Nanomaterials 13 02442 v2

nanomaterials
Article
Water Adsorption Dynamics on Metal–Organic Framework
MOF-801: Comparative Study of Loose and Glued Grains,
and Coatings
Marina Solovyeva and Larisa Gordeeva *
Boreskov Institute of Catalysis, Ak. Lavrentiev av. 5, 630090 Novosibirsk, Russia; solovyeva@catalysis.ru
* Correspondence: gordeeva@catalysis.ru
Abstract: Adsorption heat transformation and storage (AHTS) is an environmentally benign and
energy-saving alternative to common compression chillers and heat pumps. The low specific power
(SP) of adsorption systems is a key drawback that hinders their broader dissemination. The opti-
mization of adsorption dynamics is a prerequisite for SP enhancement. In this work, we studied
the dynamics of water vapor adsorption on MOF-801—a promising adsorbent for AHTS. For the
first time, two configurations of compact MOF-801 bed, namely, grains glued to the surface of a
metal support and thin adsorbent coatings, are prepared, and their porous structure is characterized.
The water adsorption dynamics is compared with a common loose grains configuration. The main
findings are: (a) the binder can both accelerate and decelerate the water adsorption, and its chemical
nature is subject to careful selection; (b) at the initial time, heat transfer between the support and
adsorbent bed controls the adsorption rate, and, at a longer time, mass transfer starts to affect it;
(c) polyvinylpyrrolidone, bentonite, thermal grease, and hydroxyethylcellulose increase the heat
transfer coefficients and accelerate adsorption; polyvinyl alcohol and polyaniline slow it down; and
(d) for the coatings prepared with polyvinylpyrrolidone, an SP of 1.6–5.1 kW/kg can be achieved,
which is about twice that for the loose grains. The new configurations can be recommended for
effective but expensive adsorbents such as MOFs, and their implementation will contribute to the
further spread of AHTS technology.
Citation: Solovyeva, M.; Gordeeva, L.
Water Adsorption Dynamics on Keywords: adsorption heat transformation and storage; MOF-801; water adsorption dynamics;
Metal–Organic Framework MOF-801: compact adsorbent beds; binder chemical nature; specific power
Comparative Study of Loose and
Glued Grains, and Coatings.
Nanomaterials 2023, 13, 2442.
https://doi.org/10.3390/
1. Introduction
nano13172442
According to the British Petroleum (BP) statistical review, the increase in primary
Academic Editor: Daniela Iannazzo energy consumption was equal to 31 × 1018 J in 2021, which was above the pre-pandemic
Received: 4 August 2023
level in 2019, with an associated growth of CO2 emissions of 5.9% [1]. For this reason,
Revised: 23 August 2023
global energy policies in recent years have been focused on the importance of decarbonizing
Accepted: 24 August 2023 energy. Adsorption heat transformation and storage (AHTS) is an emerging technology,
Published: 28 August 2023 which enables efficient use of renewable or waste heat sources for cooling/heating [2].
Due to the low consumption of electric power and the use of green working fluids (water,
methanol, and ammonia), AHTS is considered an energy-saving and environmentally
friendly alternative to common compression chillers and heat pumps. It is expected that
Copyright: © 2023 by the authors. the widespread of AHTS can lead to a significant reduction in fossil fuel consumption and
Licensee MDPI, Basel, Switzerland. greenhouse gas emissions. Nevertheless, a broader diffusion of this technology is limited
This article is an open access article by the low specific power (SP) achievable in practice, and the associated large size of AHTS
distributed under the terms and units [3].
conditions of the Creative Commons The SP of AHTS systems is mainly affected by the dynamics of the adsorption and
Attribution (CC BY) license (https://
desorption stages of the working cycle, governed by coupled heat and mass transfer in
creativecommons.org/licenses/by/
the adsorber–heat exchanger (Ad-HEx) unit. In this vein, the optimization of the Ad-HEx
4.0/).
Nanomaterials 2023, 13, 2442. https://doi.org/10.3390/nano13172442 https://www.mdpi.com/journal/nanomaterials

Nanomaterials 2023, 13, 2442 2 of 16
configuration is becoming a hot topic of research related to AHTS technology [4–6]. Nowa-
days, two basic Ad-HEx configurations are widely used, namely, the loose adsorbent grains
loaded between the HEx fins and the thin adsorbent coating on the HEx surface [7,8]. Due
to the large porosity of the loose grains configuration and high contact resistance, the poor
heat transfer between the adsorbent bed and HEx surface and inside the bed is considered to
be the factor controlling the adsorption rate and reducing the SP [9–11]. An effective way to
improve heat transfer between the adsorbent and HEx is to apply the adsorbent coating on
the HEx surface with or without a binder [12–14]. In this case, the point contact between the
adsorbent grains and the HEx surface is substituted by the tight contact between the adsor-
bent coating and the HEx surface; therefore, the coatings provide a strong reduction in the
contact resistance and an increase in the heat transfer coefficient [15]. However, the small
porosity of the coatings leads to the mass transfer in the adsorbent bed becoming slower,
which can become a new factor, limiting the adsorption kinetics and the SP of the coated
Ad-HEx [16,17]. Consequently, a smart trade-off between heat and mass transfer is needed
to accelerate the ad/desorption and improve the SP. This compromise is complicated by the
fact that both heat and mass transfer are inevitably coupled in the Ad-HEx because a large
amount of heat is released/consumed during vapor ad/desorption [3,18]. Meanwhile, the
correct and accurate comparison of adsorption dynamics for the loose grains and coated
HEx configurations is often challenging due to different grain sizes, adsorbent masses, bed
thickness, contact surface area, etc. All these factors affect both heat and mass transfer,
which makes it difficult to reveal the effect of consolidation of the adsorbent with the HEx
surface on the adsorption dynamics. Accordingly, there is room for optimizing the Ad-HEx
configuration. In particular, the influence of the binder nature and content on the kinetics
of adsorption on various adsorbents has not been sufficiently studied.
A class of porous compounds known as metal–organic frameworks (MOFs) have
attracted increasing attention in recent years as adsorbents for AHTS due to their high
porosity, huge surface area, and tunable adsorption properties [19,20]. MOF-801 is a
microporous crystalline compound, which consists of basic units of Zr6 O4 (OH)4 (–O2 C–
CH=CH–CO2 –)6 and forms a cubic structure with two tetrahedral cages, with sizes of
4.8 and 5.6 Å, and an octahedral cage, with size of 7.4 Å. MOF-801 is characterized by a
high water adsorption capacity of 0.36 g/g at relative pressure P/P0 = 0.9 [21]. Owing to its
microporous structure and a high crystal density of 1.68 g/cm3 , the adsorption capacity
related to the unit volume reaches 0.60 g/cm3 [21]. Due to the peculiar stepped shape of
the characteristic curve of water adsorption (Figure S1a in the Supplementary Materials)
and relatively high hydrophilicity, MOF-801 enables a chilling effect at a low evaporation
temperature of 5 ◦ C and adsorption temperature of 30 ◦ C, can be regenerated at a low tem-
perature of 80–85 ◦ C, and exchanges 0.21–0.23 g_water/g_ads per cycle [22]. Furthermore,
the structure and properties of MOF-801 can be tuned by the linker functionalization [23]
and partial substitution of Zr by other metals (Co and Ni) [24]. Recently, several synthetic
approaches have been developed using water instead of toxic organic solvents at room tem-
perature, which enables simple, energy-efficient, and environmentally friendly production
of MOF-801 [25,26]. These features, along with its exceptional hydrothermal stability, make
MOF-801 one of the most promising water adsorbents for energy conversion [22,25], climate
control [27], and atmospheric-water-harvesting systems [28,29]. However, the microcrys-
talline powder form of as-synthesized MOFs limits their practical application. Accordingly,
shaping MOFs in the form of pellets or coatings suitable for handling, processing, and
storage is one of the strategies that contribute to their scale-up application. The method of
compression of neat MOF-801 or MOF-801 mixed with binders (polyvinyl alcohol, sucrose,
and polyvinyl butyral) was used in [30] to produce pellets. Gökpinar et al. described the
freeze granulation method using polyvinyl alcohol as a binder, which allows MOF-801
pellets to be produced with essentially unchanged porosity [31]. He et al. [32] constructed
monolithic MOF-801 by sol–gel phase separation followed by acid–heat post-treatment.
Monolithic MOF-801 showed a moisture sorption capacity 1.2–1.4 times higher than that of
conventional powdered and compressed samples.
Nanomaterials 2023, 13, x FOR PEER REVIEW 3 of 16
post-treatment. Monolithic MOF-801 showed a moisture sorption capacity 1.2–1.4 times

higher than that of conventional powdered and compressed samples.
This work presents the results of the comparative study of the water sorption dynamics
This work presents the results of the comparative study of the water sorption dynam-
on three usable configurations of MOF-801 bed under conditions of a typical cooling cycle.
ics on three usable configurations of MOF-801 bed under conditions of a typical cooling
The first configuration is a monolayer of loose MOF-801 grains placed on the surface of
cycle. The first configuration is a monolayer of loose MOF-801 grains placed on the surface
aluminum foil, which imitates the surface of aluminum HEx, often used in AHTS systems
of aluminum foil, which imitates the surface of aluminum HEx, often used in AHTS sys-
(Figure 1a).
tems (Figure The
1a).second is an innovative
The second is an innovativeconfiguration,
configuration,composed
composed of aofmonolayer
a monolayer of of
MOF-
801 grains glued to the foil surface with a binder (Figure 1b). The
MOF-801 grains glued to the foil surface with a binder (Figure 1b). The last is the coating, last is the coating,
prepared
preparedfrom fromthethe slurry
slurry ofof MOF-801
MOF-801powder powderininthe theaqueous
aqueous solution
solution of binders
of binders usingusing
a a
drop-coating
drop-coatingmethod
method (Figure 1c). We
(Figure 1c). Wefocused
focusedon onthe
theeffects
effectsof of
thethe binder’s
binder’s chemical
chemical nature
nature
and
andcontent
contentandand the
the coating thicknesson
coating thickness onthetheadsorption
adsorption kinetics.
kinetics. To To reveal
reveal the the
effecteffect
of of
the
theadsorbent
adsorbentlayer
layer consolidation
consolidation with withthethesupport,
support,wewe fixed
fixed other
other factors
factors influencing
influencing the the
kinetics,
kinetics,namely,
namely,the theadsorbent
adsorbentmass, mass,the
thecontact
contactsurface
surface area
area between
between the adsorbent
adsorbent and and the
foil,
theand
foil,the
andadsorbent
the adsorbentgraingrain
size (for
size loose and glued
(for loose and gluedgrains). Based
grains). on the
Based on obtained
the obtainedresults,
the rate-limiting
results, stages stages
the rate-limiting are revealed for each
are revealed configuration,
for each configuration,the theeffective
effective heat heattrans-
transfer
coefficient,
fer coefficient,α, between
α, between thethealuminum
aluminum support
supportandandthetheadsorbent
adsorbent bed is is evaluated
evaluatedun- under
der conditions
conditions of theofcooling
the cooling
cycle,cycle, andSP
and the the SP achievable
achievable employing
employing the studied
the studied adsorbed
adsorbent
bent bed configurations
configurations is estimated.is estimated. Appropriate
Appropriate recommendations
recommendations are proposed
are proposed for op-
for optimizing
timizing
the adsorbentthe adsorbent bed configuration
bed configuration to increaseto increase
the SP of the SP of AHTS.
AHTS.
Figure1.1.The
Figure Thestudied
studiedadsorbent
adsorbent bed configurations:common—loose
bed configurations: common—loose grains
grains (a),(a), adsorbent/binder
adsorbent/binder
coating(c),
coating (c), and innovative—a
innovative—aconsolidated layer
consolidated of glued
layer grainsgrains
of glued on theon
heat exchanger
the (HEx) sur-
heat exchanger (HEx)
face (b).
surface (b).
2.2.Materials
Materialsand
and Methods
Methods
2.1. Sample Synthesis
2.1. Sample Synthesis
MOF-801
MOF-801 was synthesizedbyby
was synthesized a solvothermal
a solvothermal methodmethod according
according to a slightly
to a slightly modified mod-
ified procedure described in [21].
procedure described in [21]. ZrOCl2·8·H2O (3.2ZrOCl 2 · 8 · H
g, 210 mmol) and fumaric acid (1.2 g, 10acid
O (3.2 g, 10 mmol) and fumaric
(1.2 g, 10 mmol) were dissolved in a solution
mmol) were dissolved in a solution of dimethylformamide of dimethylformamide
(DMF)/formic (DMF)/formic
acid (40 mL/14acid
(40 mL/14
mL), mL),the
and then and then the
mixture wasmixture
placed was
into aplaced
100 mL into a 100 mL autoclave
Teflon-lined Teflon-linedandautoclave
heated at and
130 °Catfor
heated 130 ◦ CAfter
6 h. for 6cooling
h. Aftertocooling
room temperature, the mixturethe
to room temperature, was filteredwas
mixture and filtered
washedand
with DMF
washed withand
DMF methanol. Then, theThen,
and methanol. whitethe
solid
white precipitate obtained was
solid precipitate dried at
obtained was150dried
°C at
for◦24
150 h at24
C for continuous evacuation,
h at continuous yieldingyielding
evacuation, an activated sample ofsample
an activated MOF-801. of MOF-801.
ToToprepare
prepareMOF-801
MOF-801 grains,
grains, the
thesynthesized
synthesizedMOF-801 MOF-801 powder
powder waswaspressed, milled,
pressed, milled,
and sieved
and sieved into
intofractions, withwith
fractions, the grain
the sizes
grain Dgr sizes
= 0.4–0.5Dgrand= 0.8–0.9
0.4–0.5mm (Figure
and S2 inmm
0.8–0.9
the Supplementary
(Figure Materials). Consolidated
S2 in the Supplementary Materials). layers of MOF-801
Consolidated wereofprepared
layers MOF-801 with or- pre-
were
ganic (polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), and polyaniline
pared with organic (polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), and polyaniline (PAN)), in-
organic (bentonite, aluminum oxynitrate (AON), and heat-conductive
(PAN)), inorganic (bentonite, aluminum oxynitrate (AON), and heat-conductive compound compound CPTD),
and hybrid
CPTD), (thermal(thermal
and hybrid grease Aerocool Cog (China))
grease Aerocool Cog binders.
(China))To prepareTothe
binders. glued grains
prepare the glued
configuration (Figure 1b), the appropriate amount of the binder was added to distilled
grains configuration (Figure 1b), the appropriate amount of the binder was added to dis-
tilled water and mixed on a magnetic stirrer. A disc of fixed diameter (1.2 and 1.7 mm for
monolayers of 0.8–0.9 and 0.4–0.5 mm grains, respectively) made of Al foil was treated
with acetone for degreasing, and the obtained binder–water solution/slurry was applied to
it as a thin layer and weighted. Then, MOF-801 grains with a mass mMOF-801 = 100 mg were
evenly distributed on to the disc to form a monolayer, and the foil with the binder and MOF-
801 was weighed again. The minimum binder content was chosen, sufficient for preparing a
strong layer. The strength of the compact layers was estimated by visual control; the layers
were not destroyed or exfoliated under touch stress and after numerous (ca. 10) adsorption–
desorption cycles. To synthesize the MOF-801 coating (Figure 1b), the slurry consisting
of the known amount of MOF-801 powder, binder, and water was applied to pretreated
Al foil using the drop-coating method (Figure S2 in the Supplementary Materials) [7]. The
total mass of the slurry deposited on the foil was calculated as
msl = mMOF-801 /CMOF-801 , (1)
where CMOF-801 is the mass fraction of MOF-801 in the slurry. Thus, the MOF-801 mass
was the same (mMOF-801 = 100 ± 2 mg) for all the studied configurations. The prepared
MOF-801 wet beds were dried at room temperature for 3 h and then at 100 ◦ C for 16 h. The
binder content and the coating thickness were varied.
2.2. Adsorbent Characterization

The structure of prepared MOF-801 was confirmed by powder X-ray diffraction (PXRD)
using a Bruker D8 diffractometer with an XRK-900 reactor chamber. The diffraction patterns
were recorded using CuKα radiation in the range of 2θ from 5◦ to 60◦ . Measurements were
carried out in the scan mode with 0.02◦ increments and an accumulation time of 10 s at
each point. The porous structures of the synthesized MOF-801 and the prepared compact
layers were studied using low-temperature N2 adsorption at 77 K on a Quantachrome
Nova 1200 gas sorption analyzer. The specific surface area, Ssp , was calculated using
BET analysis of the adsorption branch of the isotherm in the relative pressure range of
0.01–0.07. The total pore volume, Vp , was calculated from the amount of N2 adsorbed
at a relative pressure P/P0 = 0.99. The micropore volume, V µ , was calculated using the
statistical thickness analysis of the isotherm adsorption branch and de Boer’s t-method. The
morphology of the prepared beds was characterized with a Stemi 2000-C optical microscope
and a scanning electron microscope Regulus 8230 (Hitachi, Tokyo, Japan) with cold field
emission at probe electron energies of 2.5 and 4 kV.
2.3. Water Adsorption Dynamics

The water adsorption dynamics on MOF-801 were studied using a large temperature
jump method [33] under operating conditions of isobaric stages of a typical adsorptive
cooling cycle (the evaporation, condensation, adsorption, and desorption temperatures
Tev /Tcon /Tads /Tdes = 5/30/30/80 ◦ C, respectively). The experimental rig, consisting of a
measuring cell, a buffering vessel, and an evaporator filled with distilled water, is described
in more detail elsewhere [22,33].
The beds MOF-801-G_S/m composed of monolayers of loose MOF-801 grains (mass
mMOF-801 = 100 ± 2 mg), were deposited on Al foil of 100 µm thickness and placed
on the bottom of the measuring cell. To reduce the contact resistance between the
Al foil and the measuring cell bottom, the foil was glued to the bottom with heat-
conductive compound CPTD. The effect of Al foil on the water adsorption kinetics is minor
(Figure S3 in the Supplementary Materials). Two fractions of loose grains of 0.4–0.5 and
0.8–0.9 mm sizes were used, which correspond to the contact surface, S, between the
monolayer of grains and the foil of 8.9 and 4.5 cm2 (or the ratio S/m = 8.9 and 4.5 m2 /kg),
respectively. The beds MOF-801-G/binder_S/m of glued grains were prepared using
0.8–0.9 mm grains. When preparing coatings MOF-801-C/binder (Cb ,wt%)_S/m, we fixed
the MOF-801 mass mMOF-801 = 100 ± 2 mg and the ratio S/m = 8.9 and 4.5 ± 0.1 m2 /kg,
which correspond to the reference beds of loose grains of 0.4–0.5 and 0.8–0.9 mm sizes,
respectively. This allows a thorough comparison of the sorption dynamics for grains and
coatings and reveals the effects of the bed configuration and binder nature.
The adsorption and desorption kinetics were measured at the vapor pressures
Pev = 9 mbar and Pcon = 43 mbar, which correspond to the temperatures of the evapo-
rator Tev = 5 ◦ C and condenser Tcon = 30 ◦ C, respectively. During adsorption runs, the
beds of loose grains of 0.4–0.5 and 0.8–0.9 mm sizes, respectively. This allows a thorough
comparison of the sorption dynamics for grains and coatings and reveals the effects of the
Nanomaterials 2023, 13, 2442 bed configuration and binder nature. 5 of 16
The adsorption and desorption kinetics were measured at the vapor pressures Pev =
9 mbar and Pcon = 43 mbar, which correspond to the temperatures of the evaporator Tev =
5 °C and condenser
temperature Tcon =support
of the metal 30 °C, respectively.
was dropped During
fromadsorption
the initial runs, the temperature
temperature 60 ◦ C
Tads.in = of
the metal support was dropped from the
◦ initial temperature T =
to the final temperature Tads = 30 C. For desorption runs, the temperature was in-
ads.in 60 °C to the final tem-
perature
creased Tads =T 30 °C.=For
from 55 desorption
◦ C to T runs, the
◦ temperature was increased from Tdes.in = 55
des.in des = 80 C. The initial temperatures of adsorption and
°C to T des = 80 °C. The initial temperatures of adsorption and desorption were selected
desorption were selected according to the isosteric chart of the “MOF-801–water” pair
according
(Figure S1b to inthe
theisosteric chart of the
Supplementary “MOF-801–water”
Materials) pair (Figure
[22]. The water S1b in the Supple-
vapor ad/desorption caused
mentary Materials) [22]. The water vapor ad/desorption caused the decrease/increase in
the decrease/increase in the pressure over the adsorbent, which did not exceed 1.2 mbar;
the pressure over the adsorbent, which did not exceed 1.2 mbar; thus, quasi-isobaric con-
thus, quasi-isobaric conditions typical of the adsorption cooling cycle were maintained.
ditions typical of the adsorption cooling cycle were maintained. The amount of water
The amount of water ad/desorbed, mH2O , was calculated by using the ideal gas equation
ad/desorbed, mH2O, was calculated by using the ideal gas equation from the evolution of
from the evolution of vapor pressure, P(t). The water uptake, ∆w(t) (g/g), was related to
vapor pressure, P(t). The water uptake, Δw(t) (g/g), was related to the unit mass of MOF-
the unit mass of MOF-801 and calculated as
801 and calculated as
∆w(t) = m=H2O
Δw(t) (t)/m
mH2O MOF-801 = =
(t)/mMOF-801 mH2O
mH2O (t), (t), (2) (2)
wheremmMOF-801
where MOF-801 is
isthe
themass
massofofMOF-801
MOF-801loaded
loadedtoto
the measuring
the cell.
measuring TheThe
cell. dimensionless
dimensionless
conversion was calculated
conversion was calculated as as
q q= =∆w(t)/∆w →∝
Δw(t)/Δwtt ,, (3) (3)
where ∆w t ∝ is
where Δwt →
is the
thefinal
finaluptake
uptakevariation.
variation.

3. Results and Discussion

3. Results and Discussion
3.1. Characterization of the MOF-801 Consolidated Beds
3.1. Characterization of the MOF-801 Consolidated Beds
The optical microscope images show that the morphology of the MOF-801 grains glued
The optical microscope images show that the morphology of the MOF-801 grains
to Al foil remains intact (Figure 2a–d). The binder particles are not observed on the grains’
glued to Al foil remains intact (Figure 2a–d). The binder particles are not observed on the
surface. The coating is homogeneous, and a slight roughness is detected on its surface
grains’ surface. The coating is homogeneous, and a slight roughness is detected on its
(Figure 2e). SEM images of MOF-801 show that loose MOF-801 grains are constituted by
surface (Figure 2e). SEM images of MOF-801 show that loose MOF-801 grains are consti-
antuted
assemblage of primary
by an assemblage particlesparticles
of primary of irregular shape and
of irregular shape0.5–1.5 µm inµm
and 0.5–1.5 size
in (Figure
size (Fig-3a,b).
These
ure 3a,b). These primary particles are observed also in SEM images of glued grainscoatings.
primary particles are observed also in SEM images of glued grains and and
The shapeThe
coatings. andshape
size and
of the
sizeprimary particles
of the primary are similar
particles for loose
are similar and
for loose glued
and gluedgrains
grainsand
coatings. A slight
and coatings. smoothening
A slight smootheningcan be
candetected in the
be detected in coating (Figure
the coating 3e),3e),
(Figure probably due to
probably
the binder (PVP).
due to the binder (PVP).
Figure 2.2. Optical

Figure Opticalmicroscopic images
microscopic of loose
images grains grains
of loose MOF-801_G_4.5 (a), glued(a),
MOF-801_G_4.5 grains
gluedMOF-grains
801_G/CPTD_4.5 (b), MOF-801_G/PVP_4.5 (c), MOF-801_G/bentonite_4.5 (d), and coating MOF-
Nanomaterials 2023, 13, x FOR PEERMOF-801_G/CPTD_4.5
REVIEW (b), MOF-801_G/PVP_4.5 (c), MOF-801_G/bentonite_4.5 (d), and 6 ofcoating
16
801_C/PVP(10)_8.9 (e).
MOF-801_C/PVP(10)_8.9 (e).
Figure3.3.SEM
Figure SEMimages
images of
of loose
loose grains
grainsMOF-801_G_4.5
MOF-801_G_4.5(a,b), glued
(a,b), grains
glued MOF-801_G/bentonite_4.5
grains MOF-801_G/bentonite_4.5
(c), MOF-801_G/PVP_4.5 (d), and coating MOF-801_C/PVP(10)_8.9 (e).
(c), MOF-801_G/PVP_4.5 (d), and coating MOF-801_C/PVP(10)_8.9 (e).
According to low-temperature N2 adsorption data (Figure S4a and Table 1), as-pre-
pared MOF-801 powder is meso-microporous, with a high specific surface area of 900 m2/g
and total pore volume of 0.49 cm3/g (Table 1). The experimental PXRD pattern (Figure S4b)
is consistent with the literature data and the pattern simulated from single-crystal X-ray
data [21]. These results confirm the genuine structure and high porosity of the synthesized
MOF-801.
According to low-temperature N2 adsorption data (Figure S4a and Table 1), as-
prepared MOF-801 powder is meso-microporous, with a high specific surface area of
900 m2 /g and total pore volume of 0.49 cm3 /g (Table 1). The experimental PXRD pattern
(Figure S4b) is consistent with the literature data and the pattern simulated from single-
crystal X-ray data [21]. These results confirm the genuine structure and high porosity of
the synthesized MOF-801.
Table 1. Composition and texture characteristics of the prepared MOF-801 beds. Binder content, Cb ,
specific surface area, Ssp , total pore volume, V p , micropore volume, V µ , and clogging degree, δ.
Sample Cb [wt%] Ssp * [m2 /g] V p * [cm3 /g] V µ * [cm3 /g] δ, %

MOF-801 as prepared - 900 0.49 0.27 -
MOF-801_G - 820 0.45 0.23 -
Glued grains, 0.8–0.9 mm
MOF-801_G/PVA 10 757 0.43 0.22 4
MOF-801_G/PVP 10 774 0.45 0.24 0
MOF-801_G/PAN 5 803 0.46 0.24 0
MOF-801_G/AON 40 724 0.41 0.21 9
MOF-801_G/bent 40 863 0.57 0.24 −27
MOF-801_G/CPTD 40 380 0.32 0.11 29
MOF-801_G/Aerocool 40 732 0.42 0.27 7
MOF-801_G/HEC 10 695 0.40 0.19 11
Coatings
MOF-801_C/PVP(5) 5 858 0.44 0.26 10
MOF-801_C/PVP(10) 10 830 0.43 0.25 12
MOF-801_C/bent(20) 20 954 0.54 0.28 −10
MOF-801_C/bent(40) 40 1089 0.67 0.37 −37
* For consolidated layers prepared with binders, the data are related to the unit mass of the MOF.
Pressing powder to form grains leads to a slight decrease in the specific surface
area to 820 m2 /g and the pore volume to 0.45 cm3 /g. Using the binders further changes
the texture characteristics of the compact beds. The pore size distribution, calculated
using the Dubinin–Astakhov model, is similar for loose grains and compact layers
(Figure S5 in the Supplementary Materials).
To characterize the influence of the binder on the texture characteristics of MOF-801,
the clogging degree is calculated as
δ = (V p − V p_l )/V p × 100%, (4)
where V p and V p_l are the specific pore volumes of the pristine MOF-801 and consolidated
layers, respectively. When calculating δ for the glued grains and coatings, V p was taken for
MOF-801 grains and the powder, respectively.
The clogging degree is minor (δ = 0–11%) for organic binders PVA, PVP, PAN, and HEC,
and thermal grease Aerocool (Table 1). CPTD strongly reduces the specific pore volume
due to partial clogging of the pores of MOF-801, or destroys its structure, with the degree
δ = 29%. On the contrary, using bentonite as a binder increases both specific pore volume
and surface area; the degree, δ, formally calculated according to Equation (2), is negative
for the compact layers prepared with bentonite (Table 1). A probable reason could be the
intrinsic porosity of bentonite clay. Bentonite is a layered clay mineral with interlayer and
intergranular porosity and a total pore volume of about 0.1–0.2 cm3 /g [34,35]. Accordingly,
the addition of porous bentonite to MOF-801 increases the specific pore volume and surface
area of the layers related to the unit mass of the MOF.
3.2. Water Vapor Adsorption Dynamics

3.2.1. Glued MOF-801 Grains
First, the final uptake variation, ∆wt→∝ = 0.22 ± 0.01 g/g, was measured for loose
grains of MOF-801 under conditions of the cooling cycle (Tev /Tads /Tdes = 5/30/80 ◦ C,
respectively) (Table 2). It is close to the uptake variation, ∆w = 0.21 g/g, calculated for the
considered cycle from the isosteric chart of water adsorption for as-synthesized MOF-801
powder (Figure S1b in the Supplementary Materials) [22]. Most binders used for gluing
the grains to Al foil change the uptake variation related to the unit mass of MOF-801 only
slightly: ∆wt→∝ = 0.20–0.24 g/g for MOF-801_G/binder_4.5 beds. Thus, they have little
effect on the adsorption capacity of MOF-801. Aluminum oxynitrate reduces dramatically
the water uptake on glued MOF-801 grains to ∆wt→∝ = 0.12 ± 0.01 g/g. The degree δ = 9%
for MOF-801/AON is moderate; consequently, pore blockage is unlikely to cause such a
decrease in uptake variation. Probable reasons for the reduction might be: (i) a chemical
interaction of AON with the adsorption sites of MOF-801, leading to their deactivation; or
(ii) a change in the crystallinity of MOF-801, which also has a strong effect on its adsorption
properties [21]. This sample was no longer considered.
Table 2. The characteristic times of water adsorption/desorption τ1 , τ2 , τ0.7 and τ0.8 and the final
water uptake, ∆wt→∝ , for the glued grains of MOF-801, Dgr = 0.8–0.9 mm.
Configuration τ1, s τ2, s A t0.7 , s t0.8 , s ∆wt→∝ , * g/g

Adsorption
MOF-801_G_4.5 88 170 0.21 170 245 0.21
MOF-801_G/CPTD_4.5 87 210 0.29 185 270 0.20
MOF-801_G/Aerocool_4.5 67 160 0.23 140 210 0.20
MOF-801_G/bent_4.5 81 150 0.15 155 220 0.22
MOF-801_G/PVA_4.5 130 330 0.21 320 460 0.20
MOF-801_G/PVP_4.5 69 160 0.29 140 200 0.21
MOF-801_G/PAN_4.5 113 200 0.15 220 300 0.20
MOF-801_G/HEC_4.5 77 130 0.20 130 185 0.20
Desorption
MOF-801-G_4.5 117 480 0.68 150 240 0.23
MOF-801_G/CPTD_4.5 98 290 0.61 130 200 0.23
MOF-801_G/Aerocool_4.5 91 310 0.64 115 185 0.22
MOF-801_G/bent_4.5 103 300 0.63 130 195 0.24
MOF-801_G/PVA_4.5 127 320 0.69 150 215 0.22
MOF-801_G/PVP_4.5 108 460 0.70 145 235 0.23
MOF-801_G/PAN_4.5 145 270 0.53 175 250 0.24
MOF-801_G/HEC_4.5 106 360 0.67 135 205 0.22
* The uptake is related to the unit mass of MOF-801.
The kinetic curves of water adsorption and desorption “dimensionless uptake, q,

vs. time, t,” for glued grains MOF-801_G/binder_4.5 and reference loose grains MOF-
801_G_4.5 of 0.8–0.9 mm size (Figure 4) are monotonically increasing lines approaching
q = 1. When presented in coordinates of the first-order equation “ln(1 − q) vs. t”, the kinetic
curves turn into two straight lines (Figures S6 and S7 in the Supplementary Materials),
indicating that they can be described by the sum of two exponents
q(t) = A [1 − exp(−t/τ 1 )] + (1 − A) [1 − exp(−t/τ 2 )], (5)
where τ1 and τ2 are the characteristic times and A is the fitting parameter (Table 2). This
may show that, during ad/desorption, the rate-limiting process changes. The characteristic
time τ 1 = 67–130 and 91–145 s for adsorption and desorption runs, respectively, describes
the initial fast process. The second time, τ2 = 130–330 and 270–460 s, respectively, is
longer for both runs and is associated with a further slower process. The relative error in
Nanomaterials 2023,
Nanomaterials 13,13,
2023, xx FOR
xx FOR
determining
PEER
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the characteristic times is 10%. The coefficient A equal to (0.11–0.29)8±8of0.05
of16
Nanomaterials
Nanomaterials
Nanomaterials 2023,
2023,
2023, x13,
13,13, FOR
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Nanomaterials 2023, 13, x FOR PEER for adsorption shows the fraction, q, of water adsorbed according to the first fast88process.
REVIEW of 16
For desorption runs, the transition to the slow process occurs at a much higher conversion:
q = A = (0.53–0.69) ± 0.05.
Figure 4. The
Figure
Figure
Figure
Figure
Figure 4.4. 4.
4.
4.Thekinetic
TheThe
The
The curves
kinetic
kinetic
kinetic
kinetic
kinetic curves ofofof
curves
curves
curves
curves water
water
of
of
ofwater vapor
water
water
water vapor adsorption
vapor
vapor
vapor
vapor adsorption
adsorption
adsorption
adsorption
adsorption (a)
(a)
(a) and
and
(a)(a)
(a)
and
and and
and desorption
desorption
desorption
desorption
desorption
desorption (b)
(b)(b)
(b)
(b) for
for
(b) for
for
for glued
glued
for glued
glued
glued
glued MOF-801
MOF-801
MOF-801
MOF-801
MOF-801
MOF-801
Figure
grains
grains 4.
grains The kinetic curves
MOF-801_G/CPTD_4.5
MOF-801_G/CPTD_4.5
MOF-801_G/CPTD_4.5 of water
(),
(,), (), vapor adsorption
MOF-801_G/Aerocool_4.5 (a)
MOF-801_G/Aerocool_4.5
MOF-801_G/Aerocool_4.5 and desorption
(),(),
((), (b) for
MOF-801_G/PVA_4.5 glued
MOF-801_G/PVA_4.5
),MOF-801_G/PVA_4.5
MOF-801_G/PVA_4.5 MOF-801
(), ),MOF-
(),
((), MOF-
MOF-
grains
grains
grains MOF-801_G/CPTD_4.5
MOF-801_G/CPTD_4.5
MOF-801_G/CPTD_4.5 (), (),MOF-801_G/Aerocool_4.5
(), MOF-801_G/Aerocool_4.5
MOF-801_G/Aerocool_4.5 (), (), MOF-801_G/PVA_4.5
MOF-801_G/PVA_4.5 (),
(), MOF-
MOF-
MOF-
grains MOF-801_G/CPTD_4.5
801_G/PVP_4.5
801_G/PVP_4.5 (),
(), (), MOF-801_G/Aerocool_4.5
MOF-801_G/bent_4.5
MOF-801_G/bent_4.5 (),
(), (), MOF-801_G/PVA_4.5
MOF-801_G/HEC_4.5
MOF-801_G/HEC_4.5 (),
(), (), MOF-
MOF-801_G/PAN_4.5
MOF-801_G/PAN_4.5 (),
(),
801_G/PVP_4.5
801_G/PVP_4.5
801_G/PVP_4.5
801_G/PVP_4.5 ( (), (),
),(), MOF-801_G/bent_4.5
MOF-801_G/bent_4.5
MOF-801_G/bent_4.5
MOF-801_G/bent_4.5 ),(),
( (),
(), MOF-801_G/HEC_4.5
MOF-801_G/HEC_4.5
MOF-801_G/HEC_4.5
MOF-801_G/HEC_4.5 ( (),
(),
(), MOF-801_G/PAN_4.5
MOF-801_G/PAN_4.5
),MOF-801_G/PAN_4.5
MOF-801_G/PAN_4.5 ((),
(),
(), ),
801_G/PVP_4.5
and
andthethe (), MOF-801_G/bent_4.5
reference
reference bedbedof loose
of loose grains
grains (), MOF-801_G/HEC_4.5
MOF-801_G_4.5
MOF-801_G_4.5 ().
(). D D
gr = (),
0.8–0.9
= MOF-801_G/PAN_4.5
mm.
0.8–0.9 mm. (),
and and
and
and
thethe the
the reference
reference
reference
reference bedbed bed
bed
ofofof of
loose
loose loose
loose grains
grains
grains
grains MOF-801_G_4.5
MOF-801_G_4.5
MOF-801_G_4.5
MOF-801_G_4.5 ().
( ).().
(). D
D D D
gr ==
gr
gr
gr gr
= = 0.8–0.9
0.8–0.9
0.8–0.9
gr
0.8–0.9 mm. mm.
mm.
mm.
and the reference bed of loose grains MOF-801_G_4.5 (). Dgr = 0.8–0.9 mm.
Table
Table
Table
Table 2.
2. The
2.
2.
TheThe
The characteristic
characteristic
characteristic
characteristic times
times
times
times of
of water
of
of adsorption/desorption
water
water
water adsorption/desorption
adsorption/desorption
adsorption/desorption τ1,τ,2τ1τ1,,22,ττ,0.7
1τ1τ
τ2τ2,,0.7 and
ττ0.7
andand
and ττ0.8 and
ττ0.8
and the
and
and final
the
the
the water
final
final
final water
water
water
For
Table reference
2.2.The
The characteristic bed times
MOF-801-G_4.5
times ofwater
water of loose grains,
adsorption/desorption ,1,ττ2,2the
ττ1mm. ,ττ0.70.7 characteristic
and
0.7 0.7
ττ0.80.8and
0.8 and
0.8 0.8 the times
final waterare
Table
uptake,
uptake, w
w w
characteristic
tw
t ,
for
, the
for glued
the glued of
grains
grainsofofadsorption/desorption
MOF-801,
MOF-801,D D
gr = 0.8–0.9
= mm.
0.8–0.9 and the final water
w
uptake, , for the glued grains of MOF-801,gr D = 0.8–0.9 mm.
uptake, tt , for
t the glued grains ofMOF-801,
MOF-801, D gr
=0.8–0.9
0.8–0.9 mm.
uptake, 
 , for the glued grains of D =
gr gr mm.
= 88 and
τ1uptake, wt120
t
, forsthe and = 170ofand
τ2 grains
glued 480 sDfor
MOF-801, gr adsorption
gr = 0.8–0.9 mm. and desorption, respectively,
Configuration
Configuration τ ,,the
1τ 1s,, ss adsorbent τ2, s ss A tbinders
,0.7
, ss,, ss cant0.8
tlead ,0.8
, ss,, sto w w
w , *,, g/g
(Table 2). Gluing τ2,22τ,s2τsτ, 22s,, grains to A
Al
A foil by 0.7 tt0.7 ,tts0.8 s both w acceleration *g/g
* g/g
ttt
Configuration
Configuration
Configuration
Configuration
1τ1τ 1s
ττ1,1,ssof waterτAdsorption
A
AA (Figurett0.7
t0.7
, ,ssFor the tgrains
0.70.7 t0.8
0.80.8
0.8, s
w
w

tt ,
t
t, * g/g
*, *g/g g/g
and deceleration ad/desorption
Adsorption
Adsorption
Adsorption
Adsorption 3). glued by Aerocool,
bentonite, PVP, and Adsorption
MOF-801_G_4.5
MOF-801_G_4.5
MOF-801_G_4.5
MOF-801_G_4.5
MOF-801_G_4.5 88
88
8888 88HEC, the 170
170characteristic
170 170
170 0.21
0.21
time, τ 1 , which
0.21
0.21
0.21 170
170170 170 describes
170 245
245
245 245
245 the initial fast 0.21
0.21
0.21
0.21
0.21
process,
MOF-801_G_4.5 decreases
MOF-801_G/CPTD_4.5 to 88
67–77 s. A 170
similar effect is0.21
observed for170
desorption, 245
where time 0.21 diminishes
MOF-801_G/CPTD_4.5
MOF-801_G/CPTD_4.5
MOF-801_G/CPTD_4.5
MOF-801_G/CPTD_4.5 8787
8787 87 210 210
210 210
210 0.29
0.29
0.29
0.29
0.29 185
185185 185
185 270270
270 270
270 τ 0.20
10.20 0.20
0.20
0.20
MOF-801_G/CPTD_4.5to
MOF-801_G/Aerocool_4.591–106
MOF-801_G/Aerocool_4.5 s. On 87the67 67 contrary, 210 PVA
160 160 and 0.29
PAN0.23
0.23 185
essentially 140 decelerate
140 270 ad/desorption,
210 210 0.20 0.20 and time
0.20
MOF-801_G/Aerocool_4.5 6767 67 160 160 160 0.23
0.23
0.23 140140 140 210210 210 0.20
0.20
0.20
MOF-801_G/Aerocool_4.5 67
τ 1 rises (Table 2).81 This 160 0.23 140 210 0.20
MOF-801_G/bent_4.5
MOF-801_G/bent_4.5
MOF-801_G/bent_4.5
MOF-801_G/bent_4.5
MOF-801_G/bent_4.5 818181 81 is quite 150
150
150
surprising,
150
150 0.15
since the grains
0.15
0.15
0.15
0.15 155
155155 155 are glued
155 220
220
220 220
220 to Al foil with 0.22
0.22
0.22
0.22
0.22
binder,
MOF-801_G/bent_4.5and the contact81surface
MOF-801_G/PVA_4.5
MOF-801_G/PVA_4.5 130130 area 150 between
330 330 0.15
the grains
0.21
0.21 and155 the
320 320 220
foil increases,
460 460 0.22
thus decreasing0.20
0.20 the
MOF-801_G/PVA_4.5
MOF-801_G/PVA_4.5
MOF-801_G/PVA_4.5 130 130130 330 330 330 0.21
0.21
0.21 320320 320 460460 460 0.20
0.20
0.20
MOF-801_G/PVA_4.5 contact
MOF-801_G/PVP_4.5
MOF-801_G/PVP_4.5 130
resistance 6969 to the 330
heat 160 transfer. 0.21
Accordingly,
0.29 320 an
140 460
increase in
200 the 0.20
sorption 0.21 rate can
MOF-801_G/PVP_4.5
MOF-801_G/PVP_4.5
MOF-801_G/PVP_4.5
MOF-801_G/PVP_4.5 be expected. 69 696969 160
160
160 160
160 0.29
0.29
0.29
0.29
0.29 140
140
140 140
140 200
200
200 200
200 0.21
0.21
0.21
0.21
0.21
MOF-801_G/PAN_4.5
MOF-801_G/PAN_4.5
MOF-801_G/PAN_4.5
MOF-801_G/PAN_4.5 113113
113113 200
200 200
200 0.15
0.15
0.15
0.15 220
220 220
220 300
300 300
300 0.20
0.20
0.20
0.20
MOF-801_G/PAN_4.5
MOF-801_G/PAN_4.5 In actual 113 113
practice, the 200
200 duration of0.15
0.15 ad/desorption 220
220 300
stages300
is185 usually 0.20
limited
0.20 by the
MOF-801_G/HEC_4.5
MOF-801_G/HEC_4.5
MOF-801_G/HEC_4.5
MOF-801_G/HEC_4.5 77
7777 77 130
130 130
130 0.20
0.20
0.20
0.20 130
130 130
130 185 185
185 0.20
0.20
0.20
0.20
MOF-801_G/HEC_4.5
MOF-801_G/HEC_4.5 conversion q = 7777
0.7–0.8 to 130
avoid
130 slowing 0.20
down
0.20 the 130
sorption
130 when 185
185approaching 0.20
0.20equilibrium
Desorption
Desorption
Desorption
Desorption
Desorption
(q = 1). Accordingly, for the convenience
Desorption of comparing different adsorbent bed configura-
MOF-801-G_4.5
MOF-801-G_4.5
MOF-801-G_4.5
MOF-801-G_4.5 117117
117 480 480
480 0.68
0.68
0.68 150 150
150 240 240
240 0.23
0.23
0.23
MOF-801-G_4.5
MOF-801-G_4.5 tions, the times 117
117 t117
0.7 and t0.8480
480 480
, corresponding 0.68
0.68
0.68 150150
to the conversion
150 =240
q 240 240
0.7 and 0.8,0.23 0.23
0.23
respectively,
MOF-801_G/CPTD_4.5
MOF-801_G/CPTD_4.5
MOF-801_G/CPTD_4.5
MOF-801_G/CPTD_4.5 98
98 98
98 290
290 290
290 0.61
0.61
0.61
0.61 130
130 130
130 200
200 200
200 0.23
0.23
0.23 trend
0.23
MOF-801_G/CPTD_4.5
MOF-801_G/CPTD_4.5were determined 98
9891 from the sorption 290
290 0.61
kinetics
0.61 (Table 2). 130
130 Similar to time 200
200 τ 1 , a downward 0.23
0.23
MOF-801_G/Aerocool_4.5 91 91 91
91 310 310
310 310
310 0.64
0.64
0.64
0.64
0.64 115
115115 115
115 185185
185 185
185 0.22
0.22
0.22
0.22
0.22
was also observed
MOF-801_G/Aerocool_4.5 91103 for times 310 t0.7 and t0.8 0.64for the grains
115 glued by185 Aerocool, bentonite, 0.22 PVP,
MOF-801_G/bent_4.5
MOF-801_G/bent_4.5
MOF-801_G/bent_4.5
MOF-801_G/bent_4.5 103
103103 300
300 300
300 0.63
0.63
0.63
0.63 130
130 130
130 195
195 195
195 0.24
0.24
0.24
0.24
MOF-801_G/bent_4.5
MOF-801_G/bent_4.5and HEC (Table 103
103 2). 300
300 0.63
0.63 130
130 195
195 0.24
0.24
MOF-801_G/PVA_4.5
MOF-801_G/PVA_4.5
MOF-801_G/PVA_4.5Thus, the effect
MOF-801_G/PVA_4.5 127127
127127of gluing 320
320 320
320
the MOF-801 0.69
0.69
0.69
0.69grains to 150
150
Al 150
150 foil on the 215
215 215
215
water sorption 0.22
0.22
0.22
0.22 kinetics
MOF-801_G/PVA_4.5
MOF-801_G/PVA_4.5 127
127 320
320 0.69
0.69 150
150 215
215 0.22
0.22
MOF-801_G/PVP_4.5
MOF-801_G/PVP_4.5
MOF-801_G/PVP_4.5
MOF-801_G/PVP_4.5
MOF-801_G/PVP_4.5strongly depends 108108108
108108on the binder’s460 460
460 460
460 chemical 0.70
0.70
0.70nature.145
0.70
0.70 145
145 145
145
Aerocool, 235235
235 235
235
bentonite, PVP, 0.23
0.23 0.23
0.23 HEC
0.23
and
MOF-801_G/PVP_4.5
MOF-801_G/PAN_4.5
MOF-801_G/PAN_4.5 108 145145 460 270 270 0.70
0.53
0.53 145 175 175 235 250 250 0.23 0.24
0.24
MOF-801_G/PAN_4.5
MOF-801_G/PAN_4.5
MOF-801_G/PAN_4.5accelerate ad/desorption.
145 145145 On
270 270 270
the contrary, 0.530.53
0.53PVA and175 175
PAN 175 slow down 250250 250them. 0.24 0.24
0.24
MOF-801_G/PAN_4.5
MOF-801_G/HEC_4.5
MOF-801_G/HEC_4.5 145 106106 270 360 360 0.53
0.67
0.67 175 135 135 250 205 205 0.24 0.22
0.22
MOF-801_G/HEC_4.5
MOF-801_G/HEC_4.5
MOF-801_G/HEC_4.5 106 106106 360 360 360 0.67
0.67
0.67 135135 135 205205 205 0.22
0.22
0.22
MOF-801_G/HEC_4.5 * The uptake
* The 106
uptake is isrelated
related toto 360
the
the unit unit mass of0.67
mass MOF-801. 135
MOF-801.
of 205 0.22
* The
* The uptake
uptake is related
isrelated
related to
tothe the
the unit
unit mass
mass ofofof MOF-801.
MOF-801.
**The
The uptake
uptake isisrelated totothe unit
unit mass
mass of MOF-801.
MOF-801.
For reference
For reference bed
bed MOF-801-G_4.5
MOF-801-G_4.5 ofofloose grains,
loose grains, the
thecharacteristic
characteristic times
timesare
are τ1 ==11 =88
For
For
For
For reference
reference
reference
reference
bed
bed
bed
bed MOF-801-G_4.5
MOF-801-G_4.5
MOF-801-G_4.5
MOF-801-G_4.5 ofof
of
of loose
loose
loose
loose
grains,
grains,
grains,
grains, the
the
the
the characteristic
characteristic
characteristic
characteristic
times
times
times
times are
are
are τ1 11τ==1ττ88
are
τ(Table 88=8888
88
and
and
and
and 120 ss sand
120
120
120 s and
and
and ττ2τ
τ=
= 170
22 =
=
170170
170and
and
and
and 480
480
480
480 s
s for
s
s adsorption
for
for
for adsorption
adsorption
adsorption and
and
and
and desorption,
desorption,
desorption,
desorption, respectively,
respectively,
respectively,
respectively, (Table
(Table
(Table 2).2).
2).2).
and120
and 120ssand
andττ2 22==170
2 170andand480
480ssforforadsorption
adsorptionand anddesorption,
desorption,respectively,
respectively,(Table
(Table2). 2).
Gluing
Gluing the
theadsorbent
adsorbent grains
grainstoto
AlAlfoil
foilbybybinders
binderscan
canlead
leadtotoboth
bothacceleration
accelerationand anddecel- decel-
3.2.2. MOF-801/Binder Coatings

We then selected two of the binders accelerating the sorption (PVP and bentonite)
and prepared MOF-801 coatings with them on the Al foil from MOF-801 powder. During
preparation of the coatings, we varied the binder content and the coating thickness. “Thick”
coating MOF-801_C/PVP(10)_4.5 was prepared with the S/m ratio equal to 4.5 m2 /g, as
for the reference monolayer of 0.8–0.9 mm grains of MOF-801. For “thin” coatings, the
S/m-ratio of 8.9 m2 /g was equal to that for the reference monolayer of 0.4–0.5 mm grains.
Similar to loose and glued MOF-801 grains, all kinetics of the water adsorption on and
desorption from the coatings (Figure S8 in the Supplementary materials) are well described
by Equation (3), with characteristic times τ 1 and τ 2 associated with the initial fast and
further slow processes, respectively (Table 3).
Table 3. The characteristic times of water adsorption/desorption τ1 , τ2 , τ0.7 , and τ0.8 and the final
water uptake, ∆wt→∝ , for MOF-801 coatings.
Sample τ1, s τ2, s A t0.7 , s t0.8 , s ∆wt→∝ , * g/g

Adsorption
MOF-801-G_4.5 88 173 0.21 170 245 0.21
MOF-801_C/PVP(10)_ 4.5 87 241 0.79 115 148 0.20
MOF-801-G_8.9 50 155 0.61 72 111 0.18
MOF-801_C/PVP(10)_8.9 28 68 0.60 40 59 0.20
MOF-801_C/PVP(5)_8.9 38 49 0.18 48 67 0.22
MOF-801_C/bent(40)_8.9 58 94 0.18 94 134 0.22
MOF-801_C/bent(20)_8.9 59 84 0.15 98 135 0.22
Desorption
MOF-801-G_4.5 103 476 0.68 150 240 0.23
MOF-801_C/PVP(10)_4.5 50 540 0.82 61 88 0.21
MOF-801-G_8.9 33 507 0.78 47 69 0.18
MOF-801_C/PVP(10)_8.9 20 602 0.77 32 56 0.21
MOF-801_C/PVP(5)_8.9 15 637 0.80 21 31 0.23
MOF-801_C/bent(40)_8.9 31 633 0.76 64 122 0.24
MOF-801_C/bent(20)_8.9 27 787 0.77 49 94 0.24
The comparison of water sorption kinetics for thick beds with S/m = 4.5 m2 /kg shows
that the ad/desorption for the coating MOF-801_C/PVP(10)_4.5 is faster than for both
reference beds of loose grains MOF-801_G_4.5 and glued grains MOF-801_G/PVP_4.5
(Figure 5). The acceleration effect is more significant at longer times (larger conversion),
so that the time, t0.8 , decreases by factors of 1.6 and 2.7 for adsorption and desorption,
respectively, compared with loose grains (Table 3). The coefficient A = 0.69 for adsorption
on the coating is much higher than A = 0.21 and 0.29 for loose and PVP-glued grains,
respectively. This indicates that, for coating MOF-801_C/PVP(10)_4.5, the transition from
the initial fast process to the further slow one occurs at a higher conversion than for loose
grains MOF-801_G_4.5 and glued grains MOF-801_G/PVP_4.5.
Nanomaterials Nanomaterials
2023, 13,
Nanomaterials
Nanomaterials
Nanomaterials x FOR
2023,
2023, 2023,
13,
2023,
13, xPEER
Nanomaterials 13,
FOR
x 13,
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MOF-801_C/bent(40)_8.931 31 3131633
MOF-801_C/bent(40)_8.9
MOF-801_C/bent(40)_8.9
MOF-801_C/bent(40)_8.9
MOF-801_C/bent(40)_8.9 31 31 633
63331633 633 0.7664
0.766330.760.76 640.7664 6464122 1220.24
12264122 122 0.24
122 0.24 0.24
0.24
Nanomaterials 2023, 13, 2442 MOF-801_C/bent(40)_8.9
MOF-801_C/bent(40)_8.9 0.76 10 of 16 0.24
MOF-801_C/bent(20)_8.9
MOF-801_C/bent(20)_8.9
MOF-801_C/bent(20)_8.9
MOF-801_C/bent(20)_8.9 27
MOF-801_C/bent(20)_8.9
MOF-801_C/bent(20)_8.9 27 27 2727787
78727 787 787
787 0.77
0.777870.77 0.77
0.77 49
490.7749 4949 94
94 49 94 9494 0.24
94
0.24 0.24 0.24 0.24
0.24
* The uptake
** The * is
TheThe
uptake *uptake
related
The* uptake is
uptake
The to is
the
is related
is therelated
unit
to
related
related
uptake to the
to
the
is to
massthe
unit
the
unit
related ofunit
unit
mass
to mass
MOF-801.
mass of
mass
theof of MOF-801.
MOF-801.
ofmass
MOF-801.
MOF-801.
unit of MOF-801.
* The uptake is related to unit mass of MOF-801.
Figure 4. The kinetic curves of water vapor adsorption (a) and desorption (b) for glued MOF-801
Figure 5.5.
FigureFigure Figure
The
5. The
FigureThe5. 5.
kinetic
kinetic
5. TheThe kinetic
curves
curves
kinetic curves
of
of water
of water
curves
kinetic of
curves of
vapor
water
of water
vapor vapor
adsorption
vapor
waterofvapor adsorption
adsorption
(a)
adsorptionand(a)
adsorption (a)(a)
(a) andand
desorption
and desorption
desorption
(b)
desorptionfor(b)
desorption (b)(b)
coatings
for forfor
(b) (b)coatings
for
MOF-
coatings coat-
MOF-
coatings MOF-M
MOF-
FigureFigure
grains MOF-801_G/CPTD_4.5 (), MOF-801_G/Aerocool_4.5
The5.kinetic
The kinetic
Figure 5.
(),
curves curves
The kineticwater
curves
MOF-801_G/PVA_4.5
of water vapor vapor adsorption
water
(), vapor (a)desorption
and
(a) andadsorption
MOF-
adsorption desorption
(a) and
(b) (b) for
fordesorption
coatingscoatings
MOF- MOF-
for coatings
801_G/PVP_4.5 (), MOF-801_G/bent_4.5ings 801_C/PVP(10)_4.5
801_C/PVP(10)_4.5 (▲),
801_C/PVP(10)_4.5
801_C/PVP(10)_4.5
801_C/PVP(10)_4.5
MOF-801_C/PVP(10)_4.5
(), MOF-801_G/HEC_4.5 glued
(▲),
(▲), (▲),
grains
glued
(▲),
glued
801_C/PVP(10)_4.5 glued
grains
(▲), grains MOF-801_G/PVP(10)_4.5
MOF-801_G/PVP(10)_4.5
grains
glued MOF-801_G/PVP(10)_4.5
grains ()
MOF-801_G/PVP(10)_4.5
MOF-801_G/PVP(10)_4.5
glued
( MOF-801_G/PAN_4.5grains and
()
()
MOF-801_G/PVP(10)_4.5
), MOF-801_G/PVP(10)_4.5
glued grains MOF-801_G/PVP(10)_4.5 ()
loose
and
()
and and
grains
loose
and loose
loose
loose
()grains
and grains
MOF-801-G_4.5
grainsgrains
loose
( MOF-801-G_4.5 MOF-801-G_4.5
MOF-801-G_4.5
MOF-801-G_4.5
MOF-801-G_4.5
grains
) and loose grains MOF-801-G
801_C/PVP(10)_4.5 (▲), glued(),
grains (), () and loose grains
(). (). (). ().
(). ().(). (().
and the reference bed of loose grainsMOF-801-G_4.5
MOF-801_G_4.5 ). Dgr = 0.8–0.9 mm.
Unfortunately,
Unfortunately, Unfortunately,
Table 2. The characteristic times of water adsorption/desorption
Unfortunately, we
Unfortunately, 1failed
, τwe
Unfortunately,
Unfortunately,
we
weτfailed we
to
2, τ0.7
failed we
toand
failed τfailed
prepare
to
failed
prepare
preparewe
0.8 to
and to
sufficiently
prepare
failed
theprepare
prepare
to
final
sufficiently sufficiently
strong
sufficiently
sufficiently
prepare
sufficiently
water
strong thick
strong strong
sufficiently
strong thick
thick thick
coatings
thick
strong thick
strong
coatings
coatings coatings
with
coatings lower
with
coatings
thick
with
with with
PVP
lower
with
coatings
lower
lower PVP lower
lower
with
PVP PVP P
PVPPVP
lower
uptake, wt, for the glued grains ofcontent
content
MOF-801, and
content
contentandD content
content
gr = and
bentonite.
and and
content
0.8–0.9
andbentonite. mm. bentonite.
For
bentonite.
bentonite.
and
bentonite. For this this
For ForFor
reason,
this
bentonite.
this reason, this
this
reason,the the
reason,
For reason,
kinetic
the
reason,
this
thekinetic the
data
kinetic
the
reason,
kineticdata kinetic
for
data
kinetic
the
dataforfor data
other
for
data
kinetic
other
other forfor other
coatings
otherother
data for
coatings
coatings coatings
were
coatings
coatings
other
were were were
prepared
were were
coatings prepared
prepared
prepared
prepared prepa
prepared were
withS/mS/m
with= ==withwith
8.9
S/m and
S/mS/m
=and
with =S/m
8.9 8.9
compared
8.9compared
=and andand
compared
= 8.9 compared
with
compared
and the
with
compared with
reference
the
with the the
reference
with reference
bed
reference
the bed
MOF-801-G_8.9
bed MOF-801-G_8.9
MOF-801-G_8.9
bed
reference of loose
MOF-801-G_8.9 loose
bed MOF-801-G_8.9 ofof
grains
ofofloose loose
looseof
grains 0.4–grains
of 0.4–
grains
of0.4–
loose ofof of
grains 0.4–
0.4– of 0
tion τ2, s with
τ1, s with
0.5
S/m
A
mm0.5 size
mm0.5
8.9and
8.9
0.5 mmt0.7size
(Figure
size
mm
compared
,(Figure
s 5).
size (Figure
The
(Figure5).
with
The
with
tcoatings
0.8, s
5).5).
the
The
coatings
The
the w reference
reference t, * g/g
coatings
prepared
coatings prepared
bed bed
prepared
with
prepared PVP
with
MOF-801-G_8.9
MOF-801-G_8.9
with PVP
of loose
grains of
(MOF-801_C/PVP(5)_8.9
(MOF-801_C/PVP(5)_8.9
PVP
with (MOF-801_C/PVP(5)_8.9
PVP (MOF-801_C/PVP(5)_8.9
grains
and and andand
0.5 mm
0.4–0.5 mm size size 0.5
(Figure
(Figure mm size
5).5).TheThe (Figure
coatings
coatings 5). The
prepared
prepared coatingswith with prepared
PVP PVP with PVP
(MOF-801_C/PVP(5)_8.9
(MOF-801_C/PVP(5)_8.9 (MOF-801_C/PVP(5)_8.9
andand a
Adsorption MOF-801_C/PVP(10)_8.9)MOF-801_C/PVP(10)_8.9)
MOF-801_C/PVP(10)_8.9)
MOF-801_C/PVP(10)_8.9) afford
MOF-801_C/PVP(10)_8.9) essential
afford afford afford essential
acceleration
essential
essential
afford acceleration acceleration
of both
acceleration
essential of of
accelerationof both
adsorption
both adsorption
both of adsorption
and
adsorption
both desorption
and and
desorption
and
adsorption desorption
desorption
and desorpt
MOF-801_C/PVP(10)_8.9) afford
MOF-801_C/PVP(10)_8.9) affordessential
essentialacceleration acceleration ofof
both
both adsorption
adsorption andand desorption
desorption
G_4.5 88 170 0.21
(Figure (Figure
5);(Figure
(Figure the 170
5);5);
characteristic
5); the the
characteristic 245
5);characteristic
time, time, 11, isτ0.21
τtime, τ, 1is, by
is τreduced by a factor 1.3–1.8 and 1.6–2.2 forfor adsorp-
(Figure
(Figure 5);5);the the (Figure the
characteristic
characteristic
characteristic
the
time, τττ111,, ,is
characteristic istime,
reduced
isreduced
reduced
1reduced
time, by
by aa1, factor
reduced factor
byreduced
aby
aisfactor
1.3–1.8
factor
a factor
1.3–1.8 by
1.3–1.8
and
1.3–1.8
and 1.6–2.2
and1.3–1.8
a 1.3–1.8
factor
and 1.6–2.2 and
1.6–2.2
for1.6–2.2
1.6–2.2
for adsorp-
andfor 1.6–2.2
adsorp-
for
adsorp- adsorp-
adsorp- for adso
PTD_4.5 87 210 tion 0.29
and
tion tiontion
desorption,
and andand185
desorption,
tion desorption,
respectively
desorption,
and 270 respectively
respectively (Table
respectively
desorption, 3).
(Table
respectively 0.20
A (Table
(Table similar
3). A 3). 3).
(Table A A
trend
similar similar
similar
3). Ais
trend trend
observed
is
trend
similar is
observed
is observed
for times
observed
trend is for t
times
for
observed for
0.7 andtimes
t
times 0.7 and
for
0.7 t t0.7and
times
0.7 and
t0.7 a
tionand
tion anddesorption,
desorption, respectively respectively (Table (Table3). 3).AAsimilar similartrend trendis isobserved
observed forfortimes
timest0.7 tand0.7 and on the
rocool_4.5 67 160 tt0.8
0.8 (Table
t
0.23 0.8 (Table
0.8
(Table3). t t
3).
0.8 0.8 (Table
Surprisingly,
(Table3).
t 140
0.8
3).Surprisingly, 3). 3).
(Table
Surprisingly,the Surprisingly,
Surprisingly, the
Surprisingly,
3). 210 bentonite
the
Surprisingly,
thebentonite
bentonitebinder the
bentonite
the bentonite
binder
bentonite
0.20
the
binderdoes does
binder binder
binder
bentonite
doesnot not
does does
accelerate
not
does
binder
notaccelerate not
not
does
acceleratethe accelerate
the
accelerate sorption
accelerate
not the thethe
accelerate
thesorption
sorptionon on
sorption sorption
the
sorption
onthe the on the
on
sorption
thecoat- the on
t0.8 (Table
ent_4.5 Nanomaterials 81
2023, 13, x FOR PEER REVIEW
150 coatings
0.15
coatings coatings
coatings MOF-801_C/bentonite(40)_8.9
MOF-801_C/bentonite(40)_8.9
coatings MOF-801_C/bentonite(40)_8.9
155
coatings
MOF-801_C/bentonite(40)_8.9 220
MOF-801_C/bentonite(40)_8.9 and
and 0.22 and and MOF-801_C/bentonite(20)_8.9
and MOF-801_C/bentonite(20)_8.9
and compared
MOF-801_C/bentonite(20)_8.9compared
10
compared with
ofcompared
compared 16
compared
with
with the with with
compared with w
ings
the
Nanomaterials
reference
the the
reference bed 2023,
reference 13,bed
xMOF-801_G_8.9
MOF-801_G_8.9
bed FOR
bed PEER REVIEW
MOF-801_G_8.9of
loose
of grains
loose of loose
(Figure
grains grains
6);
(Figure (Figure
no 6);
reduction
6); no no
reduction reduction
of the ofcharac-
the of the
charac- charac-
VA_4.5 130 330 0.21
the reference the reference
the
320 reference
bed MOF-801_G_8.9 MOF-801_G_8.9
bed
460 MOF-801_G_8.9
of loose of
0.20
grains loose of
(Figuregrains
loose (Figure
grains
6); reduction 6);
(Figure
no reduction no reduction
6); no
of the of
reduction
charac- the charac-
of the char
reference
teristic bed
times
teristic teristicMOF-801_G_8.9
teristic
was
times times
observed
timeswaswas was (Table
observed of (Table
observed
observed loose
3). (Table grains
(Table
3). 3). 3).(Figure 6); no of the characteristic
PVP_4.5 69 160 0.29
teristic times was teristic
140
observed times was
200
(Table observed
3). (Table
0.21 3).
times was observed (Table 3).
AN_4.5 MOF-801_C/bent(40)_8.9
113 200 0.15 31 220 633 300 0.76 0.20 64 122 0.24
HEC_4.5 MOF-801_C/bent(20)_8.9
77 130 0.20 27 130 787 185 0.77 0.20 49 94 0.24
Desorption
G_4.5 117 480 0.68 150 240 0.23
PTD_4.5 98 290 0.61 130 200 0.23
rocool_4.5 91 310 0.64 115 185 0.22
ent_4.5 103 300 0.63 130 195 0.24
VA_4.5 127 320 0.69 150 215 0.22
PVP_4.5 108 460 0.70 145 235 0.23
AN_4.5 145 270 0.53 175 250 0.24
HEC_4.5 106 360 0.67 135 205 0.22
For reference bed MOF-801-G_4.5 of loose grains, the characteristic times are τ1 = 88
and 120 s and τ2 = 170 and 480 s for adsorption and desorption, respectively, (Table 2).
Gluing the adsorbent grains to Al foil by binders can lead to both acceleration and decel-
eration of water ad/desorption (Figure 3). For the grains glued by Figure 4. The
Aerocool, kinetic curves of water vapor adsorption (a) and desorption
bentonite,
Figure
Figure
Figure 6.
The
FigureThe
6. The
5.Figure 6.
Figure kinetic
Figure
kinetic
The
kinetic 6.
6.curves
6.kinetic
The The curves
The
curves
kinetic kinetic
kinetic
6.of
kinetic
Figure water
curves
The of
of water
curves water
curves
of
curves vapor
water
vapor
of
kinetic of
waterofvapor
water
water
curves
grains adsorption
vapor
adsorption
vapor adsorption
ofvapor
adsorption
vapor adsorption
(a) and
(a)adsorption
adsorption
water
MOF-801_G/CPTD_4.5 and
vapor (a)
(a)
(a) and
(a)
desorption
and (a)
desorption
and
adsorption and desorption
and
(b) desorption
(b)
desorption for(b)
desorption
for
desorption
(), (a) and (b)
coatings
coatings
(b) for
for
desorption
MOF-801_G/Aerocool_4.5 for
(b)(b)
MOF- coatings
forfor
(b)coatings
MOF-
coatings MOF-
coatings
coatings MOF-
for
(), MOF-M
MOF-
coatings
MOF-801
PVP, and HEC, the characteristic Figure 6. The
time, 801_C/PVP(5)_8.9
τ1, 801_C/PVP(5)_8.9
which curves
describes of
thewater vapor
initial adsorption
fast process, (a)
de- and desorption (b) for coatings MOF-
801_C/PVP(10)_4.5 801_C/PVP(5)_8.9
801_C/PVP(5)_8.9
MOF-801_C/PVP(5)_8.9 (▲),
801_C/PVP(5)_8.9 (),
glued(
(),),
801_C/PVP(5)_8.9 (),
(),
grains MOF-801_C/PVP(10)_8.9
MOF-801_C/PVP(10)_8.9
(), MOF-801_C/PVP(10)_8.9
MOF-801_C/PVP(10)_8.9
MOF-801_G/PVP(10)_4.5
MOF-801_C/PVP(10)_8.9
MOF-801_C/PVP(10)_8.9
(), (),
MOF-801_C/PVP(10)_8.9
801_G/PVP_4.5 (), ()
(
(), (),
), (),
(), MOF-801_C/bentonite(40)_8.9
loose grains MOF-801-G_4.5
MOF-801_G/bent_4.5(), (),MOF-
(), (),MOF-
(
(),MOF-
MOF-801_G/HEC_4.5 (),MOF-
(),MOF-
), (),M
(), M
creases to 67–77 s. A similar effect is801_C/PVP(5)_8.9
observed for (), MOF-801_C/PVP(10)_8.9
desorption,
(▲), where
801_C/bentonite(20)_8.9 time
(▲), τthe
and diminishes
the
(), MOF-801_C/bentonite(40)_8.9
reference tobed of loose grains MOF-801-G_8.9
(),MOF-
).().
(). 801_C/bentonite(20)_8.9
801_C/bentonite(20)_8.9
801_C/bentonite(20)_8.9 and
(▲), the
and
(▲),reference
the
and 1the bed
reference ofbed
reference looseof
bed grains
loose
ofloose MOF-801-G_8.9
grains
loose MOF-801-G_8.9
grains ().
MOF-801-G_8.9 (). ().
801_C/bentonite(20)_8.9 (▲), and (▲),
( ),
theand the
andthe
referencereference
(▲), and
reference
bed the
reference
of bed bed
bed
loose of
of loose
reference
ofloose
grains grains
bed of
grains
grains MOF-801-G_8.9
loose grains
MOF-801_G_4.5
MOF-801-G_8.9
MOF-801-G_8.9 (). ().(().
MOF-801-G_8.9 Dgr =().
0.8–0.9 mm
91–106 s. On the contrary, PVA and PAN essentially decelerate ad/desorption, and time τ1
rises (Table 2). This is quite surprising, Forsince
both thePVP
Unfortunately, grains
weand arebentonite,
failed glued to Table
to prepare Althefoil with
sufficiently
binder
2. binder,
strong thick
content
The characteristic only
timescoatings
of waterwith
slightly affectslower thePVP
adsorption/desorption sorptionτ1, τ2, τ0.7 an
and the contact surface area between
content the grains
and and
bentonite. the foil
For increases,
this reason, thusthe
uptake, w
decreasing
kinetic  , data
for the
thefor
kinetics. All “thick” beds ad/desorb water much slower than “thin” beds, which is expected,
t other
glued coatings
grains of were
MOF-801, prepared
D gr = 0.8–0.9 mm.
with S/m = 8.9 and compared with the reference bed MOF-801-G_8.9 of loose grains of 0.4–
because they are Configuration
characterized by a larger ratio, τ1, sS/m; consequently, τ2, s bothA heat and t0.7mass
,s t0.8,
0.5 mm size
transfer occur(Figure
faster.5).The
Thescalecoatings
of theprepared
accelerating witheffect PVP for (MOF-801_C/PVP(5)_8.9
the coatings is on a and
par for thin
MOF-801_C/PVP(10)_8.9) Adsorption
and thick beds (Figure 5,afford Tableessential
3). acceleration of both adsorption and desorption
(Figure 5); the MOF-801_G_4.5
characteristic time, τ 88 170
1, is reduced by a factor 1.3–1.8 and 1.6–2.2 for adsorp-
0.21 170 245
Let us consider the main processes affecting the sorption kinetics in the system «Al foil–
tion and desorption,MOF-801_G/CPTD_4.5
respectively (Table 3). A similar 87 trend is observed 210 forof0.29
times and185
t0.7 molecules 270
binder–adsorbent». For physical adsorbents, the intrinsic interaction water
t0.8 (Table 3). Surprisingly, the bentonite binder does 67 not accelerate 160 the sorption 0.23 on the140 210
MOF-801_G/bent_4.5 and MOF-801_C/bentonite(20)_8.9
coatings MOF-801_C/bentonite(40)_8.9 81 150 0.15
compared with155 220
the reference bed MOF-801_G_8.9
MOF-801_G/PVA_4.5 of loose grains (Figure
130 6); no reduction
330 of
0.21the charac- 320 460
teristic times was observed (Table 3).
MOF-801_G/PVP_4.5 69 160 0.29 140 200
MOF-801_G/PAN_4.5 113 200 0.15 220 300
with the adsorption site is a very rapid process, and the adsorption kinetics is determined
by coupled heat and mass transfer [36]. Since the ad/desorption is initiated by a temper-
ature drop/jump at initial time t → 0, the driving temperature difference, ∆T = Tf − Tin ,
between the heat transfer fluid, Tf , and initial adsorbent temperature, Tin , is maximum.
The vapor pressure gradient over the adsorbent is absent; consequently, there is no driving
force for mass transfer. Accordingly, at the initial time, the heat transfer controls the sorp-
tion rate, and the kinetics is described by time τ1 . The temperature drop/jump initiates
ad/desorption, during which the gradient of water vapor pressure over the adsorbent
appears, which is the driving force for the mass transfer. The mass transfer starts to affect
the adsorption rate as well, and the transition to the second, slower scenario described
by time τ2 is detected. For smaller grains MOF-801-G_8.9, the resistance to intraparticle
mass transfer is lower than for larger grains MOF-801-G_4.5. Accordingly, the fraction of
water adsorbed by the first process, controlled by the heat transfer, is larger (the coefficient
A = 0.69 and 0.21 for small and large grains, respectively, Tables 2 and 3). The desorption
runs occur at a higher water vapor pressure Pcon = 43 mbar compared with Pev = 9 mbar
during adsorption, which contributes to faster mass transfer. As a result, the effect on the
desorption rate is detected at a higher conversion, q (larger A values). Gluing the grains
with binders only slightly affects the mass transfer in them, and the A values for glued and
loose grains are close. On the contrary, for adsorption on coating MOF-801_C/PVP_4.5, the
coefficient A = 0.79 is much higher than A = 0.21 and 0.29 for loose grains MOF-801_G_4.5
and glued grains MOF-801_G/PVP_4.5, respectively. A probable reason may be that the
coating is made of the as-synthesized microcrystalline powder of MOF-801 with a particle
size, Dpp , of 0.5–1.5 µm, with the particles loosely bonded to each other by PVP. Due to the
small amount of PVP, it does not fill the voids between the particles, thus proving enough
space for the diffusion of water molecules. On the contrary, pressing the grains results
in denser packing of the primary particles, which prevents water diffusion. Accordingly,
the resistance to intraparticle mass transfer is smaller for the coating than for larger grains
(Figure 1a,c), and its effect on the adsorption kinetics appears at a higher conversion.
3.3. Heat Transfer Coefficients

For deeper insight into the processes controlling the adsorption kinetics at initial times,
the effective heat transfer coefficient, U, is estimated for the studied configurations of the
adsorbent bed under conditions of the adsorption cycles. Let us consider the heat balance
in the adsorbent bed at t→0:

S
U · T f − Tin = Wmax + C p (dT ad /dt)t=o , (6)
m ad
where S is the surface area of the heat transfer between the adsorbent and the Al foil, mad
is the adsorbent mass, W max is the specific power consumed/released in the adsorbent
bed at t → 0, and CpΣ is the specific heat capacity of the adsorbent and adsorbed water.
Considering that the second summand in Equation (6) is minor, the coefficient U can be
estimated from the values of W max , calculated from the initial parts of the kinetic curves:

S d∆w(t)
U · T f − Tin = Wmax = ∆H · R0 = ∆H = ∆H ·∆wt→∝ /τ1 (7)
m ad dt t =0
where ∆H is the adsorption heat, equal to 60 kJ/mol [22], and R0 is the ad/desorption rate
at t → 0.
Gluing the MOF-801 grains using Aerocool, bentonite, HEC, and PVP enhances the
effective heat transfer coefficient, U, by 7–28% (Figure 7a). The influence of the binder on
the effective heat transfer coefficient of thin coatings is even more pronounced. For the PVP-
based coatings MOF-801_C/PVP(10)_8.9 and MOF-801_C/PVP(5)_8.9, the coefficient U
rises by a factor of 1.6–1.9 and 1.9–2.4 for adsorption and desorption, respectively, compared
where H is the adsorption heat, equal to 60 kJ/mol [22], and R0 is the ad/desorption rate
at t  0.
Gluing the MOF-801 grains using Aerocool, bentonite, HEC, and PVP enhances the
effective heat transfer coefficient, U, by 7–28% (Figure 7a). The influence of the binder on
Nanomaterials 2023, 13, 2442 the effective heat transfer coefficient of thin coatings is even more pronounced. For the 12 of 16
PVP-based coatings MOF-801_C/PVP(10)_8.9 and MOF-801_C/PVP(5)_8.9, the coefficient
U rises by a factor of 1.6–1.9 and 1.9–2.4 for adsorption and desorption, respectively, com-
pared with the reference bed of loose grains MOF-801_G_8.9 (Figure 7b). The enhanced
with the reference bed of loose grains MOF-801_G_8.9 (Figure 7b). The enhanced heat
heat transfer results in the speed up of water ad/desorption at the initial time.
transfer results in the speed up of water ad/desorption at the initial time.
Figure 7. Effective heat transfer coefficients of the water adsorption (blue) and desorption (red) runs
forFigure
glued7.grains
Effective heat transfer coefficients
MOF-801_G/binder_4.5 (a)ofand
the water adsorption
coatings (blue) and desorption
MOF-801_C/binder_8.9 (b). (red) runs
for glued grains MOF-801_G/binder_4.5 (a) and coatings MOF-801_C/binder_8.9 (b).
Surprisingly, gluing the grains with PVA and PAN does not increase the effective heat
Surprisingly, gluing the grains with PVA and PAN does not increase the effective
transfer coefficient. The overall thermal resistance in the system “Al foil–adsorbent bed”
heat transfer coefficient. The overall thermal resistance in the system “Al foil–adsorbent
comprises the contact resistances “foil–binder” and “binder–adsorbent”, as well as the
bed” comprises the contact resistances “foil–binder” and “binder–adsorbent”, as well as
resistance of the binder layer. Accordingly, it depends on the adhesion between the foil
the resistance of the binder layer. Accordingly, it depends on the adhesion between the
and binder, between the binder and grains, and on the thermal conductivity of the binder.
foil and binder, between the binder and grains, and on the thermal conductivity of the
The thermal conductivity, λ, of inorganic binder bentonite and thermal grease varies in
binder. The thermal conductivity, , of inorganic binder bentonite and thermal grease var-
the
iesrange
in the0.83–8.5 W/(mK)
range 0.83–8.5 [37,38],
W/(mK) which
[37,38], is much
which is much higher
higherthan
thanλ = =0.27–0.32
0.27–0.32W/(mK)
W/(mK) of
organic
of organic binders PVA, PVP, PAN, and HEC [39,40]. The high heat conductivity ofinorganic
binders PVA, PVP, PAN, and HEC [39,40]. The high heat conductivity of inor-
binders is expected
ganic binders to contribute
is expected to faster
to contribute heat transfer
to faster and adsorption
heat transfer and adsorption kinetics at initial
kinetics at
times.
initialHowever, the accelerating
times. However, effect effect
the accelerating on water adsorption
on water on MOF-801
adsorption on MOF-801 waswas observed
ob-
forserved
binders
for with
bindersboth high
with (bentonite
both and Aerocool)
high (bentonite and low
and Aerocool) and(PVP
low and
(PVPHEC) conductivity.
and HEC) con-
Furthermore, the opposite
ductivity. Furthermore, theeffect of the
opposite same
effect binders
of the sameon the water
binders on theadsorption dynamics
water adsorption
was detected
dynamics fordetected
was differentfor
adsorbents MOF-801 and
different adsorbents LiCl/silica,
MOF-801 reportedreported
and LiCl/silica, in [41]. Thus,
in [41].PVP
accelerates
Thus, PVPthe water vapor
accelerates the adsorption
water vaporon MOF-801 on
adsorption andMOF-801
slows down and it for LiCl/silica.
slows down it forThe
CPTD strongly
LiCl/silica. Thespeeds
CPTDup the sorption
strongly speedson upLiCl/silica
the sorption and
onhas a neutral
LiCl/silica andeffect
hasfor MOF-801.
a neutral
Probably,
effect forthe oppositeProbably,
MOF-801. effect of the
these binderseffect
opposite on theof effective heat on
these binders transfer coefficient
the effective heatand
transfer
the coefficient
sorption kineticsand the sorption
originates fromkinetics originates
the adhesion from the
between adhesion
them between
and these them
adsorbents,
and these
which adsorbents,
strongly dependswhichon thestrongly
chemical depends
natureonof the
bothchemical
binder nature of both binder
and adsorbent, as well and
as on
adsorbent,
the interactionas well as onthem.
between the interaction
Thus, thebetween them.
choice of the Thus, the choicebinder
most effective of the most effec- of
is a subject
tive binder
thorough is a for
study subject
eachofadsorbent.
thorough study for each adsorbent.
3.4. Specific Cooling Power

The specific power (SP) is an important performance index of adsorption chillers, which
determines the amount of the adsorbent needed and, consequently, the unit volume. To
avoid a drop in the power due to sorption deceleration when approaching the equilibrium, in
practice, the duration of the working cycle is usually limited by a time corresponding to the
conversion q = 0.7–0.8 [9,42]. For the cooling cycle Tev /Tcon /Tdes = 5/30/80 ◦ C restricted by
conversion q = 0.7 and 0.8, the SPq is calculated according to the following expression
SPq = ∆L∆wt→∝ q/(tq.ad + tq.des ), (8)
where L is the latent heat of water at Tev = 5 ◦ C; and tq.ad and tq.des are times corresponding
to conversion, q, for adsorption and desorption, respectively.
The power SP0.7 = 1.13 and 2.60 kW/kg can be achieved for the monolayer of loose
grains MOF-801_G_4.5 and MOF-801_G_8.9, respectively (Table 4). Gluing the grains to
the foil with CPTD, PVA, and PAN does not increase the power. On the contrary, Aerocool,
bentonite, HEC, and PVP afford an increase in the SP0.8 and SP0.7 by 10–20% compared with
the reference bed MOF-801_G_4.5 due to the enhancement of the effective heat transfer
coefficient, U (Figure 6). For the coating MOF-801_C/PVP(10)_4.5, prepared from the
suspension, the increase in SP is even larger: 65 and 95% at q = 0.7 and 0.8, respectively.
This is in accordance with a larger A value of 0.79, compared with A = 0.29 for MOF-
801_G/PVP(10)_4.5 (Tables 2 and 3), which indicates that the transition to the second
slower process occurs at a higher conversion. It can be caused by a lower resistance to the
intra-particle mass transfer due to the smaller size of the MOF particles in the coating. The
increase in the ratio S/m to 8.9 m2 /g allows further enhancement of the SCP. For thinner
coating MOF-801_C/PVP(5)_8.9, the power SCP = 4.1 and 5.1 can be achieved, which is
about twice of that for the reference bed of loose grains MOF-801_G_8.9. The considered
configurations may especially be recommended for efficient but expensive adsorbents such
as MOFs. In this case, the binder helps to realize fully the sorbent activity and minimize
the adsorbent mass and total unit cost.
Table 4. The specific powers Wmax , SCP0.8 , and SCP0.7 for the cooling cycles
Tev /Tcon /Tdes = 5/30/80 ◦ C, respectively.
Wmax , kW/kg
Configuration SCP0.8 , kW/kg SCP0.7 , kW/kg
Adsorption Desorption
Loose grains
MOF-801_G_4.5 7.8 7.4 0.85 1.13
MOF-801_G_8.9 12.0 18.3 1.95 2.60
Glued grains
MOF-801_G/CPTD_4.5 7.6 7.7 0.84 1.10
MOF-801_G/Aerocool_4.5 10.0 8.1 1.01 1.35
MOF-801_G/PVA_4.5 5.0 5.8 0.58 0.72
MOF-801_G/bentonite_4.5 8.3 7.7 1.06 1.31
MOF-801_G/HEC_4.5 8.6 6.9 1.01 1.30
MOF-801_G/PAN_4.5 5.9 5.5 0.73 0.90
MOF-801_G/PVP_4.5 10.0 7.1 0.95 1.24
Coatings
MOF-801_C/PVP(10)_4.5 7.9 13.8 1.66 1.99
MOF-801_C/PVP(10)_8.9 23.6 35.4 3.26 4.60
MOF-801_C/PVP(5)_8.9 18.8 44.6 4.09 5.16
MOF-801_C/bent(40)_8.9 12.7 25.7 1.64 2.32
MOF-801_C/bent(20)_8.9 12.3 29.2 1.86 2.54
4. Conclusions
The acceleration of the adsorption/desorption stages of adsorption heat transforma-
tion and storage (AHTS) cycles and the increase in the specific power (SP) is a key stone
for wider distribution of this energy-saving and environmentally friendly technology. This
paper is aimed at the acceleration of water vapor adsorption on MOF-801, a promising
adsorbent for adsorption cooling, the optimization of the bed configuration, and of SP
enhancement. The dynamics of water vapor adsorption on MOF-801 under conditions of
adsorption/desorption stages of a typical cooling cycle is studied and compared for three
adsorbent bed configurations, namely, the monolayer of loose MOF-801 grains located on
an aluminum support, the monolayer of grains glued to the support, and thin coatings
prepared on the support surface with binders.
It is shown that, for all studied configurations, the ad/desorption kinetics are described
by the sum of two exponents with rather different characteristic times, which indicates
a change in the rate-limiting stage during the process. The heat transfer between the
adsorbent and aluminum support controls the adsorption rate at the initial time. At longer
times, the mass transfer in the adsorbent grains/coatings starts to affect the sorption
kinetics. Gluing the grains using PVP, HEC, Aerocool, and bentonite affords an increase
in the effective heat transfer coefficient between the support and MOF-801 of 7–28%. For
PVP-based thin coatings, even stronger growth of the heat transfer coefficient by a factor
of 1.6–2.4 is observed compared with loose grains. The enhanced heat transfer results in
the speed up of the water ad/desorption and the growth of the SPq , achievable in the
adsorption cycle, restricted by conversion q = 0.7 and 0.8. Gluing the grains with HEC, PVP,
Aerocool, and bentonite affords an increase in the SPq of 10–20%. For the thin coatings
prepared with PVP, an SPq of 1.64–5.16 kW/kg can be achieved, which is about twice as
high as that for the reference beds of loose grains.
Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/nano13172442/s1, Figure S1: Characteristic curve of water ad-
sorption (a) and isosters (b) of water vapour adsorption on as-prepared MOF-801 powder. Dashed
blue lines (b) represent the adsorption cooling cycle, Figure S2: Schematic presentation of the prepa-
ration of MOF-801 beds composed of glued grains and coatings, Figure S3: The kinetic curves of
water vapour adsorption for the loose grains placed on the surface of aluminum foil and placed on
the bottom of the measuring cell, Figure S4: Isotherms of N2 adsorption on as-prepared MOF-801
and pressed grains (a). Experimental and calculated from single-crystal X-ray data (CIF-file) PXRD
patterns of the synthesized MOF-801 (b), Figure S5: Pore size distribution of as-prepared MOF-
801 powder (a), MOF-801_G (b), MOF-801_G/AON_4.5 (c), MOF-801_G/bentonite_4.5 (d), MOF-
801_G/HEC_4.5 (e), MOF-801_G/CPTD_4.5 (f), MOF-801_G/PAN_4.5 (g), and MOF-801_G/PVA_4.5
(h), Figure S6: The kinetic curves of water adsorption on (a,c) and desorption from (b,d) reference
beds of loose grains MOF-801_G_4.5 (a,b) and MOF-801_G_8.9 (c,d), Figure S7: The kinetic curves of
water adsorption on (left) and desorption from (right) beds of glued grains MOF-801_G/PVP_4.5
(a,b), MOF-801_G/bentonite_4.5 (c,d), MOF-801_G/CPTD_4.5 (e,f), MOF-801_G/PAN_4.5 (g,h),
MOF-801_G/PVA_4.5 (i,j), MOF-801_G/Aerocool_4.5 (k,l), and MOF-801_G/HEC_4.5 (m,n).
Author Contributions: Investigation, data curation, formal analysis, validation, visualization,
writing—original draft preparation, M.S.; supervision, conceptualization, formal analysis, data
curation, writing—review and editing, funding acquisition, L.G. All authors have read and agreed to
the published version of the manuscript.
Funding: This research was funded by the Russian Science Foundation, grant number 22-23-00659.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.
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Nanomaterials 2023, 13, 2442. https://doi.org/10.3390/nano13172442 https://www.mdpi.com/journal/nanomaterials

Nanomaterials 2023, 13, 2442 3 of 16

post-treatment. Monolithic MOF-801 showed a moisture sorption capacity 1.2–1.4 times

msl = mMOF-801 /CMOF-801 , (1)

2.2. Adsorbent Characterization

2.3. Water Adsorption Dynamics

3. Results and Discussion

Figure 2.2. Optical

Sample Cb [wt%] Ssp * [m2 /g] V p * [cm3 /g] V µ * [cm3 /g] δ, %

δ = (V p − V p_l )/V p × 100%, (4)

3.2. Water Vapor Adsorption Dynamics

Configuration τ1, s τ2, s A t0.7 , s t0.8 , s ∆wt→∝ , * g/g

The kinetic curves of water adsorption and desorption “dimensionless uptake, q,

q(t) = A [1 − exp(−t/τ 1 )] + (1 − A) [1 − exp(−t/τ 2 )], (5)

3.2.2. MOF-801/Binder Coatings

Sample τ1, s τ2, s A t0.7 , s t0.8 , s ∆wt→∝ , * g/g

3.3. Heat Transfer Coefficients

3.4. Specific Cooling Power

SPq = ∆L∆wt→∝ q/(tq.ad + tq.des ), (8)

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