Now, 'artificial forest' for solar water splitting



Now, `artificial forest` for solar water splitting Washington: An important advance in the race to develop carbon-neutral renewable energy sources has been achieved.

Scientists with the U.S. Department of Energy (DOE)'s Lawrence Berkeley National Laboratory (Berkeley Lab) have reported the first fully integrated nanosystem for artificial photosynthesis. While "artificial leaf" is the popular term for such a system, the key to this success was an "artificial forest."

"Similar to the chloroplasts in green plants that carry out photosynthesis, our artificial photosynthetic system is composed of two semiconductor light absorbers, an interfacial layer for charge transport, and spatially separated co-catalysts," explained Peidong Yang, a chemist with Berkeley Lab's Materials Sciences Division, who led this research.

"To facilitate solar water- splitting in our system, we synthesized tree-like nanowire heterostructures, consisting of silicon trunks and titanium oxide branches. Visually, arrays of these nanostructures very much resemble an artificial forest," he said.

Solar technologies are the ideal solutions for carbon-neutral renewable energy - there's enough energy in one hour's worth of global sunlight to meet all human needs for a year. Artificial photosynthesis, in which solar energy is directly converted into chemical fuels, is regarded as one of the most promising of solar technologies.

A major challenge for artificial photosynthesis is to produce hydrogen cheaply enough to compete with fossil fuels. Meeting this challenge requires an integrated system that can efficiently absorb sunlight and produce charge-carriers to drive separate water reduction and oxidation half-reactions.

"In natural photosynthesis the energy of absorbed sunlight produces energized charge-carriers that execute chemical reactions in separate regions of the chloroplast. We've integrated our nanowire nanoscale heterostructure into a functional system that mimics the integration in chloroplasts and provides a conceptual blueprint for better solar-to-fuel conversion efficiencies in the future," Yang said.

When sunlight is absorbed by pigment molecules in a chloroplast, an energized electron is generated that moves from molecule to molecule through a transport chain until ultimately it drives the conversion of carbon dioxide into carbohydrate sugars. This electron transport chain is called a "Z-scheme" because the pattern of movement resembles the letter Z on its side.

Yang and his colleagues also use a Z-scheme in their system only they deploy two Earth abundant and stable semiconductors - silicon and titanium oxide - loaded with co-catalysts and with an ohmic contact inserted between them.

Silicon was used for the hydrogen-generating photocathode and titanium oxide for the oxygen-generating photoanode. The tree-like architecture was used to maximize the system's performance. Like trees in a real forest, the dense arrays of artificial nanowire trees suppress sunlight reflection and provide more surface area for fuel producing reactions.

"Upon illumination photo-excited electron-hole pairs are generated in silicon and titanium oxide, which absorb different regions of the solar spectrum. The photo-generated electrons in the silicon nanowires migrate to the surface and reduce protons to generate hydrogen while the photo-generated holes in the titanium oxide nanowires oxidize water to evolve oxygen molecules. The majority charge carriers from both semiconductors recombine at the ohmic contact, completing the relay of the Z-scheme, similar to that of natural photosynthesis," Yang explained.

Arrays of tree-like nanowires consisting of Si trunks and TiO2 branches facilitate solar water-splitting in a fully integrated artificial photosynthesis system.

Under simulated sunlight, this integrated nanowire-based artificial photosynthesis system achieved a 0.12-percent solar-to-fuel conversion efficiency. Although comparable to some natural photosynthetic conversion efficiencies, this rate will have to be substantially improved for commercial use.

However, the modular design of this system allows for newly discovered individual components to be readily incorporated to improve its performance. For example, Yang noted that the photocurrent output from the system's silicon cathodes and titanium oxide anodes do not match, and that the lower photocurrent output from the anodes is limiting the system's overall performance.

A paper describing this research appeared in the journal NANO Letters.

ANI