Miaofang Chi

Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces

Giving Electrocatalysts an Edge Platinum (Pt) is an excellent catalyst for the oxygen-reduction reaction (ORR) in fuel cells and electrolyzers, but it is too expensive and scarce for widespread deployment, even when dispersed as Pt nanoparticles on carbon electrode supports (Pt/C). Alternatively, Chen et al. (p. 1339, published online 27 February; see the Perspective by Greer) made highly active ORR catalysts by dissolving away the interior of rhombic dodecahedral PtNi3 nanocrystals to leave Pt-rich Pt3Ni edges. These nanoframe catalysts are durable—remaining active after 10,000 rounds of voltage cycling—and are far more active than Pt/C. Highly active electrocatalysts are created by eroding away all but the edges of platinum-nickel nanocrystals. [Also see Perspective by Greer] Control of structure at the atomic level can precisely and effectively tune catalytic properties of materials, enabling enhancement in both activity and durability. We synthesized a highly active and durable class of electrocatalysts by exploiting the structural evolution of platinum-nickel (Pt-Ni) bimetallic nanocrystals. The starting material, crystalline PtNi3 polyhedra, transforms in solution by interior erosion into Pt3Ni nanoframes with surfaces that offer three-dimensional molecular accessibility. The edges of the Pt-rich PtNi3 polyhedra are maintained in the final Pt3Ni nanoframes. Both the interior and exterior catalytic surfaces of this open-framework structure are composed of the nanosegregated Pt-skin structure, which exhibits enhanced oxygen reduction reaction (ORR) activity. The Pt3Ni nanoframe catalysts achieved a factor of 36 enhancement in mass activity and a factor of 22 enhancement in specific activity, respectively, for this reaction (relative to state-of-the-art platinum-carbon catalysts) during prolonged exposure to reaction conditions.

Multiple-Filled Skutterudites: High Thermoelectric Figure of Merit through Separately Optimizing Electrical and Thermal Transports

Skutterudites CoSb(3) with multiple cofillers Ba, La, and Yb were synthesized and very high thermoelectric figure of merit ZT = 1.7 at 850 K was realized. X-ray diffraction of the densified multiple-filled bulk samples reveals all samples are phase pure. High-resolution scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDS) analysis confirm that multiple guest fillers occupy the nanoscale-cages in the skutterudites. The fillers are further shown to be uniformly distributed and the Co-Sb skutterudite framework is virtually unperturbed from atomic scale to a few micrometers. Our results firmly show that high power factors can be realized by adjusting the total filling fraction of fillers with different charge states to reach the optimum carrier density, at the same time, lattice thermal conductivity can also be significantly reduced, to values near the glass limit of these materials, through combining filler species of different rattling frequencies to achieve broad-frequency phonon scattering. Therefore, partially filled skutterudites with multiple fillers of different chemical nature render unique structural characteristics for optimizing electrical and thermal transports in a relatively independent way, leading to continually enhanced ZT values from single- to double-, and finally to multiple-filled skutterudites. The idea of combining multiple fillers with different charge states and rattling frequencies for performance optimization is also expected to be valid for other caged TE compounds.

Mineralogy and Petrology of Comet 81P/Wild 2 Nucleus Samples

The bulk of the comet 81P/Wild 2 (hereafter Wild 2) samples returned to Earth by the Stardust spacecraft appear to be weakly constructed mixtures of nanometer-scale grains, with occasional much larger (over 1 micrometer) ferromagnesian silicates, Fe-Ni sulfides, Fe-Ni metal, and accessory phases. The very wide range of olivine and low-Ca pyroxene compositions in comet Wild 2 requires a wide range of formation conditions, probably reflecting very different formation locations in the protoplanetary disk. The restricted compositional ranges of Fe-Ni sulfides, the wide range for silicates, and the absence of hydrous phases indicate that comet Wild 2 experienced little or no aqueous alteration. Less abundant Wild 2 materials include a refractory particle, whose presence appears to require radial transport in the early protoplanetary disk.

Design and synthesis of bimetallic electrocatalyst with multilayered Pt-skin surfaces.

Advancement in heterogeneous catalysis relies on the capability of altering material structures at the nanoscale, and that is particularly important for the development of highly active electrocatalysts with uncompromised durability. Here, we report the design and synthesis of a Pt-bimetallic catalyst with multilayered Pt-skin surface, which shows superior electrocatalytic performance for the oxygen reduction reaction (ORR). This novel structure was first established on thin film extended surfaces with tailored composition profiles and then implemented in nanocatalysts by organic solution synthesis. Electrochemical studies for the ORR demonstrated that after prolonged exposure to reaction conditions, the Pt-bimetallic catalyst with multilayered Pt-skin surface exhibited an improvement factor of more than 1 order of magnitude in activity versus conventional Pt catalysts. The substantially enhanced catalytic activity and durability indicate great potential for improving the material properties by fine-tuning of the nanoscale architecture.

Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets

Etching platinum nanocage catalysts Although platinum is an excellent catalyst for the oxygen reduction reaction that occurs in fuel cells, its scarcity continues to drive efforts to improve its utilization. Zhang et al. made nanocages of platinum by coating palladium nanocrystals with only a few layers of platinum and then etching away the palladium core (see the Perspective by Strasser). Platinum nanocages made using nanoscale octahedra and cubes of palladium displayed different catalytic activity for the oxygen reduction reaction. Science, this issue p. 412; see also p. 379 Nanocage electrocatalysts can increase the utilization of platinum and improve activity by controlling surface structure. [Also see Perspective by Strasser] A cost-effective catalyst should have a high dispersion of the active atoms, together with a controllable surface structure for the optimization of activity, selectivity, or both. We fabricated nanocages by depositing a few atomic layers of platinum (Pt) as conformal shells on palladium (Pd) nanocrystals with well-defined facets and then etching away the Pd templates. Density functional theory calculations suggest that the etching is initiated via a mechanism that involves the formation of vacancies through the removal of Pd atoms incorporated into the outermost layer during the deposition of Pt. With the use of Pd nanoscale cubes and octahedra as templates, we obtained Pt cubic and octahedral nanocages enclosed by {100} and {111} facets, respectively, which exhibited distinctive catalytic activities toward oxygen reduction.

Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study

High voltage cathode materials Li-excess layered oxide compounds Li[NixLi1/3−2x/3Mn2/3−x/3]O2 (0 < x < 1/2) are investigated in a joint study combining both computational and experimental methods. The bulk and surface structures of pristine and cycled samples of Li[Ni1/5Li1/5Mn3/5]O2 are characterized by synchrotron X-Ray diffraction together with aberration corrected Scanning Transmission Electron Microscopy (a-S/TEM). Electron Energy Loss Spectroscopy (EELS) is carried out to investigate the surface changes of the samples before/after electrochemical cycling. Combining first principles computational investigation with our experimental observations, a detailed lithium de-intercalation mechanism is proposed for this family of Li-excess layered oxides. The most striking characteristics in these high voltage high energy density cathode materials are 1) formation of tetrahedral lithium ions at voltage less than 4.45 V and 2) the transition metal (TM) ions migration leading to phase transformation on the surface of the materials. We show clear evidence of a new spinel-like solid phase formed on the surface of the electrode materials after high-voltage cycling. It is proposed that such surface phase transformation is one of the factors contributing to the first cycle irreversible capacity and the main reason for the intrinsic poor rate capability of these materials.

Platinum-Based Nanocages with Subnanometer-Thick Walls and Well-Defined Facets

Etching platinum nanocage catalysts Although platinum is an excellent catalyst for the oxygen reduction reaction that occurs in fuel cells, its scarcity continues to drive efforts to improve its utilization. Zhang et al. made nanocages of platinum by coating palladium nanocrystals with only a few layers of platinum and then etching away the palladium core (see the Perspective by Strasser). Platinum nanocages made using nanoscale octahedra and cubes of palladium displayed different catalytic activity for the oxygen reduction reaction. Science, this issue p. 412; see also p. 379 Nanocage electrocatalysts can increase the utilization of platinum and improve activity by controlling surface structure. [Also see Perspective by Strasser] A cost-effective catalyst should have a high dispersion of the active atoms, together with a controllable surface structure for the optimization of activity, selectivity, or both. We fabricated nanocages by depositing a few atomic layers of platinum (Pt) as conformal shells on palladium (Pd) nanocrystals with well-defined facets and then etching away the Pd templates. Density functional theory calculations suggest that the etching is initiated via a mechanism that involves the formation of vacancies through the removal of Pd atoms incorporated into the outermost layer during the deposition of Pt. With the use of Pd nanoscale cubes and octahedra as templates, we obtained Pt cubic and octahedral nanocages enclosed by {100} and {111} facets, respectively, which exhibited distinctive catalytic activities toward oxygen reduction.

Core/Shell Pd/FePt Nanoparticles as an Active and Durable Catalyst for the Oxygen Reduction Reaction

We report a unique synthesis of core/shell Pd/FePt nanoparticles (NPs) and their catalysis of the oxygen reduction reaction (ORR). The uniform FePt shell is formed by controlled nucleation of Fe(CO)(5) in the presence of a Pt salt and Pd NPs at designated reaction temperatures. The Pd/FePt NPs show FePt shell-dependent catalytic properties, and those having a 1 nm FePt shell exhibit a drastic increase in durability and activity (15 times more active with a 140 mV gain in onset potential in comparison with those having a 3 nm coating). These Pd/FePt NPs are promising new catalysts for practical fuel cell applications.

Soft‐Templated Mesoporous Carbon‐Carbon Nanotube Composites for High Performance Lithium‐ion Batteries

Mesoporous carbon with homogeneously dispersed multi-walled carbon nanotubes (MWNTs) are synthesized via a one-step brick and mortar soft-templating approach. Nanocomposites exhibit high rate capability and reversible lithium storage capacity of 900 mA h g-1 and good rate performance. Such homogeneous nanocomposites are ideal candidates for electric vehicle applications where high power and energy density are primary requirements.

A Highly Active Titanium Dioxide Based Visible-Light Photocatalyst with Nonmetal Doping and Plasmonic Metal Decoration†

A sandwich-structured photocatalyst shows an excellent performance in degradation reactions of a number of organic compounds under UV, visible light, and direct sunlight (see picture). The catalyst was synthesized by a combination of nonmetal doping and plasmonic metal decoration of TiO2 nanocrystals, which improves visible-light activity and enhances light harvesting and charge separation, respectively.