Isotherms of individual pores by gas adsorption crystallography

Cho, Hae Sung; Yang, Jingjing; Gong, Xuan; Zhang, Yue-Biao; Momma, Koichi; Weckhuysen, Bert M.; Deng, Hexiang; Kang, Jeung Ku; Yaghi, Omar M.; Terasaki, Osamu

doi:10.1038/s41557-019-0257-2

Cited by 105 publications

(122 citation statements)

References 50 publications

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“…NPD has previously been used to investigate primary adsorption sites in MOFs via Rietveld refinement 41–44 , however the analysis of higher loadings in mesoporous networks at elevated temperatures such as 111 K, crucial for mechanistic understanding of NGA, remains unexplored. Cho et al recently analysed the pore filling of individual pores by combined gas adsorption and in situ X-ray diffraction 45 .…”

Section: Resultsmentioning

confidence: 99%

Towards general network architecture design criteria for negative gas adsorption transitions in ultraporous frameworks

et al. 2019

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Switchable metal-organic frameworks (MOFs) have been proposed for various energy-related storage and separation applications, but the mechanistic understanding of adsorption-induced switching transitions is still at an early stage. Here we report critical design criteria for negative gas adsorption (NGA), a counterintuitive feature of pressure amplifying materials, hitherto uniquely observed in a highly porous framework compound (DUT-49). These criteria are derived by analysing the physical effects of micromechanics, pore size, interpenetration, adsorption enthalpies, and the pore filling mechanism using advanced in situ X-ray and neutron diffraction, NMR spectroscopy, and calorimetric techniques parallelised to adsorption for a series of six isoreticular networks. Aided by computational modelling, we identify DUT-50 as a new pressure amplifying material featuring distinct NGA transitions upon methane and argon adsorption. In situ neutron diffraction analysis of the methane (CD 4 ) adsorption sites at 111 K supported by grand canonical Monte Carlo simulations reveals a sudden population of the largest mesopore to be the critical filling step initiating structural contraction and NGA. In contrast, interpenetration leads to framework stiffening and specific pore volume reduction, both factors effectively suppressing NGA transitions.

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Section: Resultsmentioning

confidence: 99%

Towards general network architecture design criteria for negative gas adsorption transitions in ultraporous frameworks

et al. 2019

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“…Type-IV(b) is observed for the adsorbent having cylindrical and conical mesopores with a smaller width, which are entirely reversible and closed at the tapered end. Type-IV(b) adsorption isotherms are observed for the adsorption of argon at 87 K and nitrogen at 77 K onto IRMOF-74-V-hex having pore width less than 4 nm [36]. In this study, the Ng et al, modified Langmuir, Mahle, modified BET, and Tóth models are fitted with the experimental data of both pairs and presented in Figure 10.…”

Section: Type-iv(b) Adsorption Isothermmentioning

confidence: 96%

A Statistical Approach to Determine Optimal Models for IUPAC-Classified Adsorption Isotherms

et al. 2019

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Adsorption heat transformation (AHT) systems can play a major role in protecting our environment by decreasing the usage of fossil fuels and utilizing natural and alternative working fluids. The adsorption isotherm is the most important feature in characterizing an AHT system. There are eight types of International Union of Pure and Applied Chemistry (IUPAC) classified adsorption isotherms for different “adsorbent-adsorbate” pairs with numerous empirical or semi-empirical mathematical models to fit them. Researchers face difficulties in choosing the best isotherm model to describe their experimental findings as there are several models for a single type of adsorption isotherm. This study presents the optimal models for all eight types of isotherms employing several useful statistical approaches such as average error; confidence interval (CI), information criterion (ICs), and proportion tests using bootstrap sampling. Isotherm data of 13 working pairs (which include all eight types of IUPAC isotherms) for AHT applications are extracted from literature and fitted with appropriate models using two error functions. It was found that modified Brunauer–Emmet–Teller (BET) for Type-I(a) and Type-II; Tóth for Type-I(b); GAB for Type-III; Ng et al. model for Type-IV(a) and Type-IV(b); Sun and Chakraborty model for Type-V; and Yahia et al. model for Type-VI are the most appropriate as they ensure less information loss compared to other models. Moreover; the findings are affirmed using selection probability; overall; and pairwise proportion tests. The present findings are important in the rigorous analysis of isotherm data.

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“…[ 1,9 ] The well‐defined structures also allow crystallography and computational studies of host–guest interaction to gain fundamental understanding for rational material design. [ 10 ]…”

Section: Figurementioning

confidence: 99%

“…[ 9a,18 ] Besides, the structural properties of MOFs such as pore size, pore geometry, and aperture size significantly affect the gas adsorption behavior at high pressure. [ 10a ] Full consideration of structural properties can only be realized with extensive computational screening of a great number of MOFs. [ 10c,15b ] Our previous successful discovery of the correlation between pore volume and methane adsorption motivates us to explore such empirical equation for hydrogen adsorption with consideration of pore occupancy and pore geometry.…”

Section: Figurementioning

confidence: 99%

“…In practical application, the ideal material should also exhibit high volumetric adsorption capacity which requires high volumetric surface area for MOFs. [ 10c ] As shown in Table S6 in the Supporting Information, MOFs with ultrahigh pore volume such as NU‐1301 [ 24 ] and DUT‐60 (DUT: Dresden University of Technology) [ 25 ] exhibits only small volumetric surface area. Considering the prediction results in Figure 2b, MOFs with moderately high pore volume of ≈3.3 cm 3 g −1 and high volumetric surface area would likely possess simultaneously high gravimetric and volumetric H 2 storage capacity at 100 bar and 77 K.…”

Section: Figurementioning

confidence: 99%

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Optimization of the Pore Structures of MOFs for Record High Hydrogen Volumetric Working Capacity

et al. 2020

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Metal–organic frameworks (MOFs) are promising materials for onboard hydrogen storage thanks to the tunable pore size, pore volume, and pore geometry. In consideration of pore structures, the correlation between the pore volume and hydrogen storage capacity is examined and two empirical equations are rationalized to predict the hydrogen storage capacity of MOFs with different pore geometries. The total hydrogen adsorption under 100 bar and 77 K is predicted as ntot= 0.085× Vp − 0.013× Vp2 for cage‐type MOFs and ntot= 0.076× Vp − 0.011× Vp2 for channel‐type MOFs, where Vp is the pore volume of corresponding MOFs. The predictions by these empirical equations are validated by several MOFs with an average deviation of 5.4%. Compared with a previous equation for activated carbon materials, the empirical equations demonstrate superior accuracy especially for MOFs with high surface area (i.e., SBET over ≈3000 m2 g−1). Guided by these empirical equations, a highly porous Zr‐MOF NPF‐200 (NPF: Nebraska Porous Framework) is examined to possess outstanding hydrogen total adsorption capacity (65.7 mmol g−1) at 77 K and record high volumetric working capacity of 37.2 g L−1 between 100 and 5 bar at 77 K.

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Isotherms of individual pores by gas adsorption crystallography

Cited by 105 publications

References 50 publications

Towards general network architecture design criteria for negative gas adsorption transitions in ultraporous frameworks

Towards general network architecture design criteria for negative gas adsorption transitions in ultraporous frameworks

A Statistical Approach to Determine Optimal Models for IUPAC-Classified Adsorption Isotherms

Optimization of the Pore Structures of MOFs for Record High Hydrogen Volumetric Working Capacity

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