Sung Jong Yoo

Role of Electronic Perturbation in Stability and Activity of Pt-Based Alloy Nanocatalysts for Oxygen Reduction

The design of electrocatalysts for polymer electrolyte membrane fuel cells must satsify two equally important fundamental principles: optimization of electrocatalytic activity and long-term stability in acid media (pH <1) at high potential (0.8 V). We report here a solution-based approach to the preparation of Pt-based alloy with early transition metals and realistic parameters for the stability and activity of Pt(3)M (M = Y, Zr, Ti, Ni, and Co) nanocatalysts for oxygen reduction reaction (ORR). The enhanced stability and activity of Pt-based alloy nanocatalysts in ORR and the relationship between electronic structure modification and stability were studied by experiment and DFT calculations. Stability correlates with the d-band fillings and the heat of alloy formation of Pt(3)M alloys, which in turn depends on the degree of the electronic perturbation due to alloying. This concept provides realistic parameters for rational catalyst design in Pt-based alloy systems.

Fast switchable electrochromic properties of tungsten oxide nanowire bundles

The authors prepared uniformly shaped WO2.72 nanowire bundles using the solvothermal synthesis method. They investigated the potential of the WO2.72 nanowire bundles to be used as a cathode electrode for electrochromic devices and the effect of the Li+ insertion (or extraction) kinetics and diffusion of Li+. An electrode consisting of arrays of WO2.72 nanowire bundles was formed and used in an experiment using the Langmuir-Blodgett technique. The one-dimensional nanostructure of WO2.72 has a high Li-ion diffusion coefficient (∼5.2×10−11cm2∕s) and low charge transfer resistance (∼28.6Ω), which result in its having a fast electrochromic response time (coloring time 55cm2∕C).

Electrodeposited Ni dendrites with high activity and durability for hydrogen evolution reaction in alkaline water electrolysis

Different shapes of various nickel structures, including dendrite, particle and film are fabricated by electrodeposition under various conditions. The shape of nickel structures is definitely dependent on the deposition potential, leading to different electrochemical surface area and edge facets. The nickel particle which has a polycrystalline center and edge is obtained at high negative potential. On the other hand, the nickel dendrite deposited by relatively low negative potential exhibits large electrochemical surface area and a particularly active facet for hydrogen evolution reaction (HER) in alkaline water electrolysis. In fact the nickel dendrite shows the highest catalytic activity and stability for HER among the various nickel structures.

Effect of morphology of electrodeposited Ni catalysts on the behavior of bubbles generated during the oxygen evolution reaction in alkaline water electrolysis

We have investigated the release of active sites blocked by bubbles attached on the surface of catalysts during the oxygen evolution reaction (OER) in alkaline water electrolysis, via the modulation of the wetting properties of the four different morphologies of a nickel catalyst.

Facile preparation of carbon-supported PtNi hollow nanoparticles with high electrochemical performance

To design Pt-based materials with a hollow structure via a galvanic reaction would be one of the effective ways to prepare electro- catalysts with high activity. The galvanic reaction between Pt ions and metal template is usually conducted under limited conditions, which makes the preparation of Pt hollow nanoparticles laborious. Here, we introduce a one-step and one-pot synthetic approach for the preparation of carbon-supported PtNi alloy hollow nanoparticles with a narrow size distribution. Prepared PtNi alloys were characterized by a nonporous shell consisting of a Pt-enriched surface layer and an inner alloy layer of Pt and Ni. Due to its unique structural advantages, this material showed excellent electrocatalytic performance for oxygen reduction (3.3- and 7.8-fold enhanced mass and specific activities compared to those of a commercial carbon-supported Pt nanoparticle). A possible mechanism for the formation of PtNi hollow structure is suggested.

Promoting effects of La for improved oxygen reduction activity and high stability of Pt on Pt–La alloy electrodes

The design of polymer electrolyte fuel cell electrocatalysts depends on two equally important fundamental principles: the optimization of electrocatalytic activities as well as the long-term stability under operating conditions (e.g., pH 0.8 V). Pt-based alloys with transition metals (i.e., Pt–La) address both of these key issues. The oxygen reduction kinetics depends on the alloy composition which, in turn, is related to the d-band center position. The stability of the oxygen reduction reaction is predictable by correlation of the d-band fillings and vacancies of Pt–M (M = Ti, Fe, Zr and La).

Supported core@shell electrocatalysts for fuel cells: close encounter with reality.

Core@shell electrocatalysts for fuel cells have the advantages of a high utilization of Pt and the modification of its electronic structures toward enhancement of the activities. In this study, we suggest both a theoretical background for the design of highly active and stable core@shell/C and a novel facile synthetic strategy for their preparation. Using density functional theory calculations guided by the oxygen adsorption energy and vacancy formation energy, Pd3Cu1@Pt/C was selected as the most suitable candidate for the oxygen reduction reaction in terms of its activity and stability. These predictions were experimentally verified by the surfactant-free synthesis of Pd3Cu1/C cores and the selective Pt shell formation using a Hantzsch ester as a reducing agent. In a similar fashion, Pd@Pd4Ir6/C catalyst was also designed and synthesized for the hydrogen oxidation reaction. The developed catalysts exhibited high activity, high selectivity, and 4,000 h of long-term durability at the single-cell level.

Promotional Effect of Palladium on the Hydrogen Oxidation Reaction at a PtPd Alloy Electrode

Although these factors arepivotal for the kinetics of the HOR, direct experimentalinspectionofthecontributionsofthesefactorshasrarelybeeninvestigated in electrochemical oxidation of hydrogen.There are more than enough signs that Pd catalysts havemany of the desired electrocatalytic properties for the HOR/hydrogen evolution reaction (HER), since the electrontransfer from the Pd surface into the antibonding orbital ofthe hydrogen molecule plays an important role in breakingthe hydrogen bonds, and this process lowers the associatedactivation energy.

Multilayered Pt/Ru nanorods with controllable bimetallic sites as methanol oxidation catalysts

A physical synthesis of multilayered Pt/Ru nanorods with controllable bimetallic sites as methanol oxidation catalysts is reported for the first time. The novel nanorods were synthesized via the oblique angle deposition method, deposited prior to the formation of each individual noble metal layer, in a sequential fashion. It has been shown that the oblique angle deposition controls the morphology and electrochemical properties of the resultant nanostructures. Sequentially the multilayered nanorods comprising Pt and Ru segments exhibited superior electrocatalytic activity when compared to equivalent monometallic Pt nanorods with respect to methanol electrooxidation reaction in an acidic medium. Moreover, it has been established that the electrochemical process takes place at the Pt/Ru nanorods followed the bifunctional mechanism. The relative rates of reaction, recorded using chronoamperometry, show a linear relationship between the long-time current density and the number of Pt/Ru interfaces. Interestingly, the best catalyst for methanol oxidation was found to the surface of bimetallic Pt/Ru nanorods produced by the heat treatments via the so-called electronic effect. This reflects the fact that the ensemble effects of combined bifunctional and electronic effects via second elements could be expected in methanol oxidation reactions. Electrocatalytic activities correlate well with bimetallic pair sites and electronic properties analyzed by X-ray photoemission spectroscopy and X-ray absorption near-edge structure.

Surface Structures and Electrochemical Activities of Pt Overlayers on Ir Nanoparticles

Pt overlayers were deposited on carbon-supported Ir nanoparticles with various coverages. Structural and electrochemical characterizations were performed using transmission electron microscopy (TEM), X-ray diffraction, high-resolution powder diffraction (HRPD), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES), cyclic voltammetry (CV), CO stripping voltammetry, and N2O reduction. The surface of Ir nanoparticles was covered with Pt overlayers with thickness varying from the submonolayer scale to more than two monolayers. Surface analyses such as CV and CO stripping voltammetry indicated that the Pt overlayers were uniformly deposited on the Ir nanoparticles, and the resultant Pt overlayers exhibited gradual changes in surface characteristics toward the Pt surface as the surface coverage increased. The distinct CO stripping characteristics and the enhanced Pt utilization affected electrocatalytic activities for methanol oxidation. The electrochemical stability of the Pt overlayer was compared with a commercial carbon-supported Pt catalyst by conducting a potential cycling experiment.