Article
Multidisciplinary Sciences
Simon Krause, Jack D. Evans, Volodymyr Bon, Stefano Crespi, Wojciech Danowski, Wesley R. Browne, Sebastian Ehrling, Francesco Walenszus, Dirk Wallacher, Nico Grimm, Daniel M. Tobbens, Manfred S. Weiss, Stefan Kaskel, Ben L. Feringa
Summary: The study explores the application of photoswitches as light-responsive triggers for phase transitions of porous materials. By incorporating an azobenzene photoswitch in the backbone of a metal-organic framework, the researchers achieve light-induced structural contraction and gas adsorption control in the porous network. The complex mechanism of light-gated breathing is established, revealing a novel light-induced deformation mechanism of constrained azobenzene photoswitches.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yu-Jie Liang, Liu Liu, Jun Yao, Min Deng, Quan-Qing Xu, Ai-Xin Zhu, Bo Huang
Summary: Two new zinc-triazole-carboxylate frameworks were synthesized using a thiophene-containing dicarboxylate and two different triazole ligands. Compound 1 is a 3D anionic porous framework based on dinuclear Zn(II) tetracarboxylate paddlewheel SBUs and dinuclear [Zn-2(tz)(2)] subunits, while compound 2 is a neutral 3D framework based on Zn-triazolate layers and dicarboxylate pillars. Both frameworks exhibit irreversible solid-state structural transformations upon solvent removal/uptake, and show CO2-induced, gate-opening adsorption isotherms at 195 K. Compound 1 selectively adsorbs cationic dyes, while compound 2 hardly adsorbs any selected dyes.
Article
Chemistry, Multidisciplinary
Hannes Preissler-Kurzhoefer, Marcus Lange, Andrei Kolesnikov, Jens Moellmer, Oliver Erhart, Merten Kobalz, Harald Krautscheid, Roger Glaeser
Summary: This study reevaluates the effectiveness of the Dubinin-based universal adsorption theory (D-UAT) as a tool for analyzing sorption equilibrium data and demonstrates its fast speed in visualization and analysis, but not recommended for prediction.
Article
Multidisciplinary Sciences
Li-Hao Xu, Shen-Hui Li, Heng Mao, Yan Li, Ao-Shuai Zhang, Sen Wang, Wei-Min Liu, Jing Lv, Tao Wang, Wei-Wei Cai, Le Sang, Wen-Wen Xie, Chan Pei, Zheng-Zheng Li, Ying-Nan Feng, Zhi-Ping Zhao
Summary: This study presents a strategy to create highly flexible metal-organic framework nanosheet membranes for alcohol-water separation. The membranes exhibited ultrafast transport channels and achieved high flux and separation performance.
Article
Chemistry, Multidisciplinary
Arijit Halder, Ryan A. Klein, Sarah Shulda, Gavin A. McCarver, Philip A. Parilla, Hiroyasu Furukawa, Craig M. Brown, C. Michael McGuirk
Summary: Step-shaped adsorption-desorption of gaseous payloads by flexible metal-organic frameworks can facilitate the delivery of large usable capacities with reduced energetic penalties. The multivariate linker approach is a powerful tool for tuning the phase change behavior of flexible frameworks. In this work, a multivariate framework was developed with a considerably reduced threshold pressure and desirable adsorption-desorption profile for efficient storage and delivery of weakly physisorbing species.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Yi-Cheng Liu, Li-Hsien Yeh, Min-Jie Zheng, Kevin C-W Wu
Summary: By developing a heterogeneous subnanochannel membrane with highly selective ion transport capabilities, researchers have achieved unprecedented power output of up to 26.8 W/m(2) under a 100-fold KBr gradient. This membrane, consisting of a continuous UiO-66-NH2 metal-organic framework and an orderly alumina nanochannel membrane, demonstrates the potential for advanced separation technologies and energy-harvesting devices.
Article
Physics, Applied
Adela Chenyang Li, Lenan Zhang, Yang Zhong, Xiangyu Li, Bachir El Fil, Pasquale F. Fulvio, Krista S. Walton, Evelyn N. Wang
Summary: This study develops a generalized thermodynamic framework to elucidate the interplay between adsorbent properties and operating conditions for optimal performance of adsorption-based atmospheric water harvesting (AWH). It shows that considering temperature-dependent adsorption and optimizing the adsorption enthalpy can significantly improve the energy efficiency of AWH devices, using metal-organic frameworks (MOFs) as an example.
APPLIED PHYSICS LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Ping Wang, Ziqian Xue, Otake Ken-ichi, Susumu Kitagawa
Summary: In this study, a flexible porous coordination polymer (PCP) containing nitroxyl radicals was prepared to achieve controllable size-selective aerobic oxidation of alcohols by reversible switching between large- and contracted-pore configurations in response to solvent change.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xiang He
Summary: Flexible bimetallic MOFs have been investigated for their dynamic behaviors and catalytic abilities through density functional theory calculations. Structural modulation of the MOFs can alter the catalytic performance and provide potential avenues for enhanced efficiency.
Article
Chemistry, Multidisciplinary
Hannes Preissler-Kurzhoefer, Andrei Kolesnikov, Marcus Lange, Jens Moellmer, Oliver Erhart, Merten Kobalz, Seungtaik Hwang, Christian Chmelik, Harald Krautscheid, Roger Glaeser
Summary: The rate of sorption of n-butane on a metal-organic framework was studied using sorption gravimetry, IR spectroscopy, and powder X-ray diffraction. The study revealed complex interactions of adsorption and structural transition, which depend on pressure step, temperature, particle size, and diffusion into newly opened pores. A kinetic model based on the linear driving force approach was used to independently study the rates of diffusion and structural transition.
Article
Chemistry, Multidisciplinary
Lun Shu, Yuan Peng, Rui Yao, Hongling Song, Chenyu Zhu, Weishen Yang
Summary: A facile strategy has been developed to construct defect-free and flexible metal-organic framework (MOF)-based membranes with high selectivity. The fabricated soft-solid MOF composite membranes showed excellent separation performance for H-2/CO2 separation. This study demonstrates the potential of MOF-based membranes in practical separation applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Dongming Cai, Zhuxian Yang, Rui Tong, Haiming Huang, Chuankun Zhang, Yongde Xia
Summary: The fast development of Internet of Things and wearable electronics has created a demand for cost-effective and efficient electroactive materials for flexible energy storage devices. Binder-free nanostructured arrays have gained attention due to their ability to promote fast electron/ion transportation, withstand bending or twisting, and enhance the capacity of the whole device. The use of binder-free metal-organic framework (MOF) nanoarrays and MOF-derived nanoarrays with high surface area and unique porous structure has shown great potential in energy storage and has been extensively explored. This review compares and discusses the common substrates used for binder-free nanoarrays, analyzes the electrochemical performance of various MOF-based and MOF-derived nanoarrays, and examines their applications in flexible energy storage. The review also highlights key technical issues and future developments in this field.
Article
Chemistry, Multidisciplinary
Giasemi K. Angeli, Edward Loukopoulos, Konstantinos Kouvidis, Artemis Bosveli, Constantinos Tsangarakis, Emmanuel Tylianakis, George Froudakis, Pantelis N. Trikalitis
Summary: Studying a series of stable rare-earth MOFs showed rare continuous breathing behavior and gas-trapping properties, revealing unique swelling behavior through theoretical calculations and experimental validation, investigating the mechanisms of solvent molecules and ligands.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Dario Giovanardi, Paolo P. Mazzeo, Paolo Pelagatti, Alessia Bacchi
Summary: Metal-organic frameworks (MOFs) draw attention as crystalline sponges for loading molecules of interest. This study highlights the flexibility of a breathing MOF through soaking the crystals in different solvents, revealing a systematic framework twisting observed during the solvent exchange process. Reversible chemical pathways were confirmed via spectroscopic analysis.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Inorganic & Nuclear
Kenichiro Omoto, Shota Aoyama, Tomasz Galica, Eiji Nishibori, Shohei Katao, Kazuma Yasuhara, Gwenael Rapenne
Summary: The novel coordination polymer ZnC16 shows a thermal crystal-to-crystal phase transition behavior dominated by disordering/ordering of alkyl chains, resulting in the expansion and shrinkage of distances within the rigid 2D coordination networks. The thermal phase transition induces significant changes in crystal morphology, including reversible macroscopic elongation/shrinkage and irreversible delamination and polycrystal slippage. This research provides a new direction to modulate the dynamic behavior and properties of layered coordination polymers by utilizing the thermally responsive character of flexible alkyl chains.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Aran Lamaire, Maarten Cools-Ceuppens, Massimo Bocus, Toon Verstraelen, Veronique Van Speybroeck
Summary: Although many molecular dynamics simulations treat atomic nuclei as classical particles, it is necessary to consider nuclear quantum effects (NQEs) when studying proton transfer reactions. In this study, quantum free energy profiles for three typical proton transfers, which properly include NQEs using the path integral formalism, are constructed. The computational cost of the simulations is reduced by using machine learning potentials. The results show a significant deviation between classical/quasi-classical centroid free energy profiles and the exact quantum free energy profile for proton transfers.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Editorial Material
Chemistry, Physical
Veronique Van Speybroeck, Guillaume Maurin
Summary: 700 scientists from 45 countries gathered in Dresden for the first time since the start of the COVID-19 pandemic to share their latest findings on metal-organic frameworks and open frameworks compounds.
Article
Chemistry, Multidisciplinary
Sander Borgmans, Sven M. J. Rogge, Juul S. De Vos, Pascal van der Voort, Veronique Van Speybroeck
Summary: Soft porous crystals with stimuli responsiveness are widely studied for various applications. However, the structural flexibility in 3D covalent organic frameworks (COFs) is not well understood. This study investigates the factors affecting the phase transformations of diamondoid COFs, including structural decoration, interpenetration, temperature, and guest adsorption. It provides a comprehensive understanding of the design principles for flexible diamondoid COFs.
COMMUNICATIONS CHEMISTRY
(2023)
Article
Chemistry, Physical
Joachim Vandewalle, Juul S. De Vos, Sven M. J. Rogge
Summary: New functional materials, including mixed matrix membranes and MOF monoliths, demonstrate superior performance in gas separation and storage applications compared to traditional materials. However, simulation techniques currently available are unable to fully capture the spatial complexity exhibited by most engineered materials. This study introduces the MicMec implementation of a micromechanical model as a systematic coarse-graining approach to access larger length scales and characterize the mechanical properties of these materials. The results show that the micromechanical simulations can achieve time steps 2 to 3 orders of magnitude larger than atomistic simulations, while accurately capturing the macroscopic mechanical properties of the spatially disordered material. MicMec implementation can serve as a complementary tool to existing atomistic and coarse-grained software, facilitating the computational design of new materials for pressing applications.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Multidisciplinary Sciences
Massimo Bocus, Ruben Goeminne, Aran Lamaire, Maarten Cools-Ceuppens, Toon Verstraelen, Veronique Van Speybroeck
Summary: Proton hopping is a crucial process in zeolite catalysis, but accurately determining its kinetics is challenging. In this study, a machine learning potential (MLP) was trained to accurately reproduce the potential energy surface of proton hopping in H-CHA zeolite at the Density Functional Theory (DFT) level. The MLP significantly speeds up computations and allows for accurate determination of reaction kinetics beyond standard transition state theory. Nuclear quantum effects (NQEs) were found to have a significant impact on proton hopping kinetics, and kinetic isotope effects can be computed without additional training using PIMD simulations with deuterium.
NATURE COMMUNICATIONS
(2023)
Editorial Material
Nanoscience & Nanotechnology
Choongseok Chang, Volker L. Deringer, Kalpana S. Katti, Veronique Van Speybroeck, Christopher M. Wolverton
Summary: Exascale computers, capable of performing 10(18) floating point operations per second, have started to become operational in 2022. The United States has launched Frontier as the first public exascale supercomputer, and Aurora is set to open soon. In China, OceanLight and Tianhe-3 are already operational, while Europe is getting ready to launch JUPITER in 2023. Supercomputers present unprecedented opportunities for modeling complex materials.
NATURE REVIEWS MATERIALS
(2023)
Article
Nanoscience & Nanotechnology
Alexander E. J. Hoffman, Joao Marreiros, Sven M. J. Rogge, Rob Ameloot, Veronique Van Speybroeck
Summary: Mixed-linker zeolitic imidazolate frameworks (ZIFs) are candidate materials for gas separation. The pore size of ZIFs can be regulated by changing the linker content, which affects diffusion and adsorption. The linker distribution in mixed-linker ZIF-8/ZIF-90 is characterized using computational Raman spectroscopy, revealing the impact of hydrogen bonding behavior on the distribution.
ACS APPLIED NANO MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Amrita Chatterjee, Jiamin Sun, Kuber Singh Rawat, Veronique Van Speybroeck, Pascal van der Voort
Summary: Two donor-acceptor type tetrathiafulvalene (TTF)-based covalent organic frameworks (COFs) were studied as electrodes for symmetric supercapacitors in different electrolytes. The charge storage mechanism of IL electrolyte based supercapacitors depends on the micro pore size and surface charge density of COFs, which can be altered by different electron acceptor building blocks. The combination of these factors enhances the charge storage in highly microporous COFs. DFT calculations support this finding.
Article
Materials Science, Multidisciplinary
Kirill Titov, Matthew R. Ryder, Aran Lamaire, Zhixin Zeng, Abhijeet K. Chaudhari, James Taylor, E. M. Mahdi, Sven M. J. Rogge, Sanghamitra Mukhopadhyay, Svemir Rudic, Veronique Van Speybroeck, Felix Fernandez-Alonso, Jin-Chong Tan
Summary: Using in situ high-resolution inelastic neutron scattering, the study investigated the dynamic changes of quantum tunneling rotors in ZIF-8 with gas adsorption. It was found that nitrogen adsorption decreases the energy of the tunneling peak, ultimately hindering it completely, while argon significantly increases the energy. Ab initio calculations revealed an exception to the reported adsorption sites hierarchy and anomalous adsorption behavior in ZIF-8.
PHYSICAL REVIEW MATERIALS
(2023)
Article
Materials Science, Multidisciplinary
Sven M. J. Rogge, Sander Borgmans, Veronique Van Speybroeck
Summary: This article introduces strain engineering as a general approach to rationalize and design materials by modifying their atomic level structure. The potential of strain engineering is demonstrated through two examples, showing how it can be used to design state-of-the-art materials for challenging applications.
Article
Chemistry, Physical
Pieter Cnudde, Michel Waroquier, Veronique Van Speybroeck
Summary: The influence of pore topology and acid strength on the adsorption of (iso)butene in Bronsted acid zeolites has been studied using calculations and simulations. The adsorbed intermediates - physisorbed alkene, chemisorbed carbenium ion, and alkoxide - were evaluated for different zeolite topologies and acid site strengths. The stabilization of the carbenium ion depends on zeolite confinement and acid site strength, while alkoxides are not found at high temperature. The adsorption energies and protonation barriers can be predicted using universal descriptors such as dispersion component and ammonia adsorption energy.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Inorganic & Nuclear
Karsten Heinz, Sven M. J. Rogge, Andreas Kalytta-Mewes, Dirk Volkmer, Hana Bunzen
Summary: In this study, we investigated the potential of MOFs for long-term gas storage under ambient conditions. By loading a specific MOF, ZIF-8, with sulphur hexafluoride, we achieved high SF6 loading into the pores of ZIF-8 and demonstrated kinetic trapping of the gas guest. We also discovered that the slow release of SF6 from ZIF-8 was due to the high activation energy for guest diffusion.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Juul S. De Vos, Sander Borgmans, Pascal Van Der Voort, Sven M. J. Rogge, Veronique Van Speybroeck
Summary: This article introduces a database called ReDD-COFFEE, which contains 268,687 covalent organic frameworks (COFs) with accompanying ab initio derived force fields that outperform generic ones. The database provides a large number of computer-ready structures with high diversity in terms of geometric properties, linker cores, and linkage types. Additionally, the textural properties of the database are analyzed and the most promising COFs for vehicular methane storage are identified. By making the database freely accessible, it is hoped that it can inspire others to further explore the potential of these intriguing functional materials.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Physical
B. P. Akhouri, R. Perween, J. R. Solana
Summary: Monte Carlo simulations are used to obtain the equation of state and internal energy of fluids with Mie n-m potentials, and its performance is tested against a third order perturbation theory. The theory is then applied to tune the potentials for real fluids and achieve accurate fit with experimental data.
MOLECULAR SIMULATION
(2024)
Article
Chemistry, Physical
Malaisamy Veerapandian, Nagarajan Hemavathy, Alagesan Karthika, Jayaraman Manikandan, Umashankar Vetrivel, Jeyaraman Jeyakanthan
Summary: This study investigates the conformational stability and flexibility of SpeB enzyme and its interactions with substrate. The research finds that neutral pH 7 and alkaline pH 11 are the optimal conditions for stable binding between SpeB and substrate.
MOLECULAR SIMULATION
(2024)
Article
Chemistry, Physical
Maipelo Nyepetsi, Olayinka A. Oyetunji, Foster Mbaiwa
Summary: Biodiesel, a potential alternative to fossil-based fuels, has limitations such as high viscosity, pour point, and cloud point. This study used ReaxFF molecular dynamics to investigate the decarboxylation of methyl palmitate using different catalysts. The presence of alpha-NiMoO4 and beta-NiMoO4 accelerated the reactions and resulted in higher quantities of stable products. Ni3Mo catalyst showed an initial rapid formation of products followed by a decrease. All reactions followed first-order kinetics, and the catalysts reduced the activation energies.
MOLECULAR SIMULATION
(2024)
