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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 27617 -
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 13398 -
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 15546 -
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 11695 -
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 13606 -
Core Technology for Lithium Air Secondary Battery Developed
KAIST-Kyonggi University joint research team developed composite catalyst out of nano fiber and graphene
Five times improvement in capacity compared to lithium-ion secondary battery, driving 800 km at maximum
The core technology for lithium air secondary battery, the next generation high capacity battery, has been developed.
A research team formed by KAIST Department of Materials Science’s Professors Il-Doo Kim and Seokwoo Jeon, and Kyonggi University Department of Materials Science’s Professor Yong-Joon Park has created a lithium air secondary battery, with five times greater storage than the lithium-ion secondary battery, by developing a nano fiber-graphene composite catalyst. The research results are published in the August 8th online edition of Nano Letters.
A cathode of a lithium-ion battery consists of graphite and an anode of the battery consists of a lithium transition metal oxide. Lithium-ion batteries are widely used in mobile phones and laptops. However, lithium-ion batteries cannot support electric vehicles, providing energy for only 160 kilometers on one full charge. The lithium air secondary battery just developed by the research team uses lithium on the cathode and oxygen on the anode. It is earning a popular acknowledgement among the next generation secondary battery research community for having lightweight mass and high energy density.
However, lithium-ion batteries remain difficult to commercialize because of their short lifespan. Lithium and oxygen meet up to form lithium oxide (Li2O2) at discharge, and decompose again at charge. In a traditional lithium air battery, this cycle does not occur smoothly and results in high resistance, thereby reducing the lifespan of the battery. It is thus essential to develop high efficiency catalyst that facilitates the formation and decomposition of lithium oxides.
The research team used electric radiation to develop a nano composite catalyst by mixing cobalt oxide nano fiber and graphene. The performance of the battery has been maximized by settling nonoxidative graphene, which has high specific surface area and electrical conductivity, on catalyst active cobalt oxide nano fiber. Applying the nano composite catalyst on both poles of the lithium air battery resulted in an improved lifespan of over 80 recharge cycles with capacity greater than 100mAh/g, five times greater than a lithium ion battery. The newly discovered charge-discharge property is the highest among the reported performances of the lithium air battery so far.
The lithium air battery is cheap to make, as the main materials are metal oxide and graphene. “There are yet more issues to resolve such as stability, but we will collaborate with other organizations to open up the era of electronic vehicles,” said Professor Il-Doo Kim. “We hope to contribute to vitalizing the fields of next generation lithium air battery by leading nanocatalyst synthesis technology, one of the core materials in the fields of secondary battery,” Professor Kim spoke of his aspiration.
The graduate students participated in the research are Won-Hee Ryu, a postdoctorate at KAIST Department of Materials Science, Sungho Song, a PhD candidate at KAIST Department of Materials Science, and Taek-Han Yoon, a graduate student at Kyonggi University.
Picture I: Schematic Diagram of Lithium Air Battery Made of Nano Composite Catalysts
Picture II: Images of Cobalt Oxide Nano Fibers and Graphene Nano Composite Catalysts
Picture III: Images of Manufacturing Process of Cobalt Oxide Nano Fibers and Graphene Nano Composite Catalysts for Lithium Air Battery
2013.10.18 View 15655 -
Ten Breakthroughs of the Year 2011 by Science
Porous Zeolite Crytals
Science, an internationally renowned scientific journal based in the US, has recently released a special issue of “Breakthrough of the Year, 2011,” dated December 23, 2011. In the issue, the journal introduces ten most important research breakthroughs made this year, and Professor Ryong Ryoo, Department of Chemistry at KAIST, was one of the scientists behind such notable advancements in 2011. Professor Ryoo has been highly regarded internationally for his research on the development of synthetic version of zeolites, a family of porous minerals that is widely used for products such as laundry detergents, cat litters, etc. Below is the article from Science, stating the zeolite research:
For Science’s “Breakthrough of the Year, 2011”, please go to:
http://www.sciencemag.org/site/special/btoy2011/
[Excerpt from the December 23, 2011 Issue of Science]
Industrial Molecules, Tailor-Made
If you ever doubt that chemistry is still a creative endeavor, just look at zeolites. This family of porous minerals was first discovered in 1756. They"re formed from different arrangements of aluminum, silicon, and oxygen atoms that crystallize into holey structures pocked with a perfect arrangement of pores. Over the past 250 years, 40 natural zeolites have been discovered, and chemists have chipped in roughly 150 more synthetic versions.
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Porous zeolite crystals are widely used as filters and catalysts. This year, researchers found new ways to tailor the size of their pores and create thinner, cheaper membranes.
CREDIT: K. VAROON ET AL., SCIENCE334, 6052 (7 OCTOBER 2001)
This abundance isn"t just for show. Three million tons of zeolites are produced every year for use in laundry detergents, cat litter, and many other products. But zeolites really strut their stuff in two uses: as catalysts and molecular sieves. Oil refineries use zeolite catalysts to break down long hydrocarbon chains in oil into the shorter, volatile hydrocarbons in gasoline. And the minerals" small, regularly arranged pores make them ideal filters for purifying everything from the air on spaceships to the contaminated water around the nuclear reactors destroyed earlier this year in Fukushima, Japan.
Zeolites have their limitations, though. Their pores are almost universally tiny, making it tough to use them as catalysts for large molecules. And they"re difficult to form into ultrathin membranes, which researchers would like to do to enable cheaper separations. But progress by numerous teams on zeolite synthesis this year gave this “mature” area of chemistry new life.
Researchers in South Korea crafted a family of zeolites in which the usual network of small pores is surrounded by walls holed with larger voids. That combination of large and small pores should lead to catalysts for numerous large organic molecules.
Labs in Spain and China produced related large- and small-pore zeolites by using a combination of inorganic and organic materials to guide the structures as they formed.
Meanwhile, researchers in France and Germany discovered that, by carefully controlling growth conditions, they could form a large-pore zeolite without the need for the expensive organic compounds typically used to guide their architecture as they grow. The advance opens the way for cheaper catalysts. In yet another lab, researchers in Minnesota came up with a new route for making ultrathin zeolite membranes, which are likely to be useful as a wide variety of chemically selective filters.
This surge of molecular wizardry provides a vivid reminder that the creativity of chemists keeps their field ever young.
Related References and Web Sites
2011.12.23 View 16290 -
Scientists develop highly efficient industrial catalyst
http://english.yonhapnews.co.kr/business/2011/07/14/48/0501000000AEN20110714009600320F.HTML
SEOUL, July 15 (Yonhap) -- South Korean scientists said Friday that they have developed a highly efficient nanoporous industrial catalyst that can have a considerable impact on chemical and oil-refining sectors.
The team of scientists led by Ryoo Ryong, a chemistry professor at the Korea Advanced Institute of Science and Technology (KAIST), said the solid zeolite compound developed in the laboratory has a reaction speed five to 10 times faster than that of conventional materials.
Zeolite, which is made from silica and aluminium, is frequently used as an absorbent, water purifier and in nuclear reprocessing, although it is mainly employed in the chemical industry.
The annual size of the zeolite market is estimated at US$2.5 billion with output using the material topping $30 billion. At present, 41 percent of all catalysts used in the chemical sector are nano-scale zeolite materials.
The KAIST team said that because the new zeolite is made up of different sized pores, the material can be used as a catalyst when existing materials are unable to act as a changing agent.
"Existing zeolites only have pores under 1 nanometer in diameter, but the new material has holes that range from 1 nanometer to 3.5 nanometers, which are all arranged in a regular honeycomb arrangement," Ryoo said. A nanometer is one-billionth of a meter.
He said the ability to have both micro- and meso-sized pores is key to the faster reaction speed that is an integral part of raising efficiency. The South Korean researchers used a so-called surfactant process to make the different sizes of pores.
The development is a breakthrough because researchers and companies such as Exxon Mobil Corp. have been trying to build zeolite with different sizes of pores for the past two decades without making serious headway. There are more than 200 different types of zeolites in the world.
Ryoo, who received funding from the government, has requested intellectual property rights for the discovery, which has been published in the latest issue of Science magazine. He also developed another zeolite in the past that can transform methanol to gasoline up to 10 times more efficiently than existing catalysts.
Exxon Mobil has expressed interest in the two zeolites made by Ryoo"s team. Undisclosed South Korean petrochemical companies have also made inquiries that may lead to commercial development in the future.
"There are some technical issues to resolve, mainly related with mass production and stability," the scientist said.
He said full-fledge production will be determined by how much companies are willing to spend on research to speed up development that can bring down overall production costs.
The KAIST team said it took two years to make the new zeolite, which can be custom made to meet specific needs.
(END)
2011.07.15 View 16865