Catalytic+Materials+and+Process+Lab
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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 5363 -
Platinum Single Atom Catalysts for 'Direct Formic Acid Fuel Cells'
(Professor Hyunjoo Lee (left) and Ph.D. candidate Jiwhan Kim)
A research team co-led by Professor Hyunjoo Lee at the Department of Chemical and Biomolecular Engineering at KAIST and Professor Jeong Woo Han from the University of Seoul synthesized highly stable high-Pt-content single atom catalysts for direct formic acid fuel cells. The amount of platinum can be reduced to 1/10 of that of conventional platinum nanoparticle catalysts.
Platinum (Pt) catalysts have been used in various catalytic reactions due to their high activity and stability. However, because Pt is rare and expensive, it is important to reduce the amount of Pt used. Pt single atom catalysts can reduce the size of the Pt particles to the size of an atom. Thus, the cost of Pt catalysts can be minimized because all of the Pt atoms can participate in the catalytic reactions. Additionally, single atom catalysts have no ensemble site in which two or more atoms are attached, and thus, the reaction selectivity is different from that of nanoparticle catalysts.
Despite these advantages, single atom catalysts are easily aggregated and less stable due to their low coordination number and high surface free energy. It is difficult to develop a single atom catalyst with high content and high stability, and thus, its application in practical devices is limited.
Direct formic acid fuel cells can be an energy source for next-generation portable devices because liquid formic acid as a fuel is safer and easier to store and transport than high-pressure hydrogen gas.
To improve the stability of Pt single atom catalysts, Professor Lee’s group developed a Pt-Sn single atom alloy structure on an antimony-doped tin oxide (ATO) support. This structure has been proven by computational calculations which show that Pt single atoms substitute antimony sites in the antimony-tin alloy structure and are thermodynamically stable. This catalyst has been shown to have a higher activity up to 50 times per weight of Pt than that of the commercial catalyst, Pt/C, in the oxidation of formic acid, and the stability of the catalyst was also remarkably high.
Professor Lee’s group also used a single atomic catalyst in a 'direct formic acid fuel cell’ consisting of membranes and electrodes. It is the first attempt to apply a single atomic catalyst to a full cell. In this case, an output similar to that of the commercial catalyst could be obtained by using 1/10 of the platinum compared to the commercial Pt/C catalyst.
Ph.D. candidate Jiwhan Kim from KAIST was the first author of the research. This research was published online on September 11 in Advanced Energy Materials.
This research was carried out with the support of the Samsung Electronics Future Technology Development Center.
(Figure 1. Concept photograph for Pt single atom catalysts.)
(Figure 2. Pt single atom catalysts by HAADF-STEM analysis (bright white circles))
2017.10.31 View 6069