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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 20965 -
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 27064