Moon J. Kim

Synthesis and Characterization of 9 nm Pt–Ni Octahedra with a Record High Activity of 3.3 A/mgPt for the Oxygen Reduction Reaction

Nanoscale Pt-Ni bimetallic octahedra with controlled sizes have been actively explored in recent years owning to their outstanding activity for the oxygen reduction reaction (ORR). Here we report the synthesis of uniform 9 nm Pt-Ni octahedra with the use of oleylamine and oleic acid as surfactants and W(CO)6 as a source of CO that can promote the formation of {111} facets in the presence of Ni. Through the introduction of benzyl ether as a solvent, the coverage of both surfactants on the surface of resultant Pt-Ni octahedra was significantly reduced while the octahedral shape was still attained. By further removing the surfactants through acetic acid treatment, we observed a specific activity 51-fold higher than that of the state-of-the-art Pt/C catalyst for the ORR at 0.93 V, together with a record high mass activity of 3.3 A mgPt(-1) at 0.9 V (the highest mass activity reported in the literature was 1.45 A mgPt(-1)). Our analysis suggests that this great enhancement of ORR activity could be attributed to the presence of a clean, well-preserved (111) surface for the Pt-Ni octahedra.

Synthesis of Pd-Pt Bimetallic Nanocrystals with a Concave Structure through a Bromide-Induced Galvanic Replacement Reaction

This article describes a systematic study of the galvanic replacement reaction between PtCl(6)(2-) ions and Pd nanocrystals with different shapes, including cubes, cuboctahedrons, and octahedrons. It was found that Br(-) ions played an important role in initiating, facilitating, and directing the replacement reaction. The presence of Br(-) ions led to the selective initiation of galvanic replacement from the {100} facets of Pd nanocrystals, likely due to the preferential adsorption of Br(-) ions on this crystallographic plane. The site-selective galvanic replacement resulted in the formation of Pd-Pt bimetallic nanocrystals with a concave structure owing to simultaneous dissolution of Pd atoms from the {100} facets and deposition of the resultant Pt atoms on the {111} facets. The Pd-Pt concave nanocubes with different weight percentages of Pt at 3.4, 10.4, 19.9, and 34.4 were also evaluated as electrocatalysts for the oxygen reduction reaction (ORR). Significantly, the sample with a 3.4 wt.% of Pt exhibited the largest specific electrochemical surface area and was found to be four times as active as the commercial Pt/C catalyst for the ORR in terms of equivalent Pt mass.

Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction

An effective strategy for reducing the Pt content while retaining the activity of a Pt-based catalyst is to deposit the Pt atoms as ultrathin skins of only a few atomic layers thick on nanoscale substrates made of another metal. During deposition, however, the Pt atoms often take an island growth mode because of a strong bonding between Pt atoms. Here we report a versatile route to the conformal deposition of Pt as uniform, ultrathin shells on Pd nanocubes in a solution phase. The introduction of the Pt precursor at a relatively slow rate and high temperature allowed the deposited Pt atoms to spread across the entire surface of a Pd nanocube to generate a uniform shell. The thickness of the Pt shell could be controlled from one to six atomic layers by varying the amount of Pt precursor added into the system. Compared to a commercial Pt/C catalyst, the Pd@PtnL (n = 1-6) core-shell nanocubes showed enhancements in specific activity and durability toward the oxygen reduction reaction (ORR). Density functional theory (DFT) calculations on model (100) surfaces suggest that the enhancement in specific activity can be attributed to the weakening of OH binding through ligand and strain effects, which, in turn, increases the rate of OH hydrogenation. A volcano-type relationship between the ORR specific activity and the number of Pt atomic layers was derived, in good agreement with the experimental results. Both theoretical and experimental studies indicate that the ORR specific activity was maximized for the catalysts based on Pd@Pt2-3L nanocubes. Because of the reduction in Pt content used and the enhancement in specific activity, the Pd@Pt1L nanocubes showed a Pt mass activity with almost three-fold enhancement relative to the Pt/C catalyst.

Synthesis of Pd−Au Bimetallic Nanocrystals via Controlled Overgrowth

This paper describes the synthesis of Pd-Au bimetallic nanocrystals with controlled morphologies via a one-step seeded-growth method. Two different reducing agents, namely, L-ascorbic acid and citric acid, were utilized for the reduction of HAuCl(4) in an aqueous solution to control the overgrowth of Au on cubic Pd seeds. When L-ascorbic acid was used as the reducing agent, conformal overgrowth of Au on the Pd nanocubes led to the formation of Pd-Au nanocrystals with a core-shell structure. On the contrary, localized overgrowth of Au was observed when citric acid was used as the reducing agent, producing Pd-Au bimetallic dimers. Through this morphological control, we were able to tune the localized surface plasmon resonance peaks of Pd-Au bimetallic nanostructures in the visible region.

Conformal Al2O3 dielectric layer deposited by atomic layer deposition for graphene-based nanoelectronics

We present a facile route which combines the functionalization of a highly oriented pyrolytic graphite surface with an atomic layer deposition (ALD) process to allow for conformal Al2O3 layers. While the trimethylaluminum (TMA)∕H2O process caused selective deposition only along step edges, the TMA∕O3 process began to provide nucleation sites on the basal planes of the surface. O3 pretreatment, immediately followed by the ALD process with TMA∕O3 chemistry, formed Al2O3 layers without any preferential deposition at the step edges. This is attributed to functionalization of graphene by ozone treatment, imparting a hydrophilic character which is desirable for ALD deposition.

Facile Synthesis of Pd–Pt Alloy Nanocages and Their Enhanced Performance for Preferential Oxidation of CO in Excess Hydrogen

This article describes a new method for the facile synthesis of Pd-Pt alloy nanocages with hollow interiors and porous walls by using Pd nanocubes as sacrificial templates. Differing from our previous work (Zhang, H.; Jin, M. S.; Wang, J. G.; Li, W. Y.; Camargo, P. H. C.; Kim, M. J.; Yang, D. R.; Xie, Z. X.; Xia, Y. Synthesis of Pd-Pt Bimetallic Nanocrystals with a Concave Structure through a Bromide-Induced Galvanic Replacement Reaction. J. Am. Chem. Soc.2011, 133, 6078-6079), we complemented the galvanic replacement (between Pd nanocubes and PtCl(4)(2-)) with a coreduction process (for PdCl(4)(2-) from the galvanic reaction and PtCl(4)(2-) from the feeding) to generate Pd-Pt alloy nanocages in one step. We found that the rate of galvanic replacement (as determined by the concentrations of Br(-) and PtCl(4)(2-) and temperature) and the rates of coreduction (as determined by the type of reductant and temperature) played important roles in controlling the morphology of resultant Pd-Pt alloy nanocages. The Pd-Pt nanocages exhibited both enhanced activity and selectivity for the preferential oxidation (PROX) of CO in excess hydrogen than those of Pd nanocubes and the commercial Pt/C thanks to the alloy composition and hollow structure. In addition, as the sizes of the Pd-Pt nanocages decreased, they exhibited higher CO conversion rates and lower maximum conversion temperatures due to the increase in specific surface area.

Facile Synthesis of Bimetallic Nanoplates Consisting of Pd Cores and Pt Shells through Seeded Epitaxial Growth

Pd-Pt core-shell nanoplates with hexagonal and triangular shapes were synthesized through the heterogeneous, epitaxial growth of Pt on Pd nanoplates. The Pd nanoplates were synthesized by reducing Na2PdCl4 precursor with PVP as a reducing agent, which then served as seeds for the nucleation of Pt atoms formed by reducing H2PtCl6 with citric acid. Characterization of the as-prepared Pd-Pt nanoplates by scanning transmission electron microscopy and high-resolution transmission electron microscopy reveals that a thin, uniform Pt shell was formed around the Pd nanoplate, demonstrating the layer-by-layer epitaxial growth of Pt on Pd surface in this approach. The close lattice match between Pd and Pt (lattice mismatch of only 0.77%) and the slow reduction rate associated with the mild reducing power of citric acid play key roles in achieving the epitaxial growth of Pt shells on Pd nanoplates.

MoS2 transistors with 1-nanometer gate lengths

A flatter route to shorter channels High-performance silicon transistors can have gate lengths as short as 5 nm before source-drain tunneling and loss of electrostatic control lead to unacceptable leakage current when the device is off. Desai et al. explored the use of MoS2 as a channel material, given that its electronic properties as thin layers should limit such leakage. A transistor with a 1-nm physical gate was constructed with a MoS2 bilayer channel and a single-walled carbon nanotube gate electrode. Excellent switching characteristics and an on-off state current ratio of ∼106 were observed. Science, this issue p. 99 Molybdenum disulfide transistors with carbon nanotube gate electrodes have channel lengths below the silicon scaling limit. Scaling of silicon (Si) transistors is predicted to fail below 5-nanometer (nm) gate lengths because of severe short channel effects. As an alternative to Si, certain layered semiconductors are attractive for their atomically uniform thickness down to a monolayer, lower dielectric constants, larger band gaps, and heavier carrier effective mass. Here, we demonstrate molybdenum disulfide (MoS2) transistors with a 1-nm physical gate length using a single-walled carbon nanotube as the gate electrode. These ultrashort devices exhibit excellent switching characteristics with near ideal subthreshold swing of ~65 millivolts per decade and an On/Off current ratio of ~106. Simulations show an effective channel length of ~3.9 nm in the Off state and ~1 nm in the On state.

On the role of surface diffusion in determining the shape or morphology of noble-metal nanocrystals

Controlling the shape or morphology of metal nanocrystals is central to the realization of their many applications in catalysis, plasmonics, and electronics. In one of the approaches, the metal nanocrystals are grown from seeds of certain crystallinity through the addition of atomic species. In this case, manipulating the rates at which the atomic species are added onto different crystallographic planes of a seed has been actively explored to control the growth pattern of a seed and thereby the shape or morphology taken by the final product. Upon deposition, however, the adsorbed atoms (adatoms) may not stay at the same sites where the depositions occur. Instead, they can migrate to other sites on the seed owing to the involvement of surface diffusion, and this could lead to unexpected deviations from a desired growth pathway. Herein, we demonstrated that the growth pathway of a seed is indeed determined by the ratio between the rates for atom deposition and surface diffusion. Our result suggests that surface diffusion needs to be taken into account when controlling the shape or morphology of metal nanocrystals.

Synthesis of silver nanoplates at high yields by slowing down the polyol reduction of silver nitrate with polyacrylamide

This communication describes a simple route to Ag nanoplates by slowing the polyol reduction of silver nitrate with polyacrylamide (PAM). In addition to its role as a stabilizer for Ag colloids, the amino groups of PAM can form complexes with Ag+ ions in the solution to substantially reducing the reduction rate, leading to the formation of thin nanoplates.