Atomistic insight in the flexibility and heat transport properties of the stimuli-responsive metal–organic framework MIL-53(Al) for water-adsorption applications using molecular simulations

Lamaire, Aran; Wieme, Jelle; Hoffman, Alexander E. J.; Speybroeck, Véronique Van

doi:10.1039/d0fd00025f

Cited by 21 publications

(27 citation statements)

References 113 publications

(142 reference statements)

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“…This result indicates that compared to their lp counterparts, the np structures possess a higher thermal resistance and more significant phonon scattering between atomic bonds, which would thus weaken the thermal transport properties. Very recently, Lamiare et al 39 demonstrated that the VDOS overlap between atomic bonds in the np phase of MIL-53(Al) is much larger than that of it lp counterpart, which is in contrary to the case of isoreticular DUT crystals discussed here. This difference observed between these two MOF materials might originate from their different mechanisms of phase transition.…”

Section: Resultscontrasting

confidence: 72%

“…To the best of our knowledge, there are only two studies regarding the effect of phase transition on the thermal transport in SPCs using MD simulations. For example, by using MD simulations, Sezginel et al 38 studied the effect of pore expansion on the thermal conductivity of idealized materials, while Lamaire et al 39 compared the thermal conductivity of anisotropical MIL-53(Al) within different phases. The thermal conductivity of these two MOF materials is found to be strongly dependent on the crystal orientation, since these materials have different porosity distributions along three crystal directions.…”

Section: Introductionmentioning

confidence: 99%

“…The thermal conductivity of these two MOF materials is found to be strongly dependent on the crystal orientation, since these materials have different porosity distributions along three crystal directions. It is worth mentioning that these initial studies 38,39 ignored the impact of volume concentration due to the phase transition, 13 which, however, may have a great impact on the thermal conductivity. 28,30 Moreover, these studies only focus on some specific anisotropic SPCs, e.g., MIL-53(Al), which can not reveal the broad picture of the nature and mechanism behind the phase-dependent thermal transport properties of SPCs.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Abnormal Effect of Phase Transition on Thermal Transport in Soft Porous Crystals

Ying

Zhong²

2021

Preprint

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Soft porous crystals (SPCs) can undergo large-amplitude phase transitions under external stimulus such as mechanical pressure, gas adsorption, and temperature while retaining their structural integrity. During the gas adsorption process, the generated latent heat is needed to be effectively removed. Thus, understanding the effect of phase transition on the thermal transport in SPCs becomes extremely important for their applications in storage and separation applications. In this paper, taking isorecticular DUT series as an example, the evolution of the thermal transport in SPCs during the phase transition from the large pore (lp) phase to the narrow pore (np) phase is comprehensively investigated by molecular dynamics (MD) simulations together with the Green-Kubo method. After the phase transition, an abnormal thermal transport property is found in the np phase of DUT materials. We find that although the transformed np phase of DUT-48 has a density much larger than its parent phase, the thermal conductivity of its np phase is smaller than its lp phase. This result is in contrast to the previous finding that SPCs with larger density possess a larger thermal conductivity. However, as for other DUT crystals including DUT-47, DUT-49, DUT-50, and DUT-151, the np phase is found to have a higher thermal conductivity than their lp phase counterpart, which is in accordance with the previous finding. This complicated effect of phase transition on thermal transport in SPCs can be explained by the porosity-dominated competition mechanism between the increased volumetric heat capacity and the aggravated phonon scattering during the phase transition process. Overall, the finding extracted from the present study can greatly expand current knowledge about the thermal conductivity of metal-organic frameworks that is previously found to grow usually with increasing porosity.

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Section: Resultscontrasting

confidence: 72%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Abnormal Effect of Phase Transition on Thermal Transport in Soft Porous Crystals

Ying

Zhong²

2021

Preprint

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“…The situation is further complicated by flexible MOFs, which undergo phase transitions that can change their pore sizes. A transition to more narrow pores like, for example, those found in MIL-53 has, indeed, lead to an increased thermal conductivity [46,47], while for systematically modified model systems it was shown that a change in the linker inclination angle reduces heat transport [48]. Interestingly, the strong impact of the pore size can lead to a situation where a disordered but denser phase of a MOF displays an increased thermal conductivity compared to its ordered counterpart [38,49].…”

Section: Introductionmentioning

confidence: 99%

Exploring the Impact of the Linker Length on Heat Transport in Metal–Organic Frameworks

et al. 2022

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Metal–organic frameworks (MOFs) are a highly versatile group of porous materials suitable for a broad range of applications, which often crucially depend on the MOFs’ heat transport properties. Nevertheless, detailed relationships between the chemical structure of MOFs and their thermal conductivities are still largely missing. To lay the foundations for developing such relationships, we performed non-equilibrium molecular dynamics simulations to analyze heat transport in a selected set of materials. In particular, we focus on the impact of organic linkers, the inorganic nodes and the interfaces between them. To obtain reliable data, great care was taken to generate and thoroughly benchmark system-specific force fields building on ab-initio-based reference data. To systematically separate the different factors arising from the complex structures of MOF, we also studied a series of suitably designed model systems. Notably, besides the expected trend that longer linkers lead to a reduction in thermal conductivity due to an increase in porosity, they also cause an increase in the interface resistance between the different building blocks of the MOFs. This is relevant insofar as the interface resistance dominates the total thermal resistance of the MOF. Employing suitably designed model systems, it can be shown that this dominance of the interface resistance is not the consequence of the specific, potentially weak, chemical interactions between nodes and linkers. Rather, it is inherent to the framework structures of the MOFs. These findings improve our understanding of heat transport in MOFs and will help in tailoring the thermal conductivities of MOFs for specific applications.

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“…In addition, the thermal conductivity of idealized MOF crystals is found to be strongly dependent on the tilt angle. Similarly based on MD simulations, Lamaire et al 40 investigated the effect of phase transition on the thermal transport in MIL-53(Al). They found that the thermal conductivity of np phase of MIL-53(Al) is significantly larger than that of its lp phase counterpart, which is attributed to a larger vibrational density of states (VDOS) overlap between chemically bonded atom pairs after phase transition.…”

Section: Introductionmentioning

confidence: 99%

Effect of Phase Transition on the Thermal Transport in Isoreticular DUT Materials

Ying

Jin

Zhong

2021

Preprint

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Soft porous crystals (SPCs) or flexible metal-organic frameworks have great potential applications in gas storage and separation, in which SPCs can undergo phase transition due to external stimuli. Thus, understanding the effect of phase transition on the thermal transport in SPCs becomes extremely crucial, because the latent heat generated in aforementioned applications is needed to be effectively removed. In this paper, taking the isorecticular DUT series as an example, the thermal transport property of SPCs during the phase transition from the large pore (lp) phase to the narrow pore (np) phase is comprehensively investigated by molecular dynamics simulations together with the Green-Kubo method. According to our calculations, all DUT structures exhibit an ultralow thermal conductivity smaller than 0.2 Wm-1K-1. In addition, we find that the effect of phase transition on the thermal transport property of different DUT materials considered here strongly depends on their porosity. As for DUT-48, its lp phase has a thermal conductivity larger than that of its np phase. However, in other DUT materials, i.e, DUT-47, DUT-49, DUT-50, and DUT-151 the thermal transport property of their lp phase is found to be weaker than that of their np phase. This complicated effect of phase transition on the thermal transport in SPCs can be explained by a porosity-dominated competition mechanism between the increased volumetric heat capacity and the aggravated phonon scattering during the phase transition process.

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Atomistic insight in the flexibility and heat transport properties of the stimuli-responsive metal–organic framework MIL-53(Al) for water-adsorption applications using molecular simulations

Abstract: To exploit the full potential of metal-organic frameworks as solid adsorbents in water-adsorption applications, many challenges remain to be solved. A more fundamental insight into the properties of the host...

Cited by 21 publications

References 113 publications

Abnormal Effect of Phase Transition on Thermal Transport in Soft Porous Crystals

Abnormal Effect of Phase Transition on Thermal Transport in Soft Porous Crystals

Exploring the Impact of the Linker Length on Heat Transport in Metal–Organic Frameworks

Effect of Phase Transition on the Thermal Transport in Isoreticular DUT Materials

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