Tianpin Wu

Electronic Structure Controls Reactivity of Size-Selected Pd Clusters Adsorbed on TiO2 Surfaces

Cluster Electronics and Catalysis Many practical catalysts consist of small metal clusters on oxide supports, and the activity of these clusters usually varies with their size. In order to sort out some of the competing effects that lead to such variations, Kaden et al. (p. 826) size-selected palladium clusters (from single atoms to clusters up to 25 atoms) and deposited them on a crystal face of the rutile phase of titanium dioxide. X-ray photoemission studies and temperature-programmed reaction measurements showed that the activity of these model catalysts for CO oxidation was related to the electronic energy, which was reflected in the Pd 3d electron binding energy. Ion-scattering studies showed that the clusters formed flat single- or double-layer islands. The activity of these model catalysts for carbon monoxide oxidation reflects changes in cluster electronic structure. The catalytic activity of metal clusters of different sizes adsorbed on oxide surfaces can be explored systematically by using model catalysts. We studied the temperature-programmed reaction of CO with O2 catalyzed by Pd clusters (Pdn, for n = 1, 2, 4, 7, 10, 16, 20, and 25) that were size-selected in the gas phase and deposited on rutile TiO2(110). X-ray photoemission spectroscopy revealed that the Pd 3d binding energy varied nonmonotonically with cluster size and that the changes correlated with strong size variations in CO oxidation activity. Taking final-state effects into account, low activity was correlated with higher-than-expected Pd 3d binding energy, which is attributed to a particularly stable valence electronic structure; electron transfer from the TiO2 support to the Pd clusters also occurs. Ion scattering shows that small clusters form single-layer islands on the surface and that formation of a second layer begins to occur for clusters larger than Pd10.

Insight into the Catalytic Mechanism of Bimetallic Platinum–Copper Core–Shell Nanostructures for Nonaqueous Oxygen Evolution Reactions

The oxygen evolution reaction (OER) plays a critical role in multiple energy conversion and storage applications. However, its sluggish kinetics usually results in large voltage polarization and unnecessary energy loss. Therefore, designing efficient catalysts that could facilitate this process has become an emerging topic. Here, we present a unique Pt-Cu core-shell nanostructure for catalyzing the nonaqueous OER. The catalysts were systematically investigated with comprehensive spectroscopic techniques, and applied in nonaqueous Li-O2 electrochemical cells, which exhibited dramatically reduced charging overpotential (<0.2 V). The superior performance is explained by the robust Cu(I) surface sites stabilized by the Pt core in the nanostructure. The insights into the catalytic mechanism of the unique Pt-Cu core-shell nanostructure gained in this work are expected to serve as a guide for future design of other nanostructured bimetallic OER catalysts.

Improved Sodium-Ion Storage Performance of Ultrasmall Iron Selenide Nanoparticles

Sodium-ion batteries are potential low-cost alternatives to current lithium-ion technology, yet their performances still fall short of expectation due to the lack of suitable electrode materials with large capacity, long-term cycling stability, and high-rate performance. In this work, we demonstrated that ultrasmall (∼5 nm) iron selenide (FeSe2) nanoparticles exhibited a remarkable activity for sodium-ion storage. They were prepared from a high-temperature solution method with a narrow size distribution and high yield and could be readily redispersed in nonpolar organic solvents. In ether-based electrolyte, FeSe2 nanoparticles exhibited a large specific capacity of ∼500 mAh/g (close to the theoretical limit), high rate capability with ∼250 mAh/g retained at 10 A/g, and excellent cycling stability at both low and high current rates by virtue of their advantageous nanosizing effect. Full sodium-ion batteries were also constructed from coupling FeSe2 with NASICON-type Na3V2(PO4)3 cathode and demonstrated impressive capacity and cycle ability.

Inert, pulsed, ultrahigh-vacuum-compatible doser for study of hydrazine decomposition on a model Ir∕Al2O3∕NiAl(110) catalyst

Design of a chemically inert, ultrahigh-vacuum-compatible, pulsed gas inlet system is described. The inlet design is suitable for any gases compatible with glass, Teflon, and perfluoroalkoxy materials. The performance is illustrated by results for hydrazine decomposition on a planar model Ir∕Al2O3∕NiAl(110) catalyst. The inert, pulsed inlet system makes it possible to measure decomposition products evolving from a small (2mm) Ir-containing spot, despite the high propensity for hydrazine to decompose on the surfaces of the inlet system and vacuum chamber.