Cheonghee Kim

Shape-Controlled Nanocrystals for Catalytic Applications

The activity, selectivity, and long-term stability of catalyst nanoparticles can be enhanced by shape modulation. Such shaped catalytic nanocrystals have well-defined surface crystalline structures on which the cleavage and recombination of chemical bonds can be rationally controlled. Metal and metal oxide nanocrystals have been synthesized in various shapes using wet chemistry techniques such as reducing metal precursors in the presence of the surface-capping agents. The surface-capping agents should be removed prior to the catalytic chemical reaction, which necessitates clean catalytically active surface. The removal process should be performed very carefully because this removal often causes shape deformation. A few examples in which the surface-capping agents contribute positively to the chemical reactions have been reported. The examples described in this review include shaped metal, metal composite, and metal oxide nanocrystals that show enhanced catalytic activity, selectivity, and long-term stability for various gas-phase, liquid-phase, or electrocatalytic reactions. Although most of the studies using these shaped nanocrystals for catalytic applications have focused on low-index surfaces, nanocrystals with high-index facets and their catalytic applications have recently been reported. By bridging surface studies with nanoparticle catalysts using shape modulation, catalysts with improved properties can be rationally designed.

Mitigation of CO poisoning on functionalized Pt–TiN surfaces

It has been previously reported that the system of single Pt atoms embedded in N-vacancy (V(N)) sites on the TiN(100) surface (Pt-TiN) could be a promising catalyst for proton exchange membrane fuel cells (PEM FCs). The adsorption of molecules on Pt-TiN is an important step, when it is incorporated as the anode or cathode of PEM FCs. Utilizing first principles calculations based on density functional theory, systematic investigations are performed on the adsorption of several atomic and molecular species on the Pt-TiN system, as well as the co-adsorption of them. The favorable binding sites and adsorption energies of several molecular species, namely carbon dioxide (CO2), carbon monoxide (CO), oxygen (O2), hydrogen (H2), hydroxyl (OH), an oxygen atom (O), and a hydrogen atom (H), are explored. For each, the adsorption energy and preferred binding site are identified and the vibrational frequencies calculated. It is found that CO2, CO and H prefer the Pt top site while OH and O favorably adsorb on the Ti top site. When CO and OH are co-adsorbed on the Pt-TiN(100) surface, OH weakens the adsorption of CO. The weakening effect is enhanced by increasing the coverage of OH. A similar behavior occurs for H and OH co-adsorption on the Pt-TiN(100) surface. Because co-adsorption with OH and H species weakens the adsorption of CO on Pt-TiN, it is expected that the acid and base conditions in PEM FCs could mitigate CO poisoning on functionalized Pt-TiN surfaces.

One-pot synthesis of Pd@PdPt core–shell nanocubes on carbon supports

Cubic Pd@PdPt core–shell nanoparticles were synthesized on carbon supports using a one-pot process. The as-prepared cubic Pd@PdPt/C exhibited high electrocatalytic activity for oxygen reduction reactions. The enhancement in the mass activity increased after accelerated durability tests due to structural rearrangement.