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org/accounts Article

Process-Oriented Smart Adsorbents: Tailoring the Properties

Dynamically as Demanded by Adsorption/Desorption
Yao Jiang, Peng Tan, Xiao-Qin Liu, and Lin-Bing Sun*

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CONSPECTUS: Adsorptive separation plays a critical role in chemical, food, pharmaceutical,

and environmental industries, as well as in many other industrial areas. Adsorbents are most
important for adsorptive separation and undergo adsorption and desorption processes to
accomplish the specific tasks of separation. In the process of adsorption, adsorbates diffuse into
the pore spaces of adsorbents through pore openings, adsorb on active sites via physical or
chemical interactions, and subsequently are regenerated by temperature or pressure swings
during desorption. In the process of adsorption and desorption, however, the requirements for
pore structures and surface properties of adsorbents are different. In general, adsorbents with
small pore openings can realize selective adsorption and do not favor desorption; on the other
hand, adsorbents with large pore openings are efficient in desorption but at the expense of
adsorption selectivity. Remarkably, active sites possessing strong interactions with adsorbates
contribute to high selectivity for adsorption, while desorption becomes difficult. The trade-off
between adsorption and desorption presents an enormous challenge to develop high-efficiency
adsorbents. Restricted by their fixed structures and surface properties, conventional adsorbents are unable to meet the demands of
adsorption and desorption processes simultaneously.
To confront the obstacles, the development of advanced adsorbents to meet the demand of adsorptive separation are urgent. A key
strategy to address such issues lies in dynamically adjusting the pore structures or the surface properties of adsorbents with
controllability according to the demands of adsorption/desorption. For instance, pursuant to the requirements of varying pore
structures during adsorption/desorption, the pore openings of adsorbents can be customized through dynamic structural change of
the decorated stimuli-sensitive motifs by suitable external intervention. In addition, the active sites within the adsorbents can be
exposed to enhance the adsorption selectivity or sheltered to accelerate the desorption through stimuli-triggered adsorbent−
adsorbate interactions. Hence, we proposed a concept of process-oriented smart adsorbents (POSAs) on the basis of the
requirements of the adsorption/desorption processes. The design and development of such POSAs are based on three aspects,
namely, pore openings, pore spaces, and adsorption sites of adsorbents.
In this Account, we present the progress in the development of POSAs according to the demands of adsorption/desorption
processes. A series of POSAs with incorporated stimuli-sensitive motifs were successfully achieved. The versatility of incorporated
motifs allows them to tune the pore structures and surface properties of adsorbents dynamically and further to enhance the
adsorption and desorption efficiency simultaneously. Based on the concept of POSAs, we hope that this Account could contribute to
the development of high-efficiency adsorbents and ultimately promote their applications in practical industrial separation. Moreover,
we present an outlook on future trends and challenges on the road toward the development and applications of POSAs.

■ KEY REFERENCES • Jiang, Y.; Park, J.; Tan, P.; Feng, L.; Liu, X.-Q.; Sun, L.-
B.; Zhou, H.-C. Maximizing Photoresponsive Efficiency
• Jiang, Y.; Tan, P.; Qi, S.-C.; Liu, X.-Q.; Yan, J.-H.; Fan, by Isolating Metal−Organic Polyhedra into Confined
F.; Sun, L.-B. Metal-Organic Frameworks with Target- Nanoscaled Spaces. J. Am. Chem. Soc. 2019, 141, 8221−
Specific Active Sites Switched by Photoresponsive 8227.2 Encapsulation of light-sensitive metal−organic
Motifs: Efficient Adsorbents for Tailorable CO 2
Capture. Angew. Chem., Int. Ed. 2019, 58, 6600−6604.1 Received: September 3, 2021
A general strategy for the fabrication of process-oriented Published: December 17, 2021
smart adsorbents (POSAs) with controllable adsorption
sites by simultaneously incorporating target-specif ic adsorp-
tion sites and stimuli-sensitive motifs into the pores of
metal−organic frameworks (MOFs).

© 2021 American Chemical Society https://doi.org/10.1021/acs.accounts.1c00555

75 Acc. Chem. Res. 2022, 55, 75−86
Accounts of Chemical Research
polyhedron with tailorable adsorption sites into the pores of
porous materials to construct POSAs.
• Cheng, L.; Jiang, Y.; Qi, S.-C.; Liu, W.; Shan, S.-F.; Tan,
P.; Liu, X.-Q.; Sun, L.-B. Controllable Adsorption of
CO2 on Smart Adsorbents: An Interplay between
Amines and Photoresponsive Molecules. Chem. Mater.
2018, 30, 3429−3437.3 Regulating the af f inity of
adsorption sites for CO2 by reversible intervention of the
incorporated stimuli-sensitive motifs in POSAs.
• Zhu, J.; Ding, J.-J.; Liu, X.-Q.; Tan, P.; Sun, L.-B.
Realizing both Selective Adsorption and Efficient
Regeneration using Adsorbents with Photo-Regulated
Molecular Gates. Chem. Commun., 2016, 52, 4006−
4009.4 A general strategy for the fabrication of POSAs with
tunable pore openings by graf ting stimuli-sensitive motifs as
molecular gates onto porous materials.
1. INTRODUCTION
Separation, aiming to get purified products from mixtures, is
vital in various industrial processes. Distillation is a dominating
technology in industrial separation, and it takes up 10−15% of
global energy consumption.5 Tremendous amounts of energy
could be saved if energy-intensive distillation is replaced by
economic separation technologies. Among the technologies,
adsorption offers a promising alternative for separating, storing,
or purifying industrially demanded products with high
efficiency and lower energy input.6 Adsorbent is the key to
adsorptive separation and plays a decisive role in the whole
process. Principally, adsorptive separation based on solid
adsorbents is mainly achieved through kinetics or thermody-
namics. For instance, the discrimination of ethylene and ethane
can be accomplished through kinetic size differentiation in
elaborated adsorbents.7 Further, the selective adsorption of
methane from coal mines can be achieved within the
adsorbent-based nanotrap through strong adsorption affinity.8
Although progress has been made toward advanced
adsorbents, conventional adsorbents have the problem of the
balance between adsorption and desorption.9 Selective
adsorption can be achieved by tuning the pore structures of
adsorbents to enhance the sieving effect, but the desorption
efficiency will be lowered due to increased mass transfer
resistance. Also, the incorporation of suitable active sites can
boost the affinity of adsorbents for adsorbates to improve
adsorption selectivity. Nevertheless, more energy would be
consumed to break such strong affinity during desorption.
Hence, there is a trade-off between adsorption and desorption
for conventional adsorbents. Ideal adsorbents should be able to
present high selectivity, while allowing adsorbates to desorb
easily under mild conditions.10 Due to the fixed structures and
surface properties, it is impossible for conventional adsorbents
to achieve such an ideal scenario. Albeit challenging, it is
desirable to develop a new generation of adsorbent to break
the bottleneck of conventional adsorptive separation.
An interesting approach to solve the problem is to endow
adsorbents with switchability. Namely, adsorbents possess
enhanced sieving effect or surface affinity for adsorbates during
adsorption but show exclusion of adsorbates effectively during
desorption. The achievement of such goals relies on the
establishment of a certain linkage between the adsorbents and
their external environment, so that the adsorbents can be
regulated according to the demands of adsorption/desorption
processes. In nature, the sophistication and intelligence of
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biological systems is always a persistent source of inspiration
for scientists.11 As a typical paradigm, vertebrate vision occurs
by light-induced isomerization of retinal in the retina,
subsequently transmitting the signals to the brain through
the optic nerve.12 Inspired by nature, scientists have developed
various smart materials to mimic biological intelligent systems
and have achieved significant breakthroughs in various
applications.13 Particularly, by mimicking the intelligent self-
regulation behavior of biosomes, process-oriented smart
adsorbents (POSAs) can be formed by incorporating stimuli-
sensitive motifs into the porous materials, and their properties
can be tailored dynamically as demanded by adsorption/
desorption processes upon external intervention. The develop-
ment of POSAs will provide a solution for the trade-off issue
between adsorption and desorption. Especially, the adsorptive
process can be regulated from switchable pore structures or
surface properties of adsorbents or both by suitable external
interventions. The configuration variation of the incorporated
stimuli-sensitive motifs can differentiate the pore structures of
adsorbents with enhanced sieving or steric effect to facilitate
the adsorptive separation (Figure 1a,b). Also, the incorporated
Figure 1. POSAs with (a) tunable pore openings, (b) dynamic pore
spaces, and (c) controllable adsorption sites for adsorption and
desorption.
stimuli-sensitive motifs can be constrained by external stimuli
and boost the adsorbent−adsorbate interaction to regulate
adsorptive separation (Figure 1c).
Recent studies show the design and fabrication of POSAs by
incorporating stimuli-sensitive motifs into the porous materials
for efficient adsorptive separation (Table 1). In this Account,
we summarize the progress on the design and fabrication of
POSAs, which are promising to solve the contradiction in
requirements between adsorption and desorption. Various
strategies for the development of POSAs and their self-
regulation behavior according to the demands of adsorption/
desorption are highlighted. Moreover, the future perspectives,
the critical challenges, and the potential applications of POSAs
are presented. The current advances on POSAs summarized
here will further deepen researchers’ understanding of this field
and help to guide ongoing research efforts in materials for
efficient separation.
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Table 1. Summary of Reported POSAs beneficial for desorption due to the large diffusion resistance
from narrow pore openings. In contrast, adsorbents with wide
intervening
POSA position application ref pore openings can achieve efficient desorption but sacrifice
adsorption selectivity (Figure 2b). For ideal adsorptive
CM-2 pore opening separation of methylene blue and 4
brilliant blue separation, adsorbents are expected to possess narrow pore
AM-3 pore opening separation of methylene blue and 24 openings to achieve selective adsorption but have wide pore
brilliant blue openings to enhance desorption (Figure 2c). Kinetically, the
core−shell pore opening adsorption of 1-pyrenecarboxylic 25 adsorption process can be favored by enhancing the sieving
MOF II acid
effect, and the desorption rate could be accelerated by
MS-TRP pore opening separation of rhodamine B and 29
neutral red decreasing the diffusion resistance. This is impossible for
UiO-66− pore opening capture and release of resorufin, 30 conventional adsorbents with fixed pore structures because the
PNIPAM caffeine, and procainamide requirements of adsorption and desorption in the same
Zn-(AzDC) pore space CO2 capture 39 adsorbents are mutual contradictory. In contrast to conven-
(4,4′-BPE)0.5 tional adsorbents with fixed pore openings, the POSAs can
PCN-250 pore space CO2 capture 38 deliberately regulate the molecular gates to realize reversible
NUT-101 pore space CO2 capture 43 switching between wide and narrow pore openings. As such,
T(n)/U-azo adsorption CO2 capture 1 the POSAs can selectively screen adsorbates with different
site
Pn/azoMOF adsorption CO2 capture 47
kinetic sizes by fine-tuning the pore openings. Accordingly, it is
site extremely desirable to develop adsorbents with tunable pore
AmPn@MS adsorption CO2 capture 3 openings in light of the requirements of adsorption and
site desorption.
PNIPAM@ adsorption water harvesting 52 External stimuli controlled molecular gates based on
MIL-101(Cr) site
switchable stimuli-sensitive motifs permit ready opening and
RA@MS adsorption separation of acid orange and 53
site methylene blue closing of the gates by physical or chemical methods and
PMOP@MS adsorption adsorption of propylene 2 enable the regulation of mass transport within external and
site internal pores. Interestingly, Zink et al. incorporated stimuli-
responsive motifs into the pores of porous materials and
applied them to regulate the loading and release of cargo
2. POSAs WITH TUNABLE PORE OPENINGS molecules.15,16 For drug delivery, one kind of cargo molecule is
In a typical adsorptive separation, adsorbates first pass the pore usually investigated, and reuse of the smart materials is not
openings to enter the pore spaces of adsorbents and then required. In the case of the POSAs, however, two or more
interact with adsorption sites to accomplish adsorption. kinds of adsorbate molecules are studied from the viewpoint of
Subsequently, the adsorbed adsorbates are liberated across separation and cyclic adsorption and desorption is required. In
the pore openings to realize desorption.14 Such adsorptive spite of such differences, the reported strategy for the
separation is often achieved by continuous adsorption and construction of smart materials can be referenced in
desorption cycles of adsorbents. Some traditional adsorptive developing POSAs with tunable pore openings. Therefore,
separations adopt adsorbents with narrow pore openings to for adsorptive separation, stimuli-sensitive motifs could be
achieve selective adsorption (Figure 2a). However, this is not incorporated into the adsorbents to act as molecular gates to
regulate adsorption/desorption upon external intervention.
Based on the above assumptions, we developed POSAs with
tunable pore openings to boost the advancement of adsorptive
separation. Different stimuli-sensitive motifs were grafted onto
the porous materials to regulate the pore openings of
adsorbents. By virtue of its abundance, precise targeting, and
rapid responsiveness,17 light is considered an ideal external
intervention and was first selected to integrate into the
adsorbents. Particularly, coumarin is a typical light-sensitive
molecule that shows great potential applications in fluores-
cence,18 sensing,19 biomedicine,20 and nanogels.21 Coumarins
undergo cycloaddition to formed cyclobutene-linked dimers
upon irradiation with long-wavelength light (Figure 3a).
However, the dimerized coumarins can be cleaved by
irradiation with short-wavelength light.22
By utilizing the dimerization and dedimerization of
coumarin, we fabricated a POSA with coumarin-decorated
molecular gates by grafting coumarin-modified silane coupling
agents onto the pore openings of mesoporous silica.4 To
ensure that the coumarin-modified silane coupling agents were
Figure 2. (a) Microporous adsorbents with high selectivity but
inefficient desorption. (b) Mesoporous adsorbents with efficient grafted onto the pore openings rather than into the inner pores
desorption but low selectivity. (c) POSAs with both high selectivity of mesoporous silica, the construction strategy was to use first
and efficient desorption due to the tunable gates on pore openings. a mesoporous silica preparation in which the inner pores are
Reproduced with permission from ref 4. Copyright 2016 Royal occluded with an organic template agent so that coumarin-
Society of Chemistry. modified silane coupling agents reacted only with the silanol
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Figure 3. Scheme showing different stimuli-sensitive molecules, (a) coumarin, (b) azobenzene, and (c) PNIPAM, and their reversible
conformation transition. These stimuli-sensitive molecules are grafted onto the pore openings of POSAs as molecular gates.

Figure 4. (a) Scheme showing the fabrication of core−shell MOF-based adsorbent with tunable gates. (b) Uptake curves of guest molecules on
adsorbent with open or closed molecular gates. Reproduced with permission from ref 25. Copyright 2019 Wiley-VCH. (c) Schematic illustration of
MOF-based adsorbent (UiO-66−PNIPAM) fabricated by tethering PNIPAM onto UiO-66. (d) Reversible adsorption and desorption of guest
molecules by PNIPAM-controlled gates upon temperature variation. Reproduced with permission from ref 30. Copyright 2015 Royal Society of
Chemistry.

groups at the pore openings and the outer surface. The organic
template agent was removed after grafting. The grafted
coumarin can trigger the opening and closing of the pore
openings of adsorbent through external light exposure (Figure
2c). Upon irradiation with long-wavelength light, the pore
openings of adsorbent are partially blocked due to
intermolecular dimerization of coumarin monomers. Mean-
while, the adsorbent is suitable for selective capture of
adsorbates with smaller kinetic size. Upon irradiation with
short-wavelength light, the pore openings were opened because
78
of the dedimerization of coumarin dimers, and the captured
adsorbates can be efficiently desorbed from the pores. In a
proof-of-concept trial, two dyes with different kinetic sizes,
namely, methylene blue (MB, 1.36 nm) and Coomassie
brilliant blue (CBB, 1.91 nm), were adopted as model
adsorbates to probe the adsorption and desorption perform-
ances of the obtained adsorbent. For pristine mesoporous
silica, there are no distinctive changes on the adsorption of MB
and CBB before and after irradiation with light, and selective
adsorption cannot be achieved on pristine mesoporous silica.
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Notably, the adsorbent with coumarin-modified molecular
gates presented interesting adsorption behavior upon light
intervention. For the sample with optimal loading of coumarin,
CM-2, there was almost no detectable change for the
adsorption capacity of MB before and after irradiation with
light, while the adsorption capacity for CBB decreased
significantly after irradiation with long-wavelength light,
corresponding to 76% change. The results indicate a high
selectivity for MB over CBB on adsorbent after irradiation with
long-wavelength light, which is much higher than that before
irradiation with long-wavelength light. Calculation shows that
the selectivity for MB on adsorbent is up to 11.9, which is
much higher than that of the adsorption selectivity of CBB
(2.2) under the same conditions. More importantly, such an
adsorbent can be regenerated by desorbing the adsorbates
from the opened pore openings upon irradiation with short
wavelength light. Furthermore, the adsorbent exhibits excellent
recyclability during five cycles of adsorption and desorption
upon light intervention.
Azobenzene is another representative light-sensitive mole-
cule that can undergo reversible trans/cis isomerization with
spatial configuration variation upon light intervention (Figure
3b).23 We took advantage of the particular properties of
azobenzene to fabricate a POSA with tunable molecular gates
by grafting azobenzene-modified silane coupling agents onto
the pore openings of mesoporous silica.24 The obtained
adsorbent with optimal loading of azobenzene, CM-3, shows
selective adsorption for MB upon trans isomerization, while the
desorption efficiency can reach almost 100% upon cis
isomerization. Analogously, another POSA with tunable
molecular gates was constructed by grafting an azobenzene
derivative onto the pore openings of a metal−organic
framework (MOF) (Figure 4a).25 The reversible open/closed
molecular gates in such an adsorbent can be achieved upon
external light intervention. Interestingly, the adsorbent exhibits
a dramatic increase of 86% for the uptake of guest molecules
by opening the gates of adsorbent (Figure 4b).
In addition to light-sensitive motifs, the hydrophilicity and
hydrophobicity or structures of temperature-sensitive motifs
can be changed upon temperature variation, which can further
modulate adsorption of adsorbents.26 Poly(N-isopropylacryla-
mide) (PNIPAM) represents one of the most widely studied
temperature-sensitive polymers and has a lower critical
solution temperature (LCST) of about 32 °C in water (Figure
3c).27 Interestingly, the soluble PNIPAM shows a coil
conformation when its surrounding temperature is lower
than the LCST. However, it converts to a globule
conformation rapidly when the surrounding temperature
exceeds the LCST and then returns to coil conformation
when the surrounding temperature drops below the LCST.28
Such reversible conformation variation of PINPAM makes it a
promising stimuli-sensitive motif for temperature-dependent
adsorptive separation. By grafting PNIPAM onto the pore
openings of mesoporous silica, we obtained a POSA (MS-
TRP) with temperature-controlled molecular gates.29 At the
low temperature (25 °C), the coiled PNIPAM closes the gates,
and selective adsorption is thus achieved. Conversely, the
desorption efficiency can be accelerated significantly thanks to
the opened gates of the globular PNIPAM at high temperature
(45 °C). It is worth noting that the cyclic adsorption/
desorption using temperature-sensitive adsorbent can be
achieved in a small temperature range (25 to 45 °C). More
importantly, the energy consumed in such a temperature-
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sensitive POSA based adsorptive separation is lower owing to
the small temperature difference between adsorption and
desorption.
Analogously, a MOF-based POSA, UiO-66−PNIPAM, is
achieved by grafting PNIPAM onto the pores of UiO-66
(Figure 4c).30 In UiO-66−PNIPAM, the PNIPAM molecules
were tethered onto the pore openings but not inside the inner
pores of UiO-66 because of the high diffusion resistance
induced by the large molecular size. It was reported that on/off
switching of adsorption and desorption of guest molecules on
the adsorbent was driven by temperature variation. The
PNIPAM adopts a globule conformation, blocking the pore
openings, at the high temperature but a coil conformation,
opening the pore openings, at the low temperature (Figure
4d). It is noteworthy that the adsorbent exhibited a fast
desorption of almost 100% of the adsorbed guest molecules at
the low temperature.
In these cases, POSAs are achieved by constructing
molecular gates onto the pore openings of porous materials.
The gates of POSAs can be reversibly opened and closed by
using suitable external interventions. More importantly, the
tunable pore openings are exquisitely used to serve adsorptive
separation according to the demands of adsorption/desorp-
tion.
3. POSAs WITH DYNAMIC PORE SPACES
In typical adsorptive separation, the captured adsorbates are
gathered within the pore spaces of adsorbents and diffused
from the pore spaces to the outside of pores to regenerate the
adsorbents. Currently, the regeneration of adsorbents is
principally achieved by the conventional technologies of
temperature or pressure swings.31 However, massive energy
consumption is inevitably required to deliver such temperature
or pressure swings for driving the adsorbates to desorb from
adsorbents. Solid porous materials with rigid frameworks are
conventionally adopted as adsorbents, and their pore spaces
are fixed. It would be better if adsorbents possessed enough
pore space to store the adsorbates during adsorption but could
squeeze the pore spaces to liberate the adsorbates during
desorption. Thermodynamically, the desorption driving force
of the adsorbents is mainly acquired by the variation of pore
spaces but not temperature or pressure swings. Also, the
variation of pore spaces in adsorbents would further affect
kinetic adsorption/desorption rate during the separation
process. In this regard, developing a new generation of
adsorbents with dynamic pore spaces for high-efficiency
adsorption and low-energy regeneration is desirable. Up to
now, some porous materials with dynamic pore spaces induced
by breathing open frameworks with unusual adsorption
behavior have been reported.32 Taking MIL-53 as an example,
its breathing framework induced by hydration/dehydration
during the uptake of water molecules has been extensively
studied.33 Such breathing frameworks are often unable to meet
the requirements of practical adsorptive separation.
It was reported that the pore structures of porous materials
can be affected by the incorporated substances.34,35 Previous
studies indicated that if stimuli-sensitive motifs are introduced
into the backbones of porous materials, the resultant
composites tend to response rapidly toward external stimuli
intervention.36−38 Such strategies can also be transplanted to
adsorbents. By introduction of adjustable motifs into the
backbones of adsorbents, the flexibility of backbones can be
transformed, thereby resulting in dynamic pore spaces. For
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Figure 5. (a) Expansion and contraction of frameworks caused by isomerization of ligands, regulating the pore spaces of MOF adsorbent for
reversible adsorption/desorption of CO2. (b) Quantity adsorbed isotherms for CO2 can be modulated by light intervention. Reproduced with
permission from ref 39. Copyright 2013 Wiley-VCH. (c) Adsorption and desorption of guest molecules during expansion and contraction of
metal−organic polyhedron (MOP)-based adsorbent upon light intervention. (d) DFT-optimized possible structures of adsorbent during
adsorption/desorption of CO2. Reproduced with permission from ref 43. Copyright 2020 Chinese Chemical Society.

instance, an adsorbent, Zn-(AzDC)(4,4′-BPE)0.5, was fabri-
cated by embedding two different light-sensitive linkers,
azobenzene-4,4′-dicarboxylic acid and trans-1,2-bis(4-pyrid-
yl)-ethylene, into the framework walls of the MOF (Figure
5a).39 Upon trans isomerization of the linkers, the framework
of adsorbent is expanded, enlarging the pore spaces to adsorb
CO2. In contrast, the framework of the adsorbent contracts,
lessening the pore space to desorb the adsorbed CO2, upon cis
isomerization of the linkers (Figure 5b). Similarly, another
adsorbent, a robust light-sensitive MOF PCN-250, was
produced by integration of 3,3′,5,5′-azobenzene tetracarboxylic
acid into the backbone of a Fe2Co(μ3-O)(CH3COO)6 metal
cluster-based framework.38 Irradiation of the adsorbent with
light causes the incorporated azobenzene to undergo trans/cis
isomerization, which enables expansion and contraction of the
pore spaces. Driven by such light-induced dynamic pore
spaces, CO2 adsorption and desorption in PCN-250 can be
carried out by reversible intervention with light. Also, this
technology for the efficient separation of CO2 can be achieved
by embedding other light-sensitive motifs, like dithienylethene
and spiropyran, into the frameworks of adsorbents.40−42
Additionally, we directly adopted azobenzene-based organic
linkers as the backbone of cages to generate a POSA, NUT-
101 (Figure 5c).43 The configuration transformation of
azobenzene within the backbone lead to expansion and
contraction of the cages, thus achieving efficient adsorption/
desorption of CO2 upon light intervention. Moreover, such
adsorption/desorption behaviors are further demonstrated by
80
DFT calculations (Figure 5d). Furthermore, the adsorption
and desorption of CO2 on the POSA can be cycled by the
reversible configuration transformation of azobenzene within
the backbone upon light intervention. Consequently, by
embedding stimuli-sensitive motifs into the backbones of
adsorbents, the corresponding pore spaces can be tailored to
achieve efficient adsorption/desorption.
On the whole, the reversible expansion and contraction of
pore spaces can be achieved by installing stimuli-sensitive
motifs into the backbones of adsorbents. In such POSAs,
adsorption is realized by expanding the pore spaces while
desorption is achieved by compressing the pore spaces, which
conforms to the demands of adsorption/desorption. Note-
worthily, the POSAs are different from the conventionally
reported breathing MOFs. By external stimuli, the reversible
expansion and contraction of pore spaces within POSAs can be
freely regulated according to the demands of adsorptive
separation. Especially, POSAs mainly focus on the research of
the dynamic pore spaces induced by the external stimuli from
the viewpoint of high-efficiency adsorption and low-energy
desorption. It is foreseeable that POSAs with dynamic pore
spaces will be enriched by the continuous discovery and
improvement of new adjustable motifs in the future.
4. POSAs WITH CONTROLLABLE ADSORPTION SITES
Notably, the incorporation of target-specific adsorption sites
into adsorbents can enhance the interaction of adsorbent−
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Figure 6. (a) Schematic illustration of CO2 capture on POSAs with controllable adsorption sites through an interaction between light-sensitive
molecules and adsorption sites. (b) Alteration in the UV−vis spectra of POSA upon cis and then trans isomerization. (c) Reversible changes in
absorbance as a function of cycle upon trans and cis isomerization. Reproduced with permission from ref 1. Copyright 2019 Wiley-VCH.

Figure 7. (a) Scheme showing the fabrication of adsorbents with temperature-controlled adsorption sites for the reversible adsorption/desorption
of water. Water adsorption/desorption isotherms of adsorbents with various loading amount of PNIPAM at (b) 25 °C and (c) 40 °C, respectively.
Reproduced with permission from ref 52. Copyright 2020 Wiley-VCH.

adsorbate and improve adsorption selectivity.44 The thermo-
dynamic activation energy and adsorption heat of the
adsorbents are generally higher among the adsorption process.
However, it is not desirable in practical adsorptive separation
because relatively harsh conditions or high energy input is
needed to break the strong affinity of adsorbent−adsorbate
during desorption.45 The key issue here lies in how to design
adsorbents with high adsorption selectivity but low energy
consumption for desorption. In view of this, an effective way
was proposed to address such issues by mildly intervening in
the affinity of adsorption sites for adsorbates.
81
In recent decades, the massive emission of CO2 into the
atmosphere has caused global climate warming issues.
Considering the high demand for capture and separation of
CO2,46 we synthesized the POSA, T(n)/U-azo, with control-
lable adsorbent−adsorbate interaction by introducing tetrae-
thylenepentamine (TEPA) to an azobenzene decorated MOF
(Figure 6a).1 The reversible light-sensitive properties of this
POSA were demonstrated by UV−vis spectroscopy (Figures
6b,c). The light-sensitive azobenzene and specific adsorption
sites promote the composites to be ideal adsorbents for
controllable CO2 capture. The chemical adsorption sites of
amines within TEPA can be regulated by the incorporated
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Figure 8. (a) Crystalline structures of PMOP with dangling azobenzenes upon trans/cis isomerization. (b) PMOPs dispersed in the pores of
mesoporous silica with controllable adsorption sites upon trans/cis isomerization. (c) High-resolution transmission electron microscope image of
PMOP inside the pores of mesoporous silica. (d) Propylene adsorption isotherms of the adsorbent upon trans/cis isomerization. Reproduced with
permission from ref 2. Copyright 2019 American Chemical Society.
azobenzenes upon light intervention. Furthermore, the
excellent reversibility of POSAs was demonstrated by three
trans/cis isomerization cycles. Analogously, such CO 2
adsorption behavior can also be achieved in an azobenzene-
decorated MIL-101-type MOF with incorporated polyethyle-
nimine as adsorption sites (Pn/azoMOF).47 In addition, we
synthesized another POSA, AmPn@MS, by introducing
azobenzene and amine into the pores of mesoporous silica
simultaneously.3 The adsorption capacity for CO2 of the
adsorbents changes significantly with the isomerization of
azobenzenes. DFT calculations indicate that the adsorption
behavior originates from the interplay between azobenzene and
amine within the pores of the adsorbent. Such adsorption
behavior also appears in the POSAs modified with azobenzene
and different amines.48−50 Consequently, by utilizing the
synergistic interaction between azobenzenes and amines,
selective adsorption for CO2 is achieved, and moreover, the
energy consumption of desorption is reduced as well.
It has been reported that two-thirds of the world’s
population is experiencing a severe water shortage crisis.
Direct harvest of water from air, especially in arid air or deserts,
has attracted wide interest recently.51 However, it is hard to
achieve a satisfying adsorbent for both adsorbing and
desorbing water molecules efficiently. By in situ polymerization
of temperature-sensitive polymer into the cavities of MIL-
101(Cr), a composite of PNIPAM@MIL-101(Cr) with
controllable adsorption sites for water adsorption/desorption
is achieved (Figure 7a).52 The adsorption sites of amides
within PNIPAM can be regulated via the phase transformation
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of PNIPAM upon variation of the temperature. At low
temperature, the coiled PNIPAM enables the adsorption sites
of amides to be exposed, and the uptake of water molecules
can reach 110 wt % at 25 °C and 96% relative humidity, which
is an unprecedented uptake amount for water adsorption
(Figure 7b). Inversely, the amides in the adsorbent are
shielded at the high temperature due to the hydrophilic-to-
hydrophobic phase transition of PNIPAM, thus desorbing the
adsorbed water molecules from the adsorbent (Figure 7c). For
the saturated adsorbent, about 98% of the adsorbed water
molecules can be desorbed at a relatively mild condition of
40% relative humidity and 40 °C. Altogether, the POSA
achieves the capture of water molecules by tailoring the
adsorption sites dynamically as demanded for adsorption/
desorption.
Recently, a POSA with demand-oriented adsorption sites
was assembled and applied for the selective adsorption of
acidic dyes from wastewater. We adopted PNIPAM as the
temperature-sensitive motif and N-[3-(dimethylamino)-
propyl]methacrylamide (DMAPM) as the specific adsorption
site, putting them together into the pores of mesoporous silica
to fabricate a POSA (RA@MS).53 DMAPM is a typical
acrylamide derivative with a tertiary amine group, which can be
employed as active site for adsorption.54 The interchange
between blockage and exposure of the tertiary amine site
within RA@MS can be realized by the reversible phase
transformation of PNIPAM upon temperature variation. At the
low temperature (25 °C), the coiled PNIPAM exposes
adsorption sites for selective adsorption of acidic dyes. In
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Acc. Chem. Res. 2022, 55, 75−86
Accounts of Chemical Research
contrast, the adsorption sites in RA@MS are completely
shielded by the gloubule PNIPAM with increasing temper-
ature, and the adsorbed acidic dye molecules on the adsorption
sites can be desorbed. Remarkably, almost 100% of the
captured adsorbates can be desorbed at 50 °C, indicating that
the regeneration of adsorbent is achieved in such a small
temperature range. Compared with conventional temperature-
swing adsorption, such smaller temperature range can reduce
the energy consumption of adsorptive separation. Moreover,
the intrinsic adsorption sites of adsorbents can also be
regulated by directly immobilizing the dangling stimuli-
sensitive motifs into the pores of adsorbents. For instance,
we fabricated several POSAs by directly introducing PNIPAM
or azobenzene into the pores of mesoporous silica.55−58 The
intrinsic adsorption sites in such POSAs are dynamically
adjustable by the conformation variation of incorporated
stimuli-sensitive motifs upon external intervention, which can
also reversibly regulate the adsorption/desorption with high
efficiency. Overall, such POSAs with temperature-controlled
adsorption sites for selective adsorption and efficient
desorption are promising for the design of advanced
temperature-swing adsorptive separation.
Stimuli-responsive metal−organic polyhedra (srMOPs) can
function as controllable and predictable motifs for dynamically
regulating adsorption sites upon light intervention, but they
suffer from serious aggregation after activation (Figure 8a).59 A
POSA with enhanced stability and maximized light responsiv-
ity was achieved by encapsulation of a srMOP, namely a
photoresponsive MOP (PMOP), into the pores of mesoporous
silica (Figure 8b).2 In addition, the confined PMOP can
further regulate its active sites upon light intervention. It is
interesting that the PMOP molecules can be directly observed
in the pores of mesoporous silica by high-resolution trans-
mission electron microscopy analysis (Figure 8c). Propylene
has been known as an important raw material in the chemical
industry. We adopted it as a guest molecule to probe
adsorption properties of the POSA. Upon trans isomerization,
the azobenzenes of the PMOP exhibit an expanded
conformation and the adsorption sites are accessible for
propylene molecules, which is beneficial for adsorption. In
contrast, the PMOP contracted due to cis isomerization of the
dangling azobenzenes (Figure 8d). It is worth noting that the
contracted PMOP will block the adsorption sites and reduce
propylene adsorption.
To summarize, POSAs with controllable adsorption sites can
be obtained by simultaneously integrating stimuli-sensitive
motifs and target-specific active sites into the porous materials.
Although the structural transformation of incorporated motifs
inside the pores of adsorbents may affect the kinetic diffusion
rate of adsorbates, it is still favorable for the controllable
regulation of the adsorption sites. Adsorption and desorption
can be effectively regulated through adjusting the interactions
between stimuli-sensitive motifs and adsorption sites. During
adsorption, the interaction between stimuli-sensitive motifs
and active sites can be weakened, which enhances the affinity
of adsorption sites for adsorbates to achieve selective
adsorption. During desorption, the interaction between
stimuli-sensitive motifs and adsorption sites can be enhanced,
which weakens the affinity of adsorption sites for adsorbates
and facilitates the desorption process. As a result, selective
adsorption and efficient desorption can be realized simulta-
neously.
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5. CONCLUSIONS AND PERSPECTIVES
In comparison with conventional adsorbents, the newly
developed POSAs offer new opportunities in adsorptive
separation. Motivated by the demand for practical adsorptive
separation, in this Account, we overview the efforts toward the
design and fabrication of POSAs. POSAs can be achieved by
incorporation of stimuli-sensitive motifs, specific active sites, or
both into porous materials. The application of POSAs in
adsorptive separation is carried out by dynamically tailoring
their structures or surface properties, such as pore openings,
pore spaces, and adsorption sites. Upon external interventions,
the POSAs can be modulated to the state that is beneficial for
adsorption and switched to the state favorable for desorption.
Besides light and temperature stimuli, some other smart
materials with various intervention strategies, such as
magnetic,60 electrical,61 and pH62 stimuli, have been reported,
which may provide clues for the development of new POSAs
for efficient adsorptive separation. By judicious choice of
stimuli-sensitive motifs and active sites as well as regulation
strategy, it is possible to fabricate POSAs for adsorptive
separation with high efficiency but low energy consumption.
Although progress in developing POSAs has been achieved,
the practical application of POSAs remains in its infancy. The
following issues can be taken into consideration in future
investigations. (1) The productivity of adsorptive separation is
closely related to the modulation efficiency of POSAs upon
external stimuli. Aiming to tailor the structure and properties
of adsorbents proficiently, the development of efficient external
stimuli methods and the optimization of current external
stimuli approaches are expected. (2) The scale-up preparation
of adsorbents is a key factor that should be taken into account
before adopting POSAs for industrial separation, which urges
us to carry out related research, from laboratory-scale to utility-
scale, concerning the potential POSAs. (3) The integration of
POSAs with present adsorptive separation processes is crucial
for industrialization. It is necessary to establish an appropriate
external intervention system and integrate it into practical
operation units. Thus, future efforts should be focused on
addressing such issues to hasten the process of industrializa-
tion. Overall, the ongoing investigations on POSAs open an
avenue for future development of adsorptive separation.
Looking forward, we expect that target-specific adsorptive
separation processes can be realized by tailoring the properties
of adsorbents dynamically as demanded by adsorption/
desorption, leading to a breakthrough in industrial separation.
■
AUTHOR INFORMATION
Corresponding Author
Lin-Bing Sun − State Key Laboratory of Materials-Oriented
Chemical Engineering, College of Chemical Engineering,
Nanjing Tech University, Nanjing 211816, China;
orcid.org/0000-0002-6395-312X; Email: lbsun@
njtech.edu.cn
Authors
Yao Jiang − State Key Laboratory of Materials-Oriented
Chemical Engineering, College of Chemical Engineering,
Nanjing Tech University, Nanjing 211816, China;
orcid.org/0000-0002-2316-8274
Peng Tan − State Key Laboratory of Materials-Oriented
Chemical Engineering, College of Chemical Engineering,
https://doi.org/10.1021/acs.accounts.1c00555
Acc. Chem. Res. 2022, 55, 75−86
Accounts of Chemical Research
Nanjing Tech University, Nanjing 211816, China;
orcid.org/0000-0003-0932-6587
Xiao-Qin Liu − State Key Laboratory of Materials-Oriented
Chemical Engineering, College of Chemical Engineering,
Nanjing Tech University, Nanjing 211816, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.accounts.1c00555
Notes
The authors declare no competing financial interest.
Biographies
Yao Jiang earned his Ph.D. degree from Nanjing Tech University in
2019. He worked as a postdoctoral fellow at the University of South
Florida from 2019 to 2020. He is currently working as a postdoctoral
fellow at Nanjing Tech University. His research interest is related to
porous materials and their applications in chemical separation.
Peng Tan is an associate professor at the State Key Laboratory of
Materials-Oriented Chemical Engineering and Nanjing Tech
University. He received his Ph.D. degree from Nanjing Tech
University in 2017. His research interest focuses on the fabrication
of functional porous materials and their applications in adsorption and
heterogeneous catalysis.
Xiao-Qin Liu obtained her Ph.D. degree in 1999 from Nanjing Tech
University. She joined the faculty of Nanjing Tech University in 1982
and became a full professor in 1999. Her current research interests
focus on design, synthesis, and applications of porous functional
materials, with emphasis on large-scale adsorbents and catalysts.
Lin-Bing Sun is a full professor at Nanjing Tech University. He
received his Ph.D. degree from Nanjing University in 2008 and did his
postdoctoral research at Texas A&M University from 2011 to 2012.
His current research interests focus on fabrication of porous
functional materials as well as their applications in adsorption and
catalysis.
■ ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (Grants 22078155, 22125804, 21808110,
and 21878149) and the Project funded by China Postdoctoral
Science Foundation (Grant 2020M681567).
■
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