Advanced Functional Materials, VVCE, Mysuru

Module 2: Hydrogen Technology

Hydrogen technology refers to the production, distribution, and use of hydrogen as a renewable
energy source. Hydrogen is a clean fuel that, when consumed in a fuel cell, produces only
water. It is a clean-burning fuel, and when combined with oxygen in a fuel cell, hydrogen
produces heat and electricity with only water vapor as a by-product. The heat produced per
gram of fuel on complete combustion in oxygen is called its calorific value. Hydrogen gas has
the highest calorific value of 150 kJ g-1. These qualities make it an attractive fuel option for
transportation and electricity generation applications. It can be used in cars, in houses, for
portable power, and in many more applications.

Hydrogen Production
Today, hydrogen fuel can be produced from a variety of domestic resources. The most common
methods today are natural gas reforming (a thermal process), or it can be produced by passing
electricity through water, breaking the water into its constituent components of hydrogen and
oxygen, stored for later use, piped to where it is needed, and then converted cleanly into heat
and electricity. Other methods include nuclear power, biomass, renewable power like solar and
wind, and biological processes.

1. Electrolytic method
Water can be separated into oxygen and hydrogen through a process called electrolysis.
Electrolysis is the process of using electricity to split water into hydrogen and oxygen. This
reaction takes place in a unit called an electrolyzer.
Construction
Like fuel cells, electrolysers consist of an anode and a cathode separated by an electrolyte.
Anode: Titanium
Cathode: Carbon paper/carbon fleece
Catalyst on the anode: Iridium
Catalyst on the cathode: Platinum
Solid electrolytes: Solid poly-sulfonated membranes, such as Nafion

Dr. Vrushabendra B, VVCE, Mysuru

 Advanced Functional Materials, VVCE, Mysuru

Working
In a polymer electrolyte membrane (PEM) electrolyzer, water reacts at the anode to form
oxygen and positively charged hydrogen ions (protons). The electrons flow through an external
circuit and the hydrogen ions selectively moves across the PEM to the cathode. A gas separator
is used to prevent intermixing of hydrogen and oxygen although it allows free passage of ions.
Water reacts at the anode to form oxygen and positively charged hydrogen ions (protons).
Anode Reaction: 2H2O → O2 + 4H+ + 4e
The electrons flow through an external circuit and the hydrogen ions selectively moves across
the PEM to the cathode. At the cathode, hydrogen ions combine with electrons from the
external circuit to form hydrogen gas.
Cathode Reaction: 4H+ + 4e- → 2H2
Electrolytic water splitting is a promising way to produce carbon-free hydrogen from
renewable and nuclear resources.

2. Thermal decomposition of water

Thermal decomposition or thermolysis of water is a process where water (H₂O) is decomposed
into hydrogen (H₂) and oxygen (O₂) using high temperatures from concentrated solar power.
This method is a direct way to produce hydrogen, but it requires extremely high temperatures,
generally about 2000 to 2500 °C to drive a series of chemical reactions that produce hydrogen.
The chemicals used in the process is only water and produces hydrogen and oxygen. Here,
sunlight is concentrating onto a reactor tower using a field of mirrors called "heliostats,"
A heliostat is a device that consist of field of mirrors which keep reflecting sunlight toward a
predetermined target as shown in the following figure.

The process uses concentrated solar radiation as an energy source. Solar driven high-
temperature thermochemical water-splitting (STCH) cycles produce hydrogen with near-zero
greenhouse gas emissions using water and sunlight. Cerium oxide (CeO2) can be used to
thermally decompose water into hydrogen and oxygen in a two-step water-splitting process. It
requires higher operating temperatures compared with the more complicated hybrid cycles.

Dr. Vrushabendra B, VVCE, Mysuru

 Advanced Functional Materials, VVCE, Mysuru

The chemicals used in the process are reused within each cycle, creating a closed loop that
consumes only water and produces hydrogen and oxygen.

3. Chemical extraction
Hydrogen production through chemical extraction refers to processes that generate hydrogen
gas (H₂) by chemically breaking down hydrogen-containing compounds. The most common
chemical methods for hydrogen extraction includes Steam Methane Reforming (SMR), Coal
Gasification, Biomass Gasification.
a) Steam Methane Reforming (SMR)
SMR is the most widely used method for hydrogen production. It involves reacting methane
(CH4) with steam (H2O) at high temperatures (700–1000°C) and under 3–25 bar pressure in
the presence of a catalyst. In steam-methane reforming, methane reacts with steam in the
presence of a Nickel based catalyst to produce hydrogen, carbon monoxide, and a relatively
small amount of carbon dioxide. Subsequently, the carbon monoxide so formed made to reacts
with steam using a catalyst to produce carbon dioxide and more hydrogen called "water-gas
shift reaction". In final step carbon dioxide and other impurities are removed from the gas
stream, leaving essentially pure hydrogen called "pressure-swing adsorption".
Chemical reactions:

This produces hydrogen along with carbon dioxide (CO₂) as a byproduct. High CO₂ emissions
make this method less environmentally friendly, unless combined with carbon capture and
storage (CCS) technologies.
b) Coal Gasification
In this method, coal is converted into syngas (a mixture of hydrogen, carbon monoxide, and
other gases) by reacting coal with steam in the presence of oxygen under high temperatures.
Chemical Reaction:

Here hydrogen is extracted along with significant amount of CO₂. Like steam methane
reforming coal gasification is generally not considered sustainable without CCS technology.
c) Biomass gasification
Biomass is organic, which is made of material that comes from living organisms, such as plants
and animals. In biomass gasification, biomass is heated to produce syngas, which contains
hydrogen, carbon monoxide, and other compounds. The hydrogen is then separated.
Chemical Reaction:

Dr. Vrushabendra B, VVCE, Mysuru

 Advanced Functional Materials, VVCE, Mysuru

4. Nuclear Energy
Hydrogen production using nuclear energy is a promising path for large-scale, carbon-free
hydrogen production. Methods such as electrolysis, high-temperature steam electrolysis
(HTSE), and thermochemical water-splitting using nuclear energy are widely used to produce
clean hydrogen. Advanced nuclear reactors, such as Generation IV reactors or High-
temperature gas-cooled reactors (HTGRs) can provide the necessary heat and electricity
required for electrolysis, high-temperature steam electrolysis (HTSE), and thermochemical
water-splitting process.
Electrolysis: Electrolysis is the process of using electricity to split water into hydrogen and
oxygen. The electricity required for the electrolysis process is obtained from nuclear energy.
The splitting reaction takes place in a unit called an electrolyzer, which consist of an anode,
cathode and electrolyte.
High-temperature steam electrolysis (HTSE)
High-temperature steam electrolysis (HTSE) is a more efficient form of electrolysis that uses
both heat and electricity to split water. The process requires high temperatures, typically
between 700 °C and 900 °C, which can be provided by nuclear reactors. The high temperatures
reduce the amount of electricity needed to perform the electrolysis, making it more efficient
than conventional low-temperature electrolysis.
Thermochemical water-splitting process
Thermochemical water splitting (TWSC) is a promising technology for producing hydrogen
from water using nuclear energy. TWSC uses high temperatures (500°–2,000°C) from nuclear
energy to drive a series of chemical reactions that decompose water into hydrogen and oxygen.

5. Direct solar water splitting process

Direct solar water splitting, also known as photoelectrochemical (PEC) water splitting, is a
method of producing hydrogen using sunlight to directly split water (H₂O) into hydrogen (H₂)
and oxygen (O₂). This process mimics photosynthesis in plants, using sunlight to drive the
reaction and produce clean hydrogen fuel. It is considered a promising approach for green
hydrogen production because it does not require any fossil fuels and emits no greenhouse gases.
Photoelectrochemical (PEC) Cell:
A PEC cell is the core of the direct solar water splitting process. It consists of two electrodes
called photoanode and photocathode, submerged in water. The photoanode absorbs sunlight
and generates charge carriers (electrons and holes), which are then used to split water
molecules.
Process
The photoanode is typically made of a semiconductor material such as titanium dioxide (TiO₂)
or iron oxide (Fe₂O₃) or bismuth vanadate (BiVO₄)) that can absorb photons (light particles)
from sunlight. When these photons are absorbed, they excite electrons, creating electron-hole
pairs. The holes in the photoanode move toward the surface, where they oxidize water (H₂O),
releasing oxygen gas (O₂). Oxidation of water (H2O) takes place at the photoanode producing
oxygen.

Dr. Vrushabendra B, VVCE, Mysuru

 Advanced Functional Materials, VVCE, Mysuru

The excited electrons move toward the photocathode, where they reduce protons (H⁺) to
produce hydrogen gas (H₂). Reduction of proton (H+) takes place at the photocathode producing
hydrogen.

The overall water-splitting reaction is

The hydrogen and oxygen gases are produced at different electrodes and are separated within
the system.

6. Hydrogen from the decomposition of materials containing hydride anions

Hydride Anion (H⁻) is a hydrogen atom that has gained an extra electron, giving it a negative
charge. Hydrogen production from the decomposition of materials containing hydride anions
(H⁻) involves the breakdown of compounds in which hydrogen exists as an anion. Hydride
anions are typically present in ionic or covalent hydrides, where hydrogen is bound to metals
or other elements with a negative charge. Materials containing hydride anions can be metal
hydrides, chemical hydrides, or complex hydrides. In these compounds, hydrogen is stored in
the form of H⁻ anions and can be released through appropriate decomposition methods. The
release of hydrogen from these materials occurs through thermal decomposition, chemical
reactions, or catalysis.
Thermal decomposition: In metal hydrides, hydrogen exists in the form of H⁻ bound to metal
cations. When these hydrides are heated, they decompose to release hydrogen gas (H₂) leaving
behind the metal in its elemental form.
Example: Magnesium hydride (MgH₂) when heated, the magnesium hydride breaks down,
releasing hydrogen gas and Mg metal.
Heat
MgH2 Mg + H2
Chemical reaction: Many materials containing hydride anions will release hydrogen when
they react with water. In these reactions, hydride anions (H⁻) react with water to form hydrogen
gas (H₂) and hydroxide ions (OH⁻).
Example 1: Sodium hydride (NaH):

Example 2: Lithium hydride (LiH)

Catalysis: Catalysis uses a suitable catalyst to produce hydrogen. Photocatalysts, metal–

organic framework (MOF)-based catalysts can be used to produce hydrogen from methane,
ethanol, and biomass.

Hydrogen storage in solids

Hydrogen storage in solids refers to methods in which hydrogen is stored within solid materials,
rather than as a compressed gas or cryogenic liquid. Solid hydrogen storage materials include
metal hydrides, chemical hydrides, complex hydrides, adsorbent materials, and nanomaterials.
These materials can absorb hydrogen and release it under certain conditions, making them
useful for a variety of applications, from fuel cells to portable power systems.

Dr. Vrushabendra B, VVCE, Mysuru

 Advanced Functional Materials, VVCE, Mysuru

Metal Hydrides in the storage of hydrogen

Metal hydrides are one of the most studied materials for solid-state hydrogen storage. They
store hydrogen by chemically binding it to metals, forming a hydride phase. Hydrogen can be
released by changing temperature or pressure.
Example: Magnesium hydride (MgH2), sodium hydride (NaH), titanium hydride (TiH2), and
palladium hydride (PdHx). Metal hydrides can store hydrogen in high densities up to 7-8%
by weight for some materials like MgH₂.
Mechanism: The general reaction involves the absorption of hydrogen gas by the metal to
form a metal hydride. The process is reversible, meaning hydrogen can be re-released by
applying heat or lowering pressure.
Metal + H2 ⇌ Metal Hydride
Advantages: High volumetric hydrogen density, safety (since hydrogen is stored in solid
form), and reversibility (metal hydrides can absorb and desorb hydrogen repeatedly).
Disadvantages: Some metal hydrides require high temperatures (300°C to 400°C) for
hydrogen release, and the materials can be heavy, limiting their use in weight-sensitive
applications like transportation.

Ammonia in the storage of hydrogen

Ammonia (NH3) is emerging as a promising carrier for hydrogen storage and transportation
due to its high hydrogen content, ease of liquefaction, and well-established infrastructure for
production, storage, and transport. Ammonia is composed of 17.6% hydrogen by weight, and
it can be synthesized from nitrogen and hydrogen using the Haber-Bosch process, which is
widely utilized in the chemical industry. In addition, ammonia is less flammable and explosive,
liquefies at -33 °C at atmospheric pressure and cost effective. When needed, hydrogen can be
extracted from ammonia through various processes, such as thermal decomposition or catalytic
cracking.
Ammonia decomposition or Cracking: Hydrogen can be extracted from ammonia by
decomposing it into hydrogen and nitrogen gases. This process, known as ammonia cracking,
typically requires a catalyst such as nickel, iron, and ruthenium and high temperatures (450-
600°C). The decomposition reaction is as follows:

Applications: The hydrogen produced through ammonia cracking can be used in fuel cells to
generate electricity or in other hydrogen-based energy systems.

Reversible organic liquids in the storage of hydrogen

This is an innovative and promising method for storing and transporting hydrogen. In this
system, organic compounds are chemically hydrogenated (hydrogen is added) and later
dehydrogenated (hydrogen is released), enabling the reversible storage of hydrogen in a liquid
medium. This approach offers the safety and convenience of liquid storage at ambient
conditions, eliminating the need for high-pressure tanks or cryogenic temperatures.
Example 1: Toluene-Methylcyclohexane system:
 Hydrogenated form: Methylcyclohexane (C6H11-CH3)
 Dehydrogenated form: Toluene (C6H5-CH3)

Dr. Vrushabendra B, VVCE, Mysuru

 Advanced Functional Materials, VVCE, Mysuru

Hydrogenation: The liquid organic compound such as toluene is exposed to hydrogen at

elevated temperatures and pressures in the presence of a catalyst. The compound chemically
bonds with hydrogen, forming a hydrogen-rich version of the molecule such as
methylcyclohexane. This process occurs in a hydrogenation plant where hydrogen from an
external source either from electrolysis or steam methane reforming is chemically added to
toluene.
Dehydrogenation: When the stored hydrogen is needed, the hydrogen-rich methylcyclohexane
is heated usually at 150°C to 300°C or passed over a catalyst in a dehydrogenation plant,
causing it to release the hydrogen and revert to its original form. The hydrogen gas can then be
fed into fuel cells, combustion engines, or other applications requiring hydrogen energy.

Dr. Vrushabendra B, VVCE, Mysuru