YongMan Choi

Oxygen reduction on well-defined core-shell nanocatalysts: particle size, facet, and Pt shell thickness effects.

We examined the effects of the thickness of the Pt shell, lattice mismatch, and particle size on specific and mass activities from the changes in effective surface area and activity for oxygen reduction induced by stepwise Pt-monolayer depositions on Pd and Pd(3)Co nanoparticles. The core-shell structure was characterized at the atomic level using Z-contrast scanning transmission electron microscopy coupled with element-sensitive electron energy loss spectroscopy. The enhancements in specific activity are largely attributed to the compressive strain effect based on the density functional theory calculations using a nanoparticle model, revealing the effect of nanosize-induced surface contraction on facet-dependent oxygen binding energy. The results suggest that moderately compressed (111) facets are most conducive to oxygen reduction reaction on small nanoparticles and indicate the importance of concerted structure and component optimization for enhancing core-shell nanocatalysts activity and durability.

Highly stable Pt monolayer on PdAu nanoparticle electrocatalysts for the oxygen reduction reaction

Stability is one of the main requirements for commercializing fuel cell electrocatalysts for automotive applications. Platinum is the best-known catalyst for oxygen reduction in cathodes, but it undergoes dissolution during potential changes while driving electric vehicles, thus hampering commercial adoption. Here we report a new class of highly stable, active electrocatalysts comprising platinum monolayers on palladium-gold alloy nanoparticles. In fuel-cell tests, this electrocatalyst with its ultra-low platinum content showed minimal degradation in activity over 100,000 cycles between potentials 0.6 and 1.0u2009V. Under more severe conditions with a potential range of 0.6-1.4u2009V, again we registered no marked losses in platinum and gold despite the dissolution of palladium. These data coupled with theoretical analyses demonstrated that adding a small amount of gold to palladium and forming highly uniform nanoparticle cores make the platinum monolayer electrocatalyst significantly tolerant and very promising for the automotive application of fuel cells.

Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9u2005V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity.

Kirkendall Effect and Lattice Contraction in Nanocatalysts: A New Strategy to Enhance Sustainable Activity

Core-shell nanoparticles increasingly are found to be effective in enhancing catalytic performance through the favorable influence of the core materials on the active components at the surface. Yet, sustaining high activities under operating conditions often has proven challenging. Here we explain how differences in the components diffusivity affect the formation and stability of the core-shell and hollow nanostructures, which we ascribe to the Kirkendall effect. Using Ni nanoparticles as the templates, we fabricated compact and smooth Pt hollow nanocrystals that exhibit a sustained enhancement in Pt mass activity for oxygen reduction in acid fuel cells. This is achieved by the hollow-induced lattice contraction, high surface area per mass, and oxidation-resistant surface morphology--a new route for enhancing both the catalysts activity and durability. The results indicate challenges and opportunities brought by the nanoscale Kirkendall effect for designing, at the atomic level, nanostructures with a wide range of novel properties.

Nitride Stabilized PtNi Core–Shell Nanocatalyst for high Oxygen Reduction Activity

We describe a route to the development of novel PtNiN core-shell catalysts with low Pt content shell and inexpensive NiN core having high activity and stability for the oxygen reduction reaction (ORR). The PtNiN synthesis involves nitriding Ni nanoparticles and simultaneously encapsulating it by 2-4 monolayer-thick Pt shell. The experimental data and the density functional theory calculations indicate nitride has the bifunctional effect that facilitates formation of the core-shell structures and improves the performance of the Pt shell by inducing both geometric and electronic effects. Synthesis of inexpensive NiN cores opens up possibilities for designing of various transition metal nitride based core-shell nanoparticles for a wide range of applications in energy conversion processes.

Enhanced Oxygen Reduction Activity of IrCu Core Platinum Monolayer Shell Nano-electrocatalysts

Designing novel cathode materials for a proton exchange membrane fuel cell with high activity for the oxygen reduction reaction, low Pt loading, and enhanced long-term stability is imperative for its sustainability. To date, Pt monolayer based electrocatalysts deposited on a metallic core substrate have shown promising possibilities. In this study, we synthesized bimetallic IrCu nanoparticles and used them as a core for Pt monolayer electrocatalysts. It was found that the de-alloyed IrCu nanoparticle surfaces increased both the mass and specific activities of the resulting Pt monolayer catalyst. In addition, we demonstrated that Pt monolayer electrocatalysts with a de-alloyed IrCu core have a better stability than those using a non-dealloyed core based on a 5,000 potential cycling test. These data describe a new simple synthesis of a high-performance catalyst suitable for practical applications.

Tetrahedral Palladium Nanocrystals: A New Support for Platinum Monolayer Electrocatalysts with High Activity and Stability in the Oxygen Reduction Reaction

Abstract The recent availability of tetrahedral palladium (PdTH) nanocrystals with cleaned surfaces allowed us to evaluate their facet-specific electrochemical properties as a new support of platinum monolayer (PtML) catalysts. The Pd–PtML core-shell electrocatalyst was examined by combining structural analyses and Density Functional Theory (DFT) with electrochemical techniques. The surfaces of the PdTH core are composed of (111) facets wherein the Pd atoms are highly coordinated and have low surface energy. Our results revealed that in comparison with sphere Pd (PdSP)-supported PtML or pure Pt, the PdTH-supported PtML features more surface contraction and a downshift of d-band relative to the Fermi level. These geometric- and electronic-effects determine the higher activity of PtML/PdTH/C for the oxygen reduction reaction (ORR) compared to that of PtML/PdSP/C. This shape-property interdependence illuminated new approaches to basic- and applied- research on Pt-based ORR electrocatalysts of significant importance to the widespread use of fuel cells.

Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

The high cost of Pt-based membrane electrode assemblies (MEAs) is a critical hurdle for the commercialization of polymer electrolyte fuel cells (PEFCs). Recently, non-precious metal-based catalysts (NPMCs) have demonstrated much enhanced activity but their oxygen reduction reaction (ORR) activity is still inferior to that of Pt-based catalysts resulting in a much thicker electrode in the MEA. For the reduction of mass transport and ohmic overpotential we adopted a new concept of catalyst that combines an ultra-low amount of Pt nanoclusters with metal–nitrogen (M–Nx) doped ordered mesoporous porphyrinic carbon (FeCo–OMPC(L)). The 5 wt% Pt/FeCo–OMPC(L) showed a 2-fold enhancement in activities compared to a higher loading of Pt. Our experimental results supported by first-principles calculations indicate that a trace amount of Pt nanoclusters on FeCo–OMPC(L) significantly enhances the ORR activity due to their electronic effect as well as geometric effect from the reduced active sites. In terms of fuel cell commercialization, this class of catalysts is a promising candidate due to the limited use of Pt in the MEA.