Eco-friendly nanoparticles for artificial photosynthesis – Indium-based quantum dots produce clean hydrogen fuel from water and sunlight for a sustainable Energy Source

Synthetic Photo Synthesis id51165
Researchers at the University of Zurich have developed a nanoparticle type for novel use in artificial photosynthesis by adding zinc sulfide on the surface of indium-based quantum dots. These quantum dots produce clean hydrogen fuel from water and sunlight – a sustainable source of energy. They introduce new eco-friendly and powerful materials to solar photocatalysis.
Quantum dots are true all-rounders. These material structures, which are only a few nanometers in size, display a similar behavior to that of molecules or atoms, and their form, size and number of electrons can be modulated systematically. This means that their electrical and optical characteristics can be customized for a number of target areas, such as new display technologies, biomedical applications as well as photovoltaics and photocatalysis.

Fuel production using sunlight and water

Another current line of application-oriented research aims to generate hydrogen directly from water and solar light. Hydrogen, a clean and efficient energy source, can be converted into forms of fuel that are used widely, including methanol and gasoline. The most promising types of quantum dots previously used in energy research contain cadmium, which has been banned from many commodities due to its toxicity.
The team of Greta Patzke, Professor at the Department of Chemistry of the University of Zurich, and scientists from Southwest Petroleum University in Chengdu and the Chinese Academy of Sciences have now developed a new type of nanomaterials without toxic components for photocatalysis (Nature Communications“Efficient Photocatalytic Hydrogen Evolution with Ligand Engineered All-Inorganic InP and InP/ZnS Colloidal Quantum Dots”).

Indium-containing core with a thin layer of zinc sulfide

The three-nanometer particles consist of a core of indium phosphide with a very thin surrounding layer of zinc sulfide and sulfide ligands.
Schematic representation of photocatalytic hydrogen production with InP/ZnS quantum dots in a typical assay
Schematic representation of photocatalytic hydrogen production with InP/ZnS quantum dots in a typical assay. (Image: Shan Yu) (click on image to enlarge)
“Compared to the quantum dots that contain cadmium, the new composites are not only environmentally friendly, but also highly efficient when it comes to producing hydrogen from light and water,” explains Greta Patzke.
Sulfide ligands on the quantum dot surface were found to facilitate the crucial steps involved in light-driven chemical reactions, namely the efficient separation of charge carriers and their rapid transfer to the nanoparticle surface.

Great potential for eco-friendly applications

The newly developed cadmium-free nanomaterials have the potential to serve as a more eco-friendly alternative for a variety of commercial fields.
“The water-soluble and biocompatible indium-based quantum dots can in the future also be tested in terms of biomass conversion to hydrogen. Or they could be developed into low-toxic biosensors or non-linear optical materials, for example,” adds Greta Patzke.
She will continue to focus on the development of catalysts for artificial photosynthesis within the University Research Priority Program LightChEC. This interdisciplinary research program aims to develop new molecules, materials and processes for the direct storage of solar light energy in chemical bonds.
Source: University of Zurich

Cheap Catalysts turn Sunlight and Carbon Dioxide into Fuel – Sustainable & Abundant Energy

Photosynthesis NREL iStock-503352336_16x9Thanks to a new catalyst, sunlight has been converted into chemical energy with a record 13.4% efficiency.

Scientists have long dreamed of mimicking photosynthesis, by using the energy in sunlight to knit together hydrocarbon fuels from carbon dioxide (CO2) and water. Now, a cheap new chemical catalyst has carried out part of that process with record efficiency, using electricity from a solar cell to split CO2 into energy-rich carbon monoxide (CO) and oxygen. The conversion isn’t yet efficient enough to compete with fossil fuels like gasoline. But it could one day lead to methods for making essentially unlimited amounts of liquid fuels from sunlight, water, and CO2, the chief culprit in global warming.

A bright idea

A new catalyst made from copper and tin oxides uses electric current from a solar cell to split water (H2O) and carbon dioxide (CO2), creating energy-rich carbon monoxide (CO) that can be further refined into liquid fuels.


NREL I downloadThe new work is “a very nice result,” says John Turner, a renewable fuels expert at the National Renewable Energy Laboratory in Golden, Colorado.

The transformation begins when CO2 is broken down into oxygen and CO, the latter of which can be combined with hydrogen to make a variety of hydrocarbon fuels. Adding four hydrogen atoms, for example, creates methanol, a liquid fuel that can power cars. Over the last 2 decades, researchers have discovered a number of catalysts that enable that first step and split CO2 when the gas is bubbled up through water in the presence of an electric current. One of the best studied is a cheap, plentiful mix of copper and oxygen called copper oxide. The trouble is that the catalyst splits more water than it does CO2, making molecular hydrogen (H2), a less energy-rich compound, says Michael Graetzel, a chemist at the Swiss Federal Institute of Technology in Lausanne, whose group has long studied these CO2-splitting catalysts.

Last year, Marcel Schreier, one of Graetzel’s graduate students, was looking into the details of how copper oxide catalysts work. He put a layer of them on a tin oxide–based electrode, which fed electrons to a beaker containing water and dissolved CO2. Instead of splitting mostly water—like the copper oxide catalyst—the new catalyst generated almost pure CO. “It was a discovery made by serendipity,” Graetzel says.

The tin, Graetzel adds, seems to deactivate the catalytic hot spots that help split the water. As a result, almost all the electric current went into making the more desirable CO. Armed with the new insight, Graetzel’s team sought to speed up the catalyst’s work. To do so, they remade their electrode from copper oxide nanowires, which have a high surface area for carrying out the CO2-breaking reaction, and topped them with a single atom-thick layer of tin. As Graetzel’s team reports this week in Nature Energy, the strategy worked, converting 90% of the CO2 molecules into CO, with hydrogen and other byproducts making up the rest. They also hooked their setup to a solar cell and showed that a record 13.4% of the energy in the captured sunlight was converted into the CO’s chemical bonds. That’s far better than plants, which store energy with about 1% efficiency, and even tops recent hybrid approaches that combine catalysts with microbes to generate fuel.

Nate Lewis, a chemist at the California Institute of Technology in Pasadena, says the new result comes on the heels of other recent improvements that use different catalysts to turn CO2 into fuels. “Together, they show we’re making progress,” Lewis says. But he also cautions that current efforts to turn CO2into fuel remain squarely in the realm of basic research, because they can’t generate fuel at a price anywhere near to that of refining oil.

Still, exploding supplies of renewable electricity now occasionally generate more power than the grid can handle. So scientists are looking for a viable way to store the excess electricity. That’s likely to drive further progress in storing energy in chemical fuels, Graetzel says.


Posted in: DOI: 10.1126/science.aan6935

Solar Cell Consisting of a Single Molecule: Individual Protein Complex Generates Electric Current

ScienceDaily (Oct. 2, 2012) — An team of scientists, led by Joachim Reichert, Johannes Barth, and Alexander Holleitner (Technische Universitaet Muenchen, Clusters of Excellence MAP and NIM), and Itai Carmeli (Tel Aviv University) developed a method to measure photocurrents of a single functionalized photosynthetic protein system. The scientists could demonstrate that such a system can be integrated and selectively addressed in artificial photovoltaic device architectures while retaining their biomolecular functional properties.

The proteins represent light-driven, highly efficient single-molecule electron pumps that can act as current generators in nanoscale electric circuits.
 Photosystem-I (green) is optically excited by an electrode (on top). An electron then is transferred step by step in only 16 nanoseconds. (Credit: Christoph Hohmann (NIM))

The interdisciplinary team publishes the results in Nature Nanotechnologythis week.

The scientist investigated the photosystem-I reaction center which is a chlorophyll protein complex located in membranes of chloroplasts from cyanobacteria. Plants, algae and bacteria use photosynthesis to convert solar energy into chemical energy. The initial stages of this process — where light is absorbed and energy and electrons are transferred — are mediated by photosynthetic proteins composed of chlorophyll and carotenoid complexes. Until now, none of the available methods were sensitive enough to measure photocurrents generated by a single protein. Photosystem-I exhibits outstanding optoelectronic properties found only in photosynthetic systems. The nanoscale dimension further makes the photosystem-I a promising unit for applications in molecular optoelectronics.

The first challenge the physicists had to master was the development of a method to electrically contact single molecules in strong optical fields. The central element of the realized nanodevice are photosynthetic proteins self-assembled and covalently bound to a gold electrode via cysteine mutation groups. The photocurrent was measured by means of a gold-covered glass tip employed in a scanning near-field optical microscopy set-up. The photosynthetic proteins are optically excited by a photon flux guided through the tetrahedral tip that at the same time provides the electrical contact. With this technique, the physicists were able to monitor the photocurrent generated in single protein units.

The research was supported by the German Research Foundation (DFG) via the SPP 1243 (grants HO 3324/2 and RE 2592/2), the Clusters of Excellence Munich-Centre for Advanced Photonics and Nanosystems Initiative Munich, as well as ERC Advanced Grant MolArt (no. 47299).