Tag Archives: metal-organic frameworks (MOFs)

New design strategy for synthesizing metal-organic frameworks (MOFs)

A Jan. 24, 2017 news item on Nanowerk announces new research from South Korea,

The accurate interpretation of particle sizes and shapes in nanoporus materials is essential to understanding and optimizing the performance of porous materials used in many important existing and potentially new applications. However, only a few experimental techniques have been developed for this purpose.

A team of researchers, led by Professor Wonyoung Choe of Natural Science and Professor Ja Hun Kwak of Energy and Chemical Engineering [ at Ulsan National Institute of Science and Technology {UNIST}] has recently developed a novel design strategy for synthesizing various forms of functional materials, especially for metal-organic materials (MOMs).

The research team expects that this synthetic approach might open up a new direction for the development of diverse forms in MOMs, with highly advanced areas such as sequential drug delivery/release and heterogeneous cascade catalysis targeted in the foreseeable future.

A Jan. 6, 2017 UNIST press release, which originated the news item, provides more detail,

In the last decades, much research has been developed to the synthesis and design of functional materials, but only a few of them could control the walls of the interior of the particles within the nanoporous materials.

In the study, Professor Choe and his team denomstrated sequential self-assembly strategy for synthesizing various forms of MOM crystals, including double-shell hollow MOMs, based on single-crystal to single-crystal transformation from MOP to MOF.

Schematic representation of various forms of micro-/nanostructures. From left are Solid, core-shell, hollow, matryoshka, yolk-shell and multi-shell hollow structures.

Porous materials are highly utilized as catalysts or gas capture materials because they supply abundant surface active sites for chemical reaction. Although materials, like Zeolites, which can be obtained from nature, have the ability to act as catalysts for chemical reactions, they suffer from the difficulty of controlling pore sizes and shapes.

As one solution, scientists have developed self-assembled porous materials using organic molecules and metals. Metal-Organic Frameworks (MOFs) and Metal-Organic Polyhedral (MOPs) are notable examples and they both have holes all over their surfaces. MOPs dissolve easily in chemical solvent, while MOFs are practically insoluble.

“MOFs take the form of three-dimensional (3D) structure, linking metals with organic molecules, while MOPs agglomerate together to form larger clusters,” says Jiyoung Lee, the first contributor of the study and a graduate student in the combined master-doctoral program from Chemistry department.

Schematic illustration of form evolution.

Schematic illustration of form evolution.

According to the research team, this synthetic strategy also yields other forms, such as solid, core-shell, double and triple matryoshka, and single-shell hollow MOMs, thereby exhibiting form evolution in MOMs.

“The best feature of this technique is that it allows two very different substances to coexist within a single crystal,” says Professor Choe. “This technique also permits greater control over size and shape of the pore, which can be then used to regulate the entrance and exit of molecules.”

This particular synthetic approach also has the potential to generate new type of porous materials containing micropores with diameters less than 2nm, macropores with diameters between 20 to 50nm, as well as pores of larger than 50 nm. Such hierarchical pore structure plays a critical role during catalysis, adsorption, and separation processes.

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

Evolution of form in metal–organic frameworks by Jiyoung Lee, Ja Hun Kwak & Wonyoung Choe. Nature Communications 8, Article number: 14070 (2017) doi:10.1038/ncomms14070 Published online: 04 January 2017

This is an open access paper.

Eliminate cold storage for diagnostic tests?

There’s a nanoparticle coating that could eliminate the need for cold storage and/or refrigeration for diagnostic testing according to a Jan. 4, 2017 news item on Nanowerk,

Many diagnostic tests use antibodies to help confirm a myriad of medical conditions, from Zika infections to heart ailments and even some forms of cancer. Antibodies capture and help detect proteins, enzymes, bacteria and viruses present in injuries and illnesses, and must be kept at a constant low temperature to ensure their viability — often requiring refrigeration powered by electricity. This can make diagnostic testing in underdeveloped countries, disaster or remote areas and even war zones extremely expensive and difficult.

A team of engineers from Washington University in St. Louis and Air Force Research Laboratory have discovered an inexpensive work-around: a protective coating that could completely eliminate the need for cold storage and change the scope of medical diagnostic testing in places where it’s often needed the most.

“In many developing countries, electricity is not guaranteed,” said Srikanth Singamaneni, associate professor of mechanical engineering and materials science in Engineering & Applied Science at Washington University in St. Louis.

“So how do we best get them medical diagnostics? We did not know how to solve this problem previously.”

A Jan. 4, 2016 Washington University in St. Louis news release by Erika Ebsworth-Goold, which originated the news item, describes how previous research helped lead to a solution,

Singamaneni’s team previously used tiny gold nanorods in bio-diagnostic research, measuring changes in their optical properties to quantify protein concentrations in bio-fluids: the higher a concentration, the higher the likelihood of injury or disease.

In this new research, published in Advanced Materials, Singamaneni worked with faculty from Washington University’s School of Medicine and researchers from the Air Force Research Lab to grow metal-organic frameworks (MOFs) around antibodies attached to gold nanorods. The crystalline MOFs formed a protective layer around the antibodies and prevented them from losing activity at elevated temperatures. The protective effect lasted for a week even when the samples were stored at 60°C.

“This technology would allow point-of-care screening for biomarkers of diseases in urban and rural clinic settings where immediate patient follow-up is critical to treatment and wellbeing,” said Dr. Jeremiah J. Morrissey, professor of anesthesiology, Division of Clinical and Translational Research, Washington University School of Medicine and a co-author on the paper.

“On the spot testing eliminates the time lag in sending blood/urine samples to a central lab for testing and in tracking down patients to discuss test results. In addition, it may reduce costs associated with refrigerated shipping and storage.”

The protective MOF layer can be quickly and easily removed from the antibodies with a simple rinse of slightly acidic water, making a diagnostic strip or paper immediately ready to use. Singamaneni says this proof of concept research is now ready to be tested for clinical samples.

“As long as you are using antibodies, you can use this technology,” said Congzhou Wang, a postdoctoral researcher in Singamaneni’s lab and the paper’s lead author. “In bio-diagnostics from here on out, we will no longer need refrigeration.”

“The MOF-based protection of antibodies on sensor surfaces is ideal for preserving biorecognition abilities of sensors that are designed for deployment in the battlefield,” said Dr. Rajesh R. Naik, 711th Human Performance Wing of the Air Force Research Laboratory, Wright-Patterson Air Force Base, and a co-corresponding author of the paper.  “It provides remarkable stability and extremely easy to remove right before use.”

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

Metal-Organic Framework as a Protective Coating for Biodiagnostic Chips by Congzhou Wang, Sirimuvva Tadepalli, Jingyi Luan, Keng-Ku Liu, Jeremiah J. Morrissey, Evan D. Kharasch, Rajesh R. Naik, and Srikanth Singamaneni. Advanced Materials DOI: 10.1002/adma.201604433 Version of Record online: 7 DEC 2016

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

A final observation, there’s at least one other project aimed at eliminating the need for refrigeration in the field of medical applications and that’s the nanopatch, a replacement for syringes used for liquid medications and vaccines (see my Dec. 16, 2016 posting for a description).

Self-shading electrochromic windows from the Massachusetts Institute of Technology

It’s been a while since I’ve had a story about electrochromic windows and I’ve begun to despair that they will ever reach the marketplace. Happily, the Massachusetts Institute of Technology (MIT) has supplied a ray of light (intentional wordplay). An Aug. 11, 2016 news item on Nanowerk makes the announcement,

A team of researchers at MIT has developed a new way of making windows that can switch from transparent to opaque, potentially saving energy by blocking sunlight on hot days and thus reducing air-conditioning costs. While other systems for causing glass to darken do exist, the new method offers significant advantages by combining rapid response times and low power needs.

Once the glass is switched from clear to dark, or vice versa, the new system requires little to no power to maintain its new state; unlike other materials, it only needs electricity when it’s time to switch back again.

An Aug. 11, 2016 MIT news release (also on EurekAlert), which originated the news item, explains the technology in more detail,

The new discovery uses electrochromic materials, which change their color and transparency in response to an applied voltage, Dinca [MIT professor of chemistry Mircea Dinca] explains. These are quite different from photochromic materials, such as those found in some eyeglasses that become darker when the light gets brighter. Such materials tend to have much slower response times and to undergo a smaller change in their levels of opacity.

Existing electrochromic materials suffer from similar limitations and have found only niche applications. For example, Boeing 787 aircraft have electrochromic windows that get darker to prevent bright sunlight from glaring through the cabin. The windows can be darkened by turning on the voltage, Dinca says, but “when you flip the switch, it actually takes a few minutes for the window to turn dark. Obviously, you want that to be faster.”

The reason for that slowness is that the changes within the material rely on a movement of electrons — an electric current — that gives the whole window a negative charge. Positive ions then move through the material to restore the electrical balance, creating the color-changing effect. But while electrons flow rapidly through materials, ions move much more slowly, limiting the overall reaction speed.

The MIT team overcame that by using sponge-like materials called metal-organic frameworks (MOFs), which can conduct both electrons and ions at very high speeds. Such materials have been used for about 20 years for their ability to store gases within their structure, but the MIT team was the first to harness them for their electrical and optical properties.

The other problem with existing versions of self-shading materials, Dinca says, is that “it’s hard to get a material that changes from completely transparent to, let’s say, completely black.” Even the windows in the 787 can only change to a dark shade of green, rather than becoming opaque.

In previous research on MOFs, Dinca and his students had made material that could turn from clear to shades of blue or green, but in this newly reported work they have achieved the long-sought goal of producing a coating that can go all the way from perfectly clear to nearly black (achieved by blending two complementary colors, green and red). The new material is made by combining two chemical compounds, an organic material and a metal salt. Once mixed, these self-assemble into a thin film of the switchable material.

“It’s this combination of these two, of a relatively fast switching time and a nearly black color, that has really got people excited,” Dinca says.

The new windows have the potential, he says, to do much more than just preventing glare. “These could lead to pretty significant energy savings,” he says, by drastically reducing the need for air conditioning in buildings with many windows in hot climates. “You could just flip a switch when the sun shines through the window, and turn it dark,” or even automatically make that whole side of the building go dark all at once, he says.

While the properties of the material have now been demonstrated in a laboratory setting, the team’s next step is to make a small-scale device for further testing: a 1-inch-square sample, to demonstrate the principle in action for potential investors in the technology, and to help determine what the manufacturing costs for such windows would be.

Further testing is also needed, Dinca says, to demonstrate what they have determined from preliminary testing: that once the switch is flipped and the material changes color, it requires no further power to maintain its new state. No extra power is needed until the switch is flipped to turn the material back to its former state, whether clear or opaque. Many existing electrochromic materials, by contrast, require a continuous voltage input.

In addition to smart windows, Dinca says, the material could also be used for some kinds of low-power displays, similar to displays like electronic ink (used in devices such as the Kindle and based on MIT-developed technology) but based on a completely different approach.

Not surprisingly perhaps, the research was partly funded by an organization in a region where such light-blocking windows would be particularly useful: The Masdar Institute, based in the United Arab Emirates, through a cooperative agreement with MIT. The research also received support from the U.S. Department of Energy, through the Center for Excitonics, an Energy Frontier Center.

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

Transparent-to-Dark Electrochromic Behavior in Naphthalene-Diimide-Based Mesoporous MOF-74 Analogs by Khalid AlKaabi, Casey R. Wade, Mircea Dincă. Chem, Volume 1, Issue 2, 11 August 2016, Pages 264–272 doi:10.1016/j.chempr.2016.06.013

This paper is behind a paywall.

For those curious about the windows, there’s this .gif from MIT,

MIT_ElectrochromicWindows

Researchers from Canada and Russia find metal-organic-frameworks in nature

To date, these ‘natural’ metal-organic-frameworks have been found only in Siberian coal mines. From an Aug, 5, 2016 news item on ScienceDaily,

One of the hottest new materials is a class of porous solids known as metal-organic frameworks, or MOFs. These human-made materials were introduced in the 1990s, and researchers around the world are working on ways to use them as molecular sponges for applications such as hydrogen storage, carbon sequestration, or photovoltaics.

Now, a surprising discovery by scientists in Canada and Russia reveals that MOFs also exist in nature — albeit in the form of rare minerals found so far only in Siberian coal mines.

The finding, published in the journal Science Advances, “completely changes the normal view of these highly popular materials as solely artificial, ‘designer’ solids,” says senior author Tomislav Friščić, an associate professor of chemistry at McGill University in Montreal. “This raises the possibility that there might be other, more abundant, MOF minerals out there.”

Caption: Individual crystals of synthetic zhemchuzhnikovite, prepared by Igor Huskić, McGill University. Credit: Igor Huskić, Friščić Research Group, McGill University

Caption: Individual crystals of synthetic zhemchuzhnikovite, prepared by Igor Huskić, McGill University. Credit: Igor Huskić, Friščić Research Group, McGill University

An Aug, 8, 2016 McGill University news release (also on EurekAlert but dated Aug. 5, 2016), which originated the news item, expands on the theme,

The twisting path to the discovery began six years ago, when Friščić came across a mention of the minerals stepanovite and zhemchuzhnikovite in a Canadian mineralogy journal. The crystal structure of the minerals, found in Russia between the 1940s and 1960s, hadn’t been fully determined. But the Russian mineralogists who discovered them had analyzed their chemical composition and the basic parameters of their structures, using a technique known as X-ray powder diffraction. To Friščić, those parameters hinted that the minerals could be structurally similar to a type of man-made MOF.

His curiosity piqued, Friščić began looking for samples of the rare minerals, reaching out to experts, museums and vendors in Russia and elsewhere. After a promising lead with a mining museum in Saint Petersburg failed to pan out, Igor Huskić, a graduate student in the Friščić research group at McGill turned his attention to synthesizing analogues of the minerals in the lab – and succeeded. But a major journal last year declined to publish the team’s work, in part because the original description of the minerals had been reported in a somewhat obscure Russian mineralogical journal.

Then, the McGill chemists caught a break: with the help of a crystallographer colleague in Venezuela, they connected with two prominent Russian mineralogists: Sergey Krivovichev, a professor at Saint Petersburg State University, and Prof. Igor Pekov of Lomonosov Moscow State University.

Krivovichev and Pekov were able to obtain the original samples of the two rare minerals, which had been found decades earlier in a coal mine deep beneath the Siberian permafrost. The Russian experts were also able to determine the crystal structures of the minerals. These findings confirmed the McGill researchers’ initial results from their lab synthesis.

Stepanovite and zhemchuzhnikovite have the elaborate, honeycomb-like structure of MOFs, characterized at the molecular level by large voids. The two minerals aren’t, however, representative of the hottest varieties of MOFs — those that are being developed for use in hydrogen-fueled cars or to capture waste carbon dioxide.

As a result, Friščić and his collaborators are now broadening their research to determine if other, more abundant minerals have porous structures that could make them suitable for uses such as hydrogen storage or even drug delivery.

In any event, the discovery of MOF structures in the two rare minerals already is “paradigm-changing” Friščić says. If scientists had been able to determine those structures in the 1960s, he notes, the development of MOF materials “might have been accelerated by 30 years.”

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

Minerals with metal-organic framework structures by Igor Huskić, Igor V. Pekov, Sergey V. Krivovichev, and Tomislav Friščić. Science Advances  05 Aug 2016: Vol. 2, no. 8, e1600621 DOI: 10.1126/sciadv.1600621

This paper appears to be open access.

Cleaning up nuclear waste gases with nanotechnology-enabled materials

Swiss and US scientists have developed a nanoporous crystal that could be used to clean up nuclear waste gases according to a June 13, 2016 news item on Nanowerk (Note: A link has been removed),

An international team of scientists at EPFL [École polytechnique fédérale de Lausanne in Switzerland] and the US have discovered a material that can clear out radioactive waste from nuclear plants more efficiently, cheaply, and safely than current methods.

Nuclear energy is one of the cheapest alternatives to carbon-based fossil fuels. But nuclear-fuel reprocessing plants generate waste gas that is currently too expensive and dangerous to deal with. Scanning hundreds of thousands of materials, scientists led by EPFL and their US colleagues have now discovered a material that can absorb nuclear waste gases much more efficiently, cheaply and safely. The work is published in Nature Communications (“Metal–organic framework with optimally selective xenon adsorption and separation”).

A June 14, 2016 EPFL press release (also on EurekAlert), which originated the news item, explains further,

Nuclear-fuel reprocessing plants generate volatile radionuclides such as xenon and krypton, which escape in the so-called “off-gas” of these facilities – the gases emitted as byproducts of the chemical process. Current ways of capturing and clearing out these gases involve distillation at very low temperatures, which is expensive in both terms of energy and capital costs, and poses a risk of explosion.

Scientists led by Berend Smit’s lab at EPFL (Sion) and colleagues in the US, have now identified a material that can be used as an efficient, cheaper, and safer alternative to separate xenon and krypton – and at room temperature. The material, abbreviated as SBMOF-1, is a nanoporous crystal and belongs a class of materials that are currently used to clear out CO2 emissions and other dangerous pollutants. These materials are also very versatile, and scientists can tweak them to self-assemble into ordered, pre-determined crystal structures. In this way, they can synthesize millions of tailor-made materials that can be optimized for gas storage separation, catalysis, chemical sensing and optics.

The scientists carried out high-throughput screening of large material databases of over 125,000 candidates. To do this, they used molecular simulations to find structures that can separate xenon and krypton, and under conditions that match those involved in reprocessing nuclear waste.

Because xenon has a much shorter half-life than krypton – a month versus a decade – the scientists had to find a material that would be selective for both but would capture them separately. As xenon is used in commercial lighting, propulsion, imaging, anesthesia and insulation, it can also be sold back into the chemical market to offset costs.

The scientists identified and confirmed that SBMOF-1 shows remarkable xenon capturing capacity and xenon/krypton selectivity under nuclear-plant conditions and at room temperature.

The US partners have also made an announcement with this June 13, 2016 Pacific Northwest National Laboratory (PNNL) news release (also on EurekAlert), Note: It is a little repetitive but there’s good additional information,

Researchers are investigating a new material that might help in nuclear fuel recycling and waste reduction by capturing certain gases released during reprocessing. Conventional technologies to remove these radioactive gases operate at extremely low, energy-intensive temperatures. By working at ambient temperature, the new material has the potential to save energy, make reprocessing cleaner and less expensive. The reclaimed materials can also be reused commercially.

Appearing in Nature Communications, the work is a collaboration between experimentalists and computer modelers exploring the characteristics of materials known as metal-organic frameworks.

“This is a great example of computer-inspired material discovery,” said materials scientist Praveen Thallapally of the Department of Energy’s Pacific Northwest National Laboratory. “Usually the experimental results are more realistic than computational ones. This time, the computer modeling showed us something the experiments weren’t telling us.”

Waste avoidance

Recycling nuclear fuel can reuse uranium and plutonium — the majority of the used fuel — that would otherwise be destined for waste. Researchers are exploring technologies that enable safe, efficient, and reliable recycling of nuclear fuel for use in the future.

A multi-institutional, international collaboration is studying materials to replace costly, inefficient recycling steps. One important step is collecting radioactive gases xenon and krypton, which arise during reprocessing. To capture xenon and krypton, conventional technologies use cryogenic methods in which entire gas streams are brought to a temperature far below where water freezes — such methods are energy intensive and expensive.

Thallapally, working with Maciej Haranczyk and Berend Smit of Lawrence Berkeley National Laboratory [LBNL] and others, has been studying materials called metal-organic frameworks, also known as MOFs, that could potentially trap xenon and krypton without having to use cryogenics.

These materials have tiny pores inside, so small that often only a single molecule can fit inside each pore. When one gas species has a higher affinity for the pore walls than other gas species, metal-organic frameworks can be used to separate gaseous mixtures by selectively adsorbing.

To find the best MOF for xenon and krypton separation, computational chemists led by Haranczyk and Smit screened 125,000 possible MOFs for their ability to trap the gases. Although these gases can come in radioactive varieties, they are part of a group of chemically inert elements called “noble gases.” The team used computing resources at NERSC, the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility at LBNL.

“Identifying the optimal material for a given process, out of thousands of possible structures, is a challenge due to the sheer number of materials. Given that the characterization of each material can take up to a few hours of simulations, the entire screening process may fill a supercomputer for weeks,” said Haranczyk. “Instead, we developed an approach to assess the performance of materials based on their easily computable characteristics. In this case, seven different characteristics were necessary for predicting how the materials behaved, and our team’s grad student Cory Simon’s application of machine learning techniques greatly sped up the material discovery process by eliminating those that didn’t meet the criteria.”

The team’s models identified the MOF that trapped xenon most selectively and had a pore size close to the size of a xenon atom — SBMOF-1, which they then tested in the lab at PNNL.

After optimizing the preparation of SBMOF-1, Thallapally and his team at PNNL tested the material by running a mixture of gases through it — including a non-radioactive form of xenon and krypton — and measuring what came out the other end. Oxygen, helium, nitrogen, krypton, and carbon dioxide all beat xenon out. This indicated that xenon becomes trapped within SBMOF-1’s pores until the gas saturates the material.

Other tests also showed that in the absence of xenon, SBMOF-1 captures krypton. During actual separations, then, operators would pass the gas streams through SBMOF-1 twice to capture both gases.

The team also tested SBMOF-1’s ability to hang onto xenon in conditions of high humidity. Humidity interferes with cryogenics, and gases must be dehydrated before putting them through the ultra-cold method, another time-consuming expense. SBMOF-1, however, performed quite admirably, retaining more than 85 percent of the amount of xenon in high humidity as it did in dry conditions.

The final step in collecting xenon or krypton gas would be to put the MOF material under a vacuum, which sucks the gas out of the molecular cages for safe storage. A last laboratory test examined how stable the material was by repeatedly filling it up with xenon gas and then vacuuming out the xenon. After 10 cycles of this, SBMOF-1 collected just as much xenon as the first cycle, indicating a high degree of stability for long-term use.

Thallapally attributes this stability to the manner in which SBMOF-1 interacts with xenon. Rather than chemical reactions between the molecular cages and the gases, the relationship is purely physical. The material can last a lot longer without constantly going through chemical reactions, he said.

A model finding

Although the researchers showed that SBMOF-1 is a good candidate for nuclear fuel reprocessing, getting these results wasn’t smooth sailing. In the lab, the researchers had followed a previously worked out protocol from Stony Brook University to prepare SBMOF-1. Part of that protocol requires them to “activate” SBMOF-1 by heating it up to 300 degrees Celsius, three times the temperature of boiling water.

Activation cleans out material left in the pores from MOF synthesis. Laboratory tests of the activated SBMOF-1, however, showed the material didn’t behave as well as it should, based on the computer modeling results.

The researchers at PNNL repeated the lab experiments. This time, however, they activated SBMOF-1 at a lower temperature, 100 degrees Celsius, or the actual temperature of boiling water. Subjecting the material to the same lab tests, the researchers found SBMOF-1 behaving as expected, and better than at the higher activation temperature.

But why? To figure out where the discrepancy came from, the researchers modeled what happened to SBMOF-1 at 300 degrees Celsius. Unexpectedly, the pores squeezed in on themselves.

“When we heated the crystal that high, atoms within the pore tilted and partially blocked the pores,” said Thallapally. “The xenon doesn’t fit.”

Armed with these new computational and experimental insights, the researchers can explore SBMOF-1 and other MOFs further for nuclear fuel recycling. These MOFs might also be able to capture other noble gases such as radon, a gas known to pool in some basements.

Researchers hailed from several other institutions as well as those listed earlier, including University of California, Berkeley, Ecole Polytechnique Fédérale de Lausanne (EPFL) in Switzerland, Brookhaven National Laboratory, and IMDEA Materials Institute in Spain. This work was supported by the [US] Department of Energy Offices of Nuclear Energy and Science.

Here’s an image the researchers have provided to illustrate their work,

Caption: The crystal structure of SBMOF-1 (green = Ca, yellow = S, red = O, gray = C, white = H). The light blue surface is a visualization of the one-dimensional channel that SBMOF-1 creates for the gas molecules to move through. The darker blue surface illustrates where a Xe atom sits in the pores of SBMOF-1 when it adsorbs. Credit: Berend Smit/EPFL/University of California Berkley

Caption: The crystal structure of SBMOF-1 (green = Ca, yellow = S, red = O, gray = C, white = H). The light blue surface is a visualization of the one-dimensional channel that SBMOF-1 creates for the gas molecules to move through. The darker blue surface illustrates where a Xe atom sits in the pores of SBMOF-1 when it adsorbs. Credit: Berend Smit/EPFL/University of California Berkley

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

Metal–organic framework with optimally selective xenon adsorption and separation by Debasis Banerjee, Cory M. Simon, Anna M. Plonka, Radha K. Motkuri, Jian Liu, Xianyin Chen, Berend Smit, John B. Parise, Maciej Haranczyk, & Praveen K. Thallapally. Nature Communications 7, Article number: ncomms11831  doi:10.1038/ncomms11831 Published 13 June 2016

This paper is open access.

Final comment, this is the second time in the last month I’ve stumbled across more positive approaches to nuclear energy. The first time was a talk (Why Nuclear Power is Necessary) held in Vancouver, Canada in May 2016 (details here). I’m not trying to suggest anything unduly sinister but it is interesting since most of my adult life nuclear power has been viewed with fear and suspicion.

2015 Mustafa prize winners (two nanoscientists) announced

The $500,000US Mustafa Prize was started in 2013 according to the information on prize website’s homepage,

The Mustafa Prize is a top science and technology award granted to the top researchers and scientists of the Organization of Islamic Cooperation (OIC) member states biennially.

The Prize seeks to encourage education and research and is set to play the pioneering role in developing relations between science and technology institutions working in the OIC member countries.

It also aims to improve scientific relation between academics and researchers to facilitate the growth and perfection of science in the OIC member states.

The laureates in each section will be awarded 500,000 USD which is financed through the endowments made to the Prize. The winners will also be adorned with a special medal and certificate.

The Mustafa Prize started its job in 2013. The Policy making Council of the Prize which is tasked with supervising various procedures of the event is comprised of high-profile universities and academic centers of OIC member states.

The prize will be granted to the works which have improved the human life and have made tangible and cutting-edge innovations on the boundaries of science or have presented new scientific methodology.

The 2015 winners were announced in a Dec. 23, 2015 news item on merhnews.com,

Dr. Hossein Zohour, Chairman of the science committee of Mustafa Scientific Prize, has announced the laureates on Wednesday [Dec. 16, 2015].

According to the Public Relations Department of Mustafa (PBUH) Prize, Professor Jackie Y. Ying from Singapore and Professor Omar Yaghi from Jordan won the top science and technology award of the Islamic world.

Zohour cited that the Mustafa (PBUH) Prize is awarded in four categories including, Life Sciences and Medicine, Nanoscience and Nanotechnology, Information and Communication Technologies and Top Scientific Achievement in general fields. “In the first three categories, the nominees must be citizens of one of the 57 Islamic countries while in the fourth category the nominee must be Muslim but being citizen of an Islamic country is not mandatory,” he added.

Professor Jackie Y. Ying, CEO and faculty member of the Institute of Bioengineering and Nanotechnology of Singapore and Professor Omar Yaghi, president of Kavli Nano-energy Organization and faculty member of University of California, Berkeley are the laureates in the fields of Nano-biotechnology sciences and Nanoscience and Nanotechnology respectively.

Zohour continued, “Professor Ying is awarded in recognition of her efforts in development of ‘stimulus response systems in targeted delivery of drugs’ in the field of Nano-biotechnology.”

These systems are consisted of polymeric nanoparticles, which auto-regulate the release of insulin therapeutic depending on the blood glucose levels without the need for sampling. The technology was first developed in her knowledge-based company and now being commercialized in big pharmaceutical firms to be at the service of human health.

Professor Omar Yaghi, prominent Jordanian chemist, has also been selected for his extensive research in the field of metal-organic frameworks (MOFs) in the category of nanoscience and nanotechnology.

It’s worth noting that this [sic] MOFs have a wide range of applications in clean energy technologies, carbon dioxide capturing and hydrogen and methane storage systems due to their extremely high surface areas.

The Mustafa (PBUH) Prize Award Ceremony will take place on Friday December 25 [2015] at Vahdat Hall to honor the laureates.

Unfortunately, I’ve not profiled Dr. Yaghi’s work here. Dr. Ying has been mentioned a few times (a March 2, 2015 posting, a May 12, 2014 posting, and an Aug. 22, 2013 posting) but not for the work for which she is being honoured.

Congratulations to both Dr. Yaghi and Dr. Ying!

MOFs (metal-organic frameworks) to clean up nuclear waste?

There’s a possibility that metal-organic frameworks could be used to clean up nuclear waste according to an Aug. 5, 2015 news item on phys.org,

One of the most versatile and widely applicable classes of materials being studied today are the metal-organic frameworks. These materials, known as MOFs, are characterized by metal ions or metal-ion clusters that are linked together with organic molecules, forming ordered crystal structures that contain tiny cage-like pores with diameters of two nanometers or less.

MOFs can be thought of as highly specialized and customizable sieves. By designing them with pores of a certain size, shape, and chemical composition, researchers can tailor them for specific purposes. A few of the many, many possible applications for MOFs are storing hydrogen in fuel cells, capturing environmental contaminants, or temporarily housing catalytic agents for chemical reactions.

At [US Department of Energy] Brookhaven National Laboratory, physicist Sanjit Ghose and his collaborators have been studying MOFs designed for use in the separation of waste from nuclear reactors, which results from the reprocessing of nuclear fuel rods. He is targeting two waste products in particular: the noble gases xenon (Xe) and krypton (Kr).

An Aug. 4, 2015 Brookhaven National Laboratory news release, which originated the news item, describes not only the research and the reasons for it but also the institutional collaborations necessary to conduct the research,

There are compelling economic and environmental reasons to separate Xe and Kr from the nuclear waste stream. For one, because they have very different half-lives – about 36 days for Xe and nearly 11 years for Kr – pulling out the Xe greatly reduces the amount of waste that needs to be stored long-term before it is safe to handle. Additionally, the extracted Xe can be used for industrial applications, such as in commercial lighting and as an anesthetic. This research may also help scientists determine how to create MOFs that can remove other materials from the nuclear waste stream and expose the remaining unreacted nuclear fuel for further re-use. This could lead to much less overall waste that must be stored long-term and a more efficient system for producing nuclear energy, which is the source of about 20 percent of the electricity in the U.S.

Because Xe and Kr are noble gases, meaning their outer electron orbitals are filled and they don’t tend to bind to other atoms, they are difficult to manipulate. The current method for extracting them from the nuclear waste stream is cryogenic distillation, a process that is energy-intensive and expensive. The MOFs studied here use a very different approach: polarizing the gas atoms dynamically, just enough to draw them in using the van der Waals force. The mechanism works at room temperature, but also at hotter temperatures, which is key if the MOFs are to be used in a nuclear environment.

Recently, Ghose co-authored two papers that describe MOFs capable of adsorbing Xe and Kr, and excel at separating the Xe from the Kr. The papers are published in the May 22 online edition of the Journal of the American Chemical Society and the April 16 online edition of the Journal of Physical Chemistry Letters.

“Only a handful of noble-gas-specific MOFs have been studied so far, and we felt there was certainly scope for improvement through the discovery of more selective materials,” said Ghose.

Both MOF studies were carried out by large multi-institution collaborations, using a combination of X-ray diffraction, theoretical modeling, and other methods. The X-ray work was performed at Brookhaven’s former National Synchrotron Light Source (permanently closed and replaced by its successor, NSLS-II) and the Advanced Photon Source at Argonne National Laboratory (ANL), both DOE Office of Science User Facilities.

The JACS paper was co-authored by researchers from Brookhaven Lab, Stony Brook University (SBU), Pacific Northwest National Laboratory (PNNL), and the University of Amsterdam. Authors on the JPCL paper include scientists from Brookhaven, SBU, PNNL, ANL, the Deutsches Elektronen-Synchrotron (DESY) in Germany, and DM Strachan, LLC.

Here’s more about the first published paper in the Journal of Physical Chemistry Letters (JCPL) (from the news release)

A nickel-based MOF

The MOF studied in the JCPL paper consists of nickel (Ni) and the organic compound dioxido-benzene-dicarboxylate (DOBC), and is thus referred to as Ni-DOBDC. Ni-DOBDC can adsorb both Xe and Kr at room temperature but is highly selective toward Xe. In fact, it boasts what may be the highest Xe adsorption capacity of a MOF discovered to date.

The group studied Ni-DOBC using two main techniques: X-ray diffraction and first-principles density functional theory (DFT). The paper is the first published report to detail the adsorption mechanism by which the MOF takes in these noble gases at room temperature and pressure.

“Our results provide a fundamental understanding of the adsorption structure and the interactions between the MOF and the gas by combining direct structural analyses from experimental X-ray diffraction data and DFT calculations,” said Ghose.

The group was also able to discover the existence of a secondary site at the pore center in addition to the six-fold primary site. The seven-atom loading scheme was initially proposed by theorist Yan Li, an co-author of the JCPL paper and formerly on staff at Brookhaven (she is now an editor at Physical Review B), which was confirmed experimentally and theoretically. Data also indicate that Xe are adsorbed more strongly than Kr, due to its higher atomic polarizability. They also discovered a temperature-dependence of the adsorption that furthers this MOF’s selectivity for Xe over Kr. As the temperature was increased above room temperature, the Kr adsorption drops more drastically than for Xe. Over the entire temperature range tested, Xe adsorption always dominates that of Kr.

“The high separation capacity of Ni-DOBDC suggests that it has great potential for removing Xe from Kr in the off-gas streams in nuclear spent fuel reprocessing, as well as filtering Xe at low concentration from other gas mixtures,” said Ghose.

Ghose and Li are now preparing a manuscript that will discuss a more in-depth investigation into the possibility of packing in even more Xe atoms.

“Because of the confinement offered by each pore, we want to see if it’s possible to fit enough Xe in each chamber to form a solid,” said Li.

Ghose and Li hope to experimentally test this idea at NSLS-II in the future, at the facility’s X-ray Powder Diffraction (XPD) beamline, which Ghose has helped develop and build. Additional future studies of these and other MOFs will also take place at XPD. For example, they want to see what happens when other gases are present, such as nitrogen oxides, to mimic what happens in an actual nuclear reactor.

Then, there was the second paper published in the Journal of the American Chemical Society (JACS),

Another MOF, Another Promising Result

In the JACS paper, Ghose and researchers from Brookhaven, SBU, PNNL, and the University of Amsterdam describe a second MOF, dubbed Stony Brook MOF-2 (SBMOF-2). It also captures both Xe and Kr at room temperature and pressure, although is about ten times as effective at taking in Xe, with Xe taking up as much as 27 percent of its weight. SBMOF-2 had been theoretically predicted to be an efficient adsorbent for Xe and Kr, but until this research there had been no experimental results to back up the prediction.

“Our study is different than MOF research done by other groups,” said chemist John Parise, a coauthor of the JACS paper who holds a joint position with Brookhaven and SBU. “We did a lot of testing and investigated the capture mechanism very closely to get clues that would help us understand why the MOF worked, and how to tailor the structure to have even better properties.”

SBMOF-2 contains calcium (Ca) ions and an organic compound with the chemical formula C34H22O8. X-ray data show that its structure is unusual among microporous MOFs. It has fewer calcium sites than expected and an excess of oxygen over calcium. The calcium and oxgyen form CaO6, which takes the form of a three-dimensional octahedron. Notably, none of the six oxygen atoms bound to the calcium ion are shared with any other nearby calcium ions. The authors believe that SBMOF-2 is the first microporous MOF with these isolated CaO6 octahedra, which are connected by organic linker molecules.

The group discovered that the preference of SBMOF-2 for Xe over Kr is due to both the geometry and chemistry of its pores. All the pores have diamond-shaped cross sections, but they come in two sizes, designated type-1 and type-2. Both sizes are a better fit for the Xe molecule. The interiors of the pores have walls made of phenyl groups – ring-shaped C6H5 molecules – along with delocalized electron clouds and H atoms pointing into the pore. The type-2 pores also have hydroxyl anions (OH-) available. All of these features provide are potential sites for adsorbed Xe and Kr atoms.

In follow-up studies, Ghose and his colleagues will use these results to guide them as they determine what changes can be made to these MOFs to improve adsorption, as well as to determine what existing MOFs may yield similar or better performance.

Here are links to and citations for both papers,

Understanding the Adsorption Mechanism of Xe and Kr in a Metal–Organic Framework from X-ray Structural Analysis and First-Principles Calculations by Sanjit K. Ghose, Yan Li, Andrey Yakovenko, Eric Dooryhee, Lars Ehm, Lynne E. Ecker, Ann-Christin Dippel, Gregory J. Halder, Denis M. Strachan, and Praveen K. Thallapally. J. Phys. Chem. Lett., 2015, 6 (10), pp 1790–1794 DOI: 10.1021/acs.jpclett.5b00440 Publication Date (Web): April 16, 2015

Copyright © 2015 American Chemical Society

Direct Observation of Xe and Kr Adsorption in a Xe-Selective Microporous Metal–Organic Framework by Xianyin Chen, Anna M. Plonka, Debasis Banerjee, Rajamani Krishna, Herbert T. Schaef, Sanjit Ghose, Praveen K. Thallapally, and John B. Parise. J. Am. Chem. Soc., 2015, 137 (22), pp 7007–7010 DOI: 10.1021/jacs.5b02556 Publication Date (Web): May 22, 2015
Copyright © 2015 American Chemical Society

Both papers are behind a paywall.