Catalyst
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KAIST Develops a Fire-risk Free Self-Powered Hydrogen Production System
KAIST researchers have developed a new hydrogen production system that overcomes the current limitations of green hydrogen production. By using a water-splitting system with an aqueous electrolyte, this system is expected to block fire risks and enable stable hydrogen production.
KAIST (represented by President Kwang Hyung Lee) announced on the 22nd of October that a research team led by Professor Jeung Ku Kang from the Department of Materials Science and Engineering developed a self-powered hydrogen production system based on a high-performance zinc-air battery*.
*Zinc-air battery: A primary battery that absorbs oxygen from the air and uses it as an oxidant. Its advantage is long life, but its low electromotive force is a disadvantage.
Hydrogen (H₂) is a key raw material for synthesizing high-value-added substances, and it is gaining attention as a clean fuel with an energy density (142 MJ/kg) more than three times higher than traditional fossil fuels (gasoline, diesel, etc.). However, most current hydrogen production methods impose environmental burden as they emit carbon dioxide (CO₂).
While green hydrogen can be produced by splitting water using renewable energy sources such as solar cells and wind power, these sources are subject to irregular power generation due to weather and temperature fluctuations, leading to low water-splitting efficiency.
To overcome this, air batteries that can emit sufficient voltage (greater than 1.23V) for water splitting have been gaining attention. However, achieving sufficient capacity requires expensive precious metal catalysts and the performance of the catalyst materials becomes significantly degraded during prolonged charge and discharge cycles. Thus, it is essential to develop catalysts that are effective for the water-splitting reactions (oxygen and hydrogen evolution) and materials that can stabilize the repeated charge and discharge reactions (oxygen reduction and evolution) in zinc-air battery electrodes.
In response, Professor Kang's research team proposed a method to synthesize a non-precious metal catalyst material (G-SHELL) that is effective for three different catalytic reactions (oxygen evolution, hydrogen evolution, and oxygen reduction) by growing nano-sized, metal-organic frameworks on graphene oxide.
The team incorporated the developed catalyst material into the air cathode of a zinc-air battery, confirming that it achieved approximately five times higher energy density (797Wh/kg), high power characteristics (275.8mW/cm²), and long-term stability even under repeated charge and discharge conditions compared to conventional batteries.
Additionally, the zinc-air battery, which operates using an aqueous electrolyte, is safe from fire risks. It is expected that this system can be applied as a next-generation energy storage device when linked with water electrolysis systems, offering an environmentally friendly method for hydrogen production.
< Figure 1. Illustrations of a trifunctional graphene-sandwiched heterojunction-embedded layered lattice (G-SHELL) structure. Schematic representation of a) synthesis procedures of G-SHELL from a zeolitic imidazole framework, b) hollow core-layered shell structure with trifunctional sites for oxygen reduction evolution (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER), and c) heterojunctions, eterojunction-induced internal electric fields, and the corresponding band structure. >
Professor Kang explained, "By developing a catalyst material with high activity and durability for three different electrochemical catalytic reactions at low temperatures using simple methods, the self-powered hydrogen production system we implemented based on zinc-air batteries presents a new breakthrough to overcome the current limitations of green hydrogen production."
<Figure 2. Electrochemical performance of a ZAB-driven water-splitting cell with G-SHELL. Diagram of a self-driven water-splitting cell integrated by combining a ZAB with an alkaline water electrolyzer.>
PhD candidate Dong Won Kim and Jihoon Kim, a master's student in the Department of Materials Science and Engineering at KAIST, were co-first authors of this research, which was published in the international journal Advanced Science on September 17th in the multidisciplinary field of materials science. (Paper Title: “Trifunctional Graphene-Sandwiched Heterojunction-Embedded Layered Lattice Electrocatalyst for High Performance in Zn-Air Battery-Driven Water Splitting”)
This research was supported by the Nano and Material Technology Development Program of the Ministry of Science and ICT and the National Research Foundation of Korea’s Future Technology Research Laboratory.
2024.10.22 View 1011 -
KAIST Changes the Paradigm of Drug Discovery with World's First Atomic Editing
In pioneering drug development, the new technology that enables the easy and rapid editing of key atoms responsible for drug efficacy has been regarded as a fundamental and "dream" technology, revolutionizing the process of discovering potential drug candidates. KAIST researchers have become the first in the world to successfully develop single-atom editing technology that maximizes drug efficacy.
On October 8th, KAIST (represented by President Kwang-Hyung Lee) announced that Professor Yoonsu Park’s research team from the Department of Chemistry successfully developed technology that enables the easy editing and correction of oxygen atoms in furan compounds into nitrogen atoms, directly converting them into pyrrole frameworks, which are widely used in pharmaceuticals.
< Image. Conceptual image illustrating the main idea of the research >
This research was published in the prestigious scientific journal Science on October 3rd under the title "Photocatalytic Furan-to-Pyrrole Conversion."
Many drugs have complex chemical structures, but their efficacy is often determined by a single critical atom. Atoms like oxygen and nitrogen play a central role in enhancing the pharmacological effects of these drugs, particularly against viruses.
This phenomenon, where the introduction of specific atoms into a drug molecule dramatically affects its efficacy, is known as the "Single Atom Effect." In leading-edge drug development, discovering atoms that maximize drug efficacy is key.
However, evaluating the Single Atom Effect has traditionally required multi-step, costly synthesis processes, as it has been difficult to selectively edit single atoms within stable ring structures containing oxygen or nitrogen.
Professor Park’s team overcame this challenge by introducing a photocatalyst that uses light energy. They developed a photocatalyst that acts as a “molecular scissor,” freely cutting and attaching five-membered rings, enabling single-atom editing at room temperature and atmospheric pressure—a world first.
The team discovered a new reaction mechanism in which the excited molecular scissor removes oxygen from furan via single-electron oxidation and then sequentially adds a nitrogen atom.
Donghyeon Kim and Jaehyun You, the study's first authors and candidates in KAIST’s integrated master's and doctoral program in the Department of Chemistry, explained that this technique offers high versatility by utilizing light energy to replace harsh conditions. They further noted that the technology enables selective editing, even when applied to complex natural products or pharmaceuticals. Professor Yoonsu Park, who led the research, remarked, "This breakthrough, which allows for the selective editing of five-membered organic ring structures, will open new doors for building libraries of drug candidates, a key challenge in pharmaceuticals. I hope this foundational technology will be used to revolutionize the drug development process."
The significance of this research was highlighted in the Perspective section of Science, a feature where a peer scientist of prominence outside of the project group provides commentary on an impactful research.
This research was supported by the National Research Foundation of Korea’s Creative Research Program, the Cross-Generation Collaborative Lab Project at KAIST, and the POSCO Science Fellowship of the POSCO TJ Park Foundation.
2024.10.11 View 1289 -
A KAIST Research Team Develops Diesel Reforming Catalyst Enabling Hydrogen Production for Future Mobile Fuel Cells
This catalyst capability allowing stable hydrogen production from commercial diesel is expected to be applied in mobile fuel cell systems in the future hydrogen economy
On August 16, a joint research team led by Professors Joongmyeon Bae and Kang Taek Lee of KAIST’s Department of Mechanical Engineering and Dr. Chan-Woo Lee of Korea Institute of Energy Research (KIER) announced the successful development of a highly active and durable reforming catalyst allowing hydrogen production from commercial diesel.
Fuel reforming is a hydrogen production technique that extracts hydrogen from hydrocarbons through catalytic reactions. Diesel, being a liquid fuel, has a high storage density for hydrogen and is easy to transport and store. There have therefore been continuous research efforts to apply hydrogel supply systems using diesel reformation in mobile fuel cells, such as for auxiliary power in heavy trucks or air-independent propulsion (AIP) systems in submarines.
However, diesel is a mixture of high hydrocarbons including long-chained paraffin, double-bonded olefin, and aromatic hydrocarbons with benzene groups, and it requires a highly active catalyst to effectively break them down. In addition, the catalyst must be extremely durable against caulking and sintering, as they are often the main causes of catalyst degradation. Such challenges have limited the use of diesel reformation technologies to date.
The joint research team successfully developed a highly active and durable diesel reforming catalyst through elution (a heat treatment method used to uniformly grow active metals retained in an oxide support as ions in the form of metal nanoparticles), forming alloy nanoparticles. The design was based on the fact that eluted nanoparticles strongly interact with the support, allowing a high degree of dispersion at high temperatures, and that producing an alloy from dissimilar metals can increase the performance of catalysts through a synergistic effect.
The research team introduced a solution combustion synthesis method to produce a multi-component catalyst with a trace amount of platinum (Pt) and ruthenium (Ru) penetrated into a ceria (CeO2) lattice, which is a structure commonly used as a support for catalysts in redox reactions. When exposed to a diesel reforming reaction environment, the catalyst induces Pt-Ru alloy nanoparticle formation upon Pt and Ru elution onto the support surface.
In addition to the catalyst analysis, the research team also succeeded in characterizing the behaviour of active metal elution and alloy formation from an energetic perspective using a density functional theory-based calculation. In a performance comparison test between the Pt-Ru alloy catalyst against existing single-metal catalysts, the reforming activity was shown to have improved, as it showed a 100% fuel conversion rate even at a low temperature (600oC, compared to the original 800oC). In a long-term durability test (800oC, 200 hours), the catalyst showed commercial stability by successfully producing hydrogen from commercial diesel without performance degradation.
The study was conducted by Ph.D. candidate Jaemyung Lee of KAIST’s Department of Mechanical Engineering as the first author. Ph.D. candidate Changho Yeon of KIER, Dr. Jiwoo Oh of KAIST’s Department of Mechanical Engineering, Dr. Gwangwoo Han of KIER, Ph.D. candidate Jeong Do Yoo of KAIST’s Department of Mechanical Engineering, and Dr. Hyung Joong Yun of the Korea Basic Science Institute contributed as co-authors. Dr. Chan-Woo Lee of KIER and Professors Kang Taek Lee and Joongmyeon Bae of KAIST’s Department of Mechanical Engineering contributed as corresponding authors. The research was published in the online version of Applied Catalysis B: Environmental (IF 24.319, JCR 0.93%) on June 17, under the title “Highly Active and Stable Catalyst with Exsolved PtRu Alloy Nanoparticles for Hydrogen Production via Commercial Diesel Reforming”.
Professor Joongmyeon Bae said, “The fact that hydrogen can be stably produced from commercial diesel makes this a very meaningful achievement, and we look forward to this technology contributing to the active introduction of mobile fuel cell systems in the early hydrogen economy.” He added, “Our approach to catalyst design may be applied not only to reforming reactions, but also in various other fields.”
This research was supported by the National Research Foundation of Korea through funding from the Ministry of Science, ICT and Future Planning.
Figure. Schematic diagram of high-performance diesel reforming catalyst with eluted platinum-ruthenium alloy nanoparticles and long-term durability verification experiment results for commercial diesel reforming reaction
2022.09.07 View 8807 -
Professor Mu-Hyun Baik Honored with the POSCO TJ Park Prize
Professor Mu-Hyun Baik at the Department of Chemistry was honored to be the recipient of the 2021 POSCO TJ Park Prize in Science. The POSCO TJ Park Foundation awards every year the individual or organization which made significant contribution in science, education, community development, philanthropy, and technology.
Professor Baik, a renowned computational chemist in analyzing complicated chemical reactions to understand how molecules behave and how they change. Professor Baik was awarded in recognition of his pioneering research in designing numerous organometallic catalysts with using computational molecular modelling. In 2016, he published in Science on the catalytic borylation of methane that showed how chemical reactions can be carried out using the natural gas methane as a substrate.
In 2020, he reported in Science that electrodes can be used as functional groups with adjustable inductive effects to change the chemical reactivity of molecules that are attached to them, closely mimicking the inductive effect of conventional functional groups. This constitutes a potentially powerful new way of controlling chemical reactions, offering an alternative to preparing derivatives to install electron-withdrawing functional groups.
Joined at KAIST in 2015, Professor Baik also serves as associate director at the Center for Catalytic Hydrocarbon Functionalization at the Institute for Basic Science (IBS) since 2015. Among the many recognitions and awards that he received include the Kavli Fellowship by the Kavli Foundation and the National Academy of Science in the US in 2019 and the 2018 Friedrich Wilhelm Bessel Award by the Alexander von Humboldt Foundation in Germany.
2021.03.11 View 7396 -
Chemical Scissors Snip 2D Transition Metal Dichalcogenides into Nanoribbon
New ‘nanoribbon’ catalyst should slash cost of hydrogen production for clean fuels
Researchers have identified a potential catalyst alternative – and an innovative way to produce them using chemical ‘scissors’ – that could make hydrogen production more economical.
The research team led by Professor Sang Ouk Kim at the Department of Materials Science and Engineering published their work in Nature Communications.
Hydrogen is likely to play a key role in the clean transition away from fossil fuels and other processes that produce greenhouse gas emissions. There is a raft of transportation sectors such as long-haul shipping and aviation that are difficult to electrify and so will require cleanly produced hydrogen as a fuel or as a feedstock for other carbon-neutral synthetic fuels. Likewise, fertilizer production and the steel sector are unlikely to be “de-carbonized” without cheap and clean hydrogen.
The problem is that the cheapest methods by far of producing hydrogen gas is currently from natural gas, a process that itself produces the greenhouse gas carbon dioxide–which defeats the purpose.
Alternative techniques of hydrogen production, such as electrolysis using an electric current between two electrodes plunged into water to overcome the chemical bonds holding water together, thereby splitting it into its constituent elements, oxygen and hydrogen are very well established. But one of the factors contributing to the high cost, beyond being extremely energy-intensive, is the need for the very expensive precious and relatively rare metal platinum. The platinum is used as a catalyst–a substance that kicks off or speeds up a chemical reaction–in the hydrogen production process.
As a result, researchers have long been on the hunt for a substitution for platinum -- another catalyst that is abundant in the earth and thus much cheaper.
Transition metal dichalcogenides, or TMDs, in a nanomaterial form, have for some time been considered a good candidate as a catalyst replacement for platinum. These are substances composed of one atom of a transition metal (the elements in the middle part of the periodic table) and two atoms of a chalcogen element (the elements in the third-to-last column in the periodic table, specifically sulfur, selenium and tellurium).
What makes TMDs a good bet as a platinum replacement is not just that they are much more abundant, but also their electrons are structured in a way that gives the electrodes a boost.
In addition, a TMD that is a nanomaterial is essentially a two-dimensional super-thin sheet only a few atoms thick, just like graphene. The ultrathin nature of a 2-D TMD nanosheet allows for a great many more TMD molecules to be exposed during the catalysis process than would be the case in a block of the stuff, thus kicking off and speeding up the hydrogen-making chemical reaction that much more.
However, even here the TMD molecules are only reactive at the four edges of a nanosheet. In the flat interior, not much is going on. In order to increase the chemical reaction rate in the production of hydrogen, the nanosheet would need to be cut into very thin – almost one-dimensional strips, thereby creating many edges.
In response, the research team developed what are in essence a pair of chemical scissors that can snip TMD into tiny strips.
“Up to now, the only substances that anyone has been able to turn into these ‘nano-ribbons’ are graphene and phosphorene,” said Sang Professor Kim, one of the researchers involved in devising the process.
“But they’re both made up of just one element, so it’s pretty straightforward. Figuring out how to do it for TMD, which is made of two elements was going to be much harder.”
The ‘scissors’ involve a two-step process involving first inserting lithium ions into the layered structure of the TMD sheets, and then using ultrasound to cause a spontaneous ‘unzipping’ in straight lines.
“It works sort of like how when you split a plank of plywood: it breaks easily in one direction along the grain,” Professor Kim continued. “It’s actually really simple.”
The researchers then tried it with various types of TMDs, including those made of molybdenum, selenium, sulfur, tellurium and tungsten. All worked just as well, with a catalytic efficiency as effective as platinum’s.
Because of the simplicity of the procedure, this method should be able to be used not just in the large-scale production of TMD nanoribbons, but also to make similar nanoribbons from other multi-elemental 2D materials for purposes beyond just hydrogen production.
-ProfileProfessor Sang Ouk KimSoft Nanomaterials Laboratory (http://snml.kaist.ac.kr)Department of Materials Science and EngineeringKAIST
2020.10.29 View 6836 -
3D Hierarchically Porous Nanostructured Catalyst Helps Efficiently Reduce CO2
- This new catalyst will bring CO2 one step closer to serving as a sustainable energy source. -
KAIST researchers developed a three-dimensional (3D) hierarchically porous nanostructured catalyst with carbon dioxide (CO2) to carbon monoxide (CO) conversion rate up to 3.96 times higher than that of conventional nanoporous gold catalysts. This new catalyst helps overcome the existing limitations of the mass transport that has been a major cause of decreases in the CO2 conversion rate, holding a strong promise for the large-scale and cost-effective electrochemical conversion of CO2 into useful chemicals.
As CO2 emissions increase and fossil fuels deplete globally, reducing and converting CO2 to clean energy electrochemically has attracted a great deal of attention as a promising technology. Especially due to the fact that the CO2 reduction reaction occurs competitively with hydrogen evolution reactions (HER) at similar redox potentials, the development of an efficient electrocatalyst for selective and robust CO2 reduction reactions has remained a key technological issue.
Gold (Au) is one of the most commonly used catalysts in CO2 reduction reactions, but the high cost and scarcity of Au pose obstacles for mass commercial applications. The development of nanostructures has been extensively studied as a potential approach to improving the selectivity for target products and maximizing the number of active stable sites, thus enhancing the energy efficiency.
However, the nanopores of the previously reported complex nanostructures were easily blocked by gaseous CO bubbles during aqueous reactions. The CO bubbles hindered mass transport of the reactants through the electrolyte, resulting in low CO2 conversion rates.
In the study published in the Proceedings of the National Academy of Sciences of the USA (PNAS) on March 4, a research group at KAIST led by Professor Seokwoo Jeon and Professor Jihun Oh from the Department of Materials Science and Engineering designed a 3D hierarchically porous Au nanostructure with two different sizes of macropores and nanopores. The team used proximity-field nanopatterning (PnP) and electroplating techniques that are effective for fabricating the 3D well-ordered nanostructures.
The proposed nanostructure, comprised of interconnected macroporous channels 200 to 300 nanometers (nm) wide and 10 nm nanopores, induces efficient mass transport through the interconnected macroporous channels as well as high selectivity by producing highly active stable sites from numerous nanopores.
As a result, its electrodes show a high CO selectivity of 85.8% at a low overpotential of 0.264 V and efficient mass activity that is up to 3.96 times higher than that of de-alloyed nanoporous Au electrodes.
“These results are expected to solve the problem of mass transfer in the field of similar electrochemical reactions and can be applied to a wide range of green energy applications for the efficient utilization of electrocatalysts,” said the researchers.
This work was supported by the National Research Foundation (NRF) of Korea.
Image credit: Professor Seokwoo Jeon and Professor Jihun Oh, KAIST
Image usage restrictions: News organizations may use or redistribute this image, with proper attribution, as part of news coverage of this paper only.
Publication:
Hyun et al. (2020) Hierarchically porous Au nanostructures with interconnected channels for efficient mass transport in electrocatalytic CO2 reduction. Proceedings of the National Academy of Sciences of the USA (PNAS). Available online at https://doi.org/10.1073/pnas.1918837117
Profile:
Seokwoo Jeon, PhD
Professor
jeon39@kaist.ac.kr
http://fdml.kaist.ac.kr
Department of Materials Science and Engineering (MSE)
https://www.kaist.ac.kr
Korea Advanced Institute of Science and Technology (KAIST)Daejeon, Republic of Korea
Profile:
Jihun Oh, PhD
Associate Professor
jihun.oh@kaist.ac.kr
http://les.kaist.ac.kr
Department of Materials Science and Engineering (MSE)
Department of Energy, Environment, Water and Sustainability (EEWS)
KAIST
Profile:
Gayea Hyun
PhD Candidate
cldywkd93@kaist.ac.kr
http://fdml.kaist.ac.kr
Flexible Devices and Metamaterials Laboratory (FDML)
Department of Materials Science and Engineering (MSE)
KAIST
Profile:
Jun Tae Song, PhD
Assistant Professor
song.juntae@cstf.kyushu-u.ac.jp
http://www.cstf.kyushu-u.ac.jp/~ishihara-lab/
Department of Applied Chemistry
https://www.kyushu-u.ac.jp
Kyushu UniversityFukuoka, Japan
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2020.03.13 View 14849 -
New Catalyst Recycles Greenhouse Gases into Fuel and Hydrogen Gas
< Professor Cafer T. Yavuz (left), PhD Candidate Youngdong Song (center), and Researcher Sreerangappa Ramesh (right) >
Scientists have taken a major step toward a circular carbon economy by developing a long-lasting, economical catalyst that recycles greenhouse gases into ingredients that can be used in fuel, hydrogen gas, and other chemicals. The results could be revolutionary in the effort to reverse global warming, according to the researchers. The study was published on February 14 in Science.
“We set out to develop an effective catalyst that can convert large amounts of the greenhouse gases carbon dioxide and methane without failure,” said Cafer T. Yavuz, paper author and associate professor of chemical and biomolecular engineering and of chemistry at KAIST.
The catalyst, made from inexpensive and abundant nickel, magnesium, and molybdenum, initiates and speeds up the rate of reaction that converts carbon dioxide and methane into hydrogen gas. It can work efficiently for more than a month.
This conversion is called ‘dry reforming’, where harmful gases, such as carbon dioxide, are processed to produce more useful chemicals that could be refined for use in fuel, plastics, or even pharmaceuticals. It is an effective process, but it previously required rare and expensive metals such as platinum and rhodium to induce a brief and inefficient chemical reaction.
Other researchers had previously proposed nickel as a more economical solution, but carbon byproducts would build up and the surface nanoparticles would bind together on the cheaper metal, fundamentally changing the composition and geometry of the catalyst and rendering it useless.
“The difficulty arises from the lack of control on scores of active sites over the bulky catalysts surfaces because any refinement procedures attempted also change the nature of the catalyst itself,” Yavuz said.
The researchers produced nickel-molybdenum nanoparticles under a reductive environment in the presence of a single crystalline magnesium oxide. As the ingredients were heated under reactive gas, the nanoparticles moved on the pristine crystal surface seeking anchoring points. The resulting activated catalyst sealed its own high-energy active sites and permanently fixed the location of the nanoparticles — meaning that the nickel-based catalyst will not have a carbon build up, nor will the surface particles bind to one another.
“It took us almost a year to understand the underlying mechanism,” said first author Youngdong Song, a graduate student in the Department of Chemical and Biomolecular Engineering at KAIST. “Once we studied all the chemical events in detail, we were shocked.”
The researchers dubbed the catalyst Nanocatalysts on Single Crystal Edges (NOSCE). The magnesium-oxide nanopowder comes from a finely structured form of magnesium oxide, where the molecules bind continuously to the edge. There are no breaks or defects in the surface, allowing for uniform and predictable reactions.
“Our study solves a number of challenges the catalyst community faces,” Yavuz said. “We believe the NOSCE mechanism will improve other inefficient catalytic reactions and provide even further savings of greenhouse gas emissions.”
This work was supported, in part, by the Saudi-Aramco-KAIST CO2 Management Center and the National Research Foundation of Korea.
Other contributors include Ercan Ozdemir, Sreerangappa Ramesh, Aldiar Adishev, and Saravanan Subramanian, all of whom are affiliated with the Graduate School of Energy, Environment, Water and Sustainability at KAIST; Aadesh Harale, Mohammed Albuali, Bandar Abdullah Fadhel, and Aqil Jamal, all of whom are with the Research and Development Center in Saudi Arabia; and Dohyun Moon and Sun Hee Choi, both of whom are with the Pohang Accelerator Laboratory in Korea. Ozdemir is also affiliated with the Institute of Nanotechnology at the Gebze Technical University in Turkey; Fadhel and Jamal are also affiliated with the Saudi-Armco-KAIST CO2 Management Center in Korea.
<Newly developed catalyst that recycles greenhouse gases into ingredients that can be used in fuel, hydrogen gas and other chemicals.>
Publication:
Song et al. (2020) Dry reforming of methane by stable Ni–Mo nanocatalysts on single-crystalline MgO. Science, Vol. 367, Issue 6479, pp. 777-781. Available online at http://dx.doi.org/10.1126/science.aav2412
Profile: Prof. Cafer T. Yavuz, MA, PhD
yavuz@kaist.ac.kr
http://yavuz.kaist.ac.kr/
Associate Professor
Oxide and Organic Nanomaterials for the Environment (ONE) Laboratory
Graduate School of Energy, Environment, Water and Sustainability (EEWS)
Korea Advanced Institute of Science and Technology (KAIST)
http://kaist.ac.kr
Daejeon, Republic of Korea
Profile: Youngdong Song ydsong88@kaist.ac.kr
Ph.D. Candidate
Department of Chemical and Biomolecular Engineering
Korea Advanced Institute of Science and Technology (KAIST)
http://kaist.ac.kr
Daejeon, Republic of Korea
(END)
2020.02.17 View 14965 -
Tungsten Suboxide Improves the Efficiency of Platinum in Hydrogen Production
< PhD Candidate Jinkyu Park and Professor Jinwoo Lee >
Researchers presented a new strategy for enhancing catalytic activity using tungsten suboxide as a single-atom catalyst (SAC). This strategy, which significantly improves hydrogen evolution reaction (HER) in metal platinum (pt) by 16.3 times, sheds light on the development of new electrochemical catalyst technologies.
Hydrogen has been touted as a promising alternative to fossil fuels. However, most of the conventional industrial hydrogen production methods come with environmental issues, releasing significant amounts of carbon dioxide and greenhouse gases.
Electrochemical water splitting is considered a potential approach for clean hydrogen production. Pt is one of the most commonly used catalysts to improve HER performance in electrochemical water splitting, but the high cost and scarcity of Pt remain key obstacles to mass commercial applications.
SACs, where all metal species are individually dispersed on a desired support material, have been identified as one way to reduce the amount of Pt usage, as they offer the maximum number of surface exposed Pt atoms.
Inspired by earlier studies, which mainly focused on SACs supported by carbon-based materials, a KAIST research team led by Professor Jinwoo Lee from the Department of Chemical and Biomolecular Engineering investigated the influence of support materials on the performance of SACs.
Professor Lee and his researchers suggested mesoporous tungsten suboxide as a new support material for atomically dispersed Pt, as this was expected to provide high electronic conductivity and have a synergetic effect with Pt.
They compared the performance of single-atom Pt supported by carbon and tungsten suboxide respectively. The results revealed that the support effect occurred with tungsten suboxide, in which the mass activity of a single-atom Pt supported by tungsten suboxide was 2.1 times greater than that of single-atom Pt supported by carbon, and 16.3 times higher than that of Pt nanoparticles supported by carbon.
The team indicated a change in the electronic structure of Pt via charge transfer from tungsten suboxide to Pt. This phenomenon was reported as a result of strong metal-support interaction between Pt and tungsten suboxide.
HER performance can be improved not only by changing the electronic structure of the supported metal, but also by inducing another support effect, the spillover effect, the research group reported. Hydrogen spillover is a phenomenon where adsorbed hydrogen migrates from one surface to another, and it occurs more easily as the Pt size becomes smaller.
The researchers compared the performance of single-atom Pt and Pt nanoparticles supported by tungsten suboxide. The single-atom Pt supported by tungsten suboxide exhibited a higher degree of hydrogen spillover phenomenon, which enhanced the Pt mass activity for hydrogen evolution up to 10.7 times compared to Pt nanoparticles supported by tungsten suboxide.
Professor Lee said, “Choosing the right support material is important for improving electrocatalysis in hydrogen production. The tungsten suboxide catalyst we used to support Pt in our study implies that interactions between the well-matched metal and support can drastically enhance the efficiency of the process.”
This research was supported by the Ministry of Science and ICT and introduced in the International Edition of the German journal Angewandte Chemie.
Figure. Schematic representation of hydrogen evolution reaction (HER) of pseudo single-atom Pt supported by tungsten suboxide
-Publication
Jinkyu Park, Dr. Seonggyu Lee, Hee-Eun Kim, Ara Cho, Seongbeen Kim, Dr. Youngjin Ye, Prof. Jeong Woo Han, Prof. Hyunjoo Lee, Dr. Jong Hyun Jang, and Prof. Jinwoo Lee. 2019. Investigation of the Support Effect in Atomically Dispersed Pt on WO3−x for Utilization of Pt in the Hydrogen Evolution Reaction. International Edition of Angewandte Chemie. Volume No. 58. Issue No. 45. 6 pages. https://doi.org/10.1002/anie.201908122
-ProfileProfessor Jinwoo LeeConvergence of Energy and Nano Science Laboratoryhttp://cens.kaist.ac.kr
Department of Chemical and Biomolecular EngineeringKAIST
2019.10.28 View 18738 -
The 1st Korea Toray Science and Technology Awardee, Prof. Sukbok Chang
(Distinguished Professor Sukbok Chang from the Department of Chemistry)
The Korea Toray Science Foundation (KTSF) awarded the first Korea Toray Science Technology Award in basic science to Distinguished Professor Sukbok Chang from the Department of Chemistry on September 19.
KTSF was established in January 2018, and its award goes to researchers who have significantly contributed to the development of chemistry and materials research with funds to support research projects.
Distinguished Professor Chang has devoted himself in organocatalysis research; in particular, his work on catalysts for effective lactam formation, which was an intricate problem, received great attention.
The award ceremony will take place in The Federation of Korean Industries Hall on October 31. KTFS board members, judges, and the CEO of Toray Industries Akihiro Nikkaku will attend the ceremony. Also, Dr. Ryoji Noyori, the Nobel Laureate in Chemistry, will give a talk on the role of chemistry and creative challenges as a researcher.
2018.10.04 View 7004 -
EEWS Graduate School Team Receives the S-Oil Best Paper Award
Professor Hyungjun Kim and Dr. He-Young Shin from the EEWS (Energy, Environment, Water and Sustainability) Graduate School at KAIST received the Best Paper Award in Chemistry from S-Oil, a Korean petroleum and refinery company, on November 29, 2016.
Established in 2011, the S-Oil Best Paper Awards are bestowed annually upon ten young scientists in the fields of five basic sciences: mathematics, physics, chemistry, biology, and earth science. The scientists are selected at the recommendation of the Korean Academy of Science and Technology and the Association of Korean Universities. The awards grant a total of USD 230,000 for research funding.
Dr. Shin, the lead author of the awarded research paper, said, “My research interest has been catalyst studies based on theoretical chemistry. I am pleased to accept this award that will support my studies, and will continue to research catalyst design that can predict parameters and integrate them into catalytic systems.”
Professor Hyungjun Kim (left) and Dr. He-Young Shin (right)
2016.12.23 View 8300 -
Synthesized Microporous 3D Graphene-like Carbons
Distinguished Professor Ryong Ryoo of the Chemistry Department at KAIST, who is also the Director of the Center for Nanomaterials and Carbon Materials at the Institute for Basic Science (IBS), and his research team have recently published their research results entitled "Lanthanum-catalysed Synthesis of Microporous 3D Graphene-like Carbons in a Zeolite Template" on June 29, 2016 in Nature on a new method to synthesize carbons having graphene structures with 3D periodic micropores, a trait resulted from using a zeolite as a template for the synthesis. The research team expects this technology to find a range of useful applications such as in batteries and catalysts.
Graphene, an allotrope of carbon, which was discovered more than a decade ago, has led to myriad research that seeks to unlock its vast potential. Zeolites, commonly used microporous solid catalysts in the petrochemical industry, have recently attracted attention in the field of material science as a template for carbon synthesis. Zeolites’ individual crystal is distinguished by its unique 1 nanometer (nm)-size pore structures. These structures facilitate the accommodation of carbon nanotubes inside zeolites. In their paper, the research team showed that these nanoporous systems are an ideal template for the carbon synthesis of three-dimensional (3D) graphene architecture, but zeolite pores are too small to accommodate bulky molecular compounds like polyaromatic and furfuryl alcohol that are often used in carbon synthesis. Small molecules like ethylene and acetylene can be used as a carbon source to achieve successful carbonization within zeolite pores, but it comes at a great cost. The high temperatures required for the synthesis cause reactions of carbons being deposited randomly on the external surfaces of zeolites as well as their internal pore walls, resulting in coke deposition and consequently, causing serious diffusion limitations in the zeolite pores.
The team from the IBS Center for Nanomaterials and Carbon Materials solved this conundrum with a novel approach. First author Dr. KIM Kyoungsoo explains: “The zeolite-template carbon synthesis has existed for a long time, but the problem with temperatures has foiled many scientists from extracting their full potential. Here, our team sought to find the answer by embedding lanthanum ions (La3+), a silvery-white metal element, in zeolite pores. This lowers the temperature required for the carbonization of ethylene or acetylene. Graphene-like sp2 carbon structures can be selectively formed inside the zeolite template, without carbon deposition at the external surfaces. After the zeolite template is removed, the carbon framework exhibits the electrical conductivity two orders of magnitude higher than amorphous mesoporous carbon, which is a pretty astonishing result. This highly efficient synthesis strategy based on the lanthanum ions renders the carbon framework to be formed in pores with a less than 1 nm diameter, just like as easily reproducible as in mesoporous templates. This provides a general method to synthesize carbon nanostructures with various topologies corresponding to the template zeolite pore topologies, such as FAU, EMT, beta, LTL, MFI, and LTA. Also, all the synthesis can be readily scaled up, which is important for practical applications in areas of batteries, fuel storage, and other zeolite-like catalyst supports.”
The research team began their experiment by utilizing La3+ ions. Dr. KIM elucidates why this silvery-white element proved so beneficial to the team, “La3+ ions are unreducible under carbonization process condition, so they can stay inside the zeolite pores instead of moving to the outer zeolite surface in the form of reduced metal particles. Within the pores, they can stabilize ethylene and the pyrocondensation intermediately to form a carbon framework in zeolites.”
In order to test this hypothesis, the team compared the amount of carbon deposited in La3+-containing form of Y zeolite (LaY) sample against a host of other samples such as NaY and HY. The experimental results indicate that all the LaY, NaY, and HY zeolite samples show rapid carbon deposition at 800°C. However, as the temperature decreases, there appears to be a dramatic difference between the different ionic forms of zeolites. At 600°C, the LaY zeolite is still active as a carbon deposition template. In contrast, both NaY and HY lose their carbon deposition functions almost completely.
The results, according to their paper published in Nature, highlight a catalytic effect of lanthanum for carbonization. By making graphene with 3D periodic nanoporous architectures, it promises a wide range of useful applications such as in batteries and catalysts but due to the lack of efficient synthetic strategies, such applications have not yet been successful. By taking advantage of the pore-selective carbon filling at decreased temperatures, the synthesis can readily be scaled up for studies requiring bulk quantities of carbon, in particular high electrical conductivity, which is a highly sought aspect for the production of batteries.
YouTube Link: https://youtu.be/lkNiHiB8lBk
Image 1: (Top to Bottom) Zeolite Template: Microporous Aluminosilicate; Zeolite ion exchanged with La3+ ions in aqueous solution; and Zeolite Template with La3+ ions
Image 2: (Top to Bottom) Catalytic carbonization progressed at La3+ ions-exchanged sites using ethylene as a carbon precursor. Carbon is highlighted in grey; Zeolite template removed in an acid solution (HF/ HCl); Microporous 3D graphene-like carbon
2016.07.01 View 8631 -
Spillover Phenomenon Identified Using Model Catalyst System
Researchers at KAIST have identified spillover phenomenon, which has remained controversial since its discovery in the early 1960s.
KAIST Department of Chemical and Biomolecular Engineering’s Professor Min-Gi Choi and his team has explained the "spillover phenomenon," using their own model catalyst system where platinum is selectively located within the amorphous aluminosilicate.
The research results were published on the 25th February online edition of Nature Communications.
Spillover refers to a phenomenon that occurs when hydrogen atoms that have been activated on the surface of metals, such as platinum, move to the surface of the catalyst. It was predicted that this phenomenon can be used to design a catalyst with high activity and stability, and thus has been actively studied over the last 50 years.
However, many cases of the known catalysts involved competing reactions on the exposed metal surface, which made it impossible to directly identify the presence and formation mechanism of spillover.
The catalysts developed by the researchers at KAIST used platinum nanoparticles covered with aluminosilicate. This only allowed the hydrogen molecules to pass through and has effectively blocked the competing reactions, enabling the research team to study the spillover phenomenon.
Through various catalyst structure and reactivity analysis, as well as computer modeling, the team has discovered that Brönsted acid sites present on the aluminosilicate plays a crucial role in spillover phenomenon.
In addition, the spillover-based hydrogenation catalyst proposed by the research team showed very high hydrogenation and dehydrogenation activity. The ability of the catalyst to significantly inhibit unwanted hydrogenolysis reaction during the petrochemical processes also suggested a large industrial potential.
Professor Min-Gi Choi said, “This particular catalyst, which can trigger the reaction only by spillover phenomenon, can be properly designed to exceed the capacity of the conventional metal catalysts. The future goal is to make a catalyst with much higher activity and selectivity.”
The research was conducted through funds subsidized by SK Innovation and Ministry of Science, ICT and Future Planning.
The senior research fellow of SK Innovation Seung-Hun Oh said, “SK Innovation will continue to develop a new commercial catalyst based on the technology from this research.”
Juh-Wan Lim and Hye-Yeong Shin led the research as joint first authors under supervision of Professor Min-Gi Choi and computer modeling works were conducted by KAIST EEWS (environment, energy, water, and sustainability) graduate school’s Professor Hyeong-Jun Kim.
2014.03.03 View 9317