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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 21112 -
Algorithm Identifies Optimal Pairs for Composing Metal-Organic Frameworks
The integration of metal-organic frameworks (MOFs) and other metal nanoparticles has increasingly led to the creation of new multifunctional materials. Many researchers have integrated MOFs with other classes of materials to produce new structures with synergetic properties.
Despite there being over 70,000 collections of synthesized MOFs that can be used as building blocks, the precise nature of the interaction and the bonding at the interface between the two materials still remains unknown. The question is how to sort out the right matching pairs out of 70,000 MOFs.
An algorithmic study published in Nature Communications by a KAIST research team presents a clue for finding the perfect pairs. The team, led by Professor Ji-Han Kim from the Department of Chemical and Biomolecular Engineering, developed a joint computational and experimental approach to rationally design MOF@MOFs, a composite of MOFs where an MOF is grown on a different MOF.
Professor Kim’s team, in collaboration with UNIST, noted that the metal node of one MOF can coordinately bond with the linker of a different MOF and the precisely matched interface configurations at atomic and molecular levels can enhance the likelihood of synthesizing MOF@MOFs.
They screened thousands of MOFs and identified optimal MOF pairs that can seamlessly connect to one another by taking advantage of the fact that the metal node of one MOF can form coordination bonds with the linkers of the second MOF. Six pairs predicted from the computational algorithm successfully grew into single crystals.
This computational workflow can readily extend into other classes of materials and can lead to the rapid exploration of the composite MOFs arena for accelerated materials development. Even more, the workflow can enhance the likelihood of synthesizing MOF@MOFs in the form of large single crystals, and thereby demonstrated the utility of rationally designing the MOF@MOFs.
This study is the first algorithm for predicting the synthesis of composite MOFs, to the best of their knowledge. Professor Kim said, “The number of predicted pairs can increase even more with the more general 2D lattice matching, and it is worth investigating in the future.”
This study was supported by Samsung Research Funding & Incubation Center of Samsung Electronics.
(Figure: An example of a rationally synthesized MOF@MOFs (cubic HKUST-1@MOF-5 ))
2019.08.30 View 16777 -
Artificial Muscles Bloom, Dance, and Wave
Wearing a flower brooch that blooms before your eyes sounds like magic. KAIST researchers have made it real with robotic muscles.
Researchers have developed an ultrathin, artificial muscle for soft robotics. The advancement, recently reported in the journal Science Robotics, was demonstrated with a robotic blooming flower brooch, dancing robotic butterflies and fluttering tree leaves on a kinetic art piece.
The robotic equivalent of a muscle that can move is called an actuator. The actuator expands, contracts or rotates like muscle fibers using a stimulus such as electricity. Engineers around the world are striving to develop more dynamic actuators that respond quickly, can bend without breaking, and are very durable. Soft, robotic muscles could have a wide variety of applications, from wearable electronics to advanced prosthetics.
The team from KAIST’s Creative Research Initiative Center for Functionally Antagonistic Nano-Engineering developed a very thin, responsive, flexible and durable artificial muscle. The actuator looks like a skinny strip of paper about an inch long. They used a particular type of material called MXene, which is class of compounds that have layers only a few atoms thick.
Their chosen MXene material (T3C2Tx) is made of thin layers of titanium and carbon compounds. It was not flexible by itself; sheets of material would flake off the actuator when bent in a loop. That changed when the MXene was “ionically cross-linked” — connected through an ionic bond — to a synthetic polymer. The combination of materials made the actuator flexible, while still maintaining strength and conductivity, which is critical for movements driven by electricity.
Their particular combination performed better than others reported. Their actuator responded very quickly to low voltage, and lasted for more than five hours moving continuously.
To prove the tiny robotic muscle works, the team incorporated the actuator into wearable art: an origami-inspired brooch mimics how a narcissus flower unfolds its petals when a small amount of electricity is applied. They also designed robotic butterflies that move their wings up and down, and made the leaves of a tree sculpture flutter.
“Wearable robotics and kinetic art demonstrate how robotic muscles can have fun and beautiful applications,” said Il-Kwon Oh, lead paper author and professor of mechanical engineering. “It also shows the enormous potential for small, artificial muscles for a variety of uses, such as haptic feedback systems and active biomedical devices.”
The team next plans to investigate more practical applications of MXene-based soft actuators and other engineering applications of MXene 2D nanomaterials.
2019.08.22 View 25177 -
Research Day Highlights Most Outstanding Research Achievements
Professor Byung Jin Cho from the School of Electrical Engineering was selected as the Grand Research Prize Winner in recognition of his innovative research achievement in the fields of nano electric and flexible energy devices during the 2019 KAIST Research Day ceremony held on April 23 at the Chung Kunmo Conference Hall.
The ten most outstanding research achievements from the past year were also awarded in the three areas of Research, Innovation, Convergence Researches.
Professor Cho is an internationally recognized researcher in the field of future nano and energy device technology. Professor Cho’s team has continued to research on advanced CMOS (complementary metal-oxide semiconductors). CMOS has become his key research topic over the past three decades.
In 2014, he developed a glass fabric-based thermoelectric generator, which is extremely light and flexible and produces electricity from the heat of the human body. It is so flexible that the allowable bending radius of the generator is as low as 20 mm. There are no changes in performance even if the generator bends upward and downward for up to 120 cycles. His wearable thermoelectric generator was selected as one of the top ten most promising digital technologies by the Netexplo Forum in 2015.
He now is working on high-performance and ultra-flexible CMOS IC for biomedical applications, expanding his scope to thermal haptic technology in VR using graphene-CMOS hybrid integrated circuits; to self-powered wireless sensor nodes and self-powered ECG system using wearable thermoelectric generators .
In his special lecture at the ceremony, Professor Cho stressed the importance of collaboration in making scientific research and presented how he moved to future devices after focusing on scaling the devices.
“When I started the research on semiconductors, I focused on how to scale the device down as much as possible. For decades, we have conducted a number of procedures to produce tiny but efficient materials. Now we have shifted to develop flexible thermoelements and wearable devices,” said Professor Cho.
“We all thought the scaling down is the only way to create value-added technological breakthroughs. Now, the devices have been scaled down to 7nm and will go down to 5 nm soon. Over the past few years, I think we have gone through all the possible technological breakthroughs for reducing the size to 5nm. The semiconductor devices are made of more 1 billion transistors and go through 1,000 technological processes. So, there won’t be any possible way for a single genius to make a huge breakthrough. Without collaboration with others, it is nearly impossible to make any new technological breakthroughs.”
Professor Cho has published more than 240 papers in renowned academic journals and presented more than 300 papers at academic conferences. He has also registered approximately 50 patents in the field of semiconductor device technology.
The top ten research highlights of 2018 as follows:
- Rydberg-Atom Quantum Simulator Development by Professor Jaewook Ahn and Heung-Sun Sim from the Department of Physics
- From C-H to C-C Bonds at Room Temperature by Professor Mu-Hyun Baik from the Department of Chemistry
- The Role of Rodlike Counterions on the Interactions of DNAs by Professor Yong Woon Kim of the Graduate School of Nanoscience and Technology
- The Medal Preoptic Area Induces Hunting-Like Behaviors to Target Objects and Prey by Professor Daesoo Kim from the Department of Biological Sciences
- Identification of the Origin of Brain Tumors and New Therapeutic Strategy by Professor Jeong Ho Lee from the Graduate School of Medical Science and Engineering
- The Linear Frequency Conversion of Light at a Spatiotemporal Boundary by Professor Bumki Min from the Department of Mechanical Engineering
- An Industrial Grade Flexible Transparent Force Touch Sensor by Professor Jun-Bo Yoon from the School of Electrical Engineering
- The Detection and Clustering of Mixed-Type Defect Patterns in Wafer Bin Maps by Professor Heeyoung Kim from the Department of Industrial and Systems Engineering
- The Development of a Reconfigurable Spin-Based Logic Device by Professor Byong-Guk Park from the Department of Materials Science and Engineering
- The Development of a Miniaturized X-Ray Tube Based on Carbon Nanotube and Electronic Brachytherapy Device by Professor Sung Oh Cho from the Department of Nuclear and Quantum Engineering
Professor YongKeun Park from the Department of Physics and Professor In-Chel Park from the School of Electrical Engineering received the Research Award. For the Innovation Award, Professor Munchurl Kim from the School of Electrical Engineering was the recipient and the Convergence Research Awards was conferred to Professor Sung-Yool Choi from the School of Electrical Engineering, Professor Sung Gap Im from the Department of Chemical and Biomolecular Engineering, and Professor SangHee Park from the Department of Materials Science and Engineering during the ceremony.
For more on KAIST’s Top Research Achievements and Highlight of 2018, please refer to the attached below. click.
2019.04.25 View 16061 -
True-meaning Wearable Displays: Self-powered, Washable and Wearable
(Video: The washing process of wearing display module) When we think about clothes, they are usually formed with textiles and have to be both wearable and washable for daily use; however, smart clothing has had a problem with its power sources and moisture permeability, which causes the devices to malfunction. This problem has now been overcome by a KAIST research team, who developed a textile-based wearable display module technology that is washable and does not require an external power source.
To ease out the problem of external power sources and enhance the practicability of wearable displays, Professor Kyung Cheol Choi from the School of Electrical Engineering and his team fabricated their wearing display modules on real textiles that integrated polymer solar cells (PSCs) with organic light emitting diodes (OLEDs).
PSCs have been one of the most promising candidates for a next-generation power source, especially for wearable and optoelectronic applications because they can provide stable power without an external power source, while OLEDs can be driven with milliwatts. However, the problem was that they are both very vulnerable to external moisture and oxygen. The encapsulation barrier is essential for their reliability. The conventional encapsulation barrier is sufficient for normal environments; however, it loses its characteristics in aqueous environments, such as water. It limits the commercialization of wearing displays that must operate even on rainy days or after washing.
To tackle this issue, the team employed a washable encapsulation barrier that can protect the device without losing its characteristics after washing through atomic layer deposition (ALD) and spin coating. With this encapsulation technology, the team confirmed that textile-based wearing display modules including PSCs, OLEDs, and the proposed encapsulation barrier exhibited little change in characteristics even after 20 washings with 10-minute cycles. Moreover, the encapsulated device operated stably with a low curvature radius of 3mm and boasted high reliability.
Finally, it exhibited no deterioration in properties over 30 days even after being subjected to both bending stress and washing. Since it uses a less stressful textile, compared to conventional wearable electronic devices that use traditional plastic substrates, this technology can accelerate the commercialization of wearing electronic devices. Importantly, this wearable electronic device in daily life can save energy through a self-powered system.
Professor Choi said, “I could say that this research realized a truly washable wearable electronic module in the sense that it uses daily wearable textiles instead of the plastic used in conventional wearable electronic devices. Saving energy with PSCs, it can be self-powered, using nature-friendly solar energy, and washed. I believe that it has paved the way for a ‘true-meaning wearable display’ that can be formed on textile, beyond the attachable form of wearable technology.”
This research, in collaboration with Professor Seok Ho Cho from Chonnam National University and led by Eun Gyo Jeong, was published in Energy and Environmental Science (10.1039/c8ee03271h) on January 18, 2019.
Figure 1. Schematic and photo of a washable wearing display module
Figure 2. Cover page of Energy and Environmental Science
2019.03.21 View 31443 -
KAIST Develops Analog Memristive Synapses for Neuromorphic Chips
(Professor Sung-Yool Choi from the School of Electrical Engineering)
A KAIST research team developed a technology that makes a transition of the operation mode of flexible memristors to synaptic analog switching by reducing the size of the formed filament. Through this technology, memristors can extend their role to memristive synapses for neuromorphic chips, which will lead to developing soft neuromorphic intelligent systems.
Brain-inspired neuromorphic chips have been gaining a great deal of attention for reducing the power consumption and integrating data processing, compared to conventional semiconductor chips. Similarly, memristors are known to be the most suitable candidate for making a crossbar array which is the most efficient architecture for realizing hardware-based artificial neural network (ANN) inside a neuromorphic chip.
A hardware-based ANN consists of a neuron circuit and synapse elements, the connecting pieces. In the neuromorphic system, the synaptic weight, which represents the connection strength between neurons, should be stored and updated as the type of analog data at each synapse.
However, most memristors have digital characteristics suitable for nonvolatile memory. These characteristics put a limitation on the analog operation of the memristors, which makes it difficult to apply them to synaptic devices.
Professor Sung-Yool Choi from the School of Electrical Engineering and his team fabricated a flexible polymer memristor on a plastic substrate, and found that changing the size of the conductive metal filaments formed inside the device on the scale of metal atoms can make a transition of the memristor behavior from digital to analog.
Using this phenomenon, the team developed flexible memristor-based electronic synapses, which can continuously and linearly update synaptic weight, and operate under mechanical deformations such as bending.
The team confirmed that the ANN based on these memristor synapses can effectively classify person’s facial images even when they were damaged. This research demonstrated the possibility of a neuromorphic chip that can efficiently recognize faces, numbers, and objects.
Professor Choi said, “We found the principles underlying the transition from digital to analog operation of the memristors. I believe that this research paves the way for applying various memristors to either digital memory or electronic synapses, and will accelerate the development of a high-performing neuromorphic chip.”
In a joint research project with Professor Sung Gap Im (KAIST) and Professor V. P. Dravid (Northwestern University), this study was led by Dr. Byung Chul Jang (Samsung Electronics), Dr. Sungkyu Kim (Northwestern University) and Dr. Sang Yoon Yang (KAIST), and was published online in Nano Letters (10.1021/acs.nanolett.8b04023) on January 4, 2019.
Figure 1. a) Schematic illustration of a flexible pV3D3 memristor-based electronic synapse array. b) Cross-sectional TEM image of the flexible pV3D3 memristor
2019.02.28 View 9577 -
Noninvasive Light-Sensitive Recombinase for Deep Brain Genetic Manipulation
A KAIST team presented a noninvasive light-sensitive photoactivatable recombinase suitable for genetic manipulation in vivo. The highly light-sensitive property of photoactivatable Flp recombinase will be ideal for controlling genetic manipulation in deep mouse brain regions by illumination with a noninvasive light-emitting diode. This easy-to-use optogenetic module made by Professor Won Do Heo and his team will provide a side-effect free and expandable genetic manipulation tool for neuroscience research.
Spatiotemporal control of gene expression has been acclaimed as a valuable strategy for identifying functions of genes with complex neural circuits. Studies of complex brain functions require highly sophisticated and robust technologies that enable specific labeling and rapid genetic modification in live animals. A number of approaches for controlling the activity of proteins or expression of genes in a spatiotemporal manner using light, small molecules, hormones, and peptides have been developed for manipulating intact circuits or functions.
Among them, recombination-employing, chemically inducible systems are the most commonly used in vivo gene-modification systems. Other approaches include selective or conditional Cre-activation systems within subsets of green fluorescent protein-expressing cells or dual-promoter-driven intersectional populations of cells.
However, these methods are limited by the considerable time and effort required to establish knock-in mouse lines and by constraints on spatiotemporal control, which relies on a limited set of available genetic promoters and transgenic mouse resources.
Beyond these constraints, optogenetic approaches allow the activity of genetically defined neurons in the mouse brain to be controlled with high spatiotemporal resolution. However, an optogenetic module for gene-manipulation capable of revealing the spatiotemporal functions of specific target genes in the mouse brain has remained a challenge.
In the study published at Nature Communication on Jan. 18, the team featured photoactivatable Flp recombinase by searching out split sites of Flp recombinase that were not previously identified, being capable of reconstitution to be active. The team validated the highly light-sensitive, efficient performance of photoactivatable Flp recombinase through precise light targeting by showing transgene expression within anatomically confined mouse brain regions.
The concept of local genetic labeling presented here suggests a new approach for genetically identifying subpopulations of cells defined by the spatial and temporal characteristics of light delivery. To date, an optogenetic module for gene-manipulation capable of revealing spatiotemporal functions of specific target genes in the mouse brain has remained out of reach and no such light-inducible Flp system has been developed. Accordingly, the team sought to develop a photoactivatable Flp recombinase that takes full advantage of the high spatiotemporal control offered by light stimulation.
This activation through noninvasive light illumination deep inside the brain is advantageous in that it avoids chemical or optic fiber implantation-mediated side effects, such as off-target cytotoxicity or physical lesions that might influence animal physiology or behaviors. The technique provides expandable utilities for transgene expression systems upon Flp recombinase activity in vivo, by designing a viral vector for minimal leaky expression influenced by viral nascent promoters.
The team demonstrated the utility of PA-Flp as a noninvasive in vivo optogenetic manipulation tool for use in the mouse brain, even applicable for deep brain structures as it can reach the hippocampus or medial septum using external LED light illumination.
The study is the result of five years of research by Professor Heo, who has led the bio-imaging and optogenetics fields by developing his own bio-imaging and optogenetics technologies. “It will be a great advantage to control specific gene expression desired by LEDs with little physical and chemical stimulation that can affect the physiological phenomenon in living animals,” he explained.
2019.01.22 View 7264 -
From Concept to Reality: Changing Color of Light Using a Spatiotemporal Boundary
(from left: Professor Bumki Min, PhD candidate Jaehyeon Son and PhD Kanghee Lee)
A KAIST team developed an optical technique to change the color (frequency) of light using a spatiotemporal boundary. The research focuses on realizing a spatiotemporal boundary with a much higher degree of freedom than the results of previous studies by fabricating a thin metal structure on a semiconductor surface. Such a spatiotemporal boundary is expected to be applicable to an ultra-thin film type optical device capable of changing the color of light.
The optical frequency conversion device plays a key role in precision measurement and communication technology, and the device has been developed mainly based on optical nonlinearity.
If the intensity of light is very strong, the optical medium responds nonlinearly so the nonlinear optical phenomena, such as frequency doubling or frequency mixing, can be observed. Such optical nonlinear phenomena are realized usually by the interaction between a high-intensity laser and a nonlinear medium.
As an alternative method frequency conversion is observed by temporally modifying the optical properties of the medium through which light travels using an external stimulus. Since frequency conversion in this way can be observed even in weak light, such a technique could be particularly useful in communication technology.
However, rapid optical property modification of the medium by an external stimulus and subsequent light frequency conversion techniques have been researched only in the pertubative regime, and it has been difficult to realize these theoretical results in practical applications.
To realize such a conceptual idea, Professor Bumki Min from the Department of Mechanical Engineering and his team collaborated with Professor Wonju Jeon from the Department of Mechanical Engineering and Professor Fabian Rotermund from the Department of Physics. They developed an artificial optical material (metamaterial) by arranging a metal microstructure that mimics an atomic structure and succeeded in creating a spatiotemporal boundary by changing the optical property of the artificial material abruptly.
While previous studies only slightly modified the refractive index of the medium, this study provided a spatiotemporal boundary as a platform for freely designing and changing the spectral properties of the medium. Using this, the research team developed a device that can control the frequency of light to a large degree.
The research team said a spatiotemporal boundary, which was only conceptually considered in previous research and realized in the pertubative regime, was developed as a step that can be realized and applied.
Professor Min said, “The frequency conversion of light becomes designable and predictable, so our research could be applied in many optical applications. This research will present a new direction for time-variant media research projects in the field of optics.”
This research, led by PhD Kanghee Lee and PhD candidate Jaehyeon Son, was published online in Nature Photonics on October 8, 2018.
This work was supported by the National Research Foundation of Korea (NRF) through the government of Korea. The work was also supported by the Center for Advanced Meta-Materials (CAMM) funded by the Korea Government (MSIP) as the Global Frontier Project (NRF-2014M3A6B3063709).
Figure 1. The frequency conversion process of light using a spatiotemporal boundary.
Figure 2. The complex amplitude of light at the converted frequency with the variation of a spatiotemporal boundary.
2018.11.29 View 8142 -
Rh Ensemble Catalyst for Effective Automobile Exhaust Treatment
(from left: Professor Hyunjoo Lee and PhD candidate Hojin Jeong)
A KAIST research team has developed a fully dispersed Rh ensemble catalyst (ENS) that shows better performance than commercial diesel oxidation catalyst (DOC). This newly developed ENSs could improve low-temperature automobile exhaust treatment.
Precious metals have been used for various heterogeneous reactions, but it is crucial to maximize efficiency of catalysts due to their high cost. Single-atom catalysts (SACs) have received much attention because it is possible for all of the metal atoms to be used for reactions, yet they do not show catalytic activity for reactions that require ensemble sites.
Meanwhile, hydrocarbons, such as propylene (C3H6) and propane (C3H8) are typical automobile exhaust gas pollutants and must be converted to carbon dioxide (CO2) and water (H2O) before they are released as exhaust. Since the hydrocarbon oxidation reaction proceeds only during carbon-carbon (C-C) or carbon-hydrogen (C-H) bond cleavage, it is essential to secure the metal ensemble site for the catalytic reaction. Therefore, precious metal catalysts with high dispersion and ensemble sites are greatly needed.
To solve this issue, Professor Hyunjoo Lee from the Department of Chemical and Biomolecular Engineering and Professor Jeong Woo Han from POSTECH developed an Rh ensemble catalyst with 100% dispersion, and applied it to automobile after-treatment. Having a 100% dispersion means that every metal atom is used for the reaction since it is exposed on the surface.
SACs also have 100% dispersion, but the difference is that ENSs have the unique advantage of having an ensemble site with two or more atoms.
As a result of the experiment, the ENSs showed excellent catalytic performance in CO, NO, propylene, and propane oxidation at low temperatures. This complements the disadvantage of nanoparticle catalyst (NPs) that perform catalysis poorly at low temperatures due to low metal dispersion, or SACs without hydrocarbon oxidation.
In particular, the ENSs have superior low-temperature activity even better than commercial DOC, hence they are expected to be applied to automobile exhaust treatment.
Professor Lee said, “I believe that the ENSs have given academic contribution for proposing a new concept of metal catalysts, differentiating from conventional SACs and NPs. At the same time, they are of great value in the industry of exhaust treatment catalysts.”
This research, led by PhD candidate Hojin Jeong, was published in the Journal of the American Chemical Society on July 5.
Figure 1. Concept of Rh ensemble catalyst for automobile exhaust treatment
Figure 2. Structure and performance comparison of single-atom catalyst and ensemble catalyst
Figure 3. Energy-dispersive X-ray spectroscopy (EDS) mapping images for SAC, ENS, and NP, respectively (green, Eh; red, Ce)
2018.08.29 View 7321 -
Levitating 2D Semiconductor for Better Performance
(from top: Professor Yeon Sik Jung and PhD candidate Soomin Yim)
Atomically thin 2D semiconductors have been drawing attention for their superior physical properties over silicon semiconductors; nevertheless, they are not the most appealing materials due to their structural instability and costly manufacturing process. To shed some light on these limitations, a KAIST research team suspended a 2D semiconductor on a dome-shaped nanostructure to produce a highly efficient semiconductor at a low cost.
2D semiconducting materials have emerged as alternatives for silicon-based semiconductors because of their inherent flexibility, high transparency, and excellent carrier transport properties, which are the important characteristics for flexible electronics.
Despite their outstanding physical and chemical properties, they are oversensitive to their environment due to their extremely thin nature. Hence, any irregularities in the supporting surface can affect the properties of 2D semiconductors and make it more difficult to produce reliable and well performing devices. In particular, it can result in serious degradation of charge-carrier mobility or light-emission yield.
To solve this problem, there have been continued efforts to fundamentally block the substrate effects. One way is to suspend a 2D semiconductor; however, this method will degrade mechanical durability due to the absence of a supporter underneath the 2D semiconducting materials.
Professor Yeon Sik Jung from the Department of Materials Science and Engineering and his team came up with a new strategy based on the insertion of high-density topographic patterns as a nanogap-containing supporter between 2D materials and the substrate in order to mitigate their contact and to block the substrate-induced unwanted effects.
More than 90% of the dome-shaped supporter is simply an empty space because of its nanometer scale size. Placing a 2D semiconductor on this structure creates a similar effect to levitating the layer. Hence, this method secures the mechanical durability of the device while minimizing the undesired effects from the substrate. By applying this method to the 2D semiconductor, the charge-carrier mobility was more than doubled, showing a significant improvement of the performance of the 2D semiconductor.
Additionally, the team reduced the price of manufacturing the semiconductor. In general, constructing an ultra-fine dome structure on a surface generally involves costly equipment to create individual patterns on the surface. However, the team employed a method of self-assembling nanopatterns in which molecules assemble themselves to form a nanostructure. This method led to reducing production costs and showed good compatibility with conventional semiconductor manufacturing processes.
Professor Jung said, “This research can be applied to improve devices using various 2D semiconducting materials as well as devices using graphene, a metallic 2D material. It will be useful in a broad range of applications, such as the material for the high speed transistor channels for next-generation flexible displays or for the active layer in light detectors.”
This research, led by PhD candidate Soomin Yim, was published in Nano Letters in April.
Figure 1. Image of a 2D semiconductor using dome structures
2018.08.28 View 6729 -
Computer Simulation Identifies a Key Principle for Next-generation Carbon Fibers
(from left: Professor Yong-Hoon Kim and PhD candidate Juho Lee)
Performing state-of-the-art computer simulations, a KAIST research team identified an atomistic design principle to produce high-quality, next-generation carbon fibers.
Carbon fibers are light-weight yet excellent in mechanical strength and thermal resistance. Boasting these properties, they can be diversely applied in high-technology sectors, including automotive, aerospace, and nuclear engineering.
They are produced from a polymer precursor through a series of spinning, stabilization, and carbonization processes. However, there is a major obstacle to producing high-quality carbon fibers. That is, when there exist ill-defined regions within the polymer matrixes, they result in disorder and defects within the produced carbon fibers.
As a solution to this problem, it was proposed that the introduction of carbon nanotubes (CNT) could enhance polymer orientation and crystallization. However, although the alignment geometry of the CNT-polymer interface apparently affects the quality of produced fibers, the atomistic understanding of the CNT-polymer interface has been so far lacking, hindering further developments.
To clarify the nature of CNT-polymer interactions, Professor Yong-Hoon Kim from the Graduate School of Energy, Environment, Water and Sustainability and his team employed a multiscale approach that combines first-principles density functional theory (DFT) calculations and force-fields molecular dynamics (MD) simulations and revealed the unique structural and electronic characteristics of polymer-CNT interfaces.
Here, they studied polyacrylonitrile (PAN)-CNT hybrid structures as a representative case of polymer-CNT composites. PAN is the most common polymer precursor, taking more than 90% of carbon fiber production.
Based on their DFT calculations, the team showed that the lying-down PAN configurations give a larger PAN-CNT binding energy than their standing-up counterparts. Moreover, maximizing the lying-down PAN configuration was shown to allow linear alignments of PANs on CNT, enabling the desirable ordered long-range PAN-PAN packing.
They also identified the CNT curvature as another significant factor, giving the largest PAN-CNT binding energy in the zero-curvature graphene limit. Conducting large-scale MD simulations, they then demonstrated that graphene nanoribbons are a promising carbon nano-reinforcement candidate by explicitly showing its strong propensity to induce linear alignments of PANs adsorbed on them.
Professor Kim said, “This research can be an exemplary case where the quantum mechanical simulations identify basic principles for developing advanced materials. Computer simulation studies will play an increasingly greater role thanks to the advances in the simulation theory and computer performance.”
This research, carried out by the PhD candidate Juho Lee, was published in the inside back cover of Advanced Functional Materials on April 11.
Figure 1. Inside back cover of Advanced Functional Materials
Figure 2. Research outline
2018.08.03 View 8491 -
Visualizing Chemical Reaction on Bimetal Surfaces
Catalysts are the result of many chemists searching to unravel the beauty of molecules and the mystery of chemical reactions. Professor Jeong Young Park from the Department of Chemistry, whose research focuses on catalytic chemical reactions, is no exception. His research team recently made breakthroughs in addressing long-standing questions for understanding reaction mechanisms on bimetal catalysts.
During the studies reported in Science Advances, following a publication in Nature Communications this month, Professor Park’s research team identified that the formation of metal–oxide interfaces is the key factor responsible for the synergistic catalytic effect in bimetal catalysts. The team confirmed this fundamental reaction mechanism through in situ imaging of reaction conditions. This is the first visualization of bimetal surfaces under reaction conditions, signifying the role of metal–oxide interfaces in heterogeneous catalysis.
Bimetallic materials have outstanding catalytic performance, which opens a new pathway for controlling electronic structures and binding energy in catalysts. Despite considerable research on various catalytic reaction efficiencies, there are yet unanswered questions on the underlying principles behind the improved performance. Even more, it was very hard to figure out what led to the efficiency because the structure, chemical composition, and oxidation state of bimetallic materials change according to reaction conditions.
Recently, some research groups suggested that oxide–metal interfacial sites formed by the surface segregation of bimetallic nanoparticles might be responsible for the increased catalytic performance. However, they failed to present any definitive evidence illustrating the physical nature or the fundamental role of the oxide–metal interfaces leading to the improved performance.
To specifically address this challenge, the research team carried out in situ observations of structural modulation on platinum–nickel bimetal catalysts under carbon monoxide oxidation conditions with ambient pressure scanning tunneling microscopy and ambient pressure X-ray photoelectron spectroscopy.
The team observed that platinum–nickel bimetal catalysts exhibited a variety of different structures depending on the gas conditions. Under ultrahigh vacuum conditions, the surface exhibited a platinum skin layer on the platinum–nickel alloyed surface, selective nickel segregation followed by the formation of nickel oxide clusters using oxygen gas, and finally the coexistence of nickel oxide clusters on the platinum skin during carbon monoxide oxidation. The research team found that the formation of interfacial platinum–nickel oxide nanostructures is responsible for a highly efficient step in the carbon monoxide oxidation reaction.
These findings illustrate that the enhancement of the catalytic activity on the bimetallic catalyst surface originates from the thermodynamically efficient reaction pathways at the metal–metal oxide interface, which demonstrates a straightforward process for the strong metal–support interaction effect. The formation of these interfacial metal–metal oxide nanostructures increases catalytic activity while providing a thermodynamically efficient reaction pathway by lowering the heat of the reactions on the surface. [J. Kim et al. Adsorbate-driven reactive interfacial Pt-NiO1-x nanostructure formation on the Pt3Ni(111) alloy surface, Science Advances (DOI: 10.1126/sciadv.aat3151 ]
Professor Park said that one way to monitor catalysts is to detect hot electrons associated with energy dissipation and conversion processes during surface reactions. His team led the real-time detection of hot electrons generated on bimetallic PtCo nanoparticles during exothermic hydrogen oxidation. The team successfully clarified the origin of the synergistic catalytic activity of PtCo nanoparticles with corresponding chemicurrent values.
By estimating the chemicurrent yield, the research team conclude that the catalytic properties of the bimetallic nanoparticles are strongly governed by the oxide–metal interface, which facilitates hot electron transfer. [H. Lee et al. Boosting hot electron flux and catalytic activity at metal–oxide interfaces of PtCo bimetallic nanoparticles, Nature Comm, 9, 2235 (2018)].
Professor Park explained, “We feel that the precise measurement of hot electrons on catalysts gives insight into the mechanism for heterogeneous catalysis, which can help with the smart design of highly reactive materials. The control of catalytic activity via electronic engineering of catalysts is a promising prospect that may open the door to the new field of combining catalysis with electronics, called “catalytronics.” He added that the study also establishes a strategy for improving catalytic activity for catalytic reactions in industrial chemical reactors.
Professors Park and Yousung Jung from the Department of Chemical and Biomolecular Engineering and the Graduate School of EEWS conducted this research in collaboration with Professor Bongjin Mun from the Department of Physics at GIST.
Figure 1. Evolution of surface structures of PtNi bimetal surfaces under various ambient conditions.
Figure 2. Formation of Pt-CoO interface leads to the catalytic enhancement of PtCo bimetal catalysts.
2018.07.25 View 10083