Influence of Missing Linker Defects on the Thermal Conductivity of Metal–Organic Framework HKUST-1

Islamov, Meiirbek; Babaei, Hasan; Wilmer, Christopher E.

doi:10.1021/acsami.0c16127

Cited by 31 publications

(32 citation statements)

References 54 publications

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“…Therefore, in recent years, several studies have been performed to advance our understanding of heat transport in MOFs. They revealed that MOFs often display an unusually small negative or even positive temperature dependence of the thermal conductivity [20,21,[30][31][32] and they showed that defects such as missing linkers severely impede heat transport even at low concentrations [33]. Conversely, the interpenetration of frameworks results in materials whose thermal conductivities are essentially the sums of those of the sub-systems [34].…”

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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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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“…Based on this consideration, the organic ligands were selectively removed through a post-synthesis treatment (PST) of 2 by controlling the acid treatment time to obtain the missing-linker compound, denoted as 2-PST-V (V = 20, 40, 60, 120). [38][39][40][41][42] To illustrate the chemical composition and valences of the acid-treated samples, X-ray photoelectron spectroscopy (XPS) measurement was carried out (Figure S8). As shown in Figure 4a, the XPS spectra prove that two different N species belong to the CÀ N ( � 398.5 eV) and CoÀ N ( � 399.1 eV) groups are presented.…”

Section: Methodsmentioning

confidence: 99%

Selectively Regulating Lewis Acid–Base Sites in Metal–Organic Frameworks for Achieving Turn‐On/Off of the Catalytic Activity in Different CO₂Reactions

et al. 2022

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Regulating Lewis acid-base sites in catalysts to investigate their influence in the chemical fixation of CO 2 is significant but challenging. A metal-organic framework (MOF) with open metal Co sites, {(NH 2 Me 2 )[Co 3 (μ 3 -OH)(BTB) 2 (H 2 O)]•9 H 2 O•5 DMF} n (1), was obtained and the results of the catalytic investigation show that 1 can catalyze cycloaddition of CO 2 and aziridines to give 99 % yield. The efficiency of the cyclization of CO 2 with propargyl amines is only 32 %. To improve the catalytic ability of 1, ligand XN with Lewis base sites was introduced into 1 and coordinated with the open Co sites, resulting in a decrease of the Lewis acid sites and an increase in the Lewis base sites in a related MOF 2 ({(NH 2 Me 2 )[Co 3Selective regulation of the type of active centers causes the yield of oxazolidinones to be enhanced by about 2.4 times, suggesting that this strategy can turn on/off the catalytic activity for different reactions. The catalytic results from 2 treated with acid solution support this conclusion. This work illuminates a MOF-construction strategy that produces efficient catalysts for CO 2 conversion.

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“…The low thermal conductivity observed in the present DUTs is close to the value (0.138 -0.174 Wm −1 K −1 ) of their ZIF counterparts, 27,28 but is much smaller than the value of some other SPCs such as MOF-5 (0.31 Wm −1 K −1 ), 24,25 and HKUST-1 (1.65 Wm −1 K −1 ). 33,34 Moreover, it is found that the thermal conductivity of DUT crystals generally decreases with increasing ligand length. For example, when the ligand length increases from one unit of phenylene in DUT-48 to four units of phenylene in DUT-151, the thermal conductivity is found to decline from 0.180 Wm −1 K −1 to 0.071 Wm −1 K −1 .…”

Section: Volumetric Heat Capacity and Vibrational Analysismentioning

confidence: 99%

“…However, compared with the gas adsorption property, the study of thermal transport in SPCs is still in its very early stage. To data, only the thermal conductivity of some conventional SPCs such as MOF-5, 23-26 ZIF-8, [27][28][29][30][31][32] and HKUST-1 21, 33,34 has been investigated in detail by experimental or computational approaches, while the thermal transport properties of the aforementioned DUT series still remain unknown. In addition, the existing studies mainly focus on the influence of gas and water adsorption, 29,34 framework architecture, 24,28,[35][36][37][38] defects, 33 and physical environment including pressure 18 and temperature 20 on the thermal conductivity of SPCs, little attention has been paid to the evolution of the thermal transport properties of SPCs during their dynamic process, i.e., the 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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Influence of Missing Linker Defects on the Thermal Conductivity of Metal–Organic Framework HKUST-1

Cited by 31 publications

References 54 publications

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

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

Selectively Regulating Lewis Acid–Base Sites in Metal–Organic Frameworks for Achieving Turn‐On/Off of the Catalytic Activity in Different CO₂Reactions

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

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Influence of Missing Linker Defects on the Thermal Conductivity of Metal–Organic Framework HKUST-1

Cited by 31 publications

References 54 publications

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

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

Selectively Regulating Lewis Acid–Base Sites in Metal–Organic Frameworks for Achieving Turn‐On/Off of the Catalytic Activity in Different CO2Reactions

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

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Selectively Regulating Lewis Acid–Base Sites in Metal–Organic Frameworks for Achieving Turn‐On/Off of the Catalytic Activity in Different CO₂Reactions