Design, Parameterization, and Implementation of Atomic Force Fields for Adsorption in Nanoporous Materials

Dubbeldam, David; Walton, Krista S.; Vlugt, Thijs J. H.; Calero, Sofı́a

doi:10.1002/adts.201900135

Cited by 59 publications

(69 citation statements)

References 531 publications

(823 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Figure 7 shows that self-diffusion coefficients calculated with the modified one-site model correlate the best with experimental QENS measurements. This modified force field performed poorly in predicting H 2 adsorption isotherms, cautioning the reader that a force field that works well for diffusion does not necessarily guarantee accurate adsorption predictions (and vice versa) [184]. In contrast to the monotonically decreasing dihydrogen diffusivities from Salles et al, [182,183] dihydrogen diffusion in a suite of IRMOFs simulated by Yang and Zhong showed that hydrogen diffusivity increased slightly with loading, but then sharply decreased [170].…”

Section: Single Component Diffusion In Rigid Metal-organic Frameworkmentioning

confidence: 86%

Connecting theory and simulation with experiment for the study of diffusion in nanoporous solids

et al. 2021

View full text Add to dashboard Cite

Nanoporous solids are ubiquitous in chemical, energy, and environmental processes, where controlled transport of molecules through the pores plays a crucial role. They are used as sorbents, chromatographic or membrane materials for separations, and as catalysts and catalyst supports. Defined as materials where confinement effects lead to substantial deviations from bulk diffusion, nanoporous materials include crystalline microporous zeotypes and metal–organic frameworks (MOFs), and a number of semi-crystalline and amorphous mesoporous solids, as well as hierarchically structured materials, containing both nanopores and wider meso- or macropores to facilitate transport over macroscopic distances. The ranges of pore sizes, shapes, and topologies spanned by these materials represent a considerable challenge for predicting molecular diffusivities, but fundamental understanding also provides an opportunity to guide the design of new nanoporous materials to increase the performance of transport limited processes. Remarkable progress in synthesis increasingly allows these designs to be put into practice. Molecular simulation techniques have been used in conjunction with experimental measurements to examine in detail the fundamental diffusion processes within nanoporous solids, to provide insight into the free energy landscape navigated by adsorbates, and to better understand nano-confinement effects. Pore network models, discrete particle models and synthesis-mimicking atomistic models allow to tackle diffusion in mesoporous and hierarchically structured porous materials, where multiscale approaches benefit from ever cheaper parallel computing and higher resolution imaging. Here, we discuss synergistic combinations of simulation and experiment to showcase theoretical progress and computational techniques that have been successful in predicting guest diffusion and providing insights. We also outline where new fundamental developments and experimental techniques are needed to enable more accurate predictions for complex systems.

show abstract

Section: Single Component Diffusion In Rigid Metal-organic Frameworkmentioning

confidence: 86%

Connecting theory and simulation with experiment for the study of diffusion in nanoporous solids

et al. 2021

View full text Add to dashboard Cite

show abstract

“…f) The same six interacting malonate groups illustrated in (e) accompanied by their corresponding C60 buckyballs. g) An iRASPA view of the packing and the h) surface occupancy calculated with OLEX2 highlighting the potential cavities surrounding the [60]fullerene in red.…”

Section: Figurementioning

confidence: 99%

A Three‐Dimensional Dynamic Supramolecular “Sticky Fingers” Organic Framework

et al. 2019

View full text Add to dashboard Cite

Engineering high-recognition host-guest materials is aburgeoning area in basic and applied research. The challenge of exploring novel porous materials with advanced functionalities prompted us to develop dynamic crystalline structures promoted by soft interactions.T he first example of ap ure molecular dynamic crystalline framework is demonstrated, which is held together by means of weak "stickyf ingers" van der Waals interactions.T he presented organic-fullerene-based material exhibits an on-porous dynamic crystalline structure capable of undergoing single-crystal-to-single-crystal reactions.E xposure to hydrazine vapors induces structural and chemical changes that manifest as toposelective hydrogenation of alternating rings on the surface of the [60]fullerene.Control experiments confirm that the same reaction does not occur when performed in solution. Easy-to-detect changes in the macroscopic properties of the sample suggest utility as molecular sensors or energy-storage materials.One of the important challenges in chemical science nowadays is the search for greener processes for ac leaner world. [1] In chemistry,t his usually translates into highly selective reactions with high rates and efficiencies. [2] Recently, novel synthetic strategies were proposed that diverge from classical approaches.While the latter are usually based on the temperature,p ressure,a nd exact formulation control, reac-tivity control of the former explores novel environmental strategies (for example,t he successful surface chemistry approach, [3] chemical topology, [4] or chemical reactions performed in confined spaces [5] in which the reactivity differs in many aspects from those conducted in bulk solution). In that sense,p orous materials connected by intermolecular bonds (such as,m etal-organic frameworks [6] (MOFs), covalent organic frameworks [7] (COFs), or porous molecular materials [8] that are built from discrete molecules [9] such as porous organic cages) [10] have provided notable results.The discovery and development of these materials has spurred an interest in confined chemical reactions to determine how spatial confinement can influence the yields and reactivity pathways of reactions. [11] MOFs offer improved flexibility compared to rigid zeolites and less processable COFs. [12] This flexibility could generate novel dynamic adsorption properties under realistic conditions-similar to the liquid-protein reactions that occur for specific interactions between an enzymatic host and as ubstrate.P ure organic systems usually demonstrate excellent properties,s uch as high thermal stabilities,t unable structural properties,a nd biocompatibility;h owever,t hey also present drawbacks,s uch as rigidity and limited processability.T herefore,t he formation of dynamic structures (porous or non-porous acting as porous) by means of supramolecular interactions between molecules might be an interesting alternative.H owever,t he crystallization of stable organic structures possessing porosity or showing the ability to incorporate molecules by...

show abstract

“…Some images were created using the iRASPA software. [58] This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government.…”

mentioning

confidence: 99%

Negative Thermal Expansion Design Strategies in a Diverse Series of Metal–Organic Frameworks

Burtch

Baxter

Heinen

et al. 2019

Adv Funct Materials

Self Cite

View full text Add to dashboard Cite

Negative thermal expansion materials are of interest for an array of composite material applications whereby they can compensate for the behavior of a positive thermal expansion matrix. In this work, various design strategies for systematically tuning the coefficient of thermal expansion in a diverse series of metal-organic frameworks (MOFs) are demonstrated. By independently varying the metal, ligand, topology, and guest environment of representative MOFs, a range of negative and positive thermal expansion behaviors are experimentally achieved. Insights into the origin of these behaviors are obtained through an analysis of synchrotron-radiation total scattering and diffraction experiments, as well as complementary molecular simulations. The implications of these findings on the prospects for MOFs as an emergent negative thermal expansion material class are also discussed.

show abstract

Design, Parameterization, and Implementation of Atomic Force Fields for Adsorption in Nanoporous Materials

Cited by 59 publications

References 531 publications

Connecting theory and simulation with experiment for the study of diffusion in nanoporous solids

Connecting theory and simulation with experiment for the study of diffusion in nanoporous solids

A Three‐Dimensional Dynamic Supramolecular “Sticky Fingers” Organic Framework

Negative Thermal Expansion Design Strategies in a Diverse Series of Metal–Organic Frameworks

Contact Info

Product

Resources

About