J. Genoe, S. De Feyter, S.M.J. Rogge, A. Walsh, E.H. Sargent, P. Yang, J. Hofkens, V. Van Speybroeck, M.B.J. Roeffaers
Nature Communications
13, 7513
2022
A1

Abstract 

The black perovskite phase of CsPbI3 is promising for optoelectronic applications; however, it is unstable under ambient conditions, transforming within minutes into an optically inactive yellow phase, a fact that has so far prevented its widespread adoption. Here we use coarse photolithography to embed a PbI2-based interfacial microstructure into otherwise-unstable CsPbI3 perovskite thin films and devices. Films fitted with a tessellating microgrid are rendered resistant to moisture-triggered decay and exhibit enhanced long-term stability of the black phase (beyond 2.5 years in a dry environment), due to increasing the phase transition energy barrier and limiting the spread of potential yellow phase formation to structurally isolated domains of the grid. This stabilizing effect is readily achieved at the device level, where unencapsulated CsPbI3 perovskite photodetectors display ambient-stable operation. These findings provide insights into the nature of phase destabilization in emerging CsPbI3 perovskite devices and demonstrate an effective stabilization procedure which is entirely orthogonal to existing approaches.

DOI 

https://doi.org/10.1038/s41467-022-35255-9

Influence of the number of ligands and point group on the electronic structure of Co2+ aqua-complexes

L. De Bruecker, V. Van Speybroeck
Inorganic Chemistry
61, 51, 20743–20756
2022
A1

Abstract 

The nucleation process of zeolitic imidazolate frameworks (ZIFs) is, to date, not yet completely understood, making the search for tailored materials very difficult. Recently, it has been shown that, during the formation process, the symmetry of the precursors is reduced by ligand elimination and substitution reactions. The octahedral precursors with simple ligands, such as water, methanol, and/or NO3–, are transformed to five- and finally four-coordinated complexes with imidazole ligands. This reduction of symmetry, caused both by the changing coordination environment and distortions from the perfect symmetry leading to another point group, will have a large influence on the electronic structure and more specifically on the d-orbital splitting. This, in turn, will affect the d–d electronic excitations, which can be followed using UV–vis spectroscopy and which can help to unravel the formation process. In this work, we systematically investigate how the lowering of the number of ligands affects the symmetry and thus the geometry and electronic structure of Co2+ complexes with six, five, and four aqua ligands. Therefore, we first resort to qualitative techniques, such as crystal field theory (CFT) and ligand field theory (LFT), which reveal that the orbital splitting is characteristic for the number of ligands. However, as these techniques are not capable of providing quantitative results without the use of experimental data as input, we perform various computational calculations. Both average of configuration (AOC) and unrestricted density functional theory (UDFT) are thoroughly investigated, and we will determine which technique is the best suited to properly describe the ground state of these systems. To investigate the dependency on the d-orbital occupation, we also investigated V2+, Mn2+, and Ni2+ hexa-aqua-complexes and compared them to the Co systems.

DOI 

https://doi.org/10.1021/acs.inorgchem.2c02358

Linker Engineering of 2D Imine Covalent Organic Frameworks for Heterogeneous Palladium-catalyzed Suzuki Coupling Reaction

C. Krishnaraj, H. S. Jena, K. S. Rawat, J. Schmidt, K. Leus, V. Van Speybroeck, P. Van der Voort
ACS Applied Materials & Interfaces
14, 45, 50923-50931
2022
A1

Abstract 

Covalent organic frameworks (COFs) are an emerging class of porous organic polymers that have been utilized as scaffolds for anchoring metal active species to act as heterogeneous catalysts. Though several examples of such COFs exist, a thorough experimental and computational analysis on such catalysts is limited. In this work, a series of two-dimensional (2D) imine COFs (TTA–DFB COF (N), TTA–TBD COF (N∧O), and TTA–DFP COF(N∧N)) were synthesized by using suitable building units to obtain three different coordination sites (N, N∧O, and N∧N). These were post-modified with Pd(II) to catalyze the Suzuki–Miyaura coupling reaction. Pd@TTA–DFB COF, where Pd(II) was coordinated to N sites, showed the fastest reactivity and lower stability. Pd@TTA–DFP COF showed highest stability but slowest reactivity. Pd@TTA–TBD COF was the best among the three with both high stability and fast reactivity. By combining both experimental and computational results, we conclude that the Pd(II) to Pd(0) reduction is a key step in the difference between the catalytic reactivities of the three COFs. This study demonstrates the importance of the building block approach to design COFs for efficient heterogeneous catalysis and to understand the fate of the reaction profile.

DOI 

https://doi.org/10.1021/acsami.2c14882

Covalent Organic Framework supported Palladium Catalysts

H. Salemi, M. Debruyne, V. Van Speybroeck, P. Van der Voort, M. D'Hooghe, C. Stevens
Journal of Materials Chemistry A
10, 39, 20707-20729
2022
A1

Abstract 

Covalent organic frameworks (COFs), as highly porous crystalline structures, are newly emerging materials designed with tuneable features. They have a high potential to be a host to immobilize metal catalysts. The unique property of these materials, such as their high surface area, oriented channels, and heteroatom enrichment, make them promising materials to improve some disadvantages of heterogeneous metal catalysts. In this review, the fabrication and application of Pd anchored COFs as one of the most critical transition-metal catalysts that play a crucial role in a wide range of reactions is summarized.

DOI 

https://doi.org/10.1039/D2TA05234B

Truly combining the advantages of polymeric and zeolite membranes for gas separations

X. Tan, S. Robijns, R. Thür, Q. Ke, N. De Witte, A. Lamaire, Y. Li, I. Aslam, D. Van Havere, T. Donckels, T. Van Assche, V. Van Speybroeck, M. Dusselier, I. Vankelecom
Science
378, 1189-1194
2022
A1

Abstract 

Mixed-matrix membranes (MMMs) have been investigated to render energy-intensive separations more efficiently by combining the selectivity and permeability performance, robustness, and nonaging properties of the filler with the easy processing, handling, and scaling up of the polymer. However, truly combining all in one single material has proven very challenging. In this work, we filled a commercial polyimide with ultrahigh loadings of a high–aspect ratio, CO2-philic Na-SSZ-39 zeolite with a three-dimensional channel system that precisely separates gas molecules. By carefully designing both zeolite and MMM synthesis, we created a gas-percolation highway across a flexible and aging-resistant (more than 1 year) membrane. The combination of a CO2-CH4 mixed-gas selectivity of ~423 and a CO2 permeability of ~8300 Barrer outperformed all existing polymer-based membranes and even most zeolite-only membranes.

DOI 

http://dx.doi.org/10.1126/science.ade1411

Quantum free energy profiles for molecular proton transfers

A. Lamaire, M. Cools-Ceuppens, M. Bocus, T. Verstraelen, V. Van Speybroeck
Journal of Chemical Theory and Computation
19, 1, 18–24
2023
A1

Abstract 

Although many molecular dynamics simulations treat the atomic nuclei as classical particles, an adequate description of nuclear quantum effects (NQEs) is indispensable when studying proton transfer reactions. Herein, quantum free energy profiles are constructed for three typical proton transfers, which properly take NQEs into account using the path integral formalism. The computational cost of the simulations is kept tractable by deriving machine learning potentials. It is shown that the classical and quasi-classical centroid free energy profiles of the proton transfers deviate substantially from the exact quantum free energy profile.

DOI 

http://dx.doi.org/10.1021/acs.jctc.2c00874

Exploring the phase stability in interpenetrated diamondoid covalent organic frameworks

S. Borgmans, S.M.J. Rogge, J. De Vos, P. Van der Voort, V. Van Speybroeck
Communications Chemistry
6, 1, 5
2023
A1

Abstract 

Soft porous crystals, which are responsive to external stimuli such as temperature, pressure, or gas adsorption, are being extensively investigated for various technological applications. However, while substantial research has been devoted to stimuli-responsive metal-organic frameworks, structural flexibility in 3D covalent organic frameworks (COFs) remains ill-understood, and is almost exclusively found in COFs exhibiting the diamondoid (dia) topology. Herein, we systemically investigate how the structural decoration of these 3D dia COFs—their specific building blocks and degree of interpenetration—as well as external triggers such as temperature and guest adsorption may promote or suppress their phase transformations, as captured by a collection of 2D free energy landscapes. Together, these provide a comprehensive understanding of the necessary conditions to design flexible diamondoid COFs. This study reveals how their flexibility originates from the balance between steric hindrance and dispersive interactions of the structural decoration, thereby providing insight into how new flexible 3D COFs can be designed.

Open Access version available at UGent repository
Gold Open Access

DOI 

http://dx.doi.org/10.1038/s42004-022-00808-y

How water and ion mobility affect the NMR fingerprints of the hydrated JBW zeolite: a combined computational-experimental investigation

S. Vanlommel, A.E.J. Hoffman, S. Smet, S. Radhakrishnan, K. Asselman, C. V. Chandran, E. Breynaert, C. Kirschhock, J.A. Martens, V. Van Speybroeck
Chemistry - A European Journal
28, 68, e202202621
2022
A1

Abstract 

An important aspect within zeolite synthesis is to make fully tunable framework materials with controlled aluminium distribution. A major challenge in characterising these zeolites at operating conditions is the presence of water. In this work, we investigate the effect of hydration on the 27 Al NMR parameters of the ultracrystalline K,Na-compensated aluminosilicate JBW zeolite using experimental and computational techniques. The JBW framework, with Si/Al ratio of 1, is an ideal benchmark system as a stepping stone towards more complicated zeolites. The presence and mobility of water and extraframework species directly affect NMR fingerprints. Excellent agreement between theoretical and experimental spectra is obtained provided dynamic methods are employed with hydrated structural models. This work shows how NMR is instrumental in characterising aluminium distributions in zeolites at operating conditions.

Gold Open Access

DOI 

https://doi.org/10.1002/chem.202202621

Insights into the mechanism and reactivity of zeolite catalyzed alkylphenol dealkylation

M. Bocus, V. Van Speybroeck
ACS Catalysis
12, 22, 14227–14242
2022
A1

Abstract 

In the stride toward the production of low-carbon-footprint commodity chemicals, the development of a complete wood biorefinery plays a pivotal role. The lignin fraction of wood can be depolymerized and demethoxylated mainly into 4-alkylphenols. These phenolic compounds can further catalytically be C-dealkylated within the H-ZSM-5 zeolite at relatively high temperatures and in the presence of steam, producing phenol and olefins. Experimentally, the dealkylation reaction was found to have two striking features: first, different reactants possess very different reactivity. 4-Ethylphenol (4-EP) is somehow less reactive than 4-n-propylphenol (4-n-PP), which is in turn much less reactive than 4-isopropylphenol (4-iso-PP). Second, cofeeding of steam in the reaction mixture was necessary to prevent rapid and reversible catalyst deactivation. Herein, a combination of static and dynamic density functional theory (DFT) simulations is used to unravel the molecular and mechanistic origin of these observations. Free-energy profiles obtained from static calculations confirm the experimentally observed reactivity sequence, where our computations show that the secondary nature of the alkyl carbon involved in 4-iso-PP dealkylation strongly stabilizes the respective transition states. To investigate the effect of water on the mobility of the reactive species and their interaction with the active site, we investigated the diffusion of phenol along the H-ZSM-5 straight channel in the presence of water loadings from 0 to 3 molecules per zeolite unit cell. We show that water has a strongly beneficial effect in promoting desorption and diffusion of phenol away from the Brønsted acid site through competitive adsorption and by the formation of hydrogen bond chains with the diffusing phenol. This effect could lead to a shorter residence time inside the zeolite, preventing active site poisoning and condensation to bulkier biphenylether moieties.

DOI 

https://doi.org/10.1021/acscatal.2c03844

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