NANOTECHNOLOGY FOR GREEN HYDROGEN

GENERATION

REVIEW PAPER

SUBMITTED BY

H.M. A. Bandara

(PGIS/CH/M.Sc./CHN/17/02)

to the Board of Study in Chemical Sciences of the

POSTGRADUATE INSTITUTE OF SCIENCE

In partial fulfilment of the requirement

of independent Study (CHN 599)

MASTER OF SCIENCE PROGRAMME IN

NANOSCIENCE AND NANOTECHOLOGY

Date: 05/07/2018
 NANOTECHNOLOGY FOR GREEN HYDROGEN GENERATION

H. M. A. Bandara
M. Sc. Programme in Nanoscience and Nanotechnology, Postgraduate Institute of Science

Hydrogen is a vehicle or a vector for convert energy. It is carrying energy from

source to the requirement and is a green and clean option for fossil fuels. Hydrogen
has the ability to obstruct future energy crisis of the world and at the same time
improving the environmental quality. The use of nanotechnology to produce hydrogen
is a promising option because it gives unlimited development potentials for the
advancement of both conventional energy sources like fossil fuels and renewable
energy sources like solar energy. The application fields of nanotechnology in the solar
industry are more and more in the focus of interest due its performance improvements.
Application of nanotechnology for water splitting using photo catalysis, solar thermal,
direct decomposition, photo biological and photovoltaic electrolysis are interesting.
Anyway the knowledge of the variety of application possibilities of nanotechnology
research for renewable and green energy technologies is still lacking. The world needs
to use the fields of nanotechnologies to research and develop the green energy and
green hydrogen generation urgently.

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Table of Content

1.0 Introduction 04
2.0 Hydrogen Generation 04
2.1 Conventional Hydrogen Generation Methods 05
3.0 Why Nanotechnology for Hydrogen Generation 05
4.0 Nanotechnology options for Green Hydrogen Generation 07
4.1 Nanotechnology aided Solar Driven Green Hydrogen Generation 08
4.1.1 Water Splitting 08
4.1.2 Photo catalysis 10
4.1.3 Photovoltaic electrolysis 10
4.1.4 Artificial photosynthesis 11
4.1.5 Photoelectrolysis 11
4.1.6 Photoelectrochemical 12
4.1.7 Thermochemical 13
4.1.8 Photobiological 13
4.1.9 Photovoltaic‐Photo electrochemical hybrid 14
4.1.10 Dark and Photofermentation 14
4.1.11 Solar thermal Hydrogen Generation 15
4.1.12 Upconversion 15
5.0 Use of hydrogen 16
6.0 Research focuses and challenges 17
7.0 Summery 17
8.0 References 18

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1.0 Introduction
Presently the world is using of three main energy resources and those can be
classified as fossil fuel, nuclear fuel and renewable sources. Present world the fossil
fuel usage is a part of regular energy requirement and it is increasing day by day. This
fossil fuel usage causes to the greenhouse gas emissions to the environment and it will
pollute ambient air and now it is a global issues. Global warming [92, 94], ozone
depletion, air pollution and resource depletion are the main issues which should be
addressed urgently by the world nations. Huge volume of Fossil fuel consumption and
limited reserves of fossil fuels are encouraged and promoted the development and use
of new, clean and green energy sources, including hydrogen energy as an alternative
clean fuel.
Hydrogen is the simplest element and it is one of the most abundant elements
in the earth including sea. Hydrogen is created by joining two hydrogen atoms together
and it is a gas in earth’s ambient temperature. Hydrogen gas is not found naturally on
earth and must be manufactured. This gas is lighter than air as a result it rises into the
atmosphere. Natural hydrogen is always associated with other elements in compound
form such as water, coal and petroleum, etc. Hydrogen has the highest energy content
of any common fuel by weight and as the same way, hydrogen has the lowest energy
content by volume. Hydrogen can be considered as the cleanest vector of energy,
therefore researchers are concentrating more in hydrogen as a fuel. The production and
storage of hydrogen are challenging issues currently. These issues need to be
addressed by the researchers so that clean alternate energy can be used for the benefit
of future generation. In order to reduce world’s dependence on fossil fuels, it is
essential to explore various sustainable and green energy solutions. One options is to
develop a hydrogen based energy systems, which supports for huge environmental and
energy efficiency benefits. Hydrogen will be the potential energy carrier in future
because it is very clean and green and it produces water as a final waste product when
releasing energy.

2.0 Hydrogen Generation

Hydrogen is the vehicle of transporting and storing energy from the source to
the destination or the end user. Normally hydrogen bounds as chemical compounds
such as water, hydrocarbons or other hydrogen sources and that must be transformed
to generate hydrogen gas. Hydrogen can be generated using different resources
including fossil fuels, natural gas, coal, nuclear, hydroelectric, biomass and renewable
sources such as wind, solar, hydro, sea and geothermal [90], etc. Hydrogen production,
storage and convert into electricity are not new, but the world is still lacking efficient
methods to use and store it. Hydrogen as a vector of energy, it is clean and green
depending of the method used to produce it.

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2.1 Conventional Hydrogen Generation Methods
Hydrogen can be produced by both renewable [5] and nonrenewable methods.
As mentioned earlier hydrogen production using conventional sources like coal, oil,
and natural gas leads to environmental damage due to greenhouse gas emission.
Greenhouse gas emission can be minimized or stopped using renewable energy as the
conversion energy needed for the hydrogen. When producing hydrogen, it is required
to understand the renewable energy sources or non-renewable energy sources and then
how these energy sources can be used for hydrogen production [6, 7].
When considering various hydrogen production methods it shows that the
primary energy required for the reactions is generally electrical and thermal energy.
The materials used to generate hydrogen are basically water and fossil fuels. Organic
biomass and inorganic compounds such as hydrogen sulfide are also used to produce
hydrogen. So, it is important to recognize the energy sources which can be used as
primary energy requirements for environmental friendly hydrogen production.
There are many commercially available conventional non-renewable hydrogen
production methods which gives cheap and high purity hydrogen. As examples
different reforming methods (Steam Methane Reforming [47], Partial Oxidation
Reformer, Auto Thermal Reforming, Methanol Reforming, etc.), thermo-catalytic
cracking of methane, thermochemical decomposition [45, 46] of water, novel reformer
technologies and other non-renewable methods can be mentioned. There are methods
that will become renewable or non-renewable based on the input energy needed to
convert hydrogen. As examples pyrolysis, gasification, electrolysis of water,
biological hydrogen production can be noted.
Electricity may be produced by all the renewable energy sources like solar
[88], wind [86], hydro [87], tidal, dendro and geothermal. Renewable thermal energy
can be produced by concentrated solar energy, biomass and geothermal directly.
Hydrogen production mainly involves thermal and electrical energy as the input
energy. So, different renewable sources are used to provide input energy. Most of the
renewable sources are used to produce electricity and then the electricity is further
utilized to produce hydrogen, as example, the Photoelectrolysis based hydrogen
production by water splitting.

3.0 Why Nanotechnology for Hydrogen Generation?

The present target is to find innovative, efficient, low cost, viable and durable
methods, which can help to produce hydrogen from sustainable sources, such as solar,
wind, hydro, biomass, ocean energy, geothermal and other types of energy sources
with water breakdown, and other methods like thermochemical processers, etc. Vast
efforts are presently being made into the development of more green and clean
methods for producing hydrogen. Energy production based on solar, wind, ocean,
hydro, biomass, geothermal and other renewable energy resources represents a good
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replacement and environmental friendly solution compared to energy obtained from
combustion of fossil fuels. At the same time it is good to implement carbon dioxide
like greenhouse gas capturing methodologies for fossil fuel hydrogen generation. It is
also a good orientation for green hydrogen generation. So called eco-friendly
alternatives are still insufficiently used due to lack of convenience of using them,
efficiency is not sufficiently improved, high costs and technology to use them are not
improved yet as required.
Now the world is searching for clean and green energy, because it is important
to minimize county wise dependence on fossil fuels. Therefore, it is essential to
research on various sustainable energy options. Hydrogen might be an answer as it is
very efficient when it releases energy and the only output produced is water. Store
energy by producing hydrogen itself and use it whenever required is extremely
encouraging. So the hydrogen will be the vector of energy or energy storage. Hydrogen
is not a natural source of energy like solar power, and also it is not an organically
occurring fuel like methane, crude oil or coal. Hydrogen is usually produced by
separating water with electrical power or by thermochemical, biochemical radiolysis,
photolysis, thermal breakdown like processes. The major issue or obstacle to a future
of energy from hydrogen is the need for expensive materials, current technologies are
expensive and resources and the efficient, durable, low cost technologies have not been
invented or emerged yet. This problem or finding solutions for hydrogen energy can
be categories basically in to two orientations as of hydrogen gas production and
storage. Present technologies for producing hydrogen require a large amount of energy
which usually obtained from fossil fuels, and those are not carbon free and pollution
free or clean or green fuels. Storage of hydrogen is also an issue, because it is highly
flammable. Storing and transporting the fuel safely is also a big challenge. Much
efforts have been taken for developing a viable commercial solution to these problems,
but so far it has not been achieved successfully even though there are some less healthy
or not sufficiently developed solutions.
Solution to above said problems comes with the applications of
nanotechnology in renewable and green energy sector. Nanotechnology offers new
ways for development of new industries and renovate existing industries based on cost-
effective and cost efficient technologies and supports to a sustainable economic
growth. Nanoengineered materials and methods are playing a valuable role in rapidly
developing field of sustainable energy production and storage. Nanotechnology is a
new science field growing and developing rapidly. It gains much and considerable
attention in recent years due to the capability of applying it for different fields of
engineering and many technological applications. Nanotechnology provides rapid
improvement potentials for the development of both conventional energy sources
(fossil and nuclear fuels) and renewable energy sources like geothermal, solar, wind,
thermochemical, biochemical, hydro, tides and biomass, etc. Nanotechnology is
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considering worldwide as the key technological approach for innovations and
technological progress in all branches of economy and science. Nanotechnology refers
to the target oriented technical utilization of objects, structures and methodologies in
a size in the range of 1 and 100 nm. The scientific research community has been
exploring the nanomaterials which achieve unique and exciting properties, different
from the bulk. The unique properties of nanoparticles can be attributed to the very
small sizes which result in extremely large surface areas and quantum confinement
effects.
Nanotechnology involves the miniaturization as well as manipulation of atoms
and molecules to control their some physical properties like strength, conductivity,
reflectivity, chemical reactivity, magnetization, photonic and electronic behaviors and
many more. The behavior of nano scale materials are so different from the bulk
properties [23]. Fundamental properties of nanostructured materials are currently
extensively studied because of their potential application in numerous fields which
includes electronic devices, optoelectronics, optics, tribology, biotechnology, human
medicine, energy conversion and storage, different types of engineering and
technological sectors. Nanostructured materials have enormous surface area per unit
weight or volume so that vastly more surface area is available for interactions with
other materials around them. There are most promising applications are being
developed currently with use of nanomaterials in the energy sector for the energy
conversion and storage sectors.
So Nanotechnology could provide much answers and solutions for green
energy sector or more specifically for green hydrogen production. However. The most
promising recent developments in hydrogen production and storage have involved the
use of novel nanomaterials to produce hydrogen from water more efficiently, and to
enhance the performance of hydrogen storage technologies.

4.0 Nanotechnology options for Green Hydrogen Generation

Presently solar thermal, thermochemical and photo electrochemical processes
can be used for water splitting as green hydrogen generation options. Moreover
biological hydrogen production and biomass processors also used to generate
hydrogen. Water splitting through solar energy is an encouraging research field now a
days because it is clean, low cost and environmentally friendly hydrogen production
method. Nanotechnology is supporting and enabling enormously this solar water
splitting research field for its fast moving achievements.
There are many renewable energy sources such as wind, solar, hydro, tidal, and
geothermal and biomass. These sources can be used directly or indirectly to generate
green thermal, electrical, photonic and biochemical energy for hydrogen generation
via water splitting. The electrolysis is one of the environmentally friendly process for
hydrogen production. The energy input for hydrogen production can be used from
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solar radiation as well as above said renewable energy sources. Further, biological
hydrogen production can be done by microorganisms by dark and photofermentation.
The contributions of nanotechnology and nanoscience to increased efficiency of
different renewable energies to hydrogen conversion is invaluable. Moreover
nanotechnology support in many ways for Integrating greenhouse gas capturing
methodologies when hydrogen generation by fossil fuels. This is also an innovative
middle term solution for green orientation of hydrogen or energy generation

4.1 Nanotechnology aided Solar Driven Green Hydrogen Generation

It can be considered few main approaches to solar energy water splitting. That
is photovoltaic cells coupled with a water electrolyser, semiconductor liquid junction,
combined photovoltaic- semiconductor liquid junction and photo biological methods.
First method is expensive. The cost can be reduced using Metal semiconductor
Schottky junction cells with single or multiple p - n junctions immersed in the aqueous
system as one electrode. In a semiconductor liquid junction cell, the photo potential
needed to drive the water splitting reaction is generated directly at the semiconductor-
liquid interface. In a combined photovoltaic- liquid junction system, the solar cell can
be connected to either the reduction or oxidation photo catalyst to provide the
additional electrical bias needed for the generation of hydrogen or oxygen. Photo
biological methods are used algae or photo reacting bacteria for water splitting.

4.1.1 Water Splitting

Nanotechnology based research activities are proceeding on photolysis,
electrolysis, radiolysis and thermal breakdown for hydrogen production. Direct single
step water disassociation and requires high temperature heat source. This is
conceptually simple but it is difficult to achieve a viable dissociation of water. Further
it requires an effective technique for separating hydrogen and oxygen to avoid their
recombination [21, 25, 26].
The electrolysis of water uses current to split water into hydrogen and oxygen.
Output is depends on the applied current and voltage. The minimum potential
difference between the cathode and anode must be near 1.5 V for the efficient
electrolysis. This method is also not yet an economically feasible because overall
efficiency is of this technique is minus.
According to the Gibbs free energy for water splitting, it is a hard reaction due
to the large positive gap of energy. The semiconductor needs to convert photo energy
into chemical energy to overcome this energy gap. The basic requirement for
semiconductors is that the conduction band should be more negative than the reduction
potential of water and the valence band should be more positive than the oxidation
potential of water. The capability of splitting water of semiconductors can be improved

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using semiconductor junctions and doping semiconductors as n-type or p-type as
required with metals. This type of photolysis is a green technology.
The photolysis of water will be one of the environmental friendly hydrogen
generating technique near future. Non-oxide and oxide semiconductors are useful for
the photo dissociation of water into hydrogen and oxygen due to the direct absorption
of photons by specific materials.
Non-oxide materials only excited when it incidents visible region of the solar
spectrum, and most of the stable oxides are photo chemically active only in the
ultraviolet region. Photocorrosion is the one of the major issue in photolysis. However,
oxide semiconductors show good stability with photocorrosion problem. Electron are
jumped to the conduction band from the valence band when excitation is happened by
photons, This jumped electrons and holes can move to the surface of the
semiconductor particle and react with water or other adsorbed substrates to the
producing hydrogen. It is possible to split water into hydrogen and oxygen when the
potential of the conduction band of the semiconductor is more negative than the
potential of hydrogen separating and the valence band potential level is more positive
than the potential of oxygen separation.
Semiconductor photo catalyst + hν → e-+ h+
H₂O → OH- + H-
2e- + 2H+ → H₂
2h+ + 2OH- → 2H+ +O₂
Photo catalytic reactions for generating hydrogen needs potential difference
greater than 1.23 eV. Different types of semiconductors have been used for the
photocatalytic decomposition of water. Semiconductors with a small band gap energy
can absorb limited solar spectrum of visible region. Semiconductor materials with
small band gap are being investigated to use more active to visible light but the less
energetic.
Nano-crystalline semi-conductors which are being used to photoelectrolysis of
water are in the form of electrodes, colloids, powders and thin films. An intensive
research activities have been done in the synthesis of many nanostructural inorganic
oxides, such as titanium dioxide, manganese dioxide, and cobalt oxide, molybdenum
oxide, vanadium oxide, aluminum oxide, zirconium oxide, tin oxide and silicon oxide.
nanorange titanium dioxide has taken the greatest interest because of its enormous
applications in catalysis, photovoltaic cells and other semiconductor devices.
Catalyst used in this technique needs to be photoactive and should be capable
of generating enough charges to activate reduction and oxidation reactions. Minimum
band gap required to split water can be calculated from the relation in between Gibbs
free energy and potential as below.

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Thermodynamic band gap calculation for water splitting
ΔG =-nFE
Where ΔG is the change in Gibbs free energy,
n is number of electrons transferred in chemical reaction,
F is faraday constant and E is the band gap.
For water splitting, ΔG = 237KJ/mol, n=2 and F=96500 C/mol.
So “E = 1.23V”, is the minimum potential and minimum band gap of
1.23eV is required to split water.

4.1.2 Photo catalysis

Process of splitting water molecules into hydrogen and oxygen using solar
energy is called photocatalytic water splitting [52]. Photocatalytic hydrogen
generation methods have been developed during last few decades. The main
photocatalysts used in this field are titanium oxide, cadmium sulfide, zinc oxide, zinc
sulfide and other metal oxide based photocatalysts. The dominant benefits of
photocatalytic water splitting can be considered as economic advantages band the
environmental advantages because this technology uses solar energy and produce
hydrogen in a clean way. Au–CdS has good performance when band gap, quantum
yield and hydrogen production rates are considered and TiO2–ZnO has poor
performance. Same way CdS shows the better while other metal oxides show poor
performance. Anyway CdS research activities are obstruct due to high cost and
toxicity. Some countries have banded CdS experiments due to its toxicity. So there
are many opportunities on this field for research activities to discover innovative water
splitting photo-catalysts.

4.1.3 Photovoltaic electrolysis

Photovoltaic electrolysis systems are coupled with a water electrolyser and a
PV cell arrays[53]. Hydrogen production through electrochemical water splitting is a
good approach for storing solar energy. It needs to develop water splitting systems
with high conversion efficiencies to this technology become economically viable and
competitive. Photovoltaicelectrolysis system shows with the highest solar to hydrogen
conversion efficiency compared to any water splitting technology up to date. This is
technologically doable but it is not economically viable yet due to cost. This is viable
to make hydrogen any time electricity cannot be used, off peak in remote areas, and
during seasonal variations. Hydrogen from wind, hydro, geothermal or any other form
of solar-generated electricity is valuable when it requires to store. If there are excess
energy with renewable resources then it sounds to store excess renewable energy as
hydrogen with the purpose of later use. The easiest way of using hydrogen for storage
is making hydrogen by water electrolysis. That is why, the PV water electrolysis
10
system has been developed. This is a simple system, involving only the
combination of an electricity generation system and electrolyzes.

4.1.4 Artificial photosynthesis

Artificial photosynthesis is one of the most innovative method for the direct
conversion of solar energy into renewable chemical fuels by mimicking the nature of
leaves [102]. The technology involves splitting water by creating spatially separated
electron hole pairs and control the redox semi reactions leading to evolution of
molecular hydrogen and oxygen. Artificial photosynthesis is an integrated system
which consists of a light harvesting section and a catalytic conversion section. It is
important to maximize the performance of each section and to design a combined
system with optimum efficiency, based on complete understanding of each component
and the interactions between them. Artificial photosynthesis has taken its inspiration
from nature, in which two light absorbing components are employed. Artificial
photosynthesis comes with Z-scheme approach that is two smaller band gap materials
can be utilized to absorb a greater portion of the solar spectrum, and careful alignment
of their conduction and valence band energy positions. They can maintain a
sufficiently large photo voltage. Currently the research activities are going on
improving the performance of the major units, photo anodes and photo cathodes. Most
promising photocathode materials are Si and InP emerged up to now due to its reported
high photocurrent densities and photovoltages. Advances in nanostructuring and
nanomaterial synthesis have reduced the raw material requirements and fabrication
costs which enable orientation towards commercial implementations. The ultimate
goal of artificial photosynthesis is to create a standalone unassisted device that can
spontaneously convert solar energy into chemical bonds.

4.1.5 Photoelectrolysis
Photoelectrolysis is still in experimental levels and it is a renewable method of
hydrogen production. A photoelectrode is a semiconductor device that absorbs solar
energy and generates the necessary voltage to split water molecules. It consists of
photovoltaic, catalytic, and protective layers. This will be a good hydrogen production
method in near future. Photoelectrolysis uses solar energy to extract hydrogen directly
from water [31]. Photoelectrolysis integrates solar energy collection and water
electrolysis into a single photoelectrode. This device eliminates the need for a separate
power generator and electrolyser, reducing overall costs and increasing efficiency.
Photoelectrolysis systems are still in the experimental stage. Photo-electrolysis will
become an important hydrogen production methodology because it uses by solar
energy. Photoelectrolysis uses photoelectrochemical (PEC) light collecting systems
to power the electrolysis of water [11]. Semiconductor photoelectrode which is
submerged in an aqueous electrolyte will generate sufficient electrical energy to
11
promote hydrogen and oxygen evolution reactions (HER and OER) when exposed to
sunlight. The HER releases electrons into the electrolyte, while the OER requires free
electrons. Depending on the type of semiconductor material and the solar intensity,
the produced current density varies between 10 to 30 mA/cm². At these current
densities, the voltage required for electrolysis is approximately 1.35 V.
Photoelectrochemical decomposition of water requires several requirements to
meet. The energy band of the semiconductor materials must overlap the energy levels
of the hydrogen and oxygen reduction reactions. The semiconductor system must be
stable under photoelectrolysis conditions. The charge transfer from the surface of the
semiconductor must be fast enough to prevent corrosion and also reduce energy losses
due to overvoltage. The theoretical maximum of solar to hydrogen conversion
efficiency is for photoelectrolysis is 42%. Anyway present photoelectrolysis systems
only have 8% to 14% efficiency rates. A photoelectrode has photovoltaic, catalytic,
and protective layers, which can be modeled as separate components. Each layer
affects the overall solar to hydrogen efficiency the photoelectrochemical system.

4.1.6 Photoelectrochemical
Solar hydrogen production from direct photo electrochemical (PEC) water
splitting is the ultimate goal for a sustainable, renewable and clean hydrogen economy.
In PEC water splitting, hydrogen is produced from water using sunlight and
specialized semiconductors called photo electrochemical materials [24], which use
light energy to directly dissociate water molecules into hydrogen and oxygen. This
method of hydrogen generation has no greenhouse gas emissions. There are some
issues with this technique. One is efficiency and other one is stability. Many research
work has been done to solve said issues. The PEC water splitting process uses
semiconductor materials to convert solar energy directly to chemical energy in the
form of hydrogen. The semiconductor materials used in the PEC process are similar
to those used in photovoltaic solar electricity generation, but for PEC applications the
semiconductor is immersed in a water based electrolyte, where sunlight energizes the
water-splitting process. PEC reactors can be constructed in panel form (similar to
photovoltaic panels) as electrode systems or as slurry based particle systems, each
approach with its own advantages and challenges.
Photoelectrochemical process consists of an electrode of semiconductor
material, which is photoactive and is capable of generating electron hole pair when
light (photons) is incident on its surface. One of the advantages of
photoelectrochemical cells is reduction and oxidation reaction happens at different
electrodes eliminating the need for separation of gases. However, chemical stability of
materials inside electrolyte solution or water is a challenging issue.

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4.1.7 Thermochemical
Thermochemical splitting of water to produce hydrogen was considered as one
of the potential methods which can be scaled up for large scale generation [45]. It is
possible to use solar heat as the energy for the thermochemical process. Nanofluids
can be used to improve the efficiency of the process. The iodine sulfur (I-S) and copper
chlorine (Cu-Cl) cycles were considered having potential for scale up hydrogen
generation. Anyway, this process is complex and required multidisciplinary approach
to develop suitable technology. Currently globally, these cycles are at different stages
of development and are yet to be commercially proven with renewable resources.
Currently the same process are being used for hydrogen generation using the energy
from nuclear and fossil fuels. This non-renewable processes are cheap and
commercially viable but it is environmentally harmful seriously.
The iodine sulfur (I-S) cycle is one of the most promising and efficient
thermochemical water splitting technologies for the massive production of hydrogen.
As competing processes, other options such as HTSE (high temperature steam
electrolysis), hybrid sulfur cycle and Cu-Cl cycle are also being studied for the
production of hydrogen with renewable energy resources.

4.1.8 Photobiological
Biological hydrogen can be produced in an algae bioreactor. It seems that the
photobiological hydrogen production is now economically feasible by improving the
solar energy to hydrogen conversion efficiency. Hydrogen production by micro-
organisms combines the photosynthetic properties of oxygenic and non-oxygenic
microbes with the activity of hydrogen producing enzymes in nature. As example,
hydrogenases and nitrogenases can be considered. The overall efficiency of the
process depends on the separate efficiencies of photosynthesis and enzymatic
catalysis. Major challenges, such as inhibitory amounts of oxygen produced during
oxygenic photosynthesis and inhibition of hydrogen producing nitrogenase by
ammonia, are being overcome through genetic engineering. Genetic engineering, co-
culturing, and bioreactor designs making use of immobilized cells have the potential
to increase conversion efficiencies of light energy to hydrogen and to decrease the land
area needed for photobiological hydrogen production [17]. Overall, production of
commercially viable algal fuels in any form, including biomass and biodiesel, is
challenging, and the very few systems that are operational have yet to be evaluated.
However quality of photobiological hydrogen production can be improved with the
help of nanotechnological approaches like changing the enzymes and organisms
genetically to become more reactive as required.

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4.1.9 Photovoltaic‐Photoelectrochemical hybrid
Water electrolysis was done by monolithic photoelectrochemical-Photovoltaic
design [29]. The photo electrochemical cell, which is voltage biased with an integrated
photovoltaic device, splits water directly with solar radiation. Light is the only energy
input. The hydrogen production efficiency of this system, based on the short circuit
current and the lower heating value of hydrogen, is 12.4%.
This device is patterned after the GaInP2/GaAs p-n, p-n tandem cell device
grown at the National Renewable Energy Laboratory. The solid state tandem cell
consists of a GaAs bottom cell connected to a GaInP2 top cell through a tunnel diode
interconnect. The top p-n GaInP2 junction, with a band gap of 1.83 eV, is designed to
absorb the visible portion of the solar spectrum; and the bottom p-n GaAs junction,
with a band gap of 1.42 eV, absorbs the near infrared portion of the spectrum
transmitted through the top junction. Although single gap electrodes have a solar
conversion efficiency limit of 32%, tandem junction devices have an efficiency limit
of 42%. The maximum theoretical solar to electrical efficiency for the present
combination of band gaps is about 34%. Our device differs from the standard solid-
state tandem cell in that a PEC Schottky type junction has replaced the top p-n
junction. This device then is a PEC device that is voltage biased with an integrated PV
device. Under illumination, electrons flow toward the illuminated surface and holes
flow toward the ohmic contact.
.
4.1.10 Dark and Photofermentation
Dark-fermentative hydrogen production occurs under anoxic or anaerobic
conditions (In absence of oxygen as an electron acceptor). The key pathway is the
breakdown of carbohydrate rich substrates by bacteria to hydrogen and other
intermediate products such as volatile fatty acids and alcohols. These substrates have
provided building blocks and metabolic energy for the bacterial growth. Biological
hydrogen production has been studied in a wide range of organisms belonging to
diverse taxonomical groups. Usually anaerobic bacteria such as clostridia and
enterobacter are used for dark fermentation of carbohydrates to produce hydrogen and
volatile fatty acids.
Photofermentation is carried out by non-oxygenic photosynthetic bacteria that
use sunlight and biomass to produce hydrogen. Purple non-sulfur(PNS) and green
sulfur(GS) bacteria such as rhodobacter spheroids and chlorobium vibrioforme,
respectively, are capable of producing hydrogen gas using solar energy and reduced
compounds. Their photosynthetic systems differ from oxygenic photosynthesis due to
their requirement for reduced substrates and their inability to oxidize water.
Photosynthetic bacteria have been studied for their capacity to produce hydrogen
through the action of their nitrogenase system. However quality of dark and
14
photofermentation hydrogen production can be improved with the help of
nanotechnological approaches like changing the enzymes and organisms genetically
to become more reactive as required.

4.1.11 Solar thermal Hydrogen Generation

The high temperatures necessary to split water can be achieved through the use
of concentrating solar power. An experimental station for splitting water with solar
power is the Hydrosol-II (from 2008) is a 100 kilowatt pilot plant at the plataforma
solar de almería in Spain which uses sunlight to obtain the required 800 to 1,200 C to
split water. The design of this 100 kilowatt pilot plant is based on a modular concept.
As a result, it may be possible that this technology could be readily scaled up to
megawatt range by multiplying the available reactor units and by connecting the plant
to heliostat fields (fields of sun tracking mirrors) of a suitable size. Also, an interesting
approach to solar thermal hydrogen production [4] is proposed by Hydrogen Power
Systems. The method involves application of solar energy with high flux density
focused by a dish type concentrator for single-step thermal dissociation of water at
temperature levels above 2,000 K and separation of hydrogen from the resulting gas
mixture. Dissociation however is partial, and its extent is a function of reaction
temperature and pressure. The low dissociation rate of water despite the high
temperature and the risk of recombination of hydrogen and oxygen back to water
seriously emphasize the importance of reaction gas separation as the main feature of
the process. Presently, a commercial-scale or a pilot scale solar thermal water
decomposition plant does not exist. So far, the process of direct thermal decomposition
of water was studied from an engineering perspective thermodynamically and
economically. Recombination of hydrogen and oxygen can be avoided by effective
hydrogen separation with the use of palladium membranes. In this case also there are
many nanotechnological options to improve efficiency of the process such as by
introducing nano fluid for solar heat absorption techniques, Nano options to prevent
recombination of hydrogen and oxygen in to water, etc.

4.1.12 Upconversion
Spectral upconversion [55, 56] has been attracting growing interest for the
effective harvesting of the near infrared part of sunlight for photocatalytic hydrogen
production and environmental purification. Researcher’s present evidence of near
infrared part of sunlight to UV Visible photon conversion for degradation of organic
dyes and hydrogen and oxygen evolution via water splitting by TiO2 and Rh–Cr oxide
loaded SrTiO3, Al photo catalysts. This method expand the incident light absorption
spectrum of frequencies. It increases energy conversion efficiency. This methodology
is emerging and much attractive technique for energy harvesting and hydrogen
production[70, 71, 72].
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5.0 Use of Hydrogen.
Nanostructures and adsorption play a marvelous role in hydrogen usage.
Nanostructures and nanoscience supports storage of compressed and adsorbed gas.
When the ultimate electricity is generated using fuel cells it uses nanostructures and
related materials and methods to improve efficiency. Moreover nanoscale catalysts are
used in many usage of applications of hydrogen. All these nanotechnology related
application supports are still in child stage and developing day by day.
Hydrogen is an energy carrier for vast number of applications in many
industries. Ammonia is produced using hydrogen. Ammonia commonly used for
fertilizer production. Today, Hydrogen is used in fuel cells to produce isolated and
small scale electricity generation applications. Hydrogen can be used as a
transportation fuel for electric vehicles with fuel cells and also it can be used as
combustion fuel for engines in vehicles. Some of applications of hydrogen fuels are
metallurgical and steel industry, petrochemical and refining industry, glass and float
glass manufacturing, chemical and pharmaceutical industry, production of hydrogen
peroxide, food industry, electronics industry and use as technical gases and medical
gases.
Due to manipulation and handling of utility of hydrogen, it will create a
hydrogen economy [1] near future between production and usage. Hydrogen must be
generated, packaged, transported, stored and use like any product in business world.
Packaging can be done by compression, liquefaction, hydrides or any other ways.
Distribution can be done by pipelines, road, rail, ship or with the help of any other
transportation method. Storage can be done by pressurizing, using abortion and
adsorption and help of cryogenic containers, etc. Above said processors will create
and hydrogen economy [1] for the world. This hydrogen economy [1] will help to the
world enormously in many ways. This future hydrogen economy will be an
environmental friendly in many ways. Further it will help to solve many economic
issues in the world for instance unemployment issue.
Liquid hydrogen industry also a rapidly developing industry even though it is
under experimental stage. This is because the liquid hydrogen belongs important
properties. It has low viscosity and low molecular weight. Liquid hydrogen shows high
thermal conductivity and a very high heat of vaporization. These inherent properties
force to use the hydrogen as cryogenic coolants. So liquid hydrogen is a promising
liquid when comparing it with other low temperature cryogenic liquids such as helium
and neon. Cryogenic hydrogen can be combined with helium in different future
applications like indirect cooling schemes, etc. There is a possibility to arise
hydrogen cryo-magnetics and hydrogen cryo-superconductors like high tech products
and technologies in future.

16
6.0 Research focuses and challenges.
There are many and different orientations when doing research on hydrogen
generation. Researchers can consider to reduce cost of production and improve the
efficiency of electrolyser systems. This will help to convert electricity to hydrogen
with higher efficiency and reducing production cost. Moreover by introducing
compression into the electrolyser systems, it can minimize the cost of separate
compressor system for hydrogen storage unit. Scientist can research on efficient
carbon capture systems for fossil fuel based hydrogen generation systems. Researcher
can think zero emission vehicles and zero emission stationary engines. This will be a
giant field of thinking. These concepts will guide scientist towards fuel cell and
hydrogen internal combustion engine experiments. Countries can research and invest
to set-up hydrogen production facilities on small, medium and large scales. This will
help to understand and management of hydrogen energy infrastructure in the country.
Further any country can think of hydrogen economy. This will guide to achieve
unlimited economic advantages. The research focus will support o development of
new materials for the development of components, catalysts and new processes in the
area of hydrogen production. Most of Solar driven Hydrogen production systems are
not in commercial level. So lots of things to research, experiment and improve to
reach up to the commercial or viable level. Photo electrochemical, photochemical,
photovoltaic/photo electrochemical combined system and upconversion systems need
to be developed to achieve viable efficiency. Nanotechnology and Nanoscience help
to work with above said research focus by reducing cost, improving efficiency,
minimizing usage of materials and waste removal.

7.0 Summery
Fossil fuel is the major energy supplier in the present world. Hence, the future
energy scenario of the world as well as global warming phenomena and pollution lead
to the energy improvements related to renewable energy resources. In this regard,
hydrogen has been introduced as a promising energy carrier for clean and green
development. The World’s dominant and cheap hydrogen production is done by using
fossil fuels but current cost of hydrogen production from renewable energy resources
is very high and world does not have enough technologies and methods to develop
green hydrogen. The effect of this problem can be minimized or removed using the
different fields of nanotechnologies. Nanotechnological developments and solution
can be applied for different hydrogen generation sectors like conventional and
nonconventional hydrogen generation and including renewable energy sector as well.
The Nanotechnology can make a huge revolution in future by increasing efficiency
and performance of methodologies and optimizing the size and design of renewable
energy devices utilized for energy conversion and storage of hydrogen.
17
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