Shuifen Xie

Synthesis of Tin Dioxide Octahedral Nanoparticles with Exposed High-Energy {221} Facets and Enhanced Gas-Sensing Properties

National Natural Science Foundation of China [20725310, 20721001, 20673085, 20801045]; National Basic Research Program of China [2007CB15303, 2009CB939804]

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.

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.

Cu2+-Assisted Synthesis of Hexoctahedral Au–Pd Alloy Nanocrystals with High-Index Facets

Controlled syntheses of multicomponent metal nanocrystals (NCs) and high-index surfaces have attracted increasing attention due to the specific physical and chemical properties of such NCs. Taking advantage of copper underpotential deposition as a bridge, hexoctahedral Au-Pd alloy NCs with {hkl} facets exposed were successfully synthesized, while phase separation occurred in the absence of Cu(2+) ions. The as-prepared hexoctahedral Au-Pd alloy NCs exhibited very excellent performance in terms of both formic acid electro-oxidation and methanol tolerance due to synergism between the high-index facets and the alloy.

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 Pd-Rh Core-Frame Concave Nanocubes and Their Conversion to Rh Cubic Nanoframes by Selective Etching of the Pd Cores

NSF [DMR-1215034]; Georgia Institute of Technology; China Scholarship Council (CSC); World Class University Program from MEST through NRF [R31-10026]

Atomic layer-by-layer deposition of platinum on palladium octahedra for enhanced catalysts toward the oxygen reduction reaction

We systematically evaluated two different approaches to the syntheses of Pd@PtnL (n = 2-5) core-shell octahedra. We initially prepared the core-shell octahedra using a polyol-based route by titrating a Pt(IV) precursor into the growth solution containing Pd octahedral seeds at 200 °C through the use of a syringe pump. The number of Pt atomic layers could be precisely controlled from two to five by increasing the volume of the precursor solution while fixing the amount of seeds. We then demonstrated the synthesis of Pd@PtnL octahedra using a water-based route at 95 °C through the one-shot injection of a Pt(II) precursor. Due to the large difference in reaction temperature, the Pd@PtnL octahedra obtained via the water-based route showed sharper corners than their counterparts obtained through the polyol-based route. When compared to a commercial Pt/C catalyst based upon 3.2 nm Pt particles, the Pd@PtnL octahedra prepared using both methods showed similar remarkable enhancement in terms of activity (both specific and mass) and durability toward the oxygen reduction reaction. Calculations based upon periodic, self-consistent density functional theory suggested that the enhancement in specific activity for the Pd@PtnL octahedra could be attributed to the destabilization of OH on their PtnL*/Pd(111) surface relative to the {111} and {100} facets exposed on the surface of Pt/C. The destabilization of OH facilitates its hydrogenation, which was found to be the rate-limiting step of the oxygen reduction reaction on all these surfaces.

Synthesis of silver octahedra with controlled sizes and optical properties via seed-mediated growth.

Silver octahedra with edge lengths controlled in the range of 20-72 nm were synthesized via seed-mediated growth. The key to the success of this synthesis is the use of single-crystal Ag seeds with uniform and precisely controlled sizes to direct the growth and the use of citrate as a selective capping agent for the {111} facets. Our mechanistic studies demonstrated that Ag seeds with both cubic and quasi-spherical shapes could evolve into octahedra. For the first time, we were able to precisely control the edge lengths of Ag octahedra below 100 nm, and the lower limit of size could even be pushed down to 20 nm. Using the as-obtained Ag octahedra as sacrificial templates, Au nanocages with an octahedral shape and precisely tunable optical properties were synthesized through a galvanic replacement reaction. Such hollow nanostructures are promising candidates for a broad range of applications related to optics, catalysis, and biomedicine.

Enhancing the Photocatalytic Activity of Anatase TiO2 by Improving the Specific Facet-Induced Spontaneous Separation of Photogenerated Electrons and Holes

Recently, it has been proven that directional flow of photogenerated charge carriers occurs on specific facets of TiO(2) nanocrystals. Herein, we demonstrate that the photocatalytic activity of anatase TiO(2) nanocrystals in both photoreduction and photooxidation processes can be enhanced by selectively depositing Pt nanoparticles on the {101} facets, which strengthens spontaneously surface-induced separation between photogenerated electrons and holes in the photocatalysis process. An optimal ratio of the oxidative {001} facets to the reductive {101} facets exists with regard to the photocatalysis of the faceted TiO(2) nanocrystals, and this is crucial for balancing the recombination and redox reaction rates of photogenerated electrons and holes. The present work might help us gain deeper insight into the relation between the specific surface of semiconductor photocatalysts and their photocatalytic activities and provides us with a new route to design photocatalysts with high photocatalytic activity.

Quantitative Analysis of the Coverage Density of Br– Ions on Pd{100} Facets and Its Role in Controlling the Shape of Pd Nanocrystals

We report an approach based on a combination of inductively coupled plasma mass spectrometry and X-ray photoelectron spectroscopy for quantitative analysis of the role played by Br(-) ions in the synthesis of Pd nanocrystals. The Br(-) ions were found to adsorb onto Pd{100} facets selectively with a coverage density of ca. 0.8 ion per surface Pd atom. The chemisorbed Br(-) ions could be removed via desorption at an elevated temperature under reductive conditions. They could also be gradually released from the surface when Pd cubic seeds grew into cuboctahedrons and then octahedrons. On the basis of the coverage density information, we were able to estimate the minimum concentration of Br(-) ions needed for the formation of Pd nanocubes with a specific size. If the concentration of Br(-) ions was below this minimum value, not all of the {100} facets could be stabilized by the capping agent, leading to the formation of nanocubes with truncated corners. The quantitative analysis developed in this study is potentially extendable to other systems involving chemisorbed capping agents.