Stephen G.

Abelada BS ChE V Date Submitted: December 17, 2013

GELATIN-AIDED FUEL CELL TECHNOLOGY

A fuel cell is a device that produces electricity, particularly direct current (DC) electricity,
through a chemical reaction between a source fuel and an oxidant. The source fuel could be almost
anything that can be oxidized, including hydrogen, methane, propane, methanol, diesel fuel or gasoline.
The only by-products during such reaction are water and a small amount of nitrous oxide if air is used
as the oxidizer. These devices are often labeled as electrochemical energy conversion devices since they
involve reactant conversion to certain products and in the process produce electricity, that is, energy
generated by the chemical reaction occurring is converted into electric power (Platinum Today, 2013;
Nice and Strickland, 2013; Techtarget, 2013).

Fuel cells share many of the characteristics of a battery - silent operation: no moving parts and
an electrochemical reaction to generate power. However, unlike a battery, fuel cells need no recharging
and will run indefinitely when supplied with fuel (Platinum Today, 2013; Nice and Strickland, 2013).
Fuel cells can be used to power just about anything conceivable, from cars to mobile phones to space
vehicles and are said to offer several advantages in electricity provision over conventional power
sources (Techtarget, 2013).

Christian Schoenbein, a German scientist, was the first person to envision the possibility of
conceiving the fuel cell in the middle of the 19th century. A Welsh physicist, William Grove, developed
a working prototype by the year 1843. More than a century later in the 1950s, the American scientists
Thomas Grubb and Leonard Niedrach improved on the design by incorporating an ion-exchange
membrane and making use of hydrogen as the fuel source. Fuel cells of this type were in fact used in
some of the American space missions conducted by the National Aeronautics and Space Administration
(NASA) during the 1960s (Techtarget, 2013).

Every known fuel cell has two electrodes, one positive and one negative – the anode and
cathode respectively. The reaction between the fuel and the oxidant that leads to electricity production
takes place at these electrodes. In addition, fuel cells have an electrolyte which carries electrically
charged particles from one electrode to the other and a catalyst which hastens the rate of reactions at
these electrodes (Smithsonian Institution, 2008).

Figure 1. Mechanism of electricity generation for fuel cells (Fuel Cells, 2013).
 Generally speaking, a fuel cell does not actually burn its fuel. The oxidation process occurs at
a far lower temperature than that produced by active combustion. A fuel cell can be recharged by filling
a tank or from a continuously available external supply of fuel. Varieties of fuel cells exist, however,
the mechanism of producing electricity is basically the same. In a common form of hydrogen fuel cell
known as the proton exchange membrane (PEM), the type at which extensive research has been
focusing recently, hydrogen is delivered to a positive electrode (anode). At the anode, hydrogen atoms
are broken down or ionized into their constituent protons and electrons. The protons permeate through
an electrolyte membrane to a negative electrode called the cathode. Electrons travel from the cathode
to the anode through an external load, which converts the resulting current to useful power. Within the
cell, oxygen molecules from the cathode react with the protons permeating through electrolyte
membrane and the electrons arriving through the external load. The result is water, the principal by-
product of all hydrogen-based energy sources. The electrolyte plays a key role in fuel cells. It must
permit only the appropriate ions to pass between the anode and cathode. If free electrons or other
substances could travel through the electrolyte, they would disrupt the chemical reaction and hence
power generation (Smithsonian Institution, 2008; Techtarget, 2013).

Fuel cells inherently offer several exceptional advantages over conventional power sources.
One is the reduced dependence on fossil fuels since these devices depend on a chemical reaction
involving hydrogen and oxygen only, not relying on combustion of any non-renewable energy resource
such as coal, petroleum etc. Another would be the cell’s longer useful life, since it runs and works
indefinitely as long as fuel is supplied. Furthermore, these cells have an overall higher efficiency
compared to other electricity-generating devices. They are more efficient in extracting energy from a
fuel, they are not subject to the thermodynamic laws that limit a conventional power plant (Carnot limit)
unlike electricity-generating devices reliant on non-renewable energy sources and they have the
capability to harness waste heat from some cells which boost system efficiency further. The fuel cells
as well offer relative safety because of the essentially zero toxicity given proper and cautious handling.
They also boast significant reduction in pollution, particularly carbon emissions since the only by-
products produced during the process are water and nitrous oxide. These cells as well pose an overall
minimal maintenance costs (Smithsonian Institution, 2008; Techtarget, 2013).

These benefits obtainable from a fuel cell paved the way for its popularity as an alternative way
of power generation and hence led to numerous applications such as in the automotive industries. Fuel
cell cars were found to have similar travel range and performance to cars with internal combustion
engines. As a stationary power source, fuel cells can also provide electric power for homes and offices.
In these applications, heat produced by the cell can be circulated like the heat from a conventional
boiler. Using the combined heat and power in this way considerably raises the efficiency of the system.
This significance has been recognized for the past few years now. In fact, more than 10,000 of such
units are already in use in Japan, the USA and Europe to power hospitals and industrial plants and to
provide grid-independent, uninterrupted power supply. Fuel cells can as well compete with batteries
and generators for portable use, supplying electricity from a few kilowatts to power a mobile phone
down to a few watts to power a laptop computer (Smithsonian Institution, 2008).

Various types of fuel cell exist today but the type at which extensive research has been focusing
recently is the proton exchange membrane (PEM) fuel cell, which uses platinum as catalysts. PEM fuel
cells are capable of being used in power generation for buildings, utilized instead of batteries or
generators in portable equipment and as replacement for the internal combustion engine in a vehicle
(Platinum Today, 2013).
 Given these irrefutably significant attributes and advantages, the question remains as to why
recognition and application of these fuel cells have not been fully realized today – what barriers are
responsible for preventing fuel cells’ commercialization and extensive utilization nowadays? According
to the Smithsonian Institution (2008), the biggest existing obstacle to fuel cell commercialization is
probably thehigh cost.In fact, much research attention hasbeen directed and focused on improving cell
performance and developing low cost materials which will enable fuel cells to compete on price against
batteries and against conventional engines and power generating plant. The next big question is what is
it in fuel cells that contributes significantly to its cost? The answer is the catalyst used to hasten the
reaction between the fuel and the oxidant, the most commonly employed being platinum.

Platinum is the work-horse of many catalytic processes. It has become particularly important
recently since it can drive key reactions in new technologies such as fuel cells, photoelectrochemical
cells etc. However, platinum is scarce, difficult to mine and therefore is expected to be very expensive.
For instance, in the automotive and transport industry, large quantities (about 30 grams) of this noble
metal are required for the electrodes. The pure platinum needed contributes about 40 per cent of the
total unit cost. Without the catalytic effect of platinum, it is not currently possible to achieve the
necessary conversion rates (Nanowerk, 2013).

To address these obstacles, efforts have been made in researching viable alternatives to
platinum as catalyst for fuel cells. Doped carbons were discovered to be a possible alternative to
platinum-based materials about five years ago. This sparked a huge amount of interest in nanostructured
carbons such as carbon nanotubes and graphene and many methods have been developed to prepare
these materials. Published studies for instance include "Graphene catalyst outperforms platinum in fuel
cell" or "Unzipped carbon nanotubes could help energize fuel cells and batteries" (Nanowerk, 2013).
Other studies include use of processed nickel and graphene injected with chlorine, bromine and iodine
or graphene nanoparticles edged with iodine (Barras, 2008; Case Western Reserve University, 2013).
Though catalyst performance may have been comparably compensated by these alternatives, the
methods of producing such materials inadvertently involve relatively expensive reagents and complex
or hazardous chemical processing. “Green” or sustainable routes to platinum-free fuel cell catalysts
have as well been published, but these generally result in a significant compromise in catalytic
properties (Nanowerk, 2013).

Recently, a research team comprised of British, Japanese and Chinese scientists from the
University of Birmingham, National Institute of Materials Science in Japan and Southeast University
in Nanjing, Chinarespectively has developed a really simple route to carbon materials that perform
almost as well as a commercial platinum/carboncatalyst in a key fuel cell reaction. To make these
materials, they simply used gelatin – the same gelatin people use to make jelly or jello commonly known
as a desert (Nanowerk, 2013).
 Figure 2. Gelatin material for catalyst production (Soutter, 2013).

Dr. Zoe Schepp, a Birmingham Fellow at the school of Chemistry, University of Birmingham,
tells that the exciting thing about the research is that it is a really simple route to production of fuel cell
catalysts with activity and efficiency similar to a commercial platinum/carbon catalyst. Schnepp was
the first author of a paper in the October 1, 2013 online edition of Journal of Materials Chemistry
A entitled “Doped-carbon electrocatalysts with trimodal porosity from a homogeneous polypeptide gel”
where the team describes a versatile one-pot synthesis of nitrogen-doped carbons that exploits the
remarkable ability of biological polymers (Nanowerk, 2013).

The chemistry of the system is really interesting and the manner of producing such is relatively
simple but results to a complicated, durable material with exceptional catalytic properties. The
researchers mixed gelatin with iron and magnesium nitrates in water, making a homogeneous solution
precursor. As the material progressively dries, it spontaneously foams. This foam formation results from
or relies on the magnesium and the iron crosslinking the gelatin to form a sticky resin and the nitrate
reacting with the gelatin to produce gas bubbles. In other words, the mixture forms its own intricate
sponge-like structure. The sponge obtained is then heated under nitrogen to a temperature of 800°C in
a process called calcination, during which time the gelatin degrades or decomposes to carbon, the
magnesium nitrate oxidizes to form nanoparticles of magnesium oxide (MgO) and the iron nitrate
meanwhile oxidizes to yield nanoparticles of iron carbide (Fe3C) (Nanowerk, 2013; World of
Chemicals, 2013).

When the material is washed with some dilute acid, the MgO and Fe3C nanoparticles are
dissolved and removed, leaving behind tiny pores or holes rather like hollow capsules of different length
scales in the sponge-like carbon material. Along with this sponge-like macrostructure, these capsules
create an extremely high surface area, which is very crucial for allowing the gaseous reactants in the
fuel cell to flow through the fuel cell catalyst (Nanowerk, 2013; University of Birmingham, 2013). On
top of this, iron carbide happens to be very good at converting amorphous carbon to graphitic carbon.
That is, during heating, iron carbide converts the carbon around it to a thin sheet. This forms in onion-
like layers around the iron carbide nanoparticles. Nitrogen atoms from the gelatin as well become
embedded in this thin sheet of carbon and previous results of the experiment have shown that these
additional effects, aside from the sponge-like structure and pores, make the catalyst even more effective
(Nanowerk, 2013; World of Chemicals, 2013).
 Figure 3. Gelatin-iron foam prior heating to make the carbon catalyst (Nanowerk, 2013).

Figure 4. An overview of the process for catalyst production (Newton, 2013).

Figure 5. A Scanning Electron Microscope (SEM) image of the carbon foam (Nanowerk, 2013).

The researchers point out that the highly significant aspect about this system is that the activity
is so high. They speculate that this is the result of the complex nanostructure formed by all the different
components. The network of pores and bubbles inside the catalyst provides a very large available
surface area for chemical reactions to occur. The more places there are for hydrogen and oxygen to
react to produce water, the more efficient the catalyst is. The choice of metal salts proved to be important
too. The identity of the metals used determined the size of the pores formed, and thus affected how well
the reactions occur. As mentioned, the two metals used react differently during calcination; the
magnesium being converted to nanoparticles of magnesium oxide while iron bunches together into
much larger nanoparticles of iron carbide. This means that the ratio of magnesium to iron can be used
to tune the pore size (Nanowerk, 2013; World of Chemicals, 2013).

To design sustainable materials has continually been one of the biggest challenges for the field
of materials science. Such materials should be made from cheap, readily-available and abundant
resources and should as well be processed via simple and safe manufacturing methods. The recent
invention gives several realizable and substantial advantages. Unlike platinum which is a rare substance,
difficult to mine and hence relatively expensive, the new material is fabricated from relatively profuse
and inexpensive elements magnesium and iron. Another key is that the gelatin material, an animal
protein obtained from bones, skin, tendons and other unused parts of animals, is not only cheap but is
extremely easy to make. By combining such elements with gelatin and undergoing few simple and safe
processes, an effective material have been made which shows remarkable performance in catalyzing
reactions for generating electricity comparable to the commercial platinum catalyst (University of
Birmingham, 2013; Soutter, 2013). The bottom line result is the synthesis of a high-quality electrode
material by really simple chemistry.

While this specific work was targeted at fuel cells, the whole issue of noble metal replacement
in devices is a much broader challenge. For example, some of the best materials for splitting water in
photoelectrochemical cells rely on platinum nanostructures. The research team’s broad goal therefore
is generating a family of materials that could have many applications in catalysis. Obviously, there are
huge challenges to the specific task of platinum-free fuel cells and a lot more testing such as longevity
studies should be performed before the materials could get into a real device, Schnepp admits
(Nanowerk, 2013).

Despite these inadequacies, the relative cheapness and availability of materials, the simple and
safe methods used for fabrication and the comparable efficiency or performance to commercial catalysts
of the product make this recent discovery one of the best alternatives yet to sustainable energy source.
It is a highly significant research as it not only addresses the dilemma of the scientific community but
as well as the interest of the public since it deals with a major challenge of modern life – securing an
affordable energy supply while sparing the environment at the same time. This study debunks the myth
that “green chemistry” subsequently produces “inferior materials”.
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