Tag Archives: transmission electron microscope

Astonishing observation about gold nanoparticles and self-assembly

An Aug. 4, 2014 news item on ScienceDaily features research on self-assembling gold nanoparticles from Helmholtz-Zentrum Berlin für Materialien und Energie (HZB) and Humboldt-Universität zu Berlin (HU, Berlin),

Researchers at HZB in co-operation with Humboldt-Universität zu Berlin (HU, Berlin) have made an astonishing observation: they were investigating the formation of gold nanoparticles in a solvent and observed that the nanoparticles had not distributed themselves uniformly, but instead were self-assembled into small clusters.

An Aug. 4, 2014 HZB press release (also on EurekAlert), which originated the news item, provides additional technical information about the equipment used to make the observations,

This was determined using Small-Angle X-ray Scattering (SAXS) at BESSY II. A thorough examination with an [a transmission] electron microscope (TEM) confirmed their result. “The research on this phenomenon is now proceeding because we are convinced that such nanoclusters lend themselves as catalysts, whether in fuel cells, in photocatalytic water splitting, or for other important reactions in chemical engineering”, explains Dr. Armin Hoell of HZB. The results have just appeared in two peer reviewed international academic journals.

“What is special about the new process is that it is extremely simple and works with an environmentally friendly and inexpensive solvent”, explains Professor Klaus Rademann from HU Berlin. The solvent actually consists of two powders that one would sooner expect to find in agriculture that in a research laboratory: a supplement in chicken feed (choline chloride, aka vitamin B), and urea. British colleagues discovered a few years ago that mixing the two powders forms a transparent liquid able to dissolve metal oxides and heavy metals, called deep eutectic solvent (DES). The researchers in Berlin then positioned above the solvent gold foil that they could bombard with ions of noble gas in order to detach individual atoms of gold. This is how nanoparticles initially formed that distributed themselves in the solvent.

The researchers did not expect what happened next (from the press release),

The longer the bombardment (sputtering) of the gold foil lasted, the larger the nanoparticles could become, the scientists reasoned. However, this was not the case: the particles ceased growing at five nanometres. Instead, an increasing number of nanoparticles formed over longer sputtering times. The second surprise: these nanoparticles did not distribute themselves uniformly in the liquid, but instead self-assembled into small groups or clusters that could consist of up to twelve nanoparticles.

These kinds of observations cannot be easily made under a microscope, of course, but require instead an indirect, statistical approach: “Using small-angle X-ray scattering at BESSY II, we were not only able to ascertain that the nanoparticles are all around five nanometres in diameter, but also measure what the separations between them are. From these measurements, we found the nanoparticles arrange themselves into clusters”, explains Hoell.

“We ran computer models in advance of how the nanoparticles could distribute themselves in the solution to better understand the measurement results, and then compared the results of the simulation with the results of the small-angle X-ray scattering”, explains Dr. Vikram Singh Raghuwanshi, who works as a postdoc at HU Berlin as well as HZB. An image from the cryogenic transmission electron microscope that colleagues at HU prepared confirmed their findings. “But we could not have achieved this result using only electron microscopy, since it can only display details and sections of the specimen”, Hoell emphasised. “Small-angle X-ray scattering is indispensable for measuring general trends and averages!”

The press release concludes thusly,

It is obvious to the researchers that the special DES-solvent plays an important role in this self-organising process: various interactions between the ions of the solvent and the particles of gold result firstly in the nanoparticles reaching only a few thousand atoms in size, and secondly that they mutually attract somewhat – but only weakly – so that the small clusters arise. “We know, however, that these kinds of small clusters of nanoparticles are especially effective as catalysts for chemical reactions we want: a many-fold increase in the reaction speed due only to particle arrangement has already been demonstrated”, says Rademann.

Here are links to and citations for the two papers the team has published on their latest work,

Deep Eutectic Solvents for the Self-Assembly of Gold Nanoparticles: A SAXS, UV–Vis, and TEM Investigation by Vikram Singh Raghuwanshi, Miguel Ochmann, Armin Hoell, Frank Polzer, and Klaus Rademann. Langmuir, 2014, 30 (21), pp 6038–6046 DOI: 10.1021/la500979p Publication Date (Web): May 11, 2014

Copyright © 2014 American Chemical Society

Self-assembly of gold nanoparticles on deep eutectic solvent (DES) surfaces by V. S. Raghuwanshi, M. Ochmann, F. Polzer, A. Hoell and K. Rademann.  Chem. Commun., 2014,50, 8693-8696 DOI: 10.1039/C4CC02588A
First published online 10 Jun 2014

Both papers are behind a paywall.

This research is being presented at two conferences, one of which is taking place now (Aug.5, 2014; from the press release),

Dr. Raghuwanshi will give a talk on these results, as well as providing a preview of the catalysis research approaches now planned, at the International conference, IUCr2014, taking place from 5-12 August 2014 in Montreal, Canada.

In the coming year, HZB will incidentally be one of the hosts of the 16th International Small-Angle Scattering Conference, SAS2015.

There you have all the news.

Canada’s National Institute of Nanotechnology gets first Hitachi H-95000 microscope outside of Japan

Canada’s National Institute of Nanotechnology (NINT) has just opened a facility (which was mentioned as a future project in my July 20, 2009 posting) with three new Hitachi microscopes in a $15M funding partnership. From the July 13, 2011 article by Dave Cooper for the Edmonton Journal,

The Hitachi Electron Microscopy Products Centre [HEMiC; Note: This was formerly called the Hitachi Electron Microscopy Products Development Centre] at NINT opened Tuesday, a $15-million partnership between the federal and provincial governments and Hitachi, that marks the entry of Edmonton as the North American microscope leader.

One of the three new machines -the H-9500 environmental transmission electron microscope -is so new it is only the second in the world after one at a Toyota research centre in Japan.

“This technology suite (of three new microscopes) has enabled Alberta and Canada to establish a centre that will be the leading edge of nanotechnology research and development for many years to come,” Hidehito Obayashi, chairman of Hitachi High Technologies, said Tuesday.

I found some more information about the H-9500 microscope in this July 13, 2011 news item on Nanowerk,

The Hitachi H-9500 Environmental transmission electron microscope (ETEM) can study in-situ chemical reactions of samples in liquids and gases. It will offer a very low background pressure (in the 10-8 torr region) ensuring low sample contamination rate and low effect of background gases on the in-situ experiment. Its capabilities include the possibility to heat the sample to temperatures exceeding 1500° C while exposed to various gases or study liquid samples at temperatures exceeding 300° C. The analytical capabilities of the instrument include electron energy loss spectroscopy and energy dispersive X-ray spectrometry for chemical analysis. This instrument offers standard TEM imaging and diffraction capabilities allowing the investigation of sample structure and morphology.

As for the HEMiC facility (more from the news item on Nanowerk),

HEMiC will have two streams of activity: the provision of a wide range of electron microscopy services to industrial and academic clients; and a research collaboration between NINT and Hitachi researchers that will develop new electron microscope tools and techniques. The Centre will also be a Hitachi reference site, allowing Hitachi to showcase its latest microscopes, giving potential clients from North America an opportunity to gain hands-on experience with new instruments and techniques before buying.

I have mused on this before but I really do wonder what happens when there’s a scheduling conflict between research interests and commercial interests. In other words, what happens when you need to use the microscope for research purposes at the same time the sales people want to show it to potential customers? What is the protocol and who decides?