Tag Archives: solid

KAUST team synthesizes novel metal-organic framework for efficient CO2 removal

By Caitlin Clark

“In Professor Mohamed Eddaoudi’s research group, we are always on the quest to find novel nanostructured functionalized materialsfor specific applications,” explained KAUST Research Scientist Dr. Youssef Belmabkhout, a member of Prof. Eddaoudi’s Functional Materials Design, Discovery, and Development (FMD3) group, part of KAUST’s Advanced Membranes and Porous Materials (AMPM) research center.

Dr. Osama Shekhah, Senior Research Scientist in the FMD3 group added that the group searches “for materials that will be highly suitable for trace and low CO2 concentration removal using purely physical adsorption. These will help in energy saving and in the reduction of the cost of the production, purification, and enrichment of highly valuable commodities such as CH4, H2, O2, N2, and others.”

Drs. Shekhah and Belmabkhout and a team of researchers from Prof. Eddaoudi’s group recently discovered and synthesized a new porous, moisture-resistant, inexpensive and reusable copper-based metal-organic framework (MOF) called SIFSIX-3-Cu that can selectively adsorb and remove trace CO2 from mixtures of various gases. Their findings were published in the June 25 edition of Nature Communications (DOI: 10.1038/ncomms5228).

MOFs are a promising new class of hybrid solid-state materials for CO2 removal. “Their uniqueness,” explained Prof. Eddaoudi, “resides in the ability to control their assembly and introduce functionality on demand. This feature is not readily available in other solid-state materials.”

The researchers showed for the first time that MOF crystal chemistry permits the assembly of a new isostructural hexafluorosilicate MOF (SIFSIX-3-Cu) based on copper instead of zinc.

“This technology is anticipated to outperform the existing mature technologies for CO2 physical adsorption in terms of energy efficiency,” says Dr. Shekhah. “The key factors for this finding are the combination of suitable pore size and high, uniform charge density in the pores of the MOF.”

Using their newly synthesized MOF, the researchers examined the conditions relevant to direct air capture (DAC), a mechanism to remove CO2 from air and reduce greenhouse gas emissions uniformly around the world.

DAC is more challenging than post-combustion capture, but it may be practical if alternative “suitable adsorbent combining optimum uptake, kinetics, energetics and CO2 selectivity is available at trace CO2 concentration,” the researchers stated.

The team discovered that contracting SIFSIX-3-Cu’s pore system to 3.5 Å enhanced the material’s efficiency, making it able to adsorb relatively large CO2 amounts 10-15 times higher than zinc-based metal-organic adsorbents, such as SIFSIX-3-Zn. In SIFSIX-3-Zn, the pore size is 3.84 Å.

“We attribute this property to enhanced physical sorption through the favorable electrostatic interactions between CO2 molecules and fluorine atoms present on the surface of the adsorbent,” explained Zhijie Chen, a Ph.D. student in the FMD3 group and a co-author of the paper.

Dr. Vincent Guillerm, a post-doctoral fellow in the FMD3 group and a co-author of the paper also noted that, “the pore contraction gives CO2 uptake and selectivity at very low partial pressures. This is relevant to DAC and trace carbon dioxide removal.”

“SIFSIX-3-Cu gives enhanced CO2 physical adsorption properties, uptake, and selectivity in highly diluted gas streams, and this performance is unachievable with other classes of porous materials,” added Dr. Karim Adil, a co-author of the paper and Research Scientist in the FMD3 group.

The researchers are excited about their finding as it offers the potential to be used not only for DAC but also for other applications related to energy, the environment, and the healthcare field. For example, SIFSIX-3-Cu could be used to remove and recycle CO2 in confined spaces, such as in submarines or space shuttles, and could also be used in anesthesia machines, which require efficient CO2 sorbents.

“Our work paves the way for scientists to develop new separation agents suitable for challenging endeavor pertaining to CO2 ultra-purification processing,” said Dr. Shekhah. “Our study is also part of a greater critical effort to develop economical and practical pathways to reduce cumulative CO2 emissions provoking the undesirable greenhouse gas effect.”

Prof. Eddaoudi reiterated that “MOFs offer remarkable CO2 physical adsorption attributes in highly diluted gas streams thanks to their ability for rational pore size modification and inorganic-organics moieties substitution. Other classes of plain materials are unable to attain this.”

In the future, Prof. Eddaoudi’s FMD3 group will continue to develop topologically and chemically different MOFs. “We aim to target novel MOFs with suitable pore size and high charge density,” explained Prof. Eddaoudi. “We will then use these for the important task of removing trace and low and high concentration CO2.”

Source: KAUST


 

Solid nanoparticles can deform like a liquid|Unexpected finding shows tiny particles keep their internal crystal structure while flexing like droplets.

By David Chandler


CAMBRIDGE, Mass–A surprising phenomenon has been found in metal nanoparticles: They appear, from the outside, to be liquid droplets, wobbling and readily changing shape, while their interiors retain a perfectly stable crystal configuration.

The research team behind the finding, led by MIT professor Ju Li, says the work could have important implications for the design of components in nanotechnology, such as metal contacts for molecular electronic circuits.

The results, published in the journal Nature Materials, come from a combination of laboratory analysis and computer modeling, by an international team that included researchers in China, Japan, and Pittsburgh, as well as at MIT.

The experiments were conducted at room temperature, with particles of pure silver less than 10 nanometers across — less than one-thousandth of the width of a human hair. But the results should apply to many different metals, says Li, senior author of the paper and the BEA Professor of Nuclear Science and Engineering.

Silver has a relatively high melting point — 962 degrees Celsius, or 1763 degrees Fahrenheit — so observation of any liquidlike behavior in its nanoparticles was “quite unexpected,” Li says. Hints of the new phenomenon had been seen in earlier work with tin, which has a much lower melting point, he says.

The use of nanoparticles in applications ranging from electronics to pharmaceuticals is a lively area of research; generally, Li says, these researchers “want to form shapes, and they want these shapes to be stable, in many cases over a period of years.” So the discovery of these deformations reveals a potentially serious barrier to many such applications: For example, if gold or silver nanoligaments are used in electronic circuits, these deformations could quickly cause electrical connections to fail.

Only skin deep

The researchers’ detailed imaging with a transmission electron microscope and atomistic modeling revealed that while the exterior of the metal nanoparticles appears to move like a liquid, only the outermost layers — one or two atoms thick — actually move at any given time. As these outer layers of atoms move across the surface and redeposit elsewhere, they give the impression of much greater movement — but inside each particle, the atoms stay perfectly lined up, like bricks in a wall.

“The interior is crystalline, so the only mobile atoms are the first one or two monolayers,” Li says. “Everywhere except the first two layers is crystalline.”

By contrast, if the droplets were to melt to a liquid state, the orderliness of the crystal structure would be eliminated entirely — like a wall tumbling into a heap of bricks.

Technically, the particles’ deformation is pseudoelastic, meaning that the material returns to its original shape after the stresses are removed — like a squeezed rubber ball — as opposed to plasticity, as in a deformable lump of clay that retains a new shape.

The phenomenon of plasticity by interfacial diffusion was first proposed by Robert L. Coble, a professor of ceramic engineering at MIT, and is known as “Coble creep.”  “What we saw is aptly called Coble pseudoelasticity,” Li says.

Now that the phenomenon has been understood, researchers working on nanocircuits or other nanodevices can quite easily compensate for it, Li says. If the nanoparticles are protected by even a vanishingly thin layer of oxide, the liquidlike behavior is almost completely eliminated, making stable circuits possible.

Possible benefits

On the other hand, for some applications this phenomenon might be useful: For example, in circuits where electrical contacts need to withstand rotational reconfiguration, particles designed to maximize this effect might prove useful, using noble metals or a reducing atmosphere, where the formation of an oxide layer is destabilized, Li says.

The new finding flies in the face of expectations — in part, because of a well-understood relationship, in most materials, in which mechanical strength increases as size is reduced.

“In general, the smaller the size, the higher the strength,” Li says, but “at very small sizes, a material component can get very much weaker. The transition from ‘smaller is stronger’ to ‘smaller is much weaker’ can be very sharp.”

That crossover, he says, takes place at about 10 nanometers at room temperature — a size that microchip manufacturers are approaching as circuits shrink. When this threshold is reached, Li says, it causes “a very precipitous drop” in a nanocomponent’s strength.

The findings could also help explain a number of anomalous results seen in other research on small particles, Li says.

The research team included Jun Sun, Longbing He, Tao Xu, Hengchang Bi, and Litao Sun, all of Southeast University in Nanjing, China; Yu-Chieh Lo of MIT and Kyoto University; Ze Zhang of Zhejiang University; and Scott Mao of the University of Pittsburgh. It was supported by the National Basic Research Program of China; the National Natural Science Foundation of China; the Chinese Ministry of Education; the National Science Foundation of Jiangsu Province, China; and the U.S. National Science Foundation.

Source: MIT News Office