Chemical Engineering Journal 472 (2023) 144960

Contents lists available at ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Experimental investigation of water adsorption in MIL-101

(Cr)-coated microchannels
Faraz Ege, Darshan G Pahinkar *
Adsorption and Energy Technology Laboratory, Department of Mechanical and Civil Engineering, Florida Institute of Technology, Melbourne, FL, United States

A R T I C L E I N F O A B S T R A C T

Keywords: A novel wash-coating technique was developed to coat a porous layer of MIL-101 (Cr) adsorbent on the inner
ADSORPTION walls of fused silica microchannels. The optimum adsorbent slurry was prepared using 92.8% ethanol solvent,
WATER 1.2% silica binder, and 6% MIL-101 (Cr) and inserted into the channels, which were dried and regenerated. The
MIL-101 (CR)
coatings were characterized using scanning electron microscopy (SEM) and water adsorption performance using
WASH-COATING
ISOTHERMS
adsorption isotherms. Coating thickness as high as 60 μm was achieved, despite the unfavorably smooth surface
of fused silica microchannels. Based on gravimetric and volumetric methods, benchtop experimental setups were
constructed to measure the vapor uptake in the MIL-101 (Cr) powder and coated channels, respectively. Isotherm
experiments were conducted for coated microchannels after wash-coating at three different temperatures. The
adsorbent layer demonstrated outstanding adherence and durability after 20 adsorption and desorption cycles.
The adsorption isotherms exhibited a type V (DA-like) adsorption isotherm with a reduced magnitude of 88%
than the powdered form, which is remarkable for the coated product. The specific surface area (SSA) of the
powdered MIL-101 (Cr), which was 1320 m2/g, decreased to 894 m2/g in the coated form, corroborated with the
adsorption isotherm results. The uptake and the height of the Type-V curve decreased with increased temper­
ature. Modified Langmuir Adsorption isotherms were fitted for the coated channel adsorption performance,
furthering its suitability for use in the mass and energy balance equations using this configuration. These well-
characterized coated channels with a high-performance adsorbent can readily scale up adsorption-based heating
and cooling systems, improving their performance.

1. Introduction enthalpy, ease of availability, and no environmental penalty. Another

The demand for energy-efficient cooling systems to create a better
living environment has risen recently. Consequently, the omnipresence
of cooling systems burdens electrical infrastructure. Meanwhile, elec­
tricity consumed for cooling residential and commercial buildings is
10% of the total energy used in the United States [1]. Most commercial
building cooling systems today run on conventional vapor compression
refrigeration systems. Superior COP value and lower manufacturing
costs are just two of the reasons why they dominate the air conditioning
and cooling market. Yet, they contribute significantly to global warming
and ozone depletion due to the harmful refrigerants. Therefore, to
address these challenges, utilizing an energy source other than elec­
tricity, such as heat, with environmentally friendly operation is
necessary.
Thermally driven adsorption heat pumps perfectly satisfy these
needs. Water is the most utilized refrigerant due to its high evaporation
advantage of thermally driven systems is the possibility of low regen­
eration temperature, which allows them to work with commonly
available heat sources such as solar collectors or waste heat from other
residential applications [2]. Furthermore, the mechanical compressor is
absent in these devices, producing no vibration or noise. While the
history of the adsorption heat pumps goes back more than 150 years,
their designs have not been significantly improved over these years.
They mostly use at least two packed beds, where large adsorbent pellets
are stuffed in cylinders, where the porous spaces provide the pathways
for the vapor refrigerant to flow and adsorb. The principle of the
adsorption heat pump is that heating allows the pressurization of the
refrigerant through desorption in a closed space, while cooling allows
depressurization through the adsorption process. The packed bed design
results in poor performance because of the low thermal conductivity of
these materials and porosity in terms of heat transfer and very sluggish
mass transfer because of the large size of adsorbent pellets.

* Corresponding author at: 150 W University Blvd., OLS 226, Melbourne FL 32901, United States.
E-mail address: dpahinkar@fit.edu (D.G. Pahinkar).

https://doi.org/10.1016/j.cej.2023.144960
Received 20 May 2023; Received in revised form 19 July 2023; Accepted 20 July 2023
Available online 22 July 2023
1385-8947/© 2023 Elsevier B.V. All rights reserved.
F. Ege and D.G. Pahinkar Chemical Engineering Journal 472 (2023) 144960

Meanwhile, natural adsorbents such as silica gel and zeolite are
common in adsorption cooling applications [3–10]. These adsorbents
have a crucial limitation: linear or favorable adsorption isotherms.
Adsorption occurs at low relative pressures (P/Ps), and their adsorption
capacity is significantly low. Research has been focused on developing
and synthesizing high uptake capacity adsorbents for a wide range of
relative pressures like Metal-Organic Frameworks (MOFs) to address
these problems. One of the adsorbents with a high BET (Brunauer-
Emmett-Teller) area (surface area available for adsorption) and, in turn,
high uptake capacity for water vapor is MIL-101 (Cr) (Materials Institute
Lavoisier). It has also been deemed stable when exposed to water vapor
[11]. It is widely studied for its potential use in various applications,
including gas storage and separation. Based on the prior studies on
adsorption isotherms of the powdered MIL-101 (Cr) [12–21], the
adsorption isotherm of water on MIL-101(Cr) is typically a type V
isotherm [21], indicating a physisorption process. The water adsorption
capacity in MIL-101 (Cr) has been reported between 0.4 and 1.2 g g− 1 at
25 ◦ C and 50% relative humidity. Also, MIL-101 (Cr) has a high uptake
capacity towards water vapor over other gases such as CO2 and CH4. In
addition, it has been reported to have a higher storage capacity for CO2
than gases such as methane and nitrogen. Specifically, the adsorption
capacity of CO2 in MIL-101 (Cr) at 300 K is documented as 1.6 mmol g− 1,
equivalent to 0.11 g g− 1 [22].
Additionally, it has been observed that MIL-101 (Cr) has a high
thermal stability, which allows it to maintain its adsorption properties
even at high temperatures, making it attractive for use in applications
such as natural gas purification and temperature swing adsorption [23].
Several studies have devoted their efforts to evaluating the water vapor
adsorption performance of MIL-101 (Cr) powder and tuning the
adsorption BET surface area [12–18,21,24–37]. Recently, more syn­
thesized MOFs, such as MIL-801 [38] and Lathanide-based MOFs [39],
have been pursued by researchers. These MOFs exhibit a comparable
property to MIL-101 (Cr) and hold potential as adsorption materials for
adsorption cooling systems, gas storage and sensor technology. In­
vestigations of the adsorption capacity and isotherm curve of vapor in
MOF adsorbents, focusing on MIL-101 (Cr) and its counterparts, are
summarized in Table 1.
It shows that the maximum adsorbate adsorption capacity is directly
proportional to the BET area for the same material-adsorbate pair. From
Table 1 and after the review of relevant literature, it can be noted that
the current focus regarding MIL-101 (Cr) is on investigating the iso­
therms for powdered MIL-101 (Cr) and constructing adsorption beds by
storing the adsorbent pellets in cylinders, which links back to the large
footprint of the adsorption heat pump with two or more beds/cylinders
for a continuous operation.
Meanwhile, a few experimental studies have been conducted to
analyze the coatings of MOFs on different substrates and for different
working fluids. MOFs such as MIL-101 (Cr) and HKUST-1 have been
reported to be excellent candidates for methanol refrigerant for cooling
systems. In this study, aluminum was used as the substrate, and the
adsorption characteristics of methanol using the thermogravimetric
method were investigated. A loading capacity of 1.22 g g− 1 was ach­
ieved in this study [42]. The results were encouraging from the stand­
point of adsorption capacity; however, the surface requires significant
pretreatment with additional raw materials like xylene. Additionally, no
data on isotherms or the equations governing them was provided. A
more straightforward coating procedure can be developed without using
chemical pretreatment and additional solvents by using ethanol, as
performed in this work.
Pahinkar et al. suggested using adsorbent-coated microchannels for
designing a single-bed adsorption cooling system instead of two beds to
achieve a compact and quick-acting system while enhancing its primary
energy COP [43]. Using coated microchannels for this application
resulted in a highly asymmetric operation, where the heating and
desorption stage in a single bed resembled a pulse, with the rest of the
duration allotted to cooling and adsorption. Such asymmetric operation
precludes using two beds, paving the way to making these systems
highly compact, like electrically driven refrigerators. Adsorbent-coated
microchannels have been previously demonstrated to increase the ca­
pacity of carbon dioxide separation systems by up to two orders of
magnitude [44–46]. The rationale behind using adsorbent-coated
microchannels instead of packed beds is that microchannels have a
high surface area-to-volume ratio, low thermal mass, and thin adsorbent
layers, resulting in excellent heat and mass transfer. This warrants the
investigation of novel scalable coating methods for adsorbents and, in
turn, the development of energy-efficient and quick-acting adsorption
heat pumps with a minimal footprint. The predicted specific cooling
capacity of the heat pump by Pahinkar et al. was 176 W kg− 1 at 5 ◦ C
using silica gel and water pair with heat available at 90 ◦ C. However,
silica gel powder capacity does not exceed 0.4 g g− 1. High-performance
adsorbents, such as MIL-101 (Cr), can increase the specific cooling
power, decrease the footprint, and increase the COP of the cooling cycle.
Continuing the efforts to demonstrate the efficacy of MIL-101 (Cr)-
coated microchannels, Chauhan et al. [47] devised an inexpensive MIL-
101 (Cr) wash-coating method on cordierite honeycomb monolithic
substrates. Cordierite substrate, which has macroscopic pores, provided
excellent anchoring spots for nucleation of MIL-101 (Cr) layers and
adsorbent layers as thick as 106 μm were achieved. This thickness was
an excellent result in terms of process intensification standpoint; how­
ever, the use of cordierite substrates hinders the generalized utility of

Table 1
Adsorption properties of MOFs in the literature.
Adsorbent/fluid Temperature [K] Study Method BET m2/g Max. Adsorption Capacity g/g Ref

MIL-101/Water 298 Gravimetric method 3298 1.27 [19]

MIL-101 (Cr)/Water 298–308 Gravimetric method 3054 1.2–1.1 [18]
MIL-101 (Cr)/Water 298.15 Molecular Simulation 3298 1.44 [17]
MIL-101 (Cr)/Water 298 Thermogravimetric method 2059 1.01 [14]
MIL-101 (Cr)/Water 303 Thermogravimetric/Gravimetric method 4150 1.6 [13]
MIL-100/Water 293 gravimetric method (DVS) 1300–1600 0.45 [16]
MIL-101 298 Volumetric method 3124 0.8–1.2 [15]
MIL-101-NO2 2146
MIL-101-NH2 2509
MIL-101-SO3H 1920
MIL-101 (Cr)/Water 293 Volumetric method 4000 1–1.5 [36]
MIL-101/Water 298 Gravimetric method 2789 1.2 [20]
MIL-101/Water 298 Gravimetric method 3402 1 [40]
MIL-101 (Cr)/Water 267–343 Volumetric method 1.4–1.51 [12]
MOF-801 303 Volumetric method 894 0.44 [41]
Ni-MOF 801 303 Volumetric method 974 0.35 [41]
Co-MOF-801 303 Volumetric method 998 0.35 [41]
MOF-801 303–323-342 Gravimetric method 1151 0.45–0.44–0.38 [38]
MOF-801-RT 303–323-343 Gravimetric method 976 0.35–0.33–0.31 [38]

2
F. Ege and D.G. Pahinkar Chemical Engineering Journal 472 (2023) 144960

the method. Due to macroscopic pores that augmented the bond be­
tween silica binder, MIL-101 (Cr) and cordierite pose limitations in
sealing the individual channels for a parallel flow of working and
coupling fluids. If the refrigerant water mixes with the heat transfer fluid
(HTF) water, the heat pump will not operate. Fused silica microchannels
overcome this mass transfer limitation by providing a barrier between
two channels. However, they offer no assistance to coat the adsorbent
and the binder because of the lack of macroscopic pores (smooth sur­
face). Regarding design, the cordierite substrates or other cross-sectional
microchannels, such as trapezoidal microchannels [48], may pose dif­
ficulty sealing the bed under vacuum because of macroscopic pores.
With this motivation for devising new techniques for MIL-101 (Cr)
wash-coating on smooth surfaces like fused silica microchannels and
great attention in the literature given to the packed bed designs, despite
poor performance, this study focuses on developing an alternative wash-
coating approach for coating MIL-101 (Cr) for fused silica microchannel
substrates and characterizing this novel approach using scanning elec­
tron microscopy (SEM) and water adsorption breakthrough experi­
ments. Dedicated water adsorption setups using gravimetric and
Fig. 1. SEM image of coated microchannel using water as the base fluid.
volumetric approaches were developed and constructed for this study.
Adsorption isotherm and BET data were achieved for MIL-101 (Cr) in the
analysis of the fused silica microchannel coated by the slurry consisting
coated form and quantitatively compared with the powdered MIL-101
of water as the base fluid showing delamination of the layer from the
(Cr) adsorption isotherms in the literature.
wall surface. While the annular adsorbent layers were seen to be much
thicker than the commercially available options, like cordierite sub­
2. Development of coating method and characterization
strates, the randomized delamination of the layer from the walls war­
ranted a different approach for wash-coating the adsorbent on fused
Chauhan et al. developed a novel MIL-101 (Cr) wash-coating pro­
silica.
cedure for cordierite honeycomb microchannel monolith using water as
the solvent with silica binder. They found that the adsorbent retention
during wash-coating is the highest for a 6% solid fraction, and the 2.1. Experiment with ethanol as the solvent
adsorbent layer thickness was greater than 100 μm for this mass fraction
[47]. The lower mass fraction did not deposit enough adsorbent, while While water is a favorable adsorbent for MIL-101 (Cr), ethanol also
the high fraction resulted in the clogging of microchannels without any has a high affinity for MIL-101 (Cr) [50]. In the earlier case, water was
increase in the thickness of the adsorbent layers. In this work, the focus used as the solvent because MIL-101 (Cr) can adsorb water in excep­
shifted from cordierite to fused silica substrates because of the sealing tional quantities. During drying, this water would be desorbed from the
issues outlined earlier. It is also easy to bundle the fused silica micro­ MIL-101 (Cr) pores and form vapor passages making the layer porous.
channels into test sections for a scaled-up performance. Furthermore, This hypothesis was confirmed with SEM images of coated cordierite
when used individually, they can be connected to tube fittings using channels. Ethanol was pursued as a solvent in this new technique
capillary ferrules. The primary experiments were carried out using the because of two notable benefits.
slurry with water as the base fluid (94%) with 1.5% silica binder and First, ethanol facilitated optimal adhesion of the solution to the
4.5% MIL-101 (Cr) (Table 2) [49] from NanoChemaZone®, consistent microchannel wall. The adsorbent-binder slurry became very homoge­
with the procedure outlined for cordierite. The adsorbent and binder neous due to the excellent wetting characteristics of ethanol. Second,
mass was measured using a high-precision Vibra analytical balance HT due to its lower boiling point than water, ethanol exhibited faster
series to prepare the slurry and then mixed with water in a glass lab evaporation than water, which expedited the drying of the coated
beaker. After thoroughly mixing the components, an ultrasonic bath was microchannels during the coating process [51]. Multiple experiments
used for 20 s to ensure that the components were mixed perfectly. were conducted using different solid fractions to determine the slurry
However, the slurry with a 4.5% solid fraction of MIL-101 (Cr) did not optimum solid fraction. In the initial trial, a slurry using ethanol as the
form a continuous layer; even with the binder, it did not adhere to the base fluid was prepared using 4.5% MIL-101 (Cr) as the adsorbent ma­
wall. terial and 1.5% silica binder, with 94% ethanol as the solvent. The slurry
Meanwhile, drying mechanisms such as a heat gun or tube furnaces was mixed in a laboratory glass beaker and then subjected to ultrasonic
removed the water-based slurry from the channel rather violently, dis­ bath treatment to ensure thorough mixing. However, coating with a
placing any settled layer during the coating process. The slow heating 4.5% solid fraction did not yield satisfactory results as the slurry was not
rate yielded some positive results, and the adsorbent layer in several retained in the tube during the coating process, likely due to its low
parts was retained; however, achieving a continuous layer was still viscosity. The slurry quickly passed through the tube without adhering
tricky and subject to variability because the fused silica surface offered to the wall. To address this issue, the solid fraction of MIL-101 (Cr) was
no assistance to the depositing slurry. Fig. 1 shows an SEM image increased to 6%, while the proportions of silica binder and ethanol
changed to 1.2% and 92.8%, respectively. The process for preparing the
slurry was repeated as described earlier for the 4.5% solid fraction. This
Table 2 adjustment improved outcomes, as shown in Fig. 2. When the MIL-101
Properties of used MIL-101 (Cr). (Cr) solid fraction increased to 9%, producing a highly viscous slurry
Name MIL-101 (Cr) led to the clogging of microchannels during the coating process. These
Molecular Formula C18H6Cr3O12 clogs were found difficult to remove. Even if they were removed, the
Molecular Weight 604.87 g mol− 1 adsorbent layer was disturbed irreversibly. As a result, a solid fraction of
Color Green 6% was identified as the ideal composition for the adsorbent material.
Pore Size ~10 Å SEM images for MIL-101 (Cr) solid fractions of 4.5%, 6% and 9% are
BET Area 1320 m2g− 1
presented in Fig. 2.

3
F. Ege and D.G. Pahinkar
Fig. 2. SEM image analysis of fused silica microchannels. a) uncoated b) 7.2% solid fraction coated sample c) 9% solid fraction coated sample d) 6% solid fraction
coated sample.
The insertion of the slurry into the microchannels was identified as a
challenging step. An experimental setup was devised specifically for this
purpose, as shown in Fig. 3. The setup allows the controlled injection of
the prepared slurry into microchannels. It consists of a nitrogen tank for
pressurizing the slurry during injection, an Alicat MC-20SCCM-D/5M
flowmeter for regulating the flow rate of the injected slurry, needle
valves, Swagelok tubes and fittings, ferrules for connecting fused silica
microchannels to the steel tubes, and two storage tanks, one for holding
the slurry and another for collecting any excess solution that passed
through the fused silica microchannels.
In the initial iteration of this experiment, the fused silica micro­
channel was positioned within a tube furnace to provide heat during the
coating process. However, it was noticed that heating the tube during
the coating process resulted in the immediate removal of the slurry from
the tube without adhering to the walls of the microchannels, therefore
deemed too aggressive for drying. Instead, a slower drying method was
chosen.
The final version of the experimental setup started with the
4
Chemical Engineering Journal 472 (2023) 144960
introduction of slurry into the fused silica microchannels at 0.02 g h− 1.
Subsequently, the injected microchannels were left to dry in the labo­
ratory environment for 24 h partially. During this process, ethanol
evaporated slowly, after which coated tubes were transferred to a tube
furnace to complete the drying process. This slow drying avoided the
violent exit of the slurry, as seen in the case of the quick drying
approach. Within the tube furnace, the temperature gradually increased
from room temperature to 200 ◦ C in two hours and then was maintained
for ten hours. This approach facilitated the uniform and well-adhered
formation of adsorbent layers, preventing formation defects in the
coating process. Additionally, slow drying provided ample time for self-
leveling. As the ethanol evaporated slowly, the slurry could flow and
redistribute at the micro-scale. The coating process was completed by
introducing nitrogen gas into the dried, coated tubes for two hours to
eliminate clogs within the microchannels. This gradual evaporation of
ethanol contributed to the creation of a consistent film. Even after
subjecting the coated adsorbent material to 20 adsorption/desorption
cycles, it was observed that the film exhibited strong adhesion to the
F. Ege and D.G. Pahinkar
Fig. 3. A) photograph of experimental setup for coating silica tube microchannels b) schematic of the experimental setup.
microchannel walls. The coating process sequence is depicted in Fig. 4.
After the completion of the coating process, the fused silica micro­
channels were prepared to be incorporated into the test section, which is
hermetically sealed, as shown in Fig. 5. This test section comprises
thirteen coated fused silica microchannels joined together using epoxy
within a quarter-inch steel tube to facilitate the water adsorption
experimental setup described later. The length of the coated fused silica
tubes varies between 11 and 12 cm, while the steel tube measures 9 cm
in length.
2.2. Adsorbent layer SEM analysis
The MIL-101 (Cr) coating thickness was measured using SEM image
analysis. A portion of a coated microchannel was chosen for SEM image
analysis. A small section of the coated tube was carefully cut to prepare
the test section sample. Subsequently, the cut piece was placed in a
holder designed explicitly for SEM examination. To avoid electron
saturation on non-conductive fused silica microchannels and MIL-101
(Cr), the samples were gold-sputtered using Denton Vacuum Desk III.
Fig. 6 shows a homogeneous coated layer inside the fused silica micro­
channel (detailed view of Fig. 2(b)). The adsorbent layer exhibited
strong adhesion to the microchannel wall, which is attributed to the
change of base solvent from water to ethanol (Fig. 1 vs. Fig. 6). The
adsorbent layer thicknesses are encouraging compared to the
Fig. 4. The steps of preparing the slurry and tube coating.
5
Chemical Engineering Journal 472 (2023) 144960
commercially available coated microchannels, also known as a porous
layer, open tubular columns (PLOT).
The layer thickness in this study ranges between 30 and 60 µm for a
target thickness of 30 μm. In contrast, for PLOT columns, the maximum
claimed thickness of the adsorbent layers is 30 μm; however, upon actual
inspection, the layers were found to be irregular and non-homogeneous,
and the thickness never reached the claimed value. In many cases, there
is hardly any adsorbent in these channels [52].
The durability of these adsorbent layers was investigated by
measuring the weight of coated microchannels after each adsorption and
regeneration cycle. These adsorbent layers were first exposed to water
adsorption at 22 ◦ C and 2.645 kPa for 800 min. It was followed by
desorption with a vacuum at 170 ◦ C for the same duration. This pro­
cedure is analogous to actual experiments on powdered and coated MIL-
101 (Cr) described in later sections. After 20 adsorption/desorption
cycles, with a total exposure time of almost 16,000 min, the weight of
the microchannels changed only by 0.02%, suggesting highly durable
coatings with good adhesion between the adsorbent layers and the fused
silica microchannels.
F. Ege and D.G. Pahinkar
Fig. 5. Coated Fused silica microchannels.
Fig. 6. SEM image for 6% solid fraction coated sample.
3. Isotherm experiments and results
3.1. MIL-101 (Cr) adsorption capacity in the powder form
Before determining the adsorption characteristics for the coated
microchannels, an experimental setup shown in Fig. 7 was developed to
assess the adsorption capacity of pure powdered MIL-101 (Cr) using the
gravimetric method. The experimental setup consists of an Alicat pres­
sure gauge PS-30PSIA-D/5P, HC, a tank to store the liquid water, a
crucible holding MIL-101 (Cr) powder, furnace glass tube, Swagelok
tubes and connection fittings, and a vacuum pump.
First, the MIL-101 (Cr) powder samples from NanoChemaZone®
Fig. 7. MIL-101 (Cr) powder uptake experimental setup.
6
Chemical Engineering Journal 472 (2023) 144960
were regenerated at 170 ◦ C for 10 h inside the tube furnace before the
water adsorption experiment. This temperature is chosen for better
comparison with the coated microchannels, as beyond this temperature,
the epoxy used to seal the steel section hermetically begins to decon­
struct. After the regeneration, they were weighed using the high-
precision Vibra analytical balance HT series to determine the mass of
completely dried MIL-101 (Cr) powder. The samples were regenerated
again under the same conditions to avoid errors caused by the adsorp­
tion of atmospheric moisture before the water adsorption experiments.
The experiment began with a vacuum being applied to the entire
setup, and the water tank valve was closed at this stage. To ensure no
leaks, the valve of the water tank and the valve connecting the tube
furnace and vacuum pump were closed, and a waiting period of two
hours was observed. This procedure was conducted as standard practice
before each experiment to verify the integrity of the system and confirm
the absence of any leaks. The experiment was conducted at room tem­
perature, 22 ◦ C, corresponding to a water saturation pressure of 2.645
kPa. Once it was ensured that there were no leaks, all valves were closed.
The experiment proceeded in a closed system, with the connecting valve
between the tube furnace and vacuum pump remaining closed. The
experiment began by opening the valve on the water tank, and the valve
connecting the pressure gauge to the tube furnace was opened. As a
result of the vacuum, water evaporates from the tank and enters the test
section. The evaporation continued until the tube furnace and whole
system pressure reached 2.645 kPa. The tube pressure was gradually
monitored while the vapor was exposed to multiple MIL-101 (Cr)
powder samples. The water tank valve was closed once the pressure
reached its saturation point. The vapor accumulated in the tube, raising
the pressure, was adsorbed by the powder samples, leading to a decrease
in the tube pressure. The pressure decreased from 2.645 kPa to 1.6 kPa
within 30 min and remained constant throughout this experiment. The
mass of water vapor adsorbed measured would then for 1.6 kPa. More
water vapor was added to compensate for the pressure loss so that the
adsorption capacity could be found at 22 ◦ C at the equilibrium pressure
F. Ege and D.G. Pahinkar
of 2.645 kPa.
Powder samples were then weighed, and this mass was compared to
the same in their dried state before the experiment. The water vapor
adsorbed was found to be 0.5277 ± 0.0396 g g− 1-adsorbent. This value
represents the upper limit of the maximum adsorbed capacity for 22 ◦ C,
and MIL-101 (Cr) in the coated form may not achieve this value because
of loss of access to the adsorbent in the coated form, which is verified in
the upcoming sections. The coating procedure, the use of silica binder
resulting in the reduction of the MIL-101 (Cr) solid fraction, and the
insertion and drying procedure render some of the used powder useless
for adsorption. This is possible because of the collapse of MIL-101 (Cr)
nanopores, blocking of them because of binder, lack of void spaces and
unreachable adsorbent particles.
Note that the full spectrum of the adsorption isotherm for powdered
MIL-101 (Cr) is not pursued to avoid repeating the experiments con­
ducted and reported in the literature. This experiment was meant to
confirm the upper limit of the adsorption capacity for the procured
adsorbent powder, which also conforms with the BET trend shown in
Table 1. The BET area for this adsorbent was found to be 1320 m2/g
[47]. The coated form of the adsorbent within the fused silica micro­
channels involves both adsorbent and a binder. This mixing process has
both advantages and disadvantages. One advantage is that the binder
facilitates easier adherence of the adsorbent to the microchannel walls.
However, a disadvantage is that binders can have a negative impact on
the BET area, as explained earlier [53]. To this end, the BET area of the
coated sample was measured to be 894 m2/g, which was 67% compared
to the original powder, showing that the coating process did result in
some loss of nanopores and blocking of some adsorbent particles in the
coating. Nevertheless, this is a reasonable number considering that the
layer is homogeneous and uniform along the length. The adsorption
uptake of the coated channels should provide more insights on the effect
of this reduced BET area.
3.2. Isotherm experiments of vapor in MIL-101 (Cr) coated
microchannels
In this work, the isotherm experiments were conducted using a
developed experimental setup shown in Figs. 8 and 9. The volumetric
method was employed to find these isotherms for water in MIL-101 (Cr)
coated microchannels. The experimental setup consists of an Alicat
pressure gauge series PS-30PSIA-D/5P, HC to indicate the absolute
pressure inside the system, two tanks for storing water for evaporation
and evaporated water vapor, Swagelok ¼“ tubes, ultra-torr vacuum fit­
tings, check valves, and a set of coated microchannels (Fig. 5) with a
vacuum pump. In the setup, three check valves were used and labeled as
Fig. 8. Adsorption isotherm experimental setup.
7
Chemical Engineering Journal 472 (2023) 144960
valves 1, 2, and 3, respectively, and their operation is critical to monitor
the water vapor throughout. The entire assembly was kept in a Quincy
Lab Gravity Analog Oven to allow experiments at variable temperatures.
The oven was modified to allow connections with the vacuum pump.
As the vapor density is at least three orders less than that of liquid
water at 22 ◦ C, ample space is required to store the vapor; thus, the
capacity of the vapor storage tank is greater than that of the water
storage tank. The test section shown in Fig. 5 was used; the length and
weight of the 13 microchannels are shown in Table 3.
The volume of the complete experimental apparatus is divided into
two sections, designated as parts 1 and 2, as shown in Fig. 9. Subse­
quently, a volumetric method based on the separate volumes of these
two parts was utilized to determine the amount of water vapor adsorbed
in MIL-101 (Cr) coated microchannels at different temperatures.
The parts were assembled as shown in Figs. 8 and 9. Then a vacuum
was applied to the setup, except for the liquid water tank. The vacuum
pressure reading was seen to maintain for 14 h after the valves were
closed, verifying that the setup was leak-proof for the duration of the
tests. The experiments were conducted at three different temperatures:
22 ◦ C, 32 ◦ C, and 45 ◦ C. Each experiment started by applying an absolute
vacuum to the whole system using the vacuum pump. The vacuum pump
was operated continuously for 12 h to ensure the ultra-vacuum fittings
performed as designed. Another vacuum pump was connected to the
water tank to eliminate the air inside before the experiment (left side of
Fig. 8).
Subsequently, valve 1 was opened, the rest closed, and the liquid
water in the tank evaporated. Vapor entered the first part of the
experimental setup, where the storage tank for vapor was located. An
increase in the pressure of this part confirmed that water evaporated
after vacuum application. Once the pressure was increased by 10% of
the saturation pressure of the design temperature, valve 1 was closed,
and valve 2 was opened to allow vapor to enter the second part of the
setup where the test section was located. The total mass of the vapor in
zone 1 (Fig. 8) can be found using simple ideal gas law for that volume as
shown in Eq. (1).
P1 V1
MW,total = (1)
RW T
Here, MW,total is the mass of water vapor entering the first part of the
experimental setup when part 2 is under vacuum. P1 is the absolute
pressure for part 1, T is the test temperature, RW is the universal gas
constant for water, and V1 is the volume of part 1, which is determined
before conducting the experiment. A storage tank was used in the first
part to ensure that only vapor was exposed to the coated microchannels
rather than liquid water. Once the pressure has reached a stable state, it
was measured and recorded to determine the mass of the vapor that has
entered the first part of the setup, utilizing Eq. (1). The subsequent step
involves opening valve number 2, allowing the vapor to flow into the
second section of the experiment where the coated tubes are located.
The pressure inside the second part of the setup increased when vapor
entered, and then it gradually decreased, indicating that the adsorption
process was in progress (Fig. 9). When MIL-101 (Cr) in the adsorbent
layer became fully saturated, the joint pressure in part 1 and part 2 of the
setup would not drop any further for the given total mass of the water
vapor. The mass of adsorbed water vapor can be found using Equation
(2), where Pfinal is the steady-state pressure of both zones, V2 is the
volume of the second part of the experiment, and Mads is the mass of
adsorbed water, which is used in the next section for plotting isotherms.
Pfinal (V1 + V 2 )
Mads = MW,total − (2)
RW T
Eq. (2) aims to determine the quantity of vapor that becomes
adsorbed within the coated microchannels. As the coated microchannels
were exposed to water vapor, they initiated the process of adsorption,
which was confirmed by observing a decrease in pressure, monitored
using the pressure gauge within the experimental setup. The total
F. Ege and D.G. Pahinkar Chemical Engineering Journal 472 (2023) 144960

Fig. 9. Schematic of the adsorption isotherm experimental setup.

drying and preparation for the following data point. This was done to
Table 3
complement the volumetric method and not as a primary approach
Length and weight of Fused Silica microchannels.
because adding the stainless-steel test section, epoxy, and binder weight
Silica Tubes information affects the measurability of the gravimetric method. The regeneration
No Length (cm) Mass (g) Unit Weight (g cm− 1) temperature was controlled at 170 ◦ C to prevent melting of the epoxy
1 11.10 0.0298 0.0027 used to connect the microchannels and steel ¼“ tube. The time for each
2 10.95 0.0294 0.0027 uptake point ranged between 16 and 25 min, depending on the relative
3 11.92 0.0322 0.0027 pressure.
4 11.97 0.0324 0.0027 Fig. 10 shows a sample data point tracking for water adsorption at
5 11.95 0.0325 0.0027
22 ◦ C and relative pressure 0.20. The adsorbent layer seems to be fully
6 10.23 0.0275 0.0027
7 11.90 0.0320 0.0027 saturated within 16 min. The experiments showed that the adsorption
8 12.10 0.0329 0.0027 time depends on the temperature and steady state relative pressure. To
9 12.00 0.0325 0.0027 avoid condensation inside the microchannels, isotherms were found
10 11.90 0.0322 0.0027
until the relative pressure became 0.9 (P/Psat = 0.9) for every
11 12.02 0.0326 0.0027
12 11.90 0.0322 0.0027 temperature.
13 11.90 0.0322 0.0027 The mass of adsorption was influenced by the uncertainty stemming
from these pressure measurements conducted during the adsorption
experiment. The total uncertainty is a combination of Type-A and Type-
amount of vapor that entered the system was calculated by knowing the B uncertainties. Type-A uncertainty accounts for the random fluctua­
volumes and temperature of part one. Subsequently, some of the vapor tions of the measured variable around the average value of the sample.
became adsorbed, while the remaining portion remained inside the The standard deviation of the mean quantifies it and can be calculated
system. The ideal gas law, as expressed in Eq. (1), was employed to using Eq. (3) [55].
determine the quantity of vapor within the system. The calculated [ ]
remaining vapor mass was then subtracted from the total mass, allowing 1 ∑N
Ua = (Xi − X)2 (3)
for the determination of the amount of vapor that became adsorbed N(N − 1) 1
within the tubes.
This process was repeated until the pressure of the vapor inside the Type-B uncertainty refers to systematic errors or uncertainties
first section reached the saturated pressure for each temperature tested. specified by the Alicat pressure gauge device manufacturer. This un­
To accurately determine the isotherm of vapor, adsorption was certainty is obtained from the device documentation and is determined
measured at twelve different points of relative pressures, and the process to be ±0.5% of the reading range. This study calculates the Type-B
was repeated until a steady state pressure was obtained. Then the test uncertainty based on the maximum steady-state pressure. The total
temperature was changed. The saturated pressure for each temperature uncertainties for the pressure gauge are determined using Eq. (4) [55].
is shown in Table 4 [54].
U 2 = UA2 + UB2 (4)
After completing the adsorption measurement for a given tempera­
ture, the coated microchannels were placed inside the tube furnace and The Type-A uncertainty for the pressure sensors for the entire
dried over the course of 800 min at 170 ◦ C with a running vacuum pump duration of the adsorption cycle was determined to be 0.0066138 kPa.
to desorb water vapor and regenerate the test section for the following Uncertainty Type-B is found to be ± 0.04 kPa from the manufacturer’s
temperature reading. The weight of the coated microchannels was specification. The total uncertainty is then calculated using Eq. (4),
measured after each regeneration using a microbalance and compared yielding a value of 0.040543 kPa. Because the mass of the water vapor is
with the dried mass of the microchannels to ensure their complete directly proportional to this pressure, the uncertainty is carried over to
the uptake measurements in the same fraction, which is a maximum of
Table 4 ± 1.5% of the recorded data.
Saturated pressure at different temperatures.
Saturate Pressure
3.3. Experimental isotherm curves
Temperature [◦ C] Pressure [kPa]

22 2.645 Water vapor adsorption in MIL-101 (Cr) coated microchannels was

32 4.760 experimentally determined using a volumetric approach at three
42 8.210
different temperatures, 22–32-45 ◦ C, to examine the efficacy of the

8
F. Ege and D.G. Pahinkar
Fig. 10. Adsorption Process at temperature of 22 ◦ C and relative pressure of 0.20.
modified wash-coating method in this work. These temperatures were
chosen based on the operating environments of chillers or heat pumps
for cooling applications for future studies [56].
Fig. 11 highlights the effect of temperature on the adsorption
Fig. 11. Isotherm curves of vapor in MIL-101 (Cr) coated microchannels in a)
22 ◦ C and b) different temperatures.
9
Chemical Engineering Journal 472 (2023) 144960
process. Isotherm curves have three different phases. At lower relative
pressure (0 < P/Ps < P/Pa ), adsorbent uptake of water is low. The sec­
ond phase (P/Pa < P/Ps < P/Pb ) is characterized by a sharp increase in
adsorption capacity, while the third phase (P/Pb < P/Ps < 1) exhibits a
slower increase in adsorption rate like the first phase.
Since most adsorption occurs in the second phase, it plays a vital role
in the overall adsorption characteristics. Therefore, to achieve optimal
efficiency, heating/cooling systems for adsorption using MIL-101 (Cr)
adsorbent material should be designed to operate within the range of
relative pressures P/Pa < P/Ps < P/Pb .
Fig. 11 demonstrates that, regardless of temperature, an increase in
temperature leads to a decrease in the maximum uptake and the region
of relative pressure that produces a spike shift towards higher values.
This can be attributed to the exothermic adsorption based on Le-Cha­
telier’s principle; when an exothermic process operates at higher tem­
peratures, it tends to produce less heat [57]. As a result, when the
temperature increases while keeping the pressure constant, the number
of adsorbate molecules that are adsorbed at equilibrium decreases.
Additionally, adsorbed water molecules at higher temperatures exhibit a
greater propensity to desorb from the surface. This leads to an increase
in pressure, which increases the relative pressure and shifts the spike
towards higher pressure values, resulting in a wider gap between the
start and end points of the spike. The maximum vapor uptake at 22 ◦ C
for MIL-101 (Cr) powder was 0.5277 ± 0.0396 g g− 1-adsorbent,
consistent with values reported in the literature and summarized in
Table 1 according to its BET area. The adsorption performance of MIL-
101 (Cr) is reduced slightly due to wash-coating in the presence of a
binder [53] to 0.44 g g− 1 adsorbent (only a 12% decrease).
Furthermore, the maximum adsorption capacities for temperatures
of 32 ◦ C and 45 ◦ C are reduced to 0.42 g g− 1 and 0.38 g g− 1, respectively.
The isotherm curves for all examined temperatures exhibit a similar
trend, with an increase in relative pressure between 0.4 and 0.6.
Moreover, higher temperatures lead to a decrease in the maximum ca­
pacity of adsorbed water vapor. The S-shape isotherm, characteristic of
physisorption, is observed consistently across the examined temperature
ranges.
This is an encouraging result considering the MIL-101 (Cr) powder is
mixed with silica binder, coated, and dried in multiple microchannels,
and they were used to create test sections. The reduced uptake capacity
can also be attributed to the lower accessibility of the active adsorption
sites due to a thick coating. Nevertheless, the observed uptake capacity
of the MIL-101 (Cr) coated microchannels remains within a reasonable
range of the powdered MIL-101 (Cr). It demonstrates the effectiveness of
the developed wash-coating technique using ethanol for creating a du­
rable and permanent adsorption layer on the microchannel walls.
F. Ege and D.G. Pahinkar Chemical Engineering Journal 472 (2023) 144960

3.4. Adsorption isotherm equations for coated microchannels Table 5

Parameters of the Modified-Langmuir Model.
To comprehensively explain the adsorption process in the coated T(◦ C) Qm (g g− 1) K (Pa− 1) B R2
microchannels, it is crucial to establish a link between the empirical data
22 0.4444 3.8709 7.5338 0.9922
and well-developed classical models. This research uses the Modified 32 0.4341 3.2815 6.4907 0.9951
Langmuir model to analyze and fit the experimental results. The model 45 0.3995 3.8395 8.0095 0.9929
was developed by Gu et al. [58], a semi-theoretical model based on
Langmuir isotherm [59].
solvent, silica nanoparticles as the binder, and MIL-101 (Cr) powders as
q=
Qm (P/Ps )
(5) the adsorbent. The fused silica-coated microchannels were analyzed
K.e− B.q + (1 − K.e− B.q )(P/Ps ) using SEM analysis, and their endurance was tested through successive
This equation is valid for both type-IІ and V isotherms. q is the adsorption and desorption tests. These coated microchannels were
amount of vapor uptake, P/Ps is the relative pressure with respect to the tested for water adsorption isotherms on MIL-101 (Cr) coatings using the
saturation pressure at the test temperature, k is the affinity parameter in volumetric method. The isotherm experiments were conducted at three
Pa− 1, and B is the isotherm constants determined by fitting the experi­ different temperatures to investigate the effect of temperature on the
mental data. Qm represents the maximum adsorption capacity, which adsorption process.
could be determined through the calculation of the adsorption energy The major conclusions from the study are listed below:
and a fitted parameter, as outlined in the following manner:
( ) 1. This paper only details the development of a new MIL-101 (Cr)
Ed coating technique inside the fused silica microchannels using ethanol
Qm = q0 exp (6)
RT and silica nanoparticles, thus simplifying the coating process and
eliminating degrees of freedom in it—such coated microchannels
In this equation q0 is a fitted parameter, Ed is the adsorption energy,
open avenues to new coating technologies that are beneficial for
R is the gas constant, and T is the temperature at which the adsorption
building energy-efficient adsorption heat pumps. The image analysis
occurs. In this study Qm is determined experimentally for three different
of the coated microchannels was conducted using SEM to determine
temperatures. The fitted isotherms are shown in Fig. 12, and the pa­
the thickness of the coated MIL-101 (Cr) inside the fused silica
rameters for the isotherm model are exhibited in Table 5.
microchannels. The thickness of the coated layer was found to be
The graph demonstrates a good fit for higher pressures and adsorbed
between 30 and 60 µm which is a unique result compared with the
water for all three temperatures. This particular model is more suitable
coated microchannels available in the market in the form of PLOT
and accurately represents the isotherm behavior on coated surfaces
columns. The SEM analysis of coated microchannels confirmed that
compared to the adsorbent materials in powder form. The purpose of
this method provides a uniformly coated layer inside microchannels.
deriving this model is to use these equations directly in the mass, species
2. The durability of the coated microchannels was measured by
and energy balance equations when coated microchannels adsorb water.
measuring the coated microchannel weight after the regeneration
This adsorption isotherm can then serve as the source term for the free
process for each experiment. It was observed that after 20 adsorp­
channel space species balance, bypassing the macroscopic diffusion
tion/desorption cycles, the weight of the coated microchannels
model through the layer.
changed by less than 1%, inferring that the coating method yielded
stable coated microchannels.
4. Conclusion
3. The isotherms of MIL-101 (Cr) in the coated form at three different
temperatures showed a three-step process in the adsorption stage
A novel wash-coating method was developed for coating MIL-101
which the majority of vapor is adsorbed in the second stage of the
(Cr) inside the fused silica microchannels with a 530 µm inner diam­
adsorption process. Moreover, they showed that increasing the
eter. The adsorbent slurry was prepared using ethanol as the base

Fig. 12. Curve fitting for the experimental data.

10
F. Ege and D.G. Pahinkar
temperature, the spike in the adsorption stage shifted to the right
side. The quantity of the adsorbed vapor is decreased as temperature
increases, consistent with the adsorption isotherm theory. Finally,
the adsorption properties of water vapor in coated microchannels are
in reasonable agreement with the reported results for MIL-101 (Cr)
powders [13–18].
4. A reasonable fit to the data was obtained using a modified Langmuir
equation, with a variance of 0.99 for all temperatures indicating its
suitability for coated microchannels and a type V isotherm behavior.
5. Compared to the MIL-101 (Cr) powder BET area of 1320 m2/g, the
MIL-101 (Cr) in the coated form offers a BET area of 894 m2/g. While
there is some loss of adsorbent due to coating thickness, inaccessible
adsorbent and loss or collapse of nanopores, 67% of BET area is
preserved for utility in the adsorption process. Combined with the
water adsorption uptake results, these numbers align with the sum­
marized literature data in the introduction.
In sum, a novel wash-coating technique using ethanol as the solvent
resulted in a highly uniform and thick MIL-101 (Cr) coating of up to 60
μm providing a more repeatable, reliable and versatile alternative for
PLOT columns.
Funding
This research was supported by Florida Institute of Technology and
received no specific grant from other funding agencies in the public,
commercial, or not-for-profit sectors.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
References
[1] L. Martin, Annual Energy Outlook 2022, Independent Statistics & Analysis, https://
www.eia.gov/, 2027.
[2] M.F. de Lange, K.J.F.M. Verouden, T.J.H. Vlugt, J. Gascon, F. Kapteijn, Adsorption-
driven heat pumps: the potential of metal-organic frameworks, Chem. Rev. 115
(22) (2015) 12205–12250, https://doi.org/10.1021/acs.chemrev.5b00059.
[3] C. Feng, J. E, W. Han, Y. Deng, B. Zhang, X. Zhao, D. Han, Key technology and
application analysis of zeolite adsorption for energy storage and heat-mass transfer
process: a review, Renewable Sustain. Energy Rev. 144 (2021), 110954.
[4] S. Kayal, S. Baichuan, B.B. Saha, Adsorption characteristics of AQSOA zeolites and
water for adsorption chillers, Int. J. Heat Mass Transf. 92 (2016) 1120–1127,
https://doi.org/10.1016/j.ijheatmasstransfer.2015.09.060.
[5] K.-M. Kim, H.-T. Oh, S.-J. Lim, K. Ho, Y. Park, C.-H. Lee, Adsorption equilibria of
water vapor on zeolite 3a, zeolite 13x, and dealuminated y zeolite, J. Chem. Eng.
Data 61 (4) (2016) 1547–1554, https://doi.org/10.1021/acs.jced.5b00927.
[6] Y. Liu, K.C. Leong, The effect of operating conditions on the performance of
zeolite/water adsorption cooling systems, Appl. Therm. Eng. 25 (10) (2005)
1403–1418, https://doi.org/10.1016/j.applthermaleng.2004.09.013.
[7] T. Miltkau, B. Dawoud, Dynamic modeling of the combined heat and mass transfer
during the adsorption/desorption of water vapor into/from a zeolite layer of an
adsorption heat pump, Int. J. Therm. Sci. 41 (8) (2002) 753–762, https://doi.org/
10.1016/S1290-0729(02)01369-8.
[8] A. Myat, N. Kim Choon, K. Thu, Y.-D. Kim, Experimental investigation on the
optimal performance of Zeolite–water adsorption chiller, Appl. Energy 102 (2013)
582–590, https://doi.org/10.1016/j.apenergy.2012.08.005.
[9] G. Restuccia, A. Freni, G. Maggio, A zeolite-coated bed for air conditioning
adsorption systems: parametric study of heat and mass transfer by dynamic
simulation, Appl. Therm. Eng. 22 (6) (2002) 619–630, https://doi.org/10.1016/
S1359-4311(01)00114-4.
[10] İ. Solmuş, C. Yamalı, B. Kaftanoğlu, D. Baker, A. Çağlar, Adsorption properties of a
natural zeolite–water pair for use in adsorption cooling cycles, Appl. Energy 87 (6)
(2010) 2062–2067, https://doi.org/10.1016/j.apenergy.2009.11.027.
[11] H. Furukawa, F. Gándara, Y.B. Zhang, J. Jiang, W.L. Queen, M.R. Hudson, O.
M. Yaghi, Water adsorption in porous metal-organic frameworks and related
11
Chemical Engineering Journal 472 (2023) 144960
materials, J Am Chem Soc 136 (11) (2014) 4369–4381, https://doi.org/10.1021/
ja500330a.
[12] S. Fei, J. Gao, R. Matsuda, A. Endo, W.-L. Hsu, J.-J. Delaunay, H. Daiguji,
Temperature effect on water adsorption and desorption processes in the
mesoporous metal-organic framework MIL-101(Cr), J. Phys. Chem. C 126 (36)
(2022) 15538–15546, https://doi.org/10.1021/acs.jpcc.2c05603.
[13] Y.K. Seo, J.W. Yoon, J.S. Lee, Y.K. Hwang, C.H. Jun, J.S. Chang, S. Wuttke,
P. Bazin, A. Vimont, M. Daturi, S. Bourrelly, P.L. Llewellyn, P. Horcajada, C. Serre,
G. Férey, Energy-efficient dehumidification over hierachically porous metal-
organic frameworks as advanced water adsorbents, Adv Mater 24 (6) (2012)
806–810, https://doi.org/10.1002/adma.201104084.
[14] J. Ehrenmann, S.K. Henninger, C. Janiak, Water adsorption characteristics of mil-
101 for heat-transformation applications of MOFs, Eur. J. Inorg. Chem. 2011 (4)
(2011) 471–474, https://doi.org/10.1002/ejic.201001156.
[15] G. Akiyama, R. Matsuda, H. Sato, A. Hori, M. Takata, S. Kitagawa, Effect of
functional groups in MIL-101 on water sorption behavior, Microporous
Mesoporous Mater. 157 (2012) 89–93, https://doi.org/10.1016/j.
micromeso.2012.01.015.
[16] A. Rezk, R. Al-Dadah, S. Mahmoud, A. Elsayed, Characterisation of metal organic
frameworks for adsorption cooling, Int. J. Heat Mass Transf. 55 (25) (2012)
7366–7374, https://doi.org/10.1016/j.ijheatmasstransfer.2012.07.068.
[17] S. Fei, A. Alizadeh, W.-L. Hsu, J.-J. Delaunay, H. Daiguji, Analysis of the water
adsorption mechanism in metal-organic framework mil-101(cr) by molecular
simulations, J. Phys. Chem. C 125 (48) (2021) 26755–26769, https://doi.org/
10.1021/acs.jpcc.1c06917.
[18] Z. Liu, B. Zhao, L. Zhu, F. Lou, J. Yan, Performance of MIL-101(Cr)/water working
pair adsorption refrigeration system based on a new type of adsorbent filling
method, Materials 13 (1) (2020) 195.
[19] K. Yanagita, J. Hwang, J.A. Shamim, W.-L. Hsu, R. Matsuda, A. Endo, J.-
J. Delaunay, H. Daiguji, Kinetics of water vapor adsorption and desorption in mil-
101 metal-organic frameworks, J. Phys. Chem. C 123 (1) (2019) 387–398, https://
doi.org/10.1021/acs.jpcc.8b08211.
[20] J. Yan, Y. Yu, C. Ma, J. Xiao, Q. Xia, Y. Li, Z. Li, Adsorption isotherms and kinetics
of water vapor on novel adsorbents MIL-101(Cr)@GO with super-high capacity,
Appl. Therm. Eng. 84 (2015) 118–125, https://doi.org/10.1016/j.
applthermaleng.2015.03.040.
[21] H.W.B. Teo, A. Chakraborty, S. Kayal, Post synthetic modification of MIL-101(Cr)
for S-shaped isotherms and fast kinetics with water adsorption, Appl. Therm. Eng.
120 (2017) 453–462, https://doi.org/10.1016/j.applthermaleng.2017.04.018.
[22] K. Munusamy, G. Sethia, D.V. Patil, P.B. Somayajulu Rallapalli, R.S. Somani, H.
C. Bajaj, Sorption of carbon dioxide, methane, nitrogen and carbon monoxide on
MIL-101(Cr): Volumetric measurements and dynamic adsorption studies, Chem.
Eng. J. 195–196 (2012) 359–368, https://doi.org/10.1016/j.cej.2012.04.071.
[23] Q. Liu, L. Ning, S. Zheng, M. Tao, Y. Shi, Y. He, Adsorption of carbon dioxide by
mil-101(cr): regeneration conditions and influence of flue gas contaminants, Sci.
Rep. 3 (1) (2013) 2916, https://doi.org/10.1038/srep02916.
[24] S. Tourani, A. Behvandi, Synthesis of MIL-101(Cr)/Sulfasalazine (Cr-TA@SSZ)
hybrid and its use as a novel adsorbent for adsorptive removal of organic pollutants
from wastewaters, J. Porous Mater. 29 (5) (2022) 1441–1462, https://doi.org/
10.1007/s10934-022-01268-4.
[25] M.S. Alivand, M. Shafiei-Alavijeh, N.H.M.H. Tehrani, E. Ghasemy, A. Rashidi,
S. Fakhraie, Facile and high-yield synthesis of improved MIL-101(Cr) metal-
organic framework with exceptional CO2 and H2S uptake; the impact of excess
ligand-cluster, Microporous Mesoporous Mater. 279 (2019) 153–164, https://doi.
org/10.1016/j.micromeso.2018.12.033.
[26] M. Wickenheisser, C. Janiak, Hierarchical embedding of micro-mesoporous MIL-
101(Cr) in macroporous poly(2-hydroxyethyl methacrylate) high internal phase
emulsions with monolithic shape for vapor adsorption applications, Microporous
Mesoporous Mater. 204 (2015) 242–250, https://doi.org/10.1016/j.
micromeso.2014.11.025.
[27] J. Gao, S. Fei, Y.-L. Ho, R. Matsuda, H. Daiguji, J.-J. Delaunay, Water confined in
mil-101(cr): unique sorption-desorption behaviors revealed by diffuse reflectance
infrared spectroscopy and molecular dynamics simulation, J. Phys. Chem. C 125
(32) (2021) 17786–17795, https://doi.org/10.1021/acs.jpcc.1c03351.
[28] X. Huang, Q. Hu, L. Gao, Q. Hao, P. Wang, D. Qin, Adsorption characteristics of
metal–organic framework MIL-101(Cr) towards sulfamethoxazole and its
persulfate oxidation regeneration, RSC Adv. 8 (49) (2018) 27623–27630, https://
doi.org/10.1039/C8RA04789H.
[29] Y. Li, H.-T. Wang, Y.-L. Zhao, J. Lv, X. Zhang, Q. Chen, J.-R. Li, Regulation of
hydrophobicity and water adsorption of MIL-101(Cr) through post-synthetic
modification, Inorg. Chem. Commun. 130 (2021), 108741, https://doi.org/
10.1016/j.inoche.2021.108741.
[30] H. Zhao, Q. Li, Z. Wang, T. Wu, M. Zhang, Synthesis of MIL-101(Cr) and its water
adsorption performance, Microporous Mesoporous Mater. 297 (2020), 110044,
https://doi.org/10.1016/j.micromeso.2020.110044.
[31] M.F. De Lange, J.-J. Gutierrez-Sevillano, S. Hamad, T.J.H. Vlugt, S. Calero,
J. Gascon, F. Kapteijn, Understanding adsorption of highly polar vapors on
mesoporous mil-100(cr) and mil-101(cr): experiments and molecular simulations,
J. Phys. Chem. C 117 (15) (2013) 7613–7622, https://doi.org/10.1021/
jp3128077.
[32] M. Wickenheisser, F. Jeremias, S.K. Henninger, C. Janiak, Grafting of hydrophilic
ethylene glycols or ethylenediamine on coordinatively unsaturated metal sites in
MIL-100(Cr) for improved water adsorption characteristics, Inorg. Chim. Acta 407
(2013) 145–152, https://doi.org/10.1016/j.ica.2013.07.024.
[33] E. Elsayed, R. Al-Dadah, S. Mahmoud, P.A. Anderson, A. Elsayed, P.G. Youssef,
CPO-27(Ni), aluminium fumarate and MIL-101(Cr) MOF materials for adsorption
F. Ege and D.G. Pahinkar
water desalination, Desalination 406 (2017) 25–36, https://doi.org/10.1016/j.
desal.2016.07.030.
[34] S. Ashraf, M. Sultan, M. Bahrami, C. McCague, M.W. Shahzad, M. Amani, R.
R. Shamshiri, H.M. Ali, Recent progress on water vapor adsorption equilibrium by
metal-organic frameworks for heat transformation applications, Int. Commun. Heat
Mass Transfer 124 (2021), 105242, https://doi.org/10.1016/j.
icheatmasstransfer.2021.105242.
[35] J. Canivet, J. Bonnefoy, C. Daniel, A. Legrand, B. Coasne, D. Farrusseng,
Structure–property relationships of water adsorption in metal–organic frameworks,
New J. Chem. 38 (7) (2014) 3102–3111, https://doi.org/10.1039/C4NJ00076E.
[36] A. Khutia, H.U. Rammelberg, T. Schmidt, S. Henninger, C. Janiak, Water Sorption
cycle measurements on functionalized mil-101cr for heat transformation
application, Chem. Mater. 25 (5) (2013) 790–798, https://doi.org/10.1021/
cm304055k.
[37] R. Al-Dadah, S. Mahmoud, E. Elsayed, P. Youssef, F. Al-Mousawi, Metal-organic
framework materials for adsorption heat pumps, Energy 190 (2020), 116356,
https://doi.org/10.1016/j.energy.2019.116356.
[38] I. Jahan, T.H. Rupam, M.L. Palash, K.A. Rocky, B.B. Saha, Energy efficient green
synthesized MOF-801 for adsorption cooling applications, J. Mol. Liq. 345 (2022),
117760, https://doi.org/10.1016/j.molliq.2021.117760.
[39] A. Nasruddin, F. Zulys, A. Yulia, N. Buhori, M. Muhadzib, B.B. Ghiyats, Saha,
Synthesis and characterization of a novel microporous lanthanide based metal-
organic framework (MOF) using napthalenedicarboxylate acid, J. Mater. Res.
Technol. 9 (4) (2020) 7409–7417, https://doi.org/10.1016/j.jmrt.2020.05.015.
[40] H.W.B. Teo, A. Chakraborty, Water adsorption on various metal organic
framework, IOP Conf. Ser.: Mater. Sci. Eng. 272 (1) (2017), 012019, https://doi.
org/10.1088/1757-899X/272/1/012019.
[41] I. Jahan, M.A. Islam, T.H. Rupam, M.L. Palash, K.A. Rocky, B.B. Saha, Enhanced
water sorption onto bimetallic MOF-801 for energy conversion applications,
Sustain. Mater. Technol. 32 (2022) e00442, https://doi.org/10.1016/j.
susmat.2022.e00442.
[42] H. Kummer, M. Baumgartner, P. Hügenell, D. Fröhlich, S.K. Henninger, R. Gläser,
Thermally driven refrigeration by methanol adsorption on coatings of HKUST-1
and MIL-101(Cr), Appl. Therm. Eng. 117 (2017) 689–697, https://doi.org/
10.1016/j.applthermaleng.2016.11.026.
[43] D.G. Pahinkar, D.B. Boman, S. Garimella, High performance microchannel
adsorption heat pumps, Int. J. Refrig 119 (2020) 184–194, https://doi.org/
10.1016/j.ijrefrig.2020.07.020.
[44] D.G. Pahinkar, S. Garimella, A novel temperature swing adsorption process for
natural gas purification: Part I, model development, Sep. Purif. Technol. 203
(2018) 124–142, https://doi.org/10.1016/j.seppur.2018.04.020.
[45] D.G. Pahinkar, S. Garimella, A novel temperature swing adsorption process for
natural gas purification, Part II: performance assessment, Sep. Purif. Technol. 204
(2018) 81–89, https://doi.org/10.1016/j.seppur.2018.04.019.
12
Chemical Engineering Journal 472 (2023) 144960
[46] D.G. Pahinkar, S. Garimella, T.R. Robbins, Feasibility of temperature swing
adsorption in adsorbent-coated microchannels for natural gas purification, Ind.
Eng. Chem. Res. 56 (18) (2017) 5403–5416, https://doi.org/10.1021/acs.
iecr.7b00389.
[47] N. Chauhan, F. Accornero, A.I. Sultana, F. Ege, M.T. Reza, D.G. Pahinkar, Synthesis
and characterization of mil–101 (cr) adsorbent coating on microchannel walls for
water adsorption heat pumps, Ind. Eng. Chem. Res. 61 (39) (2022) 14573–14585,
https://doi.org/10.1021/acs.iecr.2c02163.
[48] F.E.G.E. ElİBol, T. Oğuz, A. Emre, Flow and Heat Transfer in a Trapezoidal Cross-
Sectional Microchannel Heat Sink Using Nanofluid, 34 (2023). https://doi.org/
https://dergipark.org.tr/en/pub/gujs/issue/65898/806591.
[49] Chromium MOF (Cr-MIL-101). https://www.nanochemazone.com/product/
chromium-mof-cr-mil-101/.
[50] Z. Liu, J. Gao, X. Qi, Z. Zhao, H. Sun, Experimental study on activated carbon-mil-
101(cr) composites for ethanol vapor adsorption, Materials 14 (14) (2021) 3811.
[51] UCSB, Why does rubbing alcohol evaporate quicker than water?.
[52] D.G. Pahinkar, S. Garimella, Experimental and computational investigation of gas
separation in adsorbent-coated microchannels, Chem. Eng. Sci. 173 (2017)
588–606.
[53] X.Q. Duong, N.V. Cao, W.S. Lee, M.Y. Park, J.D. Chung, K.J. Bae, O.K. Kwon, Effect
of coating thickness, binder and cycle time in adsorption cooling applications,
Appl. Therm. Eng. 184 (2021), 116265, https://doi.org/10.1016/j.
applthermaleng.2020.116265.
[54] R. Idem, M. Wilson, P. Tontiwachwuthikul, A. Chakma, A. Veawab, A. Aroonwilas,
D. Gelowitz, Pilot plant studies of the co2 capture performance of aqueous mea and
mixed mea/mdea solvents at the university of regina co2 capture technology
development plant and the boundary dam co2 capture demonstration plant, Ind.
Eng. Chem. Res. 45 (8) (2006) 2414–2420, https://doi.org/10.1021/ie050569e.
[55] H.W. Coleman, W.G. Steele (Eds.), Experimentation, Validation, and Uncertainty
Analysis for Engineers, John Wiley & Sons, Inc., Hoboken, NJ, USA, 2009,
pp. 1–27.
[56] Attune, The Ultimate Guide to Chiller Systems. Everything You Need to Know.,
November 2017. https://blog.attuneiot.com/2017/11/16/ultimate-guide-chiller-
systems.
[57] A. Gabelman, Adsorption Basics: Part 1, American Institute of Chemical Engineers
(AlChE), CEP Magazine, 2017, pp. 48–53.
[58] B. Gu, J. Schmitt, Z. Chen, L. Liang, J.F. McCarthy, Adsorption and desorption of
natural organic matter on iron oxide: mechanisms and models, Environ. Sci. Tech.
28 (1) (1994) 38–46, https://doi.org/10.1021/es00050a007.
[59] V.J. Inglezakis, S.G. Poulopoulos, H. Kazemian, Insights into the S-shaped sorption
isotherms and their dimensionless forms, Microporous Mesoporous Mater. 272
(2018) 166–176, https://doi.org/10.1016/j.micromeso.2018.06.026.