Tag Archives: Tijana Rajh

Combining bacteriorhodopsin with semiconducting nanoparticles to generate hydrogen

Scientists at the US Argonne National Laboratory have created a hybrid bio-assisted photocatalyst according to a July 19, 2013 news item on ScienceDaily,

A protein found in the membranes of ancient microorganisms that live in desert salt flats could offer a new way of using sunlight to generate environmentally friendly hydrogen fuel, according to a new study by researchers at the U.S. Department of Energy’s Argonne National Laboratory.

Argonne nanoscientist Elena Rozhkova and her colleagues combined a pigment called bacteriorhodopsin with semiconducting nanoparticles to create a system that uses light to spark a catalytic process that creates hydrogen fuel.

Before getting to the new hybrid the story starts with nano titanium dioxide (from the July 16, 2013 Argonne National Laboratory press release, which originated the news item),

Scientists have been aware of the potential of titanium dioxide nanoparticles for light-based reactions since the early 1970s, when Japanese researchers discovered that a titanium dioxide electrode exposed to bright ultraviolet light could split water molecules in a phenomenon that came to be known as the Honda-Fujishima effect. Since then, scientists have made continuous efforts to extend the light reactivity of titanium dioxide photocatalysts into the visible part of the spectrum. The promise of these photocatalysts prompted scientists to experiment with different modifications to their basic chemistry in hope of making the reaction more efficient, Rozhkova said.

“Titanium dioxide alone reacts with ultraviolet light, but not with visible light, so we used biological photoreactive molecules as a building block to create a hybrid system that could use visible light efficiently,” Rozhkova said.

Rozhkova and her colleagues turned to bacteriorhodopsin – which is responsible for the unusual purple color of a number of salt flats in California and Nevada – because it uses sunlight as an energy source that allows it to act as a “proton pump.”  Proton pumps are proteins that typically straddle a cellular membrane and transfer protons from inside the cell to the extracellular space.

Here’s an image of the purple membrane caused by bacteriorhodopsin (from University of Bari [Italy] Professor Angela Correlli’s webpage of Photorecptors and Olfactory Receptors,

Bacteriorhodopsin is the only protein of purple membranes, which contains few different lipids. [downloaded from the University of Bari: http://www.biologia.uniba.it/fisiologia/corcelli/en/ric2.html]

Bacteriorhodopsin is the only protein of purple membranes, which contains few different lipids. [downloaded from the University of Bari: http://www.biologia.uniba.it/fisiologia/corcelli/en/ric2.html]

The press release goes on to describe the hybrid system,

In the Argonne system, the protons provided by the bacteriorhodopsin are combined with free electrons at small platinum sites interspersed in the titanium dioxide matrix. “The platinum nanoparticles are essential for creating a distinct spot for the production of the hydrogen molecule,” said Peng Wang, an Argonne postdoctoral researcher in Rozhkova’s group at Argonne’s Center for Nanoscale Materials.

“It is interesting that in biology, bacteriorhodopsin does not naturally participate in these kind of reactions,” Rozhkova said. “Its natural function really doesn’t have much to do at all with creating hydrogen. But as part of this hybrid, it helps make hydrogen under white light and at environmentally friendly conditions.”

This bio-assisted hybrid photocatalyst outperforms many other similar systems in hydrogen generation and could be a good candidate for fabrication of green energy devices that consume virtually infinite sources — salt water and sunlight.

You can find the published paper with the link below,

High-Performance Bioassisted Nanophotocatalyst for Hydrogen Production by Shankar Balasubramanian, Peng Wang, Richard D. Schaller, Tijana Rajh, and Elena A. Rozhkova. Nano Lett., 2013, 13 (7), pp 3365–3371 DOI: 10.1021/nl4016655 Publication Date (Web): June 19, 2013
Copyright © 2013 American Chemical Society

The paper is behind a paywall.

*The head for this posting was corrected from Combining bacteriorhodopsin with semiconduction nanopartcles to generate hydrogen to Combining bacteriorhodopsin with semiconductor nanoparticles to generate hydrogen on July 22, 2013 at 3:03 pm PDT.

** I changed the head for this posting again from ‘semiconductor’ to ‘semiconducting’ on July 23, 2013 at 6:50 am PDT.

Self-assembling chains of nanoparticles

The Argonne National Laboratory (US) has announced that their researchers have for the first time watched nanoparticles assemble into chains in real-time. From the Apr. 20, 2013 news item on Nanowerk (Note: Links have been removed),

In a new study performed at the Center for Nanoscale Materials at the U.S. Department of Energy’s (DOE) Argonne National Laboratory, researchers have for the first time seen the self-assembly of nanoparticle chains in situ, that is, in place as it occurs in real-time (“In Situ Visualization of Self-Assembly of Charged Gold Nanoparticles”).

The Apr. 19, 2013 Argonne National Laboratory press release by Jared Sagoff, which originated the news item, provides more detail,

The scientists exposed a tiny liquid “cell” or pouch that contained gold nanoparticles covered with a positively charged coating to an intense beam of electrons generated with a transmission electron microscope. Some of the electrons that penetrated the outside of the cell became trapped in the fluid medium in the cell. These “hydrated” electrons attracted the positively charged nanoparticles, which in time reduced the intensity of charge of the positive coating.

As the hydrated electrons reduced the coating’s positive charge, the nanoparticles no longer repelled each other as strongly.  Instead, their newfound relative attraction led the nanoparticles to “jump around” and eventually stick together in long chains. This self-assembly of nanoparticle chains had been detected before in different studies, but this technique allowed researchers, for the first time, to observe the phenomenon as it occurred.

“The moment-to-moment behavior of nanoparticles is something that’s not yet entirely understood by the scientific community,” said Argonne nanoscientist Yuzi Liu, the study’s lead author. “The potential of nanoparticles in all sorts of different applications and devices – from tiny machines to harvesters of new sources of energy – requires us to bring all of our resources to bear to look at how they function on the most basic physical levels.”

Self-assembly is particularly interesting to scientists because it could lead to new materials that could be used to develop new, energy-relevant technologies. “When we look at self-assembly, we’re looking to use nature as a springboard into man-made materials,” said Argonne nanoscientist Tijana Rajh, who directed the group that carried out the study.

Because the particles under study were so tiny – just a few dozen nanometers in diameter – an optical microscope would not have been able to resolve, or see, individual nanoparticles. By using the liquid cell in the transmission electron microscope at the Center for Nanoscale Materials, Liu and his colleagues could create short movies showing the quick movement of the nanoparticles as their coatings contacted the hydrated electrons.

Here’s a video of the self-assembling nanoparticles, provided by the Argonne National Laboratory,

Here’s a link to and citation for the paper,

In Situ Visualization of Self-Assembly of Charged Gold Nanoparticles by Yuzi Liu, Xiao-Min Lin, Yugang Sun, and Tijana Rajh. J. Am. Chem. Soc., [Journal of the American Chemical Socieyt] 2013, 135 (10), pp 3764–3767
DOI: 10.1021/ja312620e Publication Date (Web): February 22, 2013
Copyright © 2013 American Chemical Society

 

Gold nanoparticle self-assembly visualization at the Argonne National Laboratory (US)

There’s a Mar. 13, 2013 news item on phys.org which seems to have been written by someone who’s very technical,

The self-assembly of gold nanoparticles (Au NPs) coated with specific organic ions in water was observed by Center for Nanoscale Materials staff in the Nanobio Interfaces, Electronic & Magnetic Materials & Devices, and Nanophotonics groups at the Argonne National Laboratory using in situ transmission electron microscopy (TEM) equipped with a liquid cell. The Au NPs formed one-dimensional chains within a few minutes.

The originating March 2013 article is on an Argonne National Laboratory’s Center for Nanoscale Materials page,

The self-assembly of NPs attracts intense attention for its potential application in the fabrication of hybrid systems with collective properties from different types of materials. The observations provided here clearly elucidate the complex mechanism of charged NP self-assembly processes. They also paint a cautionary tale on using TEM in situ cells to imitate self-assembly processes in actual solution environments. [emphasis mine]

The hydrated electrons formed in radiolysis of water decrease the overall positive charge of cetyltrimethylammonium (CTA)-coated Au NPs. The NPs also were coated with negative citrate ions. (With citrate alone, however, the Au NPs remained steady in the liquid cell regardless of electron-beam intensity). The anisotropic attractive interactions, including dipolar and Van der Waals interactions, overcome the repulsion among the NPs and induce the assembly of NPs. The spatial segregation of different sizes of NPs as a result of electric field gradients within the cell was observed as well.

I’m not sure why the observations paint a cautionary tale. Perhaps a reader could enlighten me?

The researchers also provided an image,

Cetyltrimethylammonium-ion-coated gold nanoparticles before (top) and after (bottom) 500 seconds of electron-beam exposure inside a TEM liquid cell at 200 kV. Scale bar: 100 nm. [downloaded from http://nano.anl.gov/news/highlights/2013_gold_nanoparticles.html]

Cetyltrimethylammonium-ion-coated gold nanoparticles before (top) and after (bottom) 500 seconds of electron-beam exposure inside a TEM liquid cell at 200 kV. Scale bar: 100 nm. [downloaded from http://nano.anl.gov/news/highlights/2013_gold_nanoparticles.html]

For anyone who can understand the technical explanations, here’s a citation and a link to the research paper,

In Situ Visualization of Self-Assembly of Charged Gold Nanoparticles by Yuzi Liu, Xiao-Min Lin, Yugang Sun, and Tijana Rajh. J. Am. Chem. Soc., 2013, 135 (10), pp 3764–3767 DOI: 10.1021/ja312620e Publication Date (Web): February 22, 2013

Copyright © 2013 American Chemical Society

The paper is behind a paywall.