Tag Archives: Vinayak P. Dravid

Sponge coated with nanoparticles removes lead from water

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It doesn’t look like much but who cares when it does the job and is being made available commercially,

Caption: Commercially available cellulose sponge coated in manganese-doped goethite nanoparticles. Credit: Caroline Harms/Northwestern University

A May 11, 2023 news item on Nanowerk announces the research,

Northwestern University engineers have developed a new sponge that can remove metals — including toxic heavy metals like lead and critical metals like cobalt — from contaminated water, leaving safe, drinkable water behind.

In proof-of-concept experiments, the researchers tested their new sponge on a highly contaminated sample of tap water, containing more than 1 part per million of lead. With one use, the sponge filtered lead to below detectable levels.

After using the sponge, researchers also were able to successfully recover metals and reuse the sponge for multiple cycles. The new sponge shows promise for future use as an inexpensive, easy-to-use tool in home water filters or large-scale environmental remediation efforts.

…

A May 10, 2023 Northwestern University news release on EurekAlert (also received via email) provides more detail, Note: Links have been removed,

The study was published late yesterday (May 10 [2023]) in the journal ACS ES&T Water. The paper outlines the new research and sets design rules for optimizing similar platforms for removing — and recovering — other heavy-metal toxins, including cadmium, arsenic, cobalt and chromium.

“The presence of heavy metals in the water supply is an enormous public health challenge for the entire globe,” said Northwestern’s Vinayak Dravid, senior author of the study. “It is a gigaton problem that requires solutions that can be deployed easily, effectively and inexpensively. That’s where our sponge comes in. It can remove the pollution and then be used again and again.”

Dravid is the Abraham Harris Professor of Materials Science and Engineering at Northwestern’s McCormick School of Engineering and director of global initiatives at the International Institute for Nanotechnology.

Sopping up spills

The project builds on Dravid’s previous work to develop highly porous sponges for various aspects of environmental remediation. In May 2020, his team unveiled a new sponge designed to clean up oil spills. [Note: My June 25, 2020 posting highlights the work and includes an embedded video demonstration of the technology.] The nanoparticle-coated sponge, which is now being commercialized by Northwestern spinoff MFNS Tech, offers a more efficient, economic, ecofriendly and reusable alternative to current approaches to oil spills.

But Dravid knew it wasn’t enough.

“When there is an oil spill, you can remove the oil,” he said. “But there also are toxic heavy metals — like mercury, cadmium, sulfur and lead — in those spills. So, even when you remove the oil, some of the other toxins might remain.

Rinse and repeat

To tackle this aspect of the issue, Dravid’s team, again, turned to sponges coated with an ultrathin layer of nanoparticles. After testing many different types of nanoparticles, the team found that a manganese-doped goethite coating worked best. Not only are manganese-doped goethite nanoparticles inexpensive to make, easily available and nontoxic to human, they also have the properties necessary to selectively remediate heavy metals.

“You want a material with a high surface area, so there’s more room for the lead ions to stick to it,” said Benjamin Shindel, a Ph.D. student in Dravid’s lab and the paper’s first author. “These nanoparticles have high-surface areas and abundant reactive surface sites for adsorption and are stable, so they can be reused many times.”

The team synthesized slurries of manganese-doped goethite nanoparticles, as well as several other compositions of nanoparticles, and coated commercially available cellulose sponges with these slurries. Then, they rinsed the coated sponges with water in order to wash away any loose particles. The final coatings measured just tens of nanometers in thickness.

When submerged into contaminated water, the nanoparticle-coated sponge effectively sequested lead ions. The U.S. Food and Drug Administration requires that bottled drinking water is below 5 parts per billion of lead. In filtration trials, the sponge lowered the amount of lead to approximately 2 parts per billion, making it safe to drink.

“We’re really happy with that,” Shindel said. “Of course, this performance can vary based on several factors. For instance, if you have a large sponge in a tiny volume of water, it will perform better than a tiny sponge in a huge lake.”

Recovery bypasses mining

From there, the team rinsed the sponge with mildly acidified water, which Shindel likened to “having the same acidity of lemonade.” The acidic solution caused the sponge to release the lead ions and be ready for another use. Although the sponge’s performance declined after the first use, it still recovered more than 90% of the ions during subsequent use cycles.

This ability to gather and then recover heavy metals is particularly valuable for removing rare, critical metals, such as cobalt, from water sources. A common ingredient in lithium-ion batteries, cobalt is energetically expensive to mine and accompanied by a laundry list of environmental and human costs.

If researchers could develop a sponge that selectively removes rare metals, including cobalt, from water, then those metals could be recycled into products like batteries.

“For renewable energy technologies, like batteries and fuel cells, there is a need for metal recovery,” Dravid said. “Otherwise, there is not enough cobalt in the world for the growing number of batteries. We must find ways to recover metals from very dilute solutions. Otherwise, it becomes poisonous and toxic, just sitting there in the water. We might as well make something valuable with it.”

Standardized scale

As a part of the study, Dravid and his team set new design rules to help others develop tools to target particular metals, including cobalt. Specifically, they pinpointed which low-cost and nontoxic nanoparticles also have high-surface areas and affinities for sticking to metal ions. They studied the performance of coatings of manganese, iron, aluminum and zinc oxides on lead adsorption. Then, they established relationships between the structures of these nanoparticles and their adsorptive properties.

Called Nanomaterial Sponge Coatings for Heavy Metals (or “Nano-SCHeMe”), the environmental remediation platform can help other researchers differentiate which nanomaterials are best suited for particular applications.

“I’ve read a lot of literature that compares different coatings and adsorbents,” said Caroline Harms, an undergraduate student in Dravid’s lab and paper co-author. “There really is a lack of standardization in the field. By analyzing different types of nanoparticles, we developed a comparative scale that actually works for all of them. It could have a lot of implications in moving the field forward.”

Dravid and his team imagine that their sponge could be used in commercial water filters, for environmental clean-up or as an added step in water reclamation and treatment facilities.

“This work may be pertinent to water quality issues both locally and globally,” Shindel said. “We want to see this out in the world, where it can make a real impact.”

The study, “Nano-SCHeME: Nanomaterial Sponge Coatings for Heavy Metals, an environmental remediation platform,” was supported by the National Science Foundation and U.S. Department of Energy.

Editor’s note: Dravid and Northwestern have financial interests (equities, royalties) in MFNS Tech.

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

Nano-SCHeme: Nanomaterial Sponge Coatings for Heavy Metals, an Environmental Remediation Platform by Benjamin Shindel, Stephanie M. Ribet, Caroline Harms, Vikas Nandwana, and Vinayak P. Dravid. ACS EST Water 2023, XXXX, XXX, XXX-XXX DOI: https://doi.org/10.1021/acsestwater.2c00646 Publication Date:May 10, 2023 © 2023 American Chemical Society

This paper is behind a paywall.

You can find the MFNS Tech website here.

Alloy nanoparticles make better catalysts

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A Jan. 4, 2021 news item on Nanowerk describes new insights into nanoscale catalysts derived from work at the US Argonne National Laboratory,

Catalysts are integral to countless aspects of modern society. By speeding up important chemical reactions, catalysts support industrial manufacturing and reduce harmful emissions. They also increase efficiency in chemical processes for applications ranging from batteries and transportation to beer and laundry detergent.

As significant as catalysts are, the way they work is often a mystery to scientists. Understanding catalytic processes can help scientists develop more efficient and cost-effective catalysts. In a recent study, scientists from University of Illinois Chicago (UIC) and the U.S. Department of Energy’s (DOE) Argonne National Laboratory discovered that, during a chemical reaction that often quickly degrades catalytic materials, a certain type of catalyst displays exceptionally high stability and durability.

The catalysts in this study are alloy nanoparticles, or nanosized particles made up of multiple metallic elements, such as cobalt, nickel, copper and platinum. These nanoparticles could have multiple practical applications, including water-splitting to generate hydrogen in fuel cells; reduction of carbon dioxide by capturing and converting it into useful materials like methanol; more efficient reactions in biosensors to detect substances in the body; and solar cells that produce heat, electricity and fuel more effectively.

…

A January 4, 2021 Argonne National Laboratory news release (also on EurekAlert) by Savannah Mitchem fills in some details,

In this study, the scientists investigated “high-entropy” (highly stable) alloy nanoparticles. The team of researchers, led by Reza Shahbazian-Yassar at UIC, used Argonne’s Center for Nanoscale Materials (CNM), a DOE Office of Science user facility, to characterize the particles’ compositions during oxidation, a process that degrades the material and reduces its usefulness in catalytic reactions.

“Using gas flow transmission electron microscopy (TEM) at CNM, we can capture the whole oxidation process in real time and at very high resolution,” said scientist Bob Song from UIC, a lead scientist on the study. “We found that the high-entropy alloy nanoparticles are able to resist oxidation much better than general metal particles.”

To perform the TEM, the scientists embedded the nanoparticles into a silicon nitride membrane and flowed different types of gas through a channel over the particles. A beam of electrons probed the reactions between the particles and the gas, revealing the low rate of oxidation and the migration of certain metals — iron, cobalt, nickel and copper — to the particles’ surfaces during the process.

“Our objective was to understand how fast high-entropy materials react with oxygen and how the chemistry of nanoparticles evolves during such a reaction,” said Shahbazian-Yassar, UIC professor of mechanical and industrial engineering at the College of Engineering.

According to Shahbazian-Yassar, the discoveries made in this research could benefit many energy storage and conversion technologies, such as fuel cells, lithium-air batteries, supercapacitors and catalyst materials. The nanoparticles could also be used to develop corrosion-resistant and high-temperature materials.

“This was a successful showcase of how CNM’s capabilities and services can meet the needs of our collaborators,” said Argonne’s Yuzi Liu, a scientist at CNM. “We have state-of-the-art facilities, and we want to deliver state-of-the-art science as well.”

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

In Situ Oxidation Studies of High-Entropy Alloy Nanoparticles by Boao Song, Yong Yang, Muztoba Rabbani, Timothy T. Yang, Kun He, Xiaobing Hu, Yifei Yuan, Pankaj Ghildiyal, Vinayak P. Dravid, Michael R. Zachariah, Wissam A. Saidi, Yuzi Liu, and Reza Shahbazian-Yassar. ACS Nano 2020, 14, 11, 15131–15143 DOI: https://doi.org/10.1021/acsnano.0c05250 Publication Date:October 20, 2020 Copyright © 2020 American Chemical Society

This paper is behind a paywall.

Below is one of my favourite types of video work, a ‘blob video’ from the University of Illinois showing the alloy nanoparticles as they oxidate,

Video of transmission electron microscopy, performed at Argonne’s CNM, showing the oxidation of high-entropy nanoparticles in air at 400 °C, sped up by a factor of four. The oxidation process is depicted by the dissolution of the edges of the nanoparticles in the video. (Image by University of Illinois.)

Clean up oil spills with a smart sponge?

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I love the part with the magnet,

All of the main points are made in the video but for those who like text, there’s a May 28, 2020 news item on phys.org describing this new smart sponge for cleaning up oil spills (Note: Links have been removed),

A Northwestern University-led [Chicago, Illinois, US] team has developed a highly porous smart sponge that selectively soaks up oil in water.

With an ability to absorb more than 30 times its weight in oil, the sponge could be used to inexpensively and efficiently clean up oil spills without harming marine life. After squeezing the oil out of the sponge, it can be reused many dozens of times without losing its effectiveness.

“Oil spills have devastating and immediate effects on the environment, human health and economy,” said Northwestern’s Vinayak Dravid, who led the research. “Although many spills are small and may not make the evening news, they are still profoundly invasive to the ecosystem and surrounding community. Our sponge can remediate these spills in a more economic, efficient and eco-friendly manner than any of the current state-of-the-art solutions.”

A May 28, 2020 Northwestern University news release (also on EurekAlert), which originated the news item, reveals (as did the video) the characteristics that make this smart sponge particularly interesting,

Oil spill clean-up is an expensive and complicated process that often harms marine life and further damages the environment. Currently used solutions include burning the oil, using chemical dispersants to breakdown oil into very small droplets, skimming oil floating on top of water and/or absorbing it with expensive, unrecyclable sorbents.

“Each approach has its own drawbacks and none are sustainable solutions,” Nandwana [Vikas Nandwana, a senior research associate in Dravid’s laboratory] said. “Burning increases carbon emissions and dispersants are terribly harmful for marine wildlife. Skimmers don’t work in rough waters or with thin layers of oil. And sorbents are not only expensive, but they generate a huge amount of physical waste — similar to the diaper landfill issue.”

The Northwestern solution bypasses these challenges by selectively absorbing oil and leaving clean water and unaffected marine life behind. The secret lies in a nanocomposite coating of magnetic nanostructures and a carbon-based substrate that is oleophilic (attracts oil), hydrophobic (resists water) and magnetic. The nanocomposite’s nanoporous 3D structure selectively interacts with and binds to the oil molecules, capturing and storing the oil until it is squeezed out. The magnetic nanostructures give the smart sponge two additional functionalities: controlled movement in the presence of an external magnetic field and desorption of adsorbed components, such as oil, in a simulated and remote manner.

The OHM (oleophilic hydrophobic magnetic) nanocomposite slurry can be used to coat any cheap, commercially available sponge. The researchers applied a thin coating of the slurry to the sponge, squeezed out the excess and let it dry. The sponge is quickly and easily converted into a smart sponge (or “OHM sponge”) with a selective affinity for oil.

Vinayak and his team tested the OHM sponge with many different types of crude oils of varying density and viscosity. The OHM sponge consistently absorbed up to 30 times its weight in oil, leaving the water behind. To mimic natural waves, researchers put the OHM sponge on a shaker submerged in water. Even after vigorous shaking, the sponge release less than 1% of its absorbed oil back into the water.

“Our sponge works effectively in diverse and extreme aquatic conditions that have different pH and salinity levels,” Dravid said. “We believe we can address a giga-ton problem with a nanoscale solution.”

“We are excited to introduce such smart sponges as an environmental remediation platform for selectively removing and recovering pollutants present in water, soil and air, such as excess nutrients, heavy metal contaminants, VOC/toxins and others,” Nandwana said. “The nanostructure coating can be tailored to selectively adsorb (and later desorb) these pollutants.”

The team also is working on another grade of OHM sponge that can selectively absorb (and later recover) excess dissolved nutrients, such as phosphates, from fertilizer runoff and agricultural pollution. Stephanie Ribet, a Ph.D. candidate in Dravid’s lab and paper coauthor is pursuing this topic. The team plans to develop and commercialize OHM technology for environmental clean-up.

Bravo to professor Vinayak Dravid and his team. I’m sure I’m not alone in wishing you and your team the best of luck as you continue to develop this remediation technology.

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

OHM Sponge: A Versatile, Efficient, and Ecofriendly Environmental Remediation Platform by Vikas Nandwana, Stephanie M. Ribet, Roberto D. Reis, Yuyao Kuang, Yash More, and Vinayak P. Dravid. Ind. Eng. Chem. Res. 2020, XXXX, XXX, XXX-XXX DOI: https://doi.org/10.1021/acs.iecr.0c01493 Publication Date:May 12, 2020 Copyright © 2020 American Chemical Society

This paper is behind a paywall.

Cloaking devices made from DNA and gold nanoparticles using top-down lithography

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This new technique seems promising but there’ve been a lot of ‘cloaking’ devices announced in the years I’ve been blogging and, in all likelihood, I was late to the party so I’m exercising a little caution before getting too excited. For the latest development in cloaking devices, there’s a January 18, 2018 news item on Nanowerk,

Northwestern University researchers have developed a first-of-its-kind technique for creating entirely new classes of optical materials and devices that could lead to light bending and cloaking devices — news to make the ears of Star Trek’s Spock perk up.

Using DNA [deoxyribonucleic acid] as a key tool, the interdisciplinary team took gold nanoparticles of different sizes and shapes and arranged them in two and three dimensions to form optically active superlattices. Structures with specific configurations could be programmed through choice of particle type and both DNA-pattern and sequence to exhibit almost any color across the visible spectrum, the scientists report.

A January 18, 2018 Northwestern University news release (also on EurekAlert) by Megan Fellman, which originated the news item, delves into more detail (Note: Links have been removed),

“Architecture is everything when designing new materials, and we now have a new way to precisely control particle architectures over large areas,” said Chad A. Mirkin, the George B. Rathmann Professor of Chemistry in the Weinberg College of Arts and Sciences at Northwestern. “Chemists and physicists will be able to build an almost infinite number of new structures with all sorts of interesting properties. These structures cannot be made by any known technique.”

The technique combines an old fabrication method — top-down lithography, the same method used to make computer chips — with a new one — programmable self-assembly driven by DNA. The Northwestern team is the first to combine the two to achieve individual particle control in three dimensions.

The study was published online by the journal Science today (Jan. 18). Mirkin and Vinayak P. Dravid and Koray Aydin, both professors in Northwestern’s McCormick School of Engineering, are co-corresponding authors.

Scientists will be able to use the powerful and flexible technique to build metamaterials — materials not found in nature — for a range of applications including sensors for medical and environmental uses.

The researchers used a combination of numerical simulations and optical spectroscopy techniques to identify particular nanoparticle superlattices that absorb specific wavelengths of visible light. The DNA-modified nanoparticles — gold in this case — are positioned on a pre-patterned template made of complementary DNA. Stacks of structures can be made by introducing a second and then a third DNA-modified particle with DNA that is complementary to the subsequent layers.

In addition to being unusual architectures, these materials are stimuli-responsive: the DNA strands that hold them together change in length when exposed to new environments, such as solutions of ethanol that vary in concentration. The change in DNA length, the researchers found, resulted in a change of color from black to red to green, providing extreme tunability of optical properties.

“Tuning the optical properties of metamaterials is a significant challenge, and our study achieves one of the highest tunability ranges achieved to date in optical metamaterials,” said Aydin, assistant professor of electrical engineering and computer science at McCormick.

“Our novel metamaterial platform — enabled by precise and extreme control of gold nanoparticle shape, size and spacing — holds significant promise for next-generation optical metamaterials and metasurfaces,” Aydin said.

The study describes a new way to organize nanoparticles in two and three dimensions. The researchers used lithography methods to drill tiny holes — only one nanoparticle wide — in a polymer resist, creating “landing pads” for nanoparticle components modified with strands of DNA. The landing pads are essential, Mirkin said, since they keep the structures that are grown vertical.

The nanoscopic landing pads are modified with one sequence of DNA, and the gold nanoparticles are modified with complementary DNA. By alternating nanoparticles with complementary DNA, the researchers built nanoparticle stacks with tremendous positional control and over a large area. The particles can be different sizes and shapes (spheres, cubes and disks, for example).

“This approach can be used to build periodic lattices from optically active particles, such as gold, silver and any other material that can be modified with DNA, with extraordinary nanoscale precision,” said Mirkin, director of Northwestern’s International Institute for Nanotechnology.

Mirkin also is a professor of medicine at Northwestern University Feinberg School of Medicine and professor of chemical and biological engineering, biomedical engineering and materials science and engineering in the McCormick School.

The success of the reported DNA programmable assembly required expertise with hybrid (soft-hard) materials and exquisite nanopatterning and lithographic capabilities to achieve the requisite spatial resolution, definition and fidelity across large substrate areas. The project team turned to Dravid, a longtime collaborator of Mirkin’s who specializes in nanopatterning, advanced microscopy and characterization of soft, hard and hybrid nanostructures.

Dravid contributed his expertise and assisted in designing the nanopatterning and lithography strategy and the associated characterization of the new exotic structures. He is the Abraham Harris Professor of Materials Science and Engineering in McCormick and the founding director of the NUANCE center, which houses the advanced patterning, lithography and characterization used in the DNA-programmed structures.

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

Building superlattices from individual nanoparticles via template-confined DNA-mediated assembly by Qing-Yuan Lin, Jarad A. Mason, Zhongyang, Wenjie Zhou, Matthew N. O’Brien, Keith A. Brown, Matthew R. Jones, Serkan Butun, Byeongdu Lee, Vinayak P. Dravid, Koray Aydin, Chad A. Mirkin. Science 18 Jan 2018: eaaq0591 DOI: 10.1126/science.aaq0591

This paper is behind a paywall.

As noted earlier, it could be a while before cloaking devices are made available. In the meantime, you may find this image inspiring,

Caption: Northwestern University researchers have developed a new method to precisely arrange nanoparticles of different sizes and shapes in two and three dimensions, resulting in optically active superlattices. Credit: Northwestern University

The reason the findings in a popular thermoelectricity paper can’t be replicated

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It seems to me that over the last few years there’s been a lot more discussion about errors in science. There have always been scandals but this public interest in reproducibility of scientific results seems relatively new. In any event, a Nov. 17, 2016 news item on Nanowerk highlights research that explains why scientists have been unable to reproduce results of an influential 2014 paper (Note: A link has been removed),

A team of physicists in Clemson University’s College of Science and Academia Sinica in Taiwan has determined why other scientists have been unable to replicate a highly influential thermoelectricity study published in a prestigious, peer-reviewed journal.

In the April 2014 issue of the journal Nature (“Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals”), a group of scientists described an emerging crystalline material made of tin selenide that provided the highest efficiency ever recorded for thermoelectricity, the process of capturing wasted energy which is released as heat and making it available again as electricity. The paper has been viewed 45,000 times and its findings have been referenced in 600 subsequent studies, according to Google Scholar.

A thermoelectricity (TE) module captures waste energy, released as heat, converts it to electricity and returns it to a device. Image Credit: Thomas Masservy, Clemson University

There appears to have been a mistake in the original research. A Nov. 17, 2016 Clemson University news release, which originated the news item, expands on the theme (Note: A link has been removed),

“If it were true, basically, they would have found a crown jewel,” said Apparao Rao, the Robert A. Bowen professor of Physics and the director of the Clemson Nanomaterials Institute.

On Nov. 3, 2016, Nature ran a brief communication by the Clemson-Sinica team explaining why the 2014 data could not be replicated.

Thermoelectricity could provide enormous monetary and environmental savings because it is sustainable; instead of requiring fuel it continually captures wasted heat energy and puts it to use. And there’s a lot of wasted energy; about 70 percent in most machines, including cars.

“When your laptop gets hot, energy is released as waste heat because it doesn’t use all the supplied electricity. Machines have limited efficiency,” according to Ramakrishna Podila, assistant professor of physics and astronomy at Clemson who co-authored the paper solving the mystery.

But, so far, the perfect material for capturing and creating thermoelectricity has proven elusive.

Heat and electrical current can flow through any material when heat is applied to one side. But to efficiently harness thermoelectricity, the material has to trap heat on one side while letting the current flow. The difference in temperature, from one side to the other, generates energy.

Imagine cookware. Expensive pots and pans are copper or they have copper cores. Copper is a great heat-conducting material: it quickly and evenly spreads heat so food cooks evenly. Copper makes for good cookware, but poor thermoelectric material.

In an ideal thermoelectric material, current-carrying electrons should flow unimpeded from the hot side to the cold side, but heat-carrying phonons, which are atomic vibrations, must be blocked, either by large atoms or defects where the material is of lower density.

Rao; Podila; Sriparna Bhattacharya, a research assistant professor in astronomy and physics; and Jian He, an associate professor in physics and astronomy at Clemson and a thermoelectrics expert, performed their own study on tin selenide in collaboration with Academia Sinica’s Institute of Physics in Taipei.

Right away, Bhattacharya noticed a problem. “The most puzzling thing was that when we measured our own tin-selenide material, we observed the same electrical flow as reported in the 2014 article, but the heat carried by the phonons was relatively higher,” Bhattacharya said.

The original research group “made tin-selenide crystal that was not fully dense,” Bhattacharya said. Ideally, a crystalline material matches its “theoretical density,” meaning it’s as dense as it can be expected to get.

“Instead of reaching 100 percent theoretical density, it reached 89 percent. A 10 percent difference might not seem like much,” she said, but it can have a huge implication on the electron and phonon flow.

The Clemson-Taiwan collaborators are now focusing on their own assessment of thermoelectricity in tin-selenide. They expect to publish soon.

Here’s a link to and a citation to the 2014 thermoelectricity paper and a link to and a citation for the 2016 paper critiquing it,

Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals by Li-Dong Zhao, Shih-Han Lo, Yongsheng Zhang, Hui Sun, Gangjian Tan, Ctirad Uher, C. Wolverton, Vinayak P. Dravid, & Mercouri G. Kanatzidis. Nature 508, 373–377 (17 April 2014) doi:10.1038/nature13184 Published online 16 April 2014

The intrinsic thermal conductivity of SnSe by Pai-Chun Wei, S. Bhattacharya, J. He, S. Neeleshwar, R. Podila, Y. Y. Chen, & A. M. Rao. Nature 539, E1–E2 (03 November 2016) doi:10.1038/nature19832 Published online 02 November 2016

Both papers are behind a paywall.

One final observation, scientists may mistakes as do we all. The point after all is to contribute and the mistakes can be as useful as the successes.

Ultimate discovery tool?

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For anyone familiar with the US nanomedicine scene, Chad Mirkin’s appearance in this announcement from Northwestern University isn’t much of a surprise.  From a June 23, 2016 news item on ScienceDaily,

The discovery power of the gene chip is coming to nanotechnology. A Northwestern University research team is developing a tool to rapidly test millions and perhaps even billions or more different nanoparticles at one time to zero in on the best particle for a specific use.

When materials are miniaturized, their properties—optical, structural, electrical, mechanical and chemical—change, offering new possibilities. But determining what nanoparticle size and composition are best for a given application, such as catalysts, biodiagnostic labels, pharmaceuticals and electronic devices, is a daunting task.

“As scientists, we’ve only just begun to investigate what materials can be made on the nanoscale,” said Northwestern’s Chad A. Mirkin, a world leader in nanotechnology research and its application, who led the study. “Screening a million potentially useful nanoparticles, for example, could take several lifetimes. Once optimized, our tool will enable researchers to pick the winner much faster than conventional methods. We have the ultimate discovery tool.”

A June 23, 2016 Northwestern University news release (also on EurekAlert), which originated the news item, describes the work in more detail,

Using a Northwestern technique that deposits materials on a surface, Mirkin and his team figured out how to make combinatorial libraries of nanoparticles in a very controlled way. (A combinatorial library is a collection of systematically varied structures encoded at specific sites on a surface.) Their study will be published June 24 by the journal Science.

The nanoparticle libraries are much like a gene chip, Mirkin says, where thousands of different spots of DNA are used to identify the presence of a disease or toxin. Thousands of reactions can be done simultaneously, providing results in just a few hours. Similarly, Mirkin and his team’s libraries will enable scientists to rapidly make and screen millions to billions of nanoparticles of different compositions and sizes for desirable physical and chemical properties.

“The ability to make libraries of nanoparticles will open a new field of nanocombinatorics, where size — on a scale that matters — and composition become tunable parameters,” Mirkin said. “This is a powerful approach to discovery science.”

…

“I liken our combinatorial nanopatterning approach to providing a broad palette of bold colors to an artist who previously had been working with a handful of dull and pale black, white and grey pastels,” said co-author Vinayak P. Dravid, the Abraham Harris Professor of Materials Science and Engineering in the McCormick School of Engineering.

Using five metallic elements — gold, silver, cobalt, copper and nickel — Mirkin and his team developed an array of unique structures by varying every elemental combination. In previous work, the researchers had shown that particle diameter also can be varied deliberately on the 1- to 100-nanometer length scale.

Some of the compositions can be found in nature, but more than half of them have never existed before on Earth. And when pictured using high-powered imaging techniques, the nanoparticles appear like an array of colorful Easter eggs, each compositional element contributing to the palette.

To build the combinatorial libraries, Mirkin and his team used Dip-Pen Nanolithography, a technique developed at Northwestern in 1999, to deposit onto a surface individual polymer “dots,” each loaded with different metal salts of interest. The researchers then heated the polymer dots, reducing the salts to metal atoms and forming a single nanoparticle. The size of the polymer dot can be varied to change the size of the final nanoparticle.

This control of both size and composition of nanoparticles is very important, Mirkin stressed. Having demonstrated control, the researchers used the tool to systematically generate a library of 31 nanostructures using the five different metals.

To help analyze the complex elemental compositions and size/shape of the nanoparticles down to the sub-nanometer scale, the team turned to Dravid, Mirkin’s longtime friend and collaborator. Dravid, founding director of Northwestern’s NUANCE Center, contributed his expertise and the advanced electron microscopes of NUANCE to spatially map the compositional trajectories of the combinatorial nanoparticles.

Now, scientists can begin to study these nanoparticles as well as build other useful combinatorial libraries consisting of billions of structures that subtly differ in size and composition. These structures may become the next materials that power fuel cells, efficiently harvest solar energy and convert it into useful fuels, and catalyze reactions that take low-value feedstocks from the petroleum industry and turn them into high-value products useful in the chemical and pharmaceutical industries.

Here’s a diagram illustrating the work,

Caption: A combinatorial library of polyelemental nanoparticles was developed using Dip-Pen Nanolithography. This novel nanoparticle library opens up a new field of nanocombinatorics for rapid screening of nanomaterials for a multitude of properties. Credit: Peng-Cheng Chen/James Hedrick

Caption: A combinatorial library of polyelemental nanoparticles was developed using Dip-Pen Nanolithography. This novel nanoparticle library opens up a new field of nanocombinatorics for rapid screening of nanomaterials for a multitude of properties. Credit: Peng-Cheng Chen/James Hedrick

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

Polyelemental nanoparticle libraries by Peng-Cheng Chen, Xiaolong Liu, James L. Hedrick, Zhuang Xie, Shunzhi Wang, Qing-Yuan Lin, Mark C. Hersam, Vinayak P. Dravid, Chad A. Mirkin. Science  24 Jun 2016: Vol. 352, Issue 6293, pp. 1565-1569 DOI: 10.1126/science.aaf8402

This paper is behind a paywall.