Artificial Forest for Solar Water-Splitting. First Fully Integrated Artificial Photosynthesis Nanosystem

ORIGINAL: Berkeley Lab
Lynn Yarris

May 16, 2013

Berkeley Lab Researchers Report First Fully Integrated Artificial Photosynthesis Nanosystem

InGaN nanowires grown on Si nanowires for Solar Water Splitting. Peidong Yang

Schematic shows TiO2 nanowires (blue) grown on the upper half of a Si nanowire (gray) and the two absorbing different regions of the solar spectrum. Insets display photoexcited electron−hole pairs separated at the semiconductor-electrolyte interface to carry out water splitting with the help of co-catalysts (yellow and gray dots).

In the wake of the sobering news that atmospheric carbon dioxide is now at its highest level in at least three million years, 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,” says 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.”

Yang, who also holds appointments with the University of California Berkeley’s Chemistry Department and Department of Materials Science and Engineering, is the corresponding author of a paper describing this research in the journal NANO Letters. The paper is titled “A Fully Integrated Nanosystem of Semiconductor Nanowires for Direct Solar Water Splitting.” Co-authors are Chong Liu, Jinyao Tang, Hao Ming Chen and Bin Liu.

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.

Peidong Yang (left), Hao Ming Chen and Chong Liu (glove box) have developed the first fully integrated nanoscale artificial photosynthesis system. (Photo by Roy Kaltschmidt)

“In natural photosynthesis the energy of absorbed sunlight produces energized charge-carriers that execute chemical reactions in separate regions of the chloroplast,” Yang says. “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.”

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,” Yang says. “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.”

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 notes 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.

“We have some good ideas to develop stable photoanodes with better performance than titanium oxide,” Yang says. “We’re confident that we will be able to replace titanium oxide anodes in the near future and push the energy conversion efficiency up into single digit percentages.”

This research was supported by the DOE Office of Science.

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Lawrence Berkeley National Laboratory addresses the world’s most urgent scientific challenges by advancing sustainable energy, protecting human health, creating new materials, and revealing the origin and fate of the universe. Founded in 1931, Berkeley Lab’s scientific expertise has been recognized with 13 Nobel prizes. The University of California manages Berkeley Lab for the U.S. Department of Energy’s Office of Science. For more, visit www.lbl.gov.

DOE’s Office of Science is the single largest supporter of basic research in the physical sciences in the United States, and is working to address some of the most pressing challenges of our time. For more information, please visit the Office of Science website at science.energy.gov/.

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New energy source for future medical implants: sugar

ORIGINAL: MIT

Anne Trafton, MIT News Office
June 12, 2012

Implantable fuel cell built at MIT could power neural prosthetics that help patients regain control of limbs.

This silicon wafer consists of glucose fuel cells of varying sizes; the largest is 64 by 64 mm. 

Image: Sarpeshkar Lab

MIT engineers have developed a fuel cell that runs on the same sugar that powers human cells: glucose. This glucose fuel cell could be used to drive highly efficient brain implants of the future, which could help paralyzed patients move their arms and legs again.

The fuel cell, described in the June 12 edition of the journal PLoS ONE, strips electrons from glucose molecules to create a small electric current. The researchers, led by Rahul Sarpeshkar, an associate professor of electrical engineering and computer science at MIT, fabricated the fuel cell on a silicon chip, allowing it to be integrated with other circuits that would be needed for a brain implant. 

The idea of a glucose fuel cell is not new: In the 1970s, scientists showed they could power a pacemaker with a glucose fuel cell, but the idea was abandoned in favor of lithium-ion batteries, which could provide significantly more power per unit area than glucose fuel cells. These glucose fuel cells also utilized enzymes that proved to be impractical for long-term implantation in the body, since they eventually ceased to function efficiently.

The new twist to the MIT fuel cell described in PLoS ONE is that it is fabricated from silicon, using the same technology used to make semiconductor electronic chips. The fuel cell has no biological components: It consists of a platinum catalyst that strips electrons from glucose, mimicking the activity of cellular enzymes that break down glucose to generate ATP, the cell’s energy currency. (Platinum has a proven record of long-term biocompatibility within the body.) So far, the fuel cell can generate up to hundreds of microwatts — enough to power an ultra-low-power and clinically useful neural implant.

“It will be a few more years into the future before you see people with spinal-cord injuries receive such implantable systems in the context of standard medical care, but those are the sorts of devices you could envision powering from a glucose-based fuel cell,” says Benjamin Rapoport, a former graduate student in the Sarpeshkar lab and the first author on the new MIT study. 

Rapoport calculated that in theory, the glucose fuel cell could get all the sugar it needs from the cerebrospinal fluid (CSF) that bathes the brain and protects it from banging into the skull. There are very few cells in the CSF, so it’s highly unlikely that an implant located there would provoke an immune response. There is also significant glucose in the CSF, which does not generally get used by the body. Since only a small fraction of the available power is utilized by the glucose fuel cell, the impact on the brain’s function would likely be small.

Karim Oweiss, an associate professor of electrical engineering, computer science and neuroscience at Michigan State University, says the work is a good step toward developing implantable medical devices that don’t require external power sources.

“It’s a proof of concept that they can generate enough power to meet the requirements,” says Oweiss, adding that the next step will be to demonstrate that it can work in a living animal.

A team of researchers at Brown University, Massachusetts General Hospital and other institutions recently demonstrated that paralyzed patients could use a brain-machine interface to move a robotic arm; those implants have to be plugged into a wall outlet. 

Mimicking biology with microelectronics 

Sarpeshkar’s group is a leader in the field of ultra-low-power electronics, having pioneered such designs for cochlear implants and brain implants. “The glucose fuel cell, when combined with such ultra-low-power electronics, can enable brain implants or other implants to be completely self-powered,” says Sarpeshkar, author of the book “Ultra Low Power Bioelectronics.” This book discusses how the combination of ultra-low-power and energy-harvesting design can enable self-powered devices for medical, bio-inspired and portable applications.

Sarpeshkar’s group has worked on all aspects of implantable brain-machine interfaces and neural prosthetics, including recording from nerves, stimulating nerves, decoding nerve signals and communicating wirelessly with implants. One such neural prosthetic is designed to record electrical activity from hundreds of neurons in the brain’s motor cortex, which is responsible for controlling movement. That data is amplified and converted into a digital signal so that computers — or in the Sarpeshkar team’s work, brain-implanted microchips — can analyze it and determine which patterns of brain activity produce movement. 

The fabrication of the glucose fuel cell was done in collaboration with Jakub Kedzierski at MIT’s Lincoln Laboratory. “This collaboration with Lincoln Lab helped make a long-term goal of mine — to create glucose-powered bioelectronics — a reality,” Sarpeshkar says. Although he has just begun working on bringing ultra-low-power and medical technology to market, he cautions that glucose-powered implantable medical devices are still many years away.