DOI: 10.1002/ente.
201700608
High Volumetric Hydrogen Storage Capacity using Interpenetrated Metal–
Organic Frameworks
Rafael Balderas-Xicoht8ncatl,[a] Phillip Schmieder,[b] Dmytro Denysenko,[b] Dirk Volkmer,[b] and
Michael Hirscher*[a]
Metal–organic frameworks with extremely large specific sur-
face areas can reach very high gravimetric hydrogen storage
capacities. However, these ultra-porous materials possess
typically a very low density and, therefore, a poor volumetric
hydrogen storage capacity. Here we study experimentally the
influence of interpenetration on the volumetric and gravi-
metric hydrogen storage capacity by comparing two metal–
organic frameworks of the MFU-4 family, non-interpenetrat-
ed MFU-4l and CFA-7 with an interpenetrated structure. At
77 K the absolute volumetric hydrogen uptake of CFA-7 is
more than twice that of MFU-4l.
Hydrogen as an environmentally friendly energy carrier has
the highest gravimetric calorific value of all possible fuels
(Hu = 120 MJ kg@1 = 33.33 kWh kg@1), releasing water as its
final combustion product. Despite all its advantages, its low
volumetric density under ambient conditions (0.0899 kg m@3)
strongly limits its commercial use. Physisorption of hydrogen
in a dense adsorbed layer on materials of high surface area
can be one solution for efficient and safe storage systems.[1]
The development of novel porous materials possessing ex-
tremely high surface areas and tunable pore sizes, such as
metal–organic frameworks (MOFs), has driven this field over
the past 15 years.[2] However, most of the current research is
focused on optimizing the hydrogen storage performance of
MOFs by increasing the specific surface area, which ulti-
mately enlarges the gravimetric capacity at the expense of
the volumetric capacity. Interpenetrated framework struc-
tures, which reduce the free volume in the large pores by the
wall material’s ability to adsorb hydrogen, have been pro-
[a] R. Balderas-Xicoht8ncatl, Dr. M. Hirscher
Max Planck Institute for Intelligent Systems
Heisenbergstrasse 3, 70569 Stuttgart (Germany)
E-mail: hirscher@is.mpg.de
[b] Dr. P. Schmieder, Dr. D. Denysenko, Prof. Dr. D. Volkmer
Institute of Physics
Augsburg University
Universitaetsstrasse 1, 86159 Augsburg (Germany)
Supporting information and the ORCID identification number(s) for the
author(s) of this article can be found under https://doi.org/10.1002/
ente.201700608.
T 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
This is an open access article under the terms of the Creative Commons
Attribution Non-Commercial NoDerivs License, which permits use and
distribution in any medium, provided the original work is properly cited,
the use is non-commercial, and no modifications or adaptations are
made.
This publication is part of a Special Issue on "Hydrogen Storage
Materials, Carriers, and Processes". To view the complete issue, visit:
http://dx.doi.org/10.1002/ente.v6.3.
Energy Technol. 2018, 6, 510 – 512 T 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
posed to improve the volumetric capacity over a decade
ago.[3, 4] Here we compare directly the gravimetric and volu-
metric hydrogen storage capacity using one non-interpene-
trated and one interpenetrated metal–organic framework.
The gravimetric hydrogen storage capacity of any adsorb-
ent is directly related to the specific surface area (SSA) and
there is a linear correlation between the gravimetric hydro-
gen uptake and the Brunauer–Emmett–Teller (BET) area
(ChahineQs rule).[2, 5] However, the volumetric capacity of a
material, which is the hydrogen capacity per unit volume, is
a parameter that is often omitted in the characterization of
porous materials for hydrogen storage. Enlarging the gravi-
metric hydrogen capacity by increasing the specific surface
area leads typically to mesoporous materials possessing
lower densities. The high-density phase of adsorbed hydro-
gen is located only at the surface of the cavity and the rest of
the large cavity contains hydrogen gas of a much lower den-
sity. In interpenetrated frameworks, part of the cavity
volume is filled by the interwoven second framework offer-
ing an additional surface area for adsorption of gas. Inter-
growth of two or more frameworks is often observed for
long linkers, leading to structures with reduced specific sur-
face area and smaller pore diameters. Recently, CFA-7 has
been synthesized as the first example of an interpenetrated
network of the MFU-4 family.[6] Measuring the hydrogen
uptake for non-interpenetrated MFU-4l and interpenetrated
CFA-7 will directly reveal the impact of interpenetration
on the gravimetric and volumetric storage capacities
(Scheme 1).
MOFs of the MFU-4 family contain Kuratowski-type pen-
tanuclear secondary building units (SBUs). MFU-4l is a non-
interpenetrated framework possessing a cubic structure with
alternating small and large pores of diameters 11.97 c and
Scheme 1. MFU-4l structural representation (a). Interpenetrated structure of
CFA-7 (b).
510
18.56 c (for synthesis and characterization see [7–9]). For
CFA-7, an interpenetrated framework of the MFU-4 family,
the synthesis procedure and a detailed structural characteri-
zation have been recently published yielding a porous struc-
ture with a limiting pore diameter of 6.83 c and a maximum
pore diameter of 11.71 c.[6] Hydrogen adsorption isotherms
have been measured using an automated SievertQs type appa-
ratus for the temperatures 77, 87, 97, 107, and 117 K up to a
pressure of 20 bar. Figure 1 shows the gravimetric hydrogen
isotherms at 77 K for MFU-4l and CFA-7. The uptake at
20 bar for MFU-4l is twice that of CFA-7 in accordance with
ChahineQs rule, and the specific surface areas are
2987 m2 g@1,[7] and 1718 m2 g@1,[6] respectively. Using single
crystal densities, obtained by XRD, of 0.5592 g mL@1,[7] and
1.570 g mL@1,[6] for MFU-4l and CFA-7, respectively, the
gravimetric uptake can be directly converted to the volumet-
ric hydrogen uptake (Figure 2). In contrast to the gravimetric
storage capacity behavior, CFA-7 (which possesses the lower
specific surface area but higher single crystal density) shows
over twice the volumetric storage capacity of MFU-4l.
Similar to our results, Kim et al[10] studied the hydrogen
uptake in the prototypical MOF-5 interpenetrated frame-
Figure 1. Absolute gravimetric hydrogen isotherms of MFU-4l and CFA-7 at
77 K.
Figure 2. Absolute volumetric hydrogen isotherms of MFU-4l and CFA-7 at
77 K.
Energy Technol. 2018, 6, 510 – 512 T 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
work and compared it to the non-interpenetrated structure,
observing an increase in volumetric storage capacity by inter-
penetration. However, these authors proposed the higher
heat of adsorption in the interpenetrated framework as the
origin for the improved volumetric capacity. For MFU-4l and
CFA-7 the average heats of adsorption are determined to be
3.92 and 5.2 kJ mol@1, respectively (Figure S4, Supporting In-
formation). The higher value for the interpenetrated frame-
work results from the smaller pore size, as the curvature
(and therefore the interaction with the hydrogen molecule)
is higher for smaller pore diameters.[11, 12] However, the very
high volumetric hydrogen storage capacity of CFA-7 can be
solely attributed to the extremely high surface-to-volume
ratio of this interpenetrated material. The volumetric surface
area (i.e., surface per unit volume) can be obtained by multi-
plying the specific surface area by the single crystal density,
thereby resulting in 1670 and 2697 m2 mL@1 for MFU-4l and
CFA-7, respectively. The volumetric surface area available
for the physisorption of gases is mainly governing the volu-
metric storage capacity of porous physisorption materials.[13]
In summary, the present results illustrate clearly that the
volumetric hydrogen storage capacity in porous materials
can be drastically improved by using interpenetrated metal–
organic frameworks.
Experimental Section
Adsorption isotherms
An automated Sievert type apparatus (Setaram-HyEnergy
PCTPro-2000) was used with a micro-doser (MD) from HyEner-
gy designed to measure the storage properties accurately with
only small amount of sample ( & 100 mg). The PCTPro-2000 with
a micro-doser is capable of performing pressure—composition–
temperature (PCT) measurements with the hydrogen gas at a
maximum pressure of 20 bar. A general illustration of this volu-
metric apparatus (PCTPro-2000) with the main components is
shown in the Supporting Information (Figure S1).
Acknowledgements
The measurement of MFU-4l isotherms by Barbara Streppel
is gratefully acknowledged.
Conflict of interest
The authors declare no conflict of interest.
Keywords: gravimetric density · hydrogen storage · metal–
organic frameworks · physisorption · volumetric density
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Manuscript received: August 25, 2017
Revised manuscript received: October 13, 2017
Accepted manuscript online: October 16, 2017
Version of record online: December 14, 2017
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