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August 30, 2011

Novel alloy could produce hydrogen fuel from sunlight

Scientists from the University of Kentucky and the University of Louisville have determined that an inexpensive semiconductor material can be "tweaked" to generate hydrogen from water using sunlight.

Using state-of-the-art theoretical computations, the UK-UofL team demonstrated that an alloy formed by a 2 percent substitution of antimony (Sb) in gallium nitride (GaN) has the right electrical properties to enable solar light energy to split water molecules into hydrogen and oxygen, a process known as photoelectrochemical (PEC) water splitting. When the alloy is immersed in water and exposed to sunlight, the chemical bond between the hydrogen and oxygen molecules in water is broken. The hydrogen can then be collected.

Physical Review Letters B - Visible-light absorption and large band-gap bowing of GaN1−xSbx from first principles



"Previous research on PEC has focused on complex materials," Menon said. "We decided to go against the conventional wisdom and start with some easy-to-produce materials, even if they lacked the right arrangement of electrons to meet PEC criteria. Our goal was to see if a minimal 'tweaking' of the electronic arrangement in these materials would accomplish the desired results."

Gallium nitride is a semiconductor that has been in widespread use to make bright-light LEDs since the 1990s. Antimony is a metalloid element that has been in increased demand in recent years for applications in microelectronics. The GaN-Sb alloy is the first simple, easy-to-produce material to be considered a candidate for PEC water splitting. The alloy functions as a catalyst in the PEC reaction, meaning that it is not consumed and may be reused indefinitely. UofL and UK researchers are currently working toward producing the alloy and testing its ability to convert solar energy to hydrogen.

Hydrogen has long been touted as a likely key component in the transition to cleaner energy sources. It can be used in fuel cells to generate electricity, burned to produce heat, and utilized in internal-combustion engines to power vehicles. When combusted, hydrogen combines with oxygen to form water vapor as its only waste product. Hydrogen also has wide-ranging applications in science and industry.

Because pure hydrogen gas is not found in free abundance on Earth, it must be manufactured by unlocking it from other compounds. Thus, hydrogen is not considered an energy source, but rather an "energy carrier." Currently, it takes a large amount of electricity to generate hydrogen by water splitting. As a consequence, most of the hydrogen manufactured today is derived from non-renewable sources such as coal and natural gas.

Sunkara says the GaN-Sb alloy has the potential to convert solar energy into an economical, carbon-free source for hydrogen.

"Hydrogen production now involves a large amount of CO2 emissions," Sunkara said. "Once this alloy material is widely available, it could conceivably be used to make zero-emissions fuel for powering homes and cars and to heat homes."

Applicability of the Ga(Sbx)N1−x alloys for practical realization of photoelectrochemical water splitting is investigated using first-principles density functional theory incorporating the local density approximation and generalized gradient approximation plus the Hubbard U parameter formalism. Our calculations reveal that a relatively small concentration of Sb impurities is sufficient to achieve a significant narrowing of the band gap, enabling absorption of visible light. Theoretical results predict that Ga(Sbx)N1−x alloys with 2-eV band gaps straddle the potential window at moderate to low pH values, thus indicating that dilute Ga(Sbx)N1−x alloys could be potential candidates for splitting water under visible light irradiation.



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