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Enhanced Natural Gas Storage to Help Reduce Global Warming
< Professor Atilhan (left) and Professor Yavuz (right) > Researchers have designed plastic-based materials that can store natural gas more effectively. These new materials can not only make large-scale, cost-effective, and safe natural gas storage possible, but further hold a strong promise for combating global warming. Natural gas (predominantly methane) is a clean energy alternative. It is stored by compression, liquefaction, or adsorption. Among these, adsorbed natural gas (ANG) storage is a more efficient, cheaper, and safer alternative to conventional compressed natural gas (CNG) and liquefied natural gas (LNG) storage approaches that have drawbacks such as low storage efficiency, high costs, and safety concerns. However, developing adsorptive materials that can more fully exploit the advantages of ANG storage has remained a challenging task. A KAIST research team led by Professor Cafer T. Yavuz from the Graduate School of Energy, Environment, Water, and Sustainability (EEWS), in collaboration with Professor Mert Atilhan’s group from Texas A&M University, synthesized 29 unique porous polymeric structures with inherent flexibility, and tested their methane gas uptake capacity at high pressures. These porous polymers had varying synthetic complexities, porosities, and morphologies, and the researchers subjected each porous polymer to pure methane gas under various conditions to study the ANG performances. Of these 29 distinct chemical structures, COP-150 was particularly noteworthy as it achieved a high deliverable gravimetric methane working capacity when cycled between 5 and 100 bar at 273 K, which is 98% of the total uptake capacity. This result surpassed the target set by the United States Department of Energy (US DOE). COP-150 is the first ever structure to fulfil both the gravimetric and volumetric requirements of the US DOE for successful vehicular use, and the total cost to produce the COP-150 adsorbent was only 1 USD per kilogram. COP-150 can be produced using freely available and easily accessible plastic materials, and moreover, its synthesis takes place at room temperature, open to the air, and no previous purification of the chemicals is required. The pressure-triggered flexible structure of COP-150 is also advantageous in terms of the total working capacity of deliverable methane for real applications. The research team believed that the increased pressure flexes the network structure of COP-150 showing “swelling” behavior, and suggested that the flexibility provides rapid desorption and thermal management, while the hydrophobicity and the nature of the covalently bonded framework allow these promising materials to tolerate harsh conditions. This swelling mechanism of expansion-contraction solves two other major issues, the team noted. Firstly, when using adsorbents based on such a mechanism, unsafe pressure spikes that may occur due to temperature swings can be eliminated. In addition, contamination can also be minimized, since the adsorbent remains contracted when no gas is stored. Professor Yavuz said, “We envision a whole host of new designs and mechanisms to be developed based on our concept. Since natural gas is a much cleaner fuel than coal and petroleum, new developments in this realm will help switching to the use of less polluting fuels.” Professor Atilhan agreed the most important impact of their research is on the environment. “Using natural gas more than coal and petroleum will significantly reduce greenhouse gas emissions. We believe, one day, we might see vehicles equipped with our materials that are run by a cleaner natural gas fuel,” he added. This study, reported in Nature Energy on July 8, was supported by National Research Foundation of Korea (NRF) grants ( NRF-2016R1A2B4011027, NRF-2017M3A7B4042140, and NRF-2017M3A7B4042235). < Suggested chemical structure of COP-150 > < Initial ingredients (left) and final product (right) of COP-150 synthesis > < Comparison of highest reported volumetric working capacities > (END)
Adsorbent That Can Selectively Remove Water Contaminants
Professor Cafer T. Yavuz and his team at the Graduate School of Energy, Environment, Water, and Sustainability (EEWS) have developed an adsorbent that can selectively capture soluble organic contaminants in water. This water treatment adsorbent is a fluorine-based nanoporous polymer that can selectively remove water-soluble micromolecules. It has the added advantage of being cheap and easily synthesized, while also being renewable. The results of this research have been published online in Nature Communication on November 10, 2016. The research paper is titled “Charge-specific Size-dependent Separation of Water-soluble Organic Molecules by Fluorinated Nanoporous Networks.” (DOI: 10.1038/ncomms13377) Water pollution is accelerating as a result of global industrial development and warming. As new materials are produced and applied in the agricultural and industrial sectors, the types of contaminants expelled as sewage and waste water are also becoming diverse. Chemicals such as dyes and pesticides can be especially harmful because they are made up of small and highly soluble organic particles that cannot be completely removed during the water treatment process, ultimately ending up in our drinking water. The current conventional water treatment systems utilize processes such as activated carbon, ozonolysis, and reverse osmosis membrane. These processes, however, are designed to remove larger organic molecules with lower solubility, thus removal of very small molecules with high solubility is difficult. In addition, these micromolecules tend to be charged, therefore are less easily separated in aqueous form. The research team aimed to remove these small molecules using a new adsorbent technology. In order to remove aqueous organic molecular contaminants, the team needed an adsorbent that can adsorb micro-sized molecules. It also needed to introduce a chemical function that would allow it to selectively adsorb molecules, and lastly, the adsorbent needed to be structurally stable as it would be used underwater. The team subsequently developed an adsorbent of fluorine-based porous organic polymer that met all the conditions listed above. By controlling the size of the pores, this adsorbent is able to selectively adsorb aqueous micromolecules of less than 1-2 nm in size. In addition, in order to separate specific contaminants, there should be a chemical functionality, such as the ability to strongly interact with the target material. Fluorine, the most electronegative atom, interacts strongly with charged soluble organic molecules. The research team incorporated fluorine into an adsorbent, enabling it to separate charged organic molecules up to 8 times faster than neutral molecules. The adsorbent developed by Professor Yavuz’s team has wide industrial applications. It can be used in batch-adsorption tests, as well as in column separation for size- and charge-specific adsorption. Professor Yavuz stated that “the charge-selective properties displayed by fluorine has the potential to be applied in desalination or water treatment processes using membranes." This paper was first-authored by Dr. Jeehye Byun, and the research was funded by KAIST’s High Risk High Return Program and the Ministry of Science, ICT and Future Planning of Korea’s Mid-Career Researcher Program, as well as its Technology Development Program to Solve Climate Change. Figure 1. Diagram conceptualizing the process of charge- and size-specific separation by the fluorine-based porous polymer adsorbent Figure 2. Difference in absorbance before and after using a porous fluorine polymer column to separate organic molecules Figure 3. Adsorption properties of a fluorine polymer according to the charge and size of organic molecules
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