Nanosilicon rapidly splits water without light, heat, or electricity

Jan 24, 2013 by Lisa Zyga

Illustration of the multidisciplinary approach for producing hydrogen through

silicon oxidation. The approach involves synthesizing silicon nanoparticles, the
silicon-water reaction which generates hydrogen on demand, and using the
hydrogen more
(Phys.org)Although scientists know that when silicon mixes with water,
hydrogen is produced through oxidation, no one expected how quickly silicon
nanoparticles might perform this task. As a new study has revealed, 10-nm
silicon nanoparticles can generate hydrogen 150 times faster than 100-nm
silicon nanoparticles, and 1,000 times faster than bulk silicon. The discovery
could pave the way toward rapid "just add water" hydrogen generation
technologies for portable devices without the need for light, heat, or electricity.

The researchers, Folarin Erogbogbo at the University of Buffalo and coauthors,

have published their paper on using nanosilicon to generate hydrogen in a recent
issue of Nano Letters.
If hydrogen is ever to be used to deliver energy for wide commercial
applications, one of the requirements is finding a fast, inexpensive way to
produce hydrogen. One of the most common hydrogen production techniques is
splitting water into hydrogen and oxygen. There are several ways to split water,
such as with an electric current (electrolysis), heat, sunlight, or a substance that
chemically reacts with water. Such substances include aluminum, zinc, and
silicon.

As the scientists explained, silicon-water oxidation reactions have so far been

slow and uncompetitive with other water splitting techniques. However, silicon
does have some theoretical benefits, such as being abundant, being easy to
transport, and having a high energy density. Further, upon oxidation with water,
silicon can theoretically release two moles of hydrogen per mole of silicon, or
14% of its own mass in hydrogen.
For these reasons, the scientists decided to take a closer look at silicon,
specifically silicon nanoparticles, which have not previously been studied for
hydrogen generation. Because silicon nanoparticles have a larger surface area
than larger particles or bulk silicon, it would be expected that the nanoparticles
can generate hydrogen more rapidly than the larger pieces of silicon.

But the improvements the scientists discovered with silicon nanoparticles far
exceeded their expectations. The reaction of 10-nm silicon particles with water
produced a total of 2.58 mol of hydrogen per mol of silicon (even exceeding
theoretical expectations), taking 5 seconds to produce 1 mmol of hydrogen. In
comparison, the reaction with 100-nm silicon particles produced a total of 1.25
mol of hydrogen per mole of silicon, taking 811 seconds to produce each mmol of
hydrogen. For bulk silicon, total production was only 1.03 mol of hydrogen per
mol of silicon, taking a full 12.5 hours to produce each mmol of hydrogen. For a
rate comparison, the 10-nm silicon generated hydrogen 150 times faster than
100-nm silicon and 1,000 times faster than bulk silicon.
"I believe the greatest significance of this work is the demonstration that silicon
can react with water rapidly enough to be of practical use for on-demand
hydrogen generation," coauthor Mark Swihart, Professor of Chemical and
Biological Engineering at the University of Buffalo, told Phys.org. "This result was
both unexpected and of potential practical importance. While I do not believe
that oxidation of silicon nanoparticles will become a feasible method for largescale hydrogen generation any time soon, this process could be quite interesting
for small-scale portable applications where water is available."

A comparison of hydrogen generation rates for different forms of silicon. Maximum rates are in the left
column with images of the samples on them. Average rates are in the right column. The red line
indicates the maximum reported rate for hydrogen generated from aluminum. Credit: Folarin
Erogbogbo, et al. 2013 American Chemical Society

In addition to producing hydrogen faster than larger silicon pieces, the 10-nm
silicon also produces hydrogen significantly faster than aluminum and zinc
nanoparticles. As Swihart explained, the explanation for this inequality differs for
the two materials.
"Compared to aluminum, silicon reacts faster because aluminum forms a denser
and more robust oxide (Al2O3) on its surface, which limits the reaction," he said.
"In the presence of a base like KOH [potassium hydroxide], silicon mostly
produces soluble silicic acid (Si(OH)4). Compared to zinc, silicon is simply more
reactive, especially at room temperature."
Although the larger surface area of the 10-nm silicon compared with larger
silicon pieces contributes to its fast hydrogen production rate, surface area alone
cannot account for the huge rate increase that the scientists observed. The
surface area of 10-nm silicon is 204 m2/g, about 6 times greater than the surface
area of 100-nm silicon, which is 32 m2/g.
To understand what causes the much larger increase in the hydrogen production
rate, the researchers conducted experiments during the silicon etching process.
They found that, for the 10-nm particles, etching involves the removal of an
equal number of lattice planes in each direction (isotropic etching). In contrast,
for 100-nm particles and microparticles, unequal numbers of lattice planes are
removed in each direction (anisotropic etching).
The researchers attribute this etching difference to the different geometries of
different-sized crystals. As a result of this difference, the larger particles adopt

non-spherical shapes that expose less reactive surfaces compared to the smaller
particles, which remain nearly spherical, exposing all crystal facets for reaction.
Larger particles also develop thicker layers of oxidized silicon byproducts through
which water must diffuse. Both of these factors limit the rate of the reaction on
larger particles.
To confirm that that the 10-nm silicon-water reaction generates hydrogen with no
byproducts that could interfere with applications, the researchers used the
silicon-generated hydrogen to operate a fuel cell. The fuel cell performed very
well, producing more current and voltage than the theoretical amount of pure
hydrogen, which is due to the fact that the 10-nm particles generated more
hydrogen than the theoretical 14 wt %.
The researchers hope that this surprising ability of silicon nanoparticles to rapidly
split water and generate hydrogen could lead to the development of a hydrogenon-demand technology that could enable fuel cells to be used in portable
devices. This technology would require a large-scale, energy-efficient method of
silicon nanoparticle production, but could have some advantages compared to
other hydrogen generation techniques.
"The key advantage of silicon oxidation for hydrogen generation is its simplicity,"
Swihart said. "With this approach, hydrogen is produced rapidly, at room
temperature, and without the need for any external energy source. The energy
needed for hydrogen generation is effectively stored in the silicon. All of the
energy input required for producing the silicon can be provided at a central
location, and the silicon can then be used in portable applications.
"The key disadvantage of silicon oxidation is its relative inefficiency. The energy
input required to create the silicon nanoparticles is much greater than the energy
available from the hydrogen that is finally produced. For large scale applications,
this would be a problem. For portable applications, it is not. For example, the cost
of electricity supplied by an ordinary household battery can easily be 10 to 100
times higher than the cost of electricity from a utility, but batteries still play an
important role in our lives."
In the future, the researchers plan to further increase the hydrogen generation
capacity of silicon oxidation by experimenting with different mixtures.
"One direction that we are presently pursuing is the use of mixtures of silicon
nanoparticles with metal hydrides, which also react with water to produce
hydrogen," Swihart said. "Compounds like lithium hydride and sodium hydride
react with water to produce the base (LiOH or NaOH) that is needed to catalyze
the silicon oxidation. However, they can react too fast with water (explosively)
and are not stable in air. Mixing them with silicon nanoparticles or coating them
with silicon nanoparticles may serve to both temper their reactivity and increase
the hydrogen generation capacity of the system by replacing the added base
(e.g., KOH in the published paper) with a material that also generates hydrogen."
Explore further: Tiny carbon nanotube pores make big impact
More information: Folarin Erogbogbo, et al. "On-Demand Hydrogen Generation
using Nanosilicon: Splitting Water without Light, Heat, or Electricity." Nano
Letters. DOI: 10.1021/nl304680w

Journal reference: Nano Letters

Just Add Water: How Scientists Are Using Silicon to Produce

Hydrogen on Demand

Transmission electron microscopy image showing spherical silicon nanoparticles about 10 nanometers in diameter. These particles,
created in a UB lab, react with water to quickly produce hydrogen, according to new UB research. Credit: Swihart Research Group,
University at Buffalo.

New technology could help power portable devices like satellite phones and radios
By: Charlotte Hsu
Release Date: January 22, 2013
- See more at: http://www.buffalo.edu/news/releases/2013/01/017.html#sthash.syxpmpU2.dpuf

BUFFALO, N.Y. Super-small particles of silicon react with water to produce hydrogen almost instantaneously, according to
University at Buffalo researchers.
In a series of experiments, the scientists created spherical silicon particles about 10 nanometers in diameter. When combined
with water, these particles reacted to form silicic acid (a nontoxic byproduct) and hydrogen a potential source of energy for
fuel cells.
The reaction didnt require any light, heat or electricity, and also created hydrogen about 150 times faster than similar
reactions using silicon particles 100 nanometers wide, and 1,000 times faster than bulk silicon, according to the study.
The findings appeared online in Nano Letters on Jan. 14. The scientists were able to verify that the hydrogen they made was
relatively pure by testing it successfully in a small fuel cell that powered a fan.
When it comes to splitting water to produce hydrogen, nanosized silicon may be better than more obvious choices that people
have studied for a while, such as aluminum, said researcher Mark T. Swihart, UB professor of chemical and biological
engineering and director of the universitys Strategic Strength in Integrated Nanostructured Systems.
With further development, this technology could form the basis of a just add water approach to generating hydrogen on
demand, said researcher Paras Prasad, executive director of UBs Institute for Lasers, Photonics and Biophotonics (ILPB) and a
SUNY Distinguished Professor in UBs Departments of Chemistry, Physics, Electrical Engineering and Medicine. The most
practical application would be for portable energy sources.

Swihart and Prasad led the study, which was completed by UB scientists, some of whom have affiliations with Nanjing
University in China or Korea University in South Korea. Folarin Erogbogbo, a research assistant professor in UBs ILPB and a UB
PhD graduate, was first author.
The speed at which the 10-nanometer particles reacted with water surprised the researchers. In under a minute, these particles
yielded more hydrogen than the 100-nanometer particles yielded in about 45 minutes. The maximum reaction rate for the 10nanometer particles was about 150 times as fast.
Swihart said the discrepancy is due to geometry. As they react, the larger particles form nonspherical structures whose surfaces
react with water less readily and less uniformly than the surfaces of the smaller, spherical particles, he said.
Though it takes significant energy and resources to produce the super-small silicon balls, the particles could help power
portable devices in situations where water is available and portability is more important than low cost. Military operations and
camping trips are two examples of such scenarios.
It was previously unknown that we could generate hydrogen this rapidly from silicon, one of Earths most abundant elements,
Erogbogbo said. Safe storage of hydrogen has been a difficult problem even though hydrogen is an excellent candidate for
alternative energy, and one of the practical applications of our work would be supplying hydrogen for fuel cell power. It could be
military vehicles or other portable applications that are near water.
Perhaps instead of taking a gasoline or diesel generator and fuel tanks or large battery packs with me to the campsite (civilian
or military) where water is available, I take a hydrogen fuel cell (much smaller and lighter than the generator) and some plastic
cartridges of silicon nanopowder mixed with an activator, Swihart said, envisioning future applications. Then I can power my
satellite radio and telephone, GPS, laptop, lighting, etc. If I time things right, I might even be able to use excess heat generated
from the reaction to warm up some water and make tea.

Media Contact Information

Charlotte Hsu
Director of News Content, Architecture and Regional Planning, Sciences
Tel: 716-645-4655
chsu22@buffalo.edu
Twitter: @UBScience
Pinterest: UB Science
- See more at: http://www.buffalo.edu/news/releases/2013/01/017.html#sthash.syxpmpU2.dpuf