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OPEN Enhanced atmospheric

water harvesting efficiency
through green‑synthesized
MOF‑801: a comparative study
with solvothermal synthesis
Mohammad Aghajani Hashjin , Shadi Zarshad , Hosein Banna Motejadded Emrooz * &
Sadegh Sadeghzadeh

Adsorption-based atmospheric water harvesting has emerged as a compelling solution in response

to growing global water demand. In this context, Metal–organic frameworks (MOFs) have garnered
considerable interest due to their unique structure and intrinsic porosity. Here, MOF 801 was
synthesized using two different methods: solvothermal and green room temperature synthesis.
Comprehensive characterization indicated the formation of MOF-801 with high phase purity, small
crystallite size, and excellent thermal stability. Nitrogen adsorption–desorption analysis revealed
that green-synthesized MOF-801 possessed an 89% higher specific surface area than its solvothermal-
synthesized counterpart. Both adsorbents required activation at a minimum temperature of 90 °C
for optimal adsorption performance. Additionally, green-synthesized MOF-801 demonstrated
superior adsorption performance compared to solvothermal-synthesized MOF-801, attributed to
its small crystal size (around 66 nm), more hydrophilic functional groups, greater specific surface
area (691.05 ­m2/g), and the possibility of having a higher quantity of defects. The maximum water
adsorption capacity in green-synthesized MOF-801 was observed at 25 °C and 80% relative humidity,
with a value of 41.1 g/100 g, a 12% improvement over the solvothermal-synthesized MOF-801.
Remarkably, even at a 30% humidity level, green-synthesized MOF-801 displayed a considerable
adsorption capacity of 31.5 g/100 g. Importantly, MOF-801 exhibited long-term effectiveness in
multiple adsorption cycles without substantial efficiency decline.

Currently, freshwater scarcity stands as one of humanity’s most pressing concerns. It is expected that water
stress will worsen in the near future, particularly for individuals residing in dry a­ reas1,2. Only a minor fraction,
approximately 2.5%, of the global water supply is freshwater, while the overwhelming majority, around 97.5%, is
saltwater in oceans. Out of the freshwater sources, only 0.4% is easily accessible and available for u ­ se3,4. World-
wide, research efforts have been taken to harvest water, including rainwater collection, groundwater harvesting,
and water desalination. However, these methods heavily rely on the presence of liquid water sources and face
significant limitations in regions that are ­landlocked5,6. It is a well-established fact that freshwater on Earth also
includes water vapor present in the atmosphere, amounting to a total of 15 trillion l­ iters7,8. Surprisingly, even in
landlocked regions, a significant amount of water vapor exists. The atmospheric water generation technique not
only presents labor and energy saving but also demonstrates its applicability across vast areas on ­Earth9–12. Fur-
thermore, the harvested water by this method is suitable for drinking without the need for complex sterilization
­processes7,13. Typically, there are three main approaches to achieving atmospheric water generation: fog collec-
tion, cooling air to a temperature below the dew point, and employing sorbents to assist in water ­harvesting14,15.
However, the first two methods face significant restrictions due to specific geographical or climatic conditions.
As a result, considerable research efforts have been dedicated to investigating sorbent-assisted water c­ apture16,17.
In recent years, there has been significant interest in a newly developed category of adsorbent materials known
as "metal–organic frameworks (MOFs)"18,19. MOFs are a unique class of crystalline porous materials composed

Nanotechnology Department, School of Advanced Technologies, Iran University of Science and Technology (IUST),
Narmak, Tehran 16846, Iran. *email: [email protected]

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of metal ions or clusters connected by organic bridging ­ligands20,21. While MOFs have attracted considerable
attention for various applications such as ­photocatalysis22, separation ­techniques23,24, electro-catalysis25, bio-
medical ­imaging26, drug ­delivery27, electronic and gas ­sensors28,29, researchers have recently begun exploring
their potential as adsorbents for capturing water due to their exceptional porosity and expansive surface a­ rea30.
MOFs designed for atmospheric water harvesting can be categorized into three main groups: (1) those based on
aluminum, including MOF-303, CAU-10, and MIL-53; (2) zirconium-based MOFs, such as MOF-801, MOF-808,
and MOF-841; and (3) other types like MIL-101 and C ­ o2Cl2(BTDD)31. Among the MOFs, MOF-801, MOF-
808, and MOF-841, stand out for their exceptional water adsorption capacity. They are notable for their ease of
regeneration at temperatures below 150 °C. Even after five cycles of adsorption and desorption, these materials
retained their water adsorption c­ apabilities32. MOF-801 [Zr6 O4 (OH)4 (fumarate)6 ] is a highly researched material
in this category due to its several advantages such as its low cost and exceptional stability. Additionally, MOF-
801 possesses three distinct cavities providing the ability to capture and concentrate water molecules within
­them33–36. It has been previously reported that MOF-801 exhibits excellent water adsorption performance even
in regions with low h­ umidity4. Kim et al. demonstrated a remarkable water adsorption capacity of ~ 25 g/100 g
by utilizing MOF-801 at a low relative humidity of 20%37. In another study, Yaghi et al. demonstrated a maxi-
mum adsorption capacity of 22.5 g/100 g for MOF-801 at 10% ­RH18. The same research group designed a water
harvesting device based on MOF-801, which is capable of collecting 2.8 L of water per kilogram of adsorbent
per day at 20% RH without requiring any additional energy i­ nput38. In another study, Mi et al. suggested a way
for synthesizing defective MOF-801 which results in an exceptional level of water harvesting efficiency (1.60 kg
water/kg adsorbent/day at 20% RH)39.
Despite the numerous studies conducted on the application of Zr-based MOFs for water harvesting, a com-
prehensive investigation that thoroughly assesses the effect of surface characteristics and environmental param-
eters such as temperature and humidity level on the water harvesting performance of MOF-801 is noticeably
lacking. Moreover, there is a scarcity of research that specifically examines the optimum activation temperature
and water adsorption rate of MOF-801. Additionally, existing research in this domain have not sufficiently
explored the morphology, structure, and adsorption performance of MOF-801 after undergoing multiple and
prolonged cycles. To overcome the mentioned lack of information, in this study, MOF-801 was synthesized as a
water adsorbent using two different methods: (1) solvothermal method with DMF as the solvent, and (2) room
temperature green-synthesis with water as the solvent. The synthesized samples were compared in terms of their
characteristics, morphology, and structure. Subsequently, the optimum activation temperature of MOF-801 was
investigated to determine the temperature at which all adsorbed water is desorbed, resulting in complete water
removal. The performance of the adsorbents was then examined under various temperature and humidity condi-
tions. Additionally, the adsorption rate in MOF-801 was studied to assess its performance within a specific time
frame. Finally, the characteristics, adsorption performance, and stability of MOF-801 over multiple adsorption
cycles were discussed, to evaluate its efficiency for repeated use.

Experimental section
Materials
Fumaric acid (C4 H4 O4 , purity ≥ 99.0%), Zirconium oxychloride octahydrate (ZrO Cl2·8 H2 O, purity ≥ 99.5%),
Formic acid (HCOOH, purity ≥ 98.0%), N,N’-dimethylformamide (DMF, HPLC grade), Ethanol (purity ≥ 99.0%),
Methanol (HPLC grade), and Sulfuric acid (purity: 95–97%) all from Sigma-Aldrich Co, and Deionized water.
It is noteworthy that all the materials were used without any additional treatment.

Solvothermal‑synthesized MOF‑801
In the first method (solvothermal synthesis), MOF-801 was synthesized according to the synthesis procedure
described by Yaghi and co-workers40 as follows: Firstly, in a screw-capped jar, 1.24 g fumaric acid and 3.42 g ZrO
Cl2·8 H2 O were dissolved in a solvent mixture consisting of 42.8 mL of DMF and 14.98 mL of formic acid under
magnetic stirring. The resulting solution was then transferred into an autoclave and heated at 130 °C for 10 h.
The white product was filtrated and washed three times with 50 mL of DMF over a period of 3 days. The washed
particles were dried overnight at ambient temperature, followed by another round of three daily washes with
50 mL of methanol for 3 days and subsequently dried in air again. Finally activated MOF-801 was obtained by
drying the white solid at 150 °C under vacuum for 24 h. For the sake of naming convenience, during this study,
the solvothermal-synthesized MOF-801 is named SS-MOF-801.

Green‑synthesized MOF‑801
The second method (green room temperature synthesis) used water instead of DMF as the solvent to synthesize
MOF-801 according to the previous ­report41,42. In this case, 3.5 g ZrO Cl2·8 H2 O was dissolved in a distilled
water/formic acid mixed solvent (80 mL/20 mL). After 1 min of stirring, 1.75 g of fumaric acid was added and
stirred at 600 rpm for 90 min to form a homogeneous solution. The resulting solution was left at room tempera-
ture for 48 h to produce a cloudy solution, indicating the formation of MOF-801. Afterward, the white precipitate
was collected by centrifugation, followed by washing one time with water and two times with ethanol, placing at
room temperature for 48 h, and finally drying at 150 °C under vacuum for 7 h. The green-synthesized MOF-801
is named GS-MOF-801 during this study.

Characterization
The crystallinity of the MOF-801 was carried out by X-ray diffraction (XRD, PW 1730 diffractometer, PHILIPS,
Netherlands) in the 2θ range from 5° to 80° with a step of 0.04° using CuKα radiation (λ = 1.5417 Å). The
instrument’s settings included a voltage of 40 kV and a current of 30 mA. The functional groups and chemical

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bonds of synthesized MOF were analyzed by Fourier transform infrared spectroscopy (FTIR, Spectrum RX1,
PERKIN-ELMER, USA) over the scanning range of 400 to 4000 c­ m−1 wavenumbers with a spectral resolution of
1 ­cm-1. The thermal behavior of MOF-801 was investigated using a Thermogravimetric analyzer (TGA, STA504,
­ in−1, under a nitrogen
BAHR, Germany) over a temperature range of 50 to 1000 °C, using a heating rate of 10 °C m
atmosphere. The specific surface area and porosity of the samples were evaluated from the nitrogen adsorp-
tion–desorption isotherms at 77 K (BELSORP-mini II, Bel Inc., Japan). The morphology and elemental com-
position of MOF-801 crystals were analyzed by field emission scanning electron microscopy (FESEM, EM8000,
KYKY, China). A Transmission electron microscope (TEM, CM120, PHILIPS, Netherlands) was employed to
investigate the structure and crystal morphology of the samples.

Water adsorption test

To set up a constant temperature and humidity environment, a desiccator filled with different concentrations
of sulfuric acid solution was used. To this end, sulfuric acid was diluted with deionized water to make specific
relative humanity inside the desiccator. Besides, for monitoring the temperature and humidity, a digital tempera-
ture humidity meter was placed in the desiccator. A schematic of the set-up for determination the adsorption
performance is presented in Fig. 1. As a first step, the samples were placed in an oven to remove the adsorbed
water vapor before the adsorption test. After the desorption process, dried samples were weighed and placed in
a Petri dish inside the desiccator and allowed to adsorb water vapor from the moisture-controlled environment.
The weight increase method was utilized to measure the adsorption capacity of the adsorbent which is expressed
as the water uptake per unit weight of adsorbent and with unit g/100 g. The water uptake of samples is g­ iven43
by the following equation:
mad − mde
Water uptake =
mde (1)

where mad is the mass of the MOF-801 after the water adsorption test and mde is the mass of the MOF-801 after
desorption by heating. This method was employed for multiple sets of conditions in terms of temperature and
humidity to determine the adsorption performance of MOF-801. All adsorption tests in this study were con-
ducted over 24 h. “The maximum adsorption capacity” for each sample, which represents the adsorption capacity
of the adsorbent at the end of the 24-h adsorption process, was compared with the others.

Activation temperature
The activation temperature plays a crucial role in the efficiency of an adsorbent. It signifies the temperature at
which the adsorbed water within the adsorbent structure is completely eliminated. To investigate the optimal
activation temperature, the synthesized samples that had been exposed to 80% (± 5%) RH for 2 h, were subjected
to different temperature conditions (70 °C, 90 °C and 110 °C) to remove the adsorbed water from the adsorbents.
Subsequently, the mass changes of the samples were measured after a 1-h desorption process. Following that, the
adsorption test was carried out under the conditions of 25 °C ± 1 °C and 80% (± 5%) RH. Finally, the adsorption
performance of samples during the 24-h adsorption process was compared. Each sample was labeled with the
corresponding activation temperature of the adsorbent. For instance, SS-MOF-801-70 refers to SS-MOF-801
that has undergone a heating process at 70 °C in order to eliminate the water adsorbed within it.

Figure 1.  Schematic of the equipment for determination of adsorption performance of MOF-801: (1)
desiccator, (2) digital temperature humidity meter, (3) sample in the Petri dish, (4) sulfuric acid solution.

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Results and discussion

Characterization
The XRD patterns of both the SS-MOF-801 and GS-MOF-801 are depicted in Fig. 2a. It can be seen that both
samples exhibit distinct peaks at angles of 8.5° and 9.8°. These peaks correspond to the crystal faces of MOF-801,
specifically the (1 1 1) and (2 0 0) planes, respectively. This result is in good agreement with the XRD patterns
of previous ­studies44,45 indicating the high phase purity of the powder samples. The crystallite size of the SS-
MOF-801 and GS-MOF-801 is ~ 46 nm and ~ 66 nm respectively. According to Grosu’s report, small crystallite
size can lead to a significant decrease in intrusion and extrusion pressures, which can be an advantage for water
harvesting ­systems46. From the FTIR spectrum of the synthesized SS-MOF-801 and GS-MOF-801 shown in
Fig. 2b, a broad peak around 3416 c­ m−1 indicates the presence of the OH g­ roup47. The peaks at 1654 c­ m−1,1581
­cm−1, and 1401 ­cm−1 could be attributed to –C=O–O b ­ onds48. On the other hand, the peaks at 1206 c­ m−1, 986
­cm , and 794 c­ m are identified as the C–H v­ ibrations49. Finally, the absorption at 657 c­ m−1 and 487 c­ m−1 could
−1 −1

be assigned to Zr6 (OH)4 O4 vibrations and Zr-(OC) asymmetric stretching, r­ espectively50. As can be seen, the
increase in the OH peak area of GS-MOF-801 can signify the sample contains more hydrophilic functional groups
compared to SS-MOF-801. And there may be more opportunities for intermolecular interactions and hydrogen
bonding, which could lead to a better water adsorption behavior of GS-MOF-801. Consequently, the utilization
of water in the synthesis of MOF-801 not only addresses the drawback of employing harmful solvents like DMF
but also leads to the formation of more hydrophilic functional groups, which offers benefits for water adsorption.
The graph in Fig. 2c displays the nitrogen adsorption–desorption isotherms and micropore size distribution
of the powder samples of MOF-801, which are related to Type-I adsorption i­ sotherm51. It should be highlighted
that a slight inflexion of the adsorption isotherm curve in both samples, can be related to the occurrence of
some ­defects52. Besides, according to Li’s report, the enhanced nitrogen uptake during the physisorption of

Figure 2.  XRD patterns (a), FTIR spectra (b), and the nitrogen adsorption at 77 K and pore size distribution
curve (inset) (c) of SS-MOF-801 and GS-MOF-801; TGA curve of GS-MOF-801 (d).

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GS-MOF-801 can be attributed to the presence of the highest defects in its framework compared to the SS-
MOF-801. The mentioned defects within the crystal lattices provide numerous adsorption sites for water. Addi-
tionally, the concentration of defects in the GS-MOF-801 can be adjusted by varying the amount of the modulator
(formic acid) used in the aqueous synthesis. It is important to mention that the amount of formic acid employed
in the present work was determined as the optimal quantity based on the previous study to achieve the highest
possible defect concentration in GS-MOF-80139,42. The specific surface area of SS-MOF-801 and GS-MOF-801 is
365.43 ­m2/g and 691.05 m ­ 2/g respectively. On the other hand, SS-MOF-801 shows two distinct types of micropo-
res, which have radii of 0.7 nm and 1.4 nm. In contrast, GS-MOF-801 has a main pore size, located at a radius of
0.7 nm. GS-MOF-801 is expected to outperform SS-MOF-801 in terms of water adsorption. This expectation is
based on the potential for GS-MOF-801 to possess a greater quantity of defects and an 89% larger specific surface
area, enabling more active sites for water molecules to interact with and be adsorbed. Figure 2d shows the TGA
curve of synthesized GS-MOF-801 crystals. A 23% weight loss occurs below ~ 200 °C, owing to the removal of
adsorbed water and guest molecules trapped within the adsorbent’s pores. Subsequently, the sharp declining
trend starts to begin above 350 °C and extends up to 500 °C which is attributed to the loss of fumaric acid and
breaking of the carboxylate groups. This observation points to the adsorbent’s excellent thermal s­ tability42,51.
The morphology and size of the synthesized samples were subsequently analyzed using FESEM and TEM.
The FESEM micrographs demonstrate that both SS-MOF-801 and GS-MOF-801 have a uniform dispersion and
size distribution (Fig. 3a–d). Nevertheless, SS-MOF-801 displays an octahedral structure, whereas GS-MOF-801
tends to crystallize in a rounded form. These findings align with previous research indicating that the water-based
synthesis of MOF-801 predominantly yields spherical particles instead of octahedral o­ nes53. On the other hand,
based on the FESEM (Fig. 3a–d) and TEM (Fig. 3e,f) images, it can be observed that the particle size of both
MOF-801 samples is less than 200 nm, which is in accordance with previously reported v­ alues54.

Activation temperature
It can be seen from Fig. 4 that the adsorption performance of the adsorbents varies depending on the activation
temperature. In Fig. 4a, it can be observed that SS-MOF-801-90 achieves a maximum adsorption capacity of
36.7 g/100 g at the end of the 24-h adsorption process. This value represents a 71% increase compared to the
adsorption capacity of SS-MOF-801-70, which is 21.5 g/100 g. This significant difference can be attributed to the
fact that a temperature of 70 °C is inadequate for the complete removal of adsorbed water from the adsorbent
cavities and preparing the adsorption sites sufficiently for the adsorption ­process42,44. Additionally, as observed
in Fig. 4b, similar findings are observed for GS-MOF-801-90 too, and its maximum adsorption capacity exceeds
that of GS-MOF-801-70 by 92%. Furthermore, the inset of Fig. 4a and b displays the amount of water removed
from the total adsorbed water in corresponding samples at the end of the desorption process. It can be seen
that the adsorbed water content in MOF-801-90 and MOF-801-110 has been completely removed during the
desorption process, whereas in the case of SS-MOF-801-70 and GS-MOF-801-70, it has been reduced by 71%
and 61% respectively. In earlier studies, it has been indicated that MOF-801 demonstrates a lower activation
temperature in comparison to other a­ dsorbents55,56, and the current observation confirms that the optimum
activation temperature for both SS-MOF-801 and GS-MOF-801 adsorbents is 90 °C. It is obvious that the impact
of the activation temperature of 110 °C on the water adsorption performance of both samples is also favorable. It
is worth mentioning that the maximum adsorption capacity of GS-MOF-801-90 is 41.1 g/100 g, which represents
a 12% increase compared to SS-MOF-801-90. This difference can be attributed to GS-MOF-801’s significantly
larger specific surface area, which is 89% greater than that of SS-MOF-801. Additionally, the potential for a
higher quantity of defects and the presence of more hydrophilic functional groups in GS-MOF-801 compared
to SS-MOF-801 may further contribute to this difference. Therefore, alongside the use of water instead of the
harmful DMF as the solvent for the synthesis of GS-MOF-801, it exhibits superior water adsorption performance
in comparison to SS-MOF-801.

The effect of temperature on water sorption

In order to investigate the influence of temperature on the adsorption performance of the synthesized adsorbents,
the samples were first activated at the temperature of 90 °C. Subsequently, adsorption tests were conducted under
a controlled relative humidity of 50% (± 5%) at different temperatures: 15 °C, 25 °C, and 35 °C (± 1 °C). The
results are depicted in Fig. 5. As observed in Fig. 5a, the maximum adsorption capacity of SS-MOF-801 at 25 °C
is 31.2 g/100 g, but it decreases to 28.4 g/100 g when the temperature drops to 15 °C. In other words, the maxi-
mum adsorption capacity of SS-MOF-801 at 15 °C is 9% lower than that at 25 °C. Overall, at a constant relative
humidity of 50%, SS-MOF-801 demonstrates its optimum adsorption performance at a temperature of 25 °C.
When the temperature is 35 °C, the maximum adsorption capacity of SS-MOF-801 decreases by 4% compared to
that at 25 °C. Furthermore, as depicted in Fig. 5, the water adsorption curves of MOF-801 at 35 °C exhibit signs
of instability after a duration of 6 h. The findings suggested that elevated temperatures can lead to a slight reduc-
tion in the water adsorption capacity of adsorbents under the condition of constant relative humidity. A similar
behavior was also previously observed in the MIL-101(Cr) ­adsorbent57. This can be attributed to the activation
of certain water molecules at higher temperatures, causing them to detach from the sorption sites within the
adsorbents. Consequently, this results in a decline in the adsorption efficiency of the ­samples58. According to
Fig. 5b, the highest adsorption capacity of GS-MOF-801 is also observed at 25 °C, reaching 36.2 g/100 g. This
value is 16% higher than that of SS-MOF-801.

The effect of relative humidity on water sorption

It is expected that humidity would significantly impact the water adsorption performance of an adsorbent. In this
regard, the water adsorption performance of synthesized adsorbents was investigated at a constant temperature

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Figure 3.  FESEM images of SS-MOF-801 (a, b) and GS-MOF-801 (c, d); TEM images of GS-MOF-801 (e, f).

of 25 °C (± 1 °C), under various relative humidity conditions of 30%, 50%, and 80% (± 5%) (Fig. 6). As seen
in Fig. 6, both SS-MOF-801 and GS-MOF-801 exhibit an increase in adsorption performance with increasing
humidity. Specifically, the maximum adsorption capacity of SS-MOF-801 and GS-MOF-801 increases by 19% and
15%, respectively, when the humidity rises from 30 to 50%. Furthermore, with an increase in humidity from 50
to 80%, the maximum adsorption capacity of the mentioned adsorbents also increases by 17% and 13% respec-
tively. Naturally, this phenomenon can be attributed to the fact that as the relative humidity increases, the pres-
sure of water vapor also increases at a constant temperature leading to better water adsorption in a­ dsorbents57.
Furthermore, as observed in Fig. 6, GS-MOF-801 exhibits better performance in water adsorption compared
to SS-MOF-801 at all humidity levels. It should be noted that even at a relative humidity of 30%, GS-MOF-801
demonstrates a considerable adsorption capacity of 31.5 g/100 g. This indicates that MOF-801 can also be effec-
tive in low humidity conditions (e.g., in North Africa).

Adsorption rate of adsorbents

The adsorption rate during the initial hours plays a pivotal role in determining the efficiency of water intake
when employing adsorbents for this p ­ urpose57,59. One crucial observation that can be seen in all water adsorp-
tion curves of MOF-801 is the high adsorption rate of adsorbents in the initial four hours of the adsorption
process. As a result, the majority of water adsorption occurs within the mentioned time frame. For example,

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Figure 4.  Water sorption behavior of SS-MOF-801 (a) and GS-MOF-801 (b) with time; Inset: the amount of
water removed from the total adsorbed water in corresponding samples after a 1-h desorption process.

Figure 5.  Water sorption behavior of SS-MOF-801 (a) and GS-MOF-801 (b) at different temperatures.

when considering GS-MOF-801 under the conditions of 25 °C and 50% RH (Fig. 6a), ~ 78% of the maximum
adsorption capacity is achieved within the first four hours. Similarly, at a temperature of 25 °C and relative
humidity of 80% (Fig. 6a), this value increases to ~ 90%. Therefore, in order to examine the adsorption rates
of SS-MOF-801 and GS-MOF-801 under different temperature and humidity conditions, the adsorption rate
during the first four hours, referred to as " Adsorption rate I" was compared with the adsorption rate during the
subsequent four hours, referred to as " Adsorption rate II". The results can be observed in Tables 1 and 2. Based
on the findings presented in Tables 1 and 2, it is apparent that the adsorbents exhibit a noticeably higher rate of
water adsorption during the first four hours compared to the subsequent four hours. Hence, in situations where
there is a time limitation for utilizing the adsorbent for water adsorption, MOF-801 can be considered as a suit-
able option since it proves to exhibit a substantial level of adsorption within the initial hours of the adsorption
process. Furthermore, the highest adsorption rate is observed in GS-MOF-801 at a temperature of 25 °C and
relative humidity of 80% RH. Moreover, it can be seen that as the temperature and relative humidity levels rise, the
water adsorption rate I also increases. From Table 2, it can be concluded that the cavities of adsorbents become
saturated more quickly in high humidity levels compared to low humidity levels. As a result, the adsorption rate
II decreases as the humidity level increases.

Reuse performance of adsorbent

It is crucial for an appropriate adsorbent to sustain its efficiency over consecutive sorption cycles without expe-
riencing a significant performance ­decline32. Hence, this aspect will be thoroughly examined in this section.
Furthermore, as GS-MOF-801 exhibits superior adsorption performance in comparison to SS-MOF-801, the

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Figure 6.  Water Sorption Behavior of SS-MOF-801 and GS-MOF-801 at different relative humidity (a); The
maximum adsorption capacity of SS-MOF-801 and GS-MOF-801 at various relative humidity and constant
temperature of 25 °C (b).

Adsorption rate II (g ­kg−1

Sample Temperature (°C) Maximum adsorption capacity (g/100 g) Adsorption rate I (g ­kg−1 ­h−1) ­h−1h )
−1

15 28.4 54.7 10.0

SS-MOF-801 25 31.2 63.7 8.0
35 29.9 68.7 1.0
15 31.3 59.0 10.7
GS-MOF-801 25 36.2 70.2 14.2
35 36.0 77.0 12.7

Table 1.  Maximum adsorption capacity and adsorption rate of SS-MOF-801 and GS-MOF-801 at 50% RH.

Sample RH (%) Maximum adsorption capacity (g/100 g) Adsorption rate I (g ­kg−1 ­h−1) Adsorption rate II (g ­kg−1 ­h−1)
30 26.2 38.2 7.7
SS-MOF-801 50 31.2 63.7 8.0
80 36.7 84.7 4.0
30 31.5 44.2 17.0
GS-MOF-801 50 36.2 70.2 14.2
80 41.1 92.5 7.5

Table 2.  Maximum adsorption capacity and adsorption rate of SS-MOF-801 and GS-MOF-801 at 25 °C.

characteristics and performance of GS-MOF-801 will be discussed over multiple cycles. It is worth mentioning
that each cycle lasted 24 h, and the cycles were carried out under varying conditions of temperature and humidity
levels. For this purpose, after each adsorption cycle, GS-MOF-801 underwent a desorption process at a tempera-
ture of 90 °C to remove the adsorbed water, and it was subsequently used for the next adsorption cycle. Figure 7a
and b depict the FESEM images of GS-MOF-801 before the first cycle and after the 20th adsorption–desorption
cycle, respectively. The FESEM images show that the GS-MOF-801 particles exhibit a sign of slight deforma-
tion compared to their initial shape after undergoing consecutive adsorption–desorption cycles. Besides, based
on the observations in Fig. 7c, it is evident that even after undergoing multiple cycles, the crystallinity of GS-
MOF-801 remains unaffected. The graph in Fig. 7d and its inset demonstrate the impact of 20 cycles of water
adsorption–desorption on nitrogen physisorption and pore size distribution of GS-MOF-801. As can be seen,
after consecutive adsorption cycles, the pore size of GS-MOF-801 remained relatively stable with no significant
changes. And the specific surface area of the adsorbent decreased to 600.35 m ­ 2/g after 20 cycles, representing a
13% reduction compared to its initial value which could be attributed to factors such as slight structural degrada-
tion or exhaustion of the adsorbent. Nevertheless, this decrease can be considered negligible. As a consequence,
the aforementioned results indicate that MOF-801 exhibits excellent stability over multiple cycles.

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Figure 7.  FESEM images of GS-MOF-801 before the first adsorption cycle (a) and after the 20th adsorption–
desorption cycle (b); XRD pattern (c) and the nitrogen physisorption at 77 K and pore size distribution curve
(inset) (d) of GS-MOF-801 during adsorption–desorption cycling test.

In order to investigate the recycling performance of the adsorbent, the adsorption performance of GS-
MOF-801 was examined over 6 cycles at a temperature of 25 °C (± 1 °C) and 80% (± 5%) RH. This evaluation
aimed to assess whether MOF-801 maintains its water adsorption properties consistently and remains durable
and reliable over extended periods of use. For this purpose, after each adsorption test under the mentioned tem-
perature and humidity conditions, the adsorbent was heated to 90 °C to remove the adsorbed water before the
next cycle and then tested again under similar conditions. The maximum adsorption capacity of GS-MOF-801 at
the end of the 24-h adsorption process, for each cycle is shown in Fig. 8. As observed, the adsorption performance
of GS-MOF-801 remains relatively constant throughout the 6 cycles, with ~ 39.5 g/100 g of the adsorption capacity
remaining. Therefore, the adsorbent demonstrates high-performance stability during the 6 cycles. It should be
noted that the slight increase observed in the fourth and fifth cycles, could be attributed to improved removal of
water inside the pores during the pre-cycle desorption process. Furthermore, the absence of a significant decrease
in adsorption capacity throughout the cycles indicates that the adsorbent has not suffered from any exhaustion
or structural degradation over the 6 cycles.

Conclusion
In this study, we investigated the water adsorption performance of MOF-801, focusing on factors such as hydro-
philic functional groups, specific surface area of the adsorbent, and environmental conditions. MOF-801 was
synthesized using two different methods, solvothermal and green synthesis. The green-synthesized MOF-801
outperformed solvothermal-synthesized MOF-801, attributed to several factors including its small crystallite size,
increased presence of hydrophilic functional groups, larger specific surface area, and the possibility of having a
higher quantity of defects. Furthermore, both adsorbents need to be activated at a minimum temperature of 90 °C

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Figure 8.  The water adsorption performance of GS-MOF-801 during adsorption–desorption cycling test.

to exhibit their best adsorption performance. The maximum adsorption capacity for MOF-801 was found under
the conditions of 25 °C and 80% RH. MOF-801 also exhibited a considerable adsorption capacity even under low
humidity conditions. Additionally, the high adsorption rate of MOF-801 during the initial hours highlights its
suitability for applications where time constraint is a concern. Finally, the adsorption–desorption cycling tests
revealed the long-term effectiveness of MOF-801 in multiple water adsorption cycles, with no significant decline
in its efficiency. Overall, these findings demonstrate the potential of MOF-801 as a promising water adsorbent
with excellent stability and enhanced adsorption performance, making it suitable for water harvesting even at
low humidity conditions.

Data availability
All data presented in this study are included in this published article.

Received: 31 July 2023; Accepted: 6 October 2023

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Author contributions
H.B.M.E. and S.S. designed and supervised the research. M.A.H. performed all the experimental work and carried
out analytical characterizations. S.Z. and M.A.H. wrote the main manuscript text and prepared all the figures.
All authors contributed to discussions and manuscript review.

Competing interests
The authors declare no competing interests.

Additional information
Correspondence and requests for materials should be addressed to H.B.M.E.
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