A Bifunctional System for Atmospheric Water

Harvesting and Direct Air Electrolysis for

Hydrogen Production
Research plan

Submitted By : Fatima Al Arfaj

Mentored By : Dr.Mahmoud Abdelnaby , PhD & Research Scientist at KFUPM

Interdisciplinary Research Center for Hydrogen and Energy Storage (IRC-HES)

King Fahad University of Petroleum and Minerals

Dhahran, Kingdom of Saudi Arabia

Background Information
Due to its high energy density, sustainability, and zero emissions during use, hydrogen produced through
water splitting is commonly considered to be one of the most promising alternatives to fossil fuels. And
yet, by the end of the next 30 years, more than half of the world's population will experience a water
shortage[1]. Despite the fact that it is the factor that differentiates life and death. This number is predicted
to harshly increase [2], which will pose a significant challenge to  the production of hydrogen or the
availability of fresh drinkable water  Water is scarce in dry areas due to a lack of rain, and in watered
areas due to a lack of access to clean, fresh water [2].

In this regard, seawater treatment is a powerful technology, yet it is limited to more opulent countries,
especially those with ample fossil fuels and access to seawater as well as the environmental costs such as
the emissions of greenhouse gases from the immense amount of energy used, as well as the fact that
seawater is extremely salty and contains toxic treatment chemicals[3]. That will make producing
hydrogen extremely costly and more challenging.

Nevertheless, the extraction of water from the atmosphere is a potential solution since there is plenty of
water in the atmosphere in the form of water vapor and water droplets that could be extracted to produce
clean water at any time of the day anywhere at the world[4]. It is estimated that the air contains six times
as much water as all the rivers on our planet [4]. Therefore, an innovative technology to utilize this
source is highly needed. since it will help to address the world's water crisis and offer humanity with an
additional supply of fresh, clean water. However, finding a porous material that is capable of capturing
water at low humidity and releases water with great facility has been a vital quest over the past years. One
idea is to use a porous material capable of trapping water from the air .
In recent years, Metal-Organic Frameworks (MOFs), have emerged as crystalline materials with
exceptional porosity and internal surface areas extending beyond 6,000 m2/g [5]. MOFs are a viable
choice for numerous applications, including gas separation and storage, particularly for hydrogen and
methane [6], . MOF-303 and MOF-801 are promising MOFs due to their porous, crystalline
structure, low cost of metal, high capacity at low relative, fast water sorption , excellent mechanical
properties and high chemical and hydrolytic stability. Initial experiments in the laboratory showed
that MOF-303 and MOF-801 could extract water from low humidity and significantly can take up
water and release it with great facility.These observations meant that several cycles could be carried
out for the adsorption-desorption of water within an order of minutes [7].
 Figure (1): A schematic figure of the water harvesting cycle.

The water that MOFs can harvest could be used in several applications, such as drinking
water , agriculture uses as previous researches did but here in this project water was used
as a feedstock for alkaline water electrolysis, to produce oxygen and clean hydrogen,
which is the most valuable element and as drinkable water .According to the literature,
hydrogen production from the air system would enable carbon-free hydrogen production
even in areas with limited access to fresh water from the ground[8].

Hydrogen is the most promising clean energy source [9]. That, when burned, produces
only water as a byproduct [10]. Even with being the most abundant element in the
universe, water is the most ubiquitous source of hydrogen [11], but we need to split it
using water-electrolysis, the process of using electricity to split water to produce
hydrogen. This reaction takes place in a unit called an electrolyzer. An anode, a cathode,
and an electrolyte are the three basic components of the electrolysis cell. The cathode
electrode is the negative electrode, whereas the anode is the positive electrode. Positive
ions are drawn to the cathode (the negative electrode), where they take an electron and
change their charge to be neutral[12]. H2 can be utilized to store energy for intermittent
sources of power like solar, wind, and tidal [13].

The geographic limitations on the use of water electrolyzes are caused by the
unavailability of fresh water, which can occasionally be a rare resource, substantially
increasing the cost and complexity of hydrogen production. as per literature, studies
regarding the reduction of water shortage for electrolysis [14].

Direct saline water splitting can also produce hydrogen, but it has a number of
drawbacks, including high cost and chlorine as a byproduct [15]. A high vapor feed to
the anode can be used by some protons exchange membrane electrolyzes, which is
why they are failing [16]. To ensure that none of these electrolyzes fail, the cathode
of every single one of them must be able to operate anytime, anywhere  [17].

This project aims to develop a bifunctional system for water harvesting and in situ
hydrogen production from the desert air that can operate in air as dry as 4% relative
humidity and produces hydrogen that is purer than 99% [18]. Thus, microwave-assisted
synthesis for scaling up both MOF-801 and MOF-303 will be metal doped with Pd/C to
make them electroactive for water splitting and a custom made cell was done to split the
water harvested from the air as gas phase H 2 production. This project paves a way for
both purified water and hydrogen from moisture in the air.
Problem of the study
Hydrogen produced by water splitting has been regarded as one of the most promising alternatives to
fossil fuels due to its high energy density, sustainability and zero emissions during consumption. Yet it’s
scarce due to the unavailability of clean water and the direct saline water splitting is limited to
more opulent countries and that its expensive from the immense amount of energy used which
poses a significant challenge regarding its production.

Questions of study

 Will the microwave synthesized MOFs enhance the surface area and ultimately water uptake?
 Will mixing the MOFs with a catalyst enhance the wetting interaction?
 Will the fabricated gas diffusion cell produce hydrogen efficiently?

Hypothesis

The microwaved synthesized and metal doped MOF’s will be able to harvest atmospheric
water and produce hydrogen .

Objectives
The objectives of this research are:

1. Synthesis of a MOF and developing a system that could simultaneously harvest atmospheric
water and produce hydrogen.

2. Introduce a catalyst (palladuim on carbon) into MOF-303 and MOF-801 to make them
electroactive for water splitting

3. Utillizing the microwave synthesis to increase the surface area, enhance the water-uptake and to
balance the cost

4. Test the water harvesting efficiency of the MOF by exposing it to varying humidity levels and
measuring the amount of water adsorbed.

5. Test the hydrogen production efficiency by measuring the amount of hydrogen produced
Variables

Control:

- MOFs type
- Catalyst ratios

Dependent:

- water harvesting efficiency

- hydrogen production efficiency of the MOF.

Independent:  

- Type and ratio of metal ions

- organic linkers used in the synthesis of the MOF.

Methodology
a) Materials:

1. Pyrazole carboxylic acid

2. Aluminum chloride
3. Deionized water.
4. Sodium hydroxide
5. Fumaric acid
6. Zirconyl chloride octahydrate
7. Formic acid
8. Methanol
9. -Dimethylformamide

(will be purchased from commercial suppliers and used as received.)

b) Experimental Procedure:

All the procedures will be conducted by the student researcher, unless otherwise noted.

Synthesis of MOF-303 using Solvothermal method

In a 100 mL screw-capped jar, 0.375g of the 3,5-pyrazole dicarboxylic monohydrate and 0.13 of NaOH
will be dissolved in a solvent of deionized water, then the mixture will be sonicated for 10 minutes and
heated for 30 minutes in a preheated oven at 100 °C after that 0.52 g Aluminum chloride hexahydrate will
be added .

The mixture will then be heated in an isothermal oven at 100 °C for 24 h to give a prepared MOF-303 as
a white precipitate. Then it will be centrifuged to separate the mixture at 6000rpm for 10 minutes for 6
days, the first three days will be with water three times per day and the other three days with methanol
afterward it will be dried at room temperature for 24h.

The sample will then be moved to a dynamic vacuum oven for 3 days at 100 °C then it will be heated in
an oven at 70 °C for four days.

Figure (2): A schematic figure of solvothermal synthesis of MOF-303.

Synthesis of MOF-303 using Microwave method

In a 100 mL screw-capped jar, 0.375 g of the 3,5-pyrazole dicarboxylic monohydrate and 0.13 of
NaOH will be dissolved in a solvent of deionized water, then the mixture will be sonicated for 10
minutes and heated for 30 minutes in a preheated oven at 100 °C after that 0.52 g Aluminum chloride
hexahydrate will be added

The mixture will then transferred to a microwave oven and will give a prepared MOF-303 as a white
precipitate. Then centrifuge will be used to separate the mixture at 6000rpm for 10 minutes for 6
days, the first three days will be with water three times per day and the other three days with
methanol afterward it will be dried at room temperature for 24h.

The sample will then be moved to a dynamic vacuum oven for 3 days at 100 °C then it will be heated
in an oven at 70 °C for four days.

Figure (3): A schematic figure of a microwaved synthesis MOF-303.

Synthesis of MOF-801 using solvothermal method

1.12 g of fumaric acid and 3.2 g of zirconyl chloride octahydrate ( Zrocl2.8h2o) will be dissolved in a
mixture of 40ml of N,N dimethylformamide (DMF) and 14 ml of Formic acid in a 100ml autoclave then
it will be transferred to an oven at 130° for 24hAnd then the resultant mixture will be washed three days
with DMF and the next three days with methanol and then subsequently dried in air.

This sample will be then transferred to a vacuum chamber for 5 hours at room temperature, and then
evacuate at 70 °C for 12 hours and 150°C for 48 hours. then transferred to a vacuum chamber for 5 hours
at room temperature, and then evacuate at 70 °C for 12 hours and 150°C for 48 hours.

Figure (4): A schematic figure of a solvothermal synthesis of MOF-801.

Synthesis of MOF-801 using microwave method

1.12 g of fumaric acid and 3.2 g of zirconyl chloride octahydrate ( Zrocl2.8h2o) will be dissolved in a
mixture of 40ml of N,N dimethylformamide (DMF) and 14 ml of Formic acid in a 100ml autoclave then
it will be transferred to a microwave And then the resultant mixture will be washed three days with
DMF and the next three days with methanol and then subsequently dried in air.

This sample will be then transferred to a vacuum chamber for 5 hours at room temperature, and then
evacuate at 70 °C for 12 hours and 150°C for 48 hours.

Figure (5): A schematic figure of microwave synthesis of MOF-801.

Electrodes preparation
In a total of 10mg there will be 750ml of ethanol,200ml of water and 50ml of nafeon then
the solution will be droped on a carbon paper

Samples :

1-10mg/MOF-801

2-10mg/MOF-303

3-10mg/catalyst

4-5mg/MOF-303 and 5mg/catalyst

5-5mg/MOF-801 and 5mg/catalyst

6-MOF-303/25%catalyst

Figure (6): A schematic figure of doping the composite on a carbon paper

Cell Fabrication

To prepare the electrodes 0.5ml from ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate )

will be loaded to the porous layer between the electrodes then the electrodes will be sprayed by water and
nitrogen then drying using a hot oven

Scheme1. Illustration for the gas diffusion cell

Characterization
The synthesized samples will be characterized by:

- Scanning electron microscope (SEM): to study the surface morphology.

- Transmission electron microscope (TEM): to study the samples structure and crystallinity.
- X-ray photoelectron spectroscopy (XPS): to evaluate the elemental composition on the surface
- X-ray diffraction (XRD): to measure the degree of crystallinity.
- Thermogravimetric analysis (TGA): to study the thermal stability
- Inductively Coupled Plasma (ICP):to identify elements within the samples matrix
- Energy Dispersive X-Ray Spectroscopy (EDXS): to study the elemental mapping on the surface
- Brunauer–Emmett–Teller (BET), will show the porosity and surface area that is essential to
prove that the material is capable of increasing the water uptake.

Performance Evaluation
Water adsorption isotherms plots, will show the water harvesting performance for the synthesized
MOF-801,MOF-303 and Pd/C that will be investigated by the water sorption at 25 °C.

Electrochemical impedance spectroscopy (EIS), will show the conductivity of the material with
different amount of MOFs.

linear sweep voltammetry (LSV), curves of different electrodes in 0.1 M H2SO4 solution which will
reflect an enhancement in the wetting interaction when mixing the MOF with the palladium .

Chronoamperometry, will be tested to reflect the stability at a constant potential with different time
ratio

gas chromatography (GC), GC peaks at Potential 4 V/ 2-electrode system will reflect only hydrogen
peaks.

Applications
The MOF that will be synthesized in this study has the potential for a wide range of applications in both
water harvesting and hydrogen production. In terms of water harvesting, the MOF could be used in arid
regions to collect water vapor from the air, providing a sustainable source of water for agriculture and
human consumption.
In terms of hydrogen production, the MOF could be used as a catalyst in the production of hydrogen from
water vapor, providing a clean and renewable source of energy. Additionally, the MOF could be used in a
hybrid system for water harvesting and hydrogen production, where water vapor is collected and then
used as a feedstock for hydrogen production.which will be tested in the water harvesting prototype and
gas diffusion cell.

Risk and safety

I am working in the lab under supervision of my mentor, and with following all lab safety rules such as
wearing the lab coat, goggles , gloves and staying under supervision while working in the lab and Any
waste disposal will be done by following the safety regulations adopted by KFUPM through the specialist
contractors.

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