Feature
https://doi.org/10.1038/s41563-023-01763-2
Better standards are needed for
membrane materials
Tae Hoon Lee and Zachary P. Smith argue that some of the most exciting materials that could be
used for gas separations are metastable or crystalline, with properties that are altered by sample
preparation and testing, but there are no widely accepted standards.
F
or well over half a century, mem-
branes have been heralded as the dis-
ruptive technology that can displace
the giants of chemical engineering
unit operations: distillation, absorp-
tion, adsorption and liquid–liquid extraction.
Unfortunately, commercial membrane materi-
als still lack the performance needed for this
future industry, which has led to a prolifera-
tion of materials discovery research. The spe-
cific materials that will win out are still unclear,
but we are beginning to see some trends.
For gas-separation membranes, the way
to benchmark materials performance over
the past 30 years has been to use the Robeson
upper bounds1,2, an approach that is equally
loved and hated. Although a bit of a misno-
mer, given that the upper bounds have actu-
ally been surpassed time and time again
owing to their empirical nature, these plots
do provide some guidance. They tell us how
materials operate at around 25–35 °C and with
pressure differentials of around 1–10 atmos-
pheres. This type of benchmarking is the
simplest approach to determining whether a
material is potentially worth further investiga-
tion. However, there is no information about
how materials perform over a range of tem-
peratures, pressures and compositions. The
Robeson upper bound tells us nothing about
the thermodynamic and transport landscape
of a separation.
Put another way, each data point on an
upper bound is like a signpost in a strange
land. It provides some indication about
the direction in which we should go, but we
need to understand the topography better.
Further complicating matters, some of the
best-performing materials today are meta-
stable glassy polymers that physically age
over time, so, to stick with our metaphor,
the newest and most exciting signposts are
placed on a surface that is slowly flowing away
under our feet. There are related issues for
nature materials
Check for updates
a b
6
2015
2008
5
O2/N2 ideal selectivity
1991
4
3 Published year
2005
2023
2
2
10 103
O2 permeability (barrer)
Fig. 1 | Structure and properties of PIM-1 film. a, Chemical structure of PIM-1 and photograph of PIM-1 dense
film. b, Reported data on PIM-1 films for O2/N2 separation plotted with 1991 (ref. 1), 2008 (ref. 2) and 2015
(ref. 7) upper bounds for polymeric membranes8. Red triangles represent the as-cast films and blue circles
represent the films that were measured after certain post-treatment steps like methanol soaking. The inset
gradation bars depict the published year. Note: 1 barrer = 10−10 cm3 (STP) cm cm−2 s−1 (cmHg)−1.
metal–organic frameworks (MOFs), which PIM-1. Its O2 permeabilities (the rate of gas flux
have hard-to-control defects. As a research normalized by feed pressure and film thick-
community, we need to map out the entire ness) and O2/N2 ideal selectivities (the ratio
ensemble of properties for our system — how of O2 and N2 permeabilities evaluated using
does performance change with temperature, pure component tests) can vary by 1,700% and
pressure and gas composition? And of equal 120%, respectively.
importance, we need to carefully consider As another example, within the MOF com-
the physical state of the membrane material, munity, ZIF-8 has been widely viewed as the
especially when this physical state is a slowly best material for propylene/propane (C3H6/
flowing glass. C3H8) separation. However, when we collect
As a starting point, we should consider PIM-1 various data points on an upper bound (Fig. 2),
as the archetypal polymer of intrinsic micr- it becomes clear that the results are about as
oporosity (PIM). PIM-1 is a metastable glassy predictable as winning the lottery. Although
ladder polymer, which means that the specific Fig. 2 only shows permeance (calculated as
volume and entropy of the solid-state material permeability divided by thickness, because
change over time. Interestingly, the way the it is very challenging to prepare freestand-
polymer is cast, the way it is post-treated (for ing ZIF-8 films in which the permeability can
example, soaking in methanol), the way it is be measured directly), its range spans three
stored and even the thickness of the polymer orders of magnitude and the selectivity, which
all influence its upper-bound performance. is independent of thickness, spans nearly two
Figure 1 presents an upper-bound plot for orders of magnitude. Besides, the collected
Volume 23 | January 2024 | 11–12 | 11
Feature

a b

102

3.4 Å

C3H6/C3H8 selectivity
Zn
N
C 101

Published year
2012

ZIF-8 layer
2023

Porous support 100

100 101 102 103
C3H6 permeance (GPU)

Fig. 2 | Structure and properties of ZIF-8 membrane. a, Schematic illustration constant-pressure variable-volume and constant-volume variable-pressure
of ZIF-8 membrane on a porous support. b, Reported data on supported methods, respectively. The inset gradation bars depict the published year.
ZIF-8 membranes for C3H6/C3H8 separation9. Red triangles, blue circles and Note: 1 GPU = 10−6 cm3 (STP) cm−2 s−1 (cmHg)−1. Crystalline structure in a adapted
green diamonds represent the films measured using the Wicke–Kallenbach, with permission from ref. 10, American Chemical Society.

ZIF-8 data do not converge on a singular point
over time, similar to what we see for PIM-1.
Further complicating this analysis, there are
no American Society for Testing and Materials
(ASTM) standards for typical gas-permeation
testing, and it appears that a surprising degree
of reported performance data depends on
the method used to determine permeability.
There are even some papers that report
non-physical behaviour for certain characteri-
zation techniques. For example, the Wicke–
Kallenbach method measures gas flux driven
by the partial pressure difference in the mem-
brane cell, and the mixed-gas selectivity can be
overestimated because of the counterflow of
the sweep gas on the permeating side.
These concerns bring us to perhaps the
greatest need in membrane science today. As
the 2019 National Academies report A Research
Agenda for Transforming Separation Science
clearly noted, an urgent need for the com-
munity is “establishing standards to enhance
reproducibility”3. These standards come in
three forms: materials standards, synthe-
sis/processing standards and testing stand-
ards. Within gas separations, there are a few
examples of understanding uncertainty in
permeation measurements for well-known
commercial polymers like polysulfone4, and
there are studies on understanding the repro-
ducibility of permeation through MOFs with
systematically controlled defects5. However,
similar studies with modern microporous
polymers (such as PIM-1) have not been per-
formed to develop standard protocols for syn-
thesis, casting and testing. There are standard
mixtures that have been proposed for testing6,
but multi-laboratory and round-robin studies
are missing, precluding uncertainty analysis.
Similar studies are also lacking for under­lying
separation phenomena like diffusivity and sorp-
tion — where diffusivity depicts the mobi­lity of
gas molecules and sorption reflects the parti-
tioning of gas molecules in the membrane mate-
rials. Given the extraordinary variation in the
properties of MOF materials caused by differ-
ences in synthesis, there is an even greater need
to develop control samples within this field, and
a great unknown is whether various measure-
ment methods, like the Wicke–Kallenbach
method, can be used to cross-compare data
with other measurement techniques.
This Feature is a call to action. For researchers
publishing individual studies, there is a need
to synthesize multiple batches of material
and to collect multiple data points for per-
meation and selectivity. Doing so enables
an understanding of reproducibility within
one’s own laboratory. However, a far greater
need is multi-laboratory studies and protocol
development to understand uncertainty and
reproducibility across laboratories, especially
for metastable materials.
Beyond gas separations, similar mecha-
nisms of transport apply for membranes
being used for water purification and critical
element recovery, and in non-aqueous separa-
tions, such as solvent separations, crude oil
fractionation and flow battery membranes.
These ideas certainly extend far beyond the
primary focus of this Feature on gas perme-
ability. To reach our larger goal of displacing
legacy unit operations, we must better under-
stand the properties of the gas-separation
membranes we have.
Tae Hoon Lee & Zachary P. Smith
Department of Chemical Engineering,
Massachusetts Institute of Technology,
Cambridge, MA, USA.
e-mail: zpsmith@mit.edu
Published online: 3 January 2024
References
1. Robeson, L. M. J. Membr. Sci. 62, 165–185 (1991).
2. Robeson, L. M. J. Membr. Sci. 320, 390–400 (2008).
3. A Research Agenda for Transforming Separation Science
(The National Academies Press, 2019); https://go.nature.
com/48aKKqK
4. Rodriguez, K. M. et al. J. Membr. Sci. 659, 1207846 (2022).
5. Teesdale, J. J., Lee, M., Lu, R. & Smith, Z. P. J. Am. Chem.
Soc. 145, 830–840 (2023).
6. Sholl, D. S. & Lively, R. P. JACS Au 2, 322–327 (2022).
7. Swaidan, R., Ghanem, B. & Pinnau, I. ACS Macro Lett. 4,
947–951 (2015).
8. Lee, T. H. & Smith, Z. P. figshare https://doi.org/10.6084/
m9.figshare.24498583 (2023).
9. Lee, T. H. & Smith, Z. P. figshare https://doi.org/10.6084/
m9.figshare.24498607 (2023).
10. Qian, Q. et al. Chem. Rev. 120, 8161–8266 (2020).
Competing interests
The authors declare no competing interests.

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