9 research outputs found
Doped Silicon Nanocrystal Plasmonics
Doped semiconductor nanocrystals
represent an exciting new type
of plasmonic material with optical resonances in the infrared. Unlike
noble metal nanoparticles, the plasmon resonance can be tuned by altering
the doping density. Recently, it has been shown that silicon nanocrystals
can be doped using phosphorus and boron resulting in highly tunable
infrared plasmon resonances. Due to the band structure of silicon,
doping with phosphorus contributes light (transverse) and heavy (longitudinal)
electrons, while boron contributes light and heavy holes and one would
expect two distinct plasmon branches. Here we develop a classical
hybridization theory and a full quantum mechanical TDLDA approach
for two-component carrier plasmas and show that the interaction between
the two plasmon branches results in strongly hybridized plasmon modes.
The antibonding mode where the two components move in phase is bright
and depends sensitively on the doping densities. The low energy bonding
mode with opposite charge alignment can only be observed in the quantum
regime when strong Coulomb screening is present. The theoretical results
are in good agreement with the experimental data
Flexible 2D Boron Imidazolate Framework for Polysulfide Adsorption in Lithium–Sulfur Batteries
The “polysulfide shuttle,” a process initiated
by
the dissolution of polysulfides, is recognized to be one of the major
failure mechanisms of lithium–sulfur (Li–S) batteries.
Much research effort has been dedicated toward efficient cathode additives
and host materials to suppress the leaching of polysulfide species.
Herein, we report a new 2D metal–organic framework constituted
by a tritopic ligand, boron imidazolate ([BH(Im)3]−, Im = imidazole), and Co2+ ions for lithium
polysulfide adsorption. The cobalt imidazolate framework (CoN6-BIF) contains octahedrally coordinated Co centers that form
two-dimensional layers in the a,b plane. Composite cathodes containing CoN6-BIF exhibited
high sulfur utilization and capacity retention, resulting in improved
specific capacity and cycle life compared to sulfur/carbon controls.
Density functional theory (DFT) calculations suggest that CoN6-BIF linkers are rotationally flexible, allowing the framework
to accommodate polysulfide in the expanded pores. This unusual property
of BIFs opens up new avenues for exploring flexible metal–organic
frameworks (MOFs) and their applications to energy storage
Flexible 2D Boron Imidazolate Framework for Polysulfide Adsorption in Lithium–Sulfur Batteries
The “polysulfide shuttle,” a process initiated
by
the dissolution of polysulfides, is recognized to be one of the major
failure mechanisms of lithium–sulfur (Li–S) batteries.
Much research effort has been dedicated toward efficient cathode additives
and host materials to suppress the leaching of polysulfide species.
Herein, we report a new 2D metal–organic framework constituted
by a tritopic ligand, boron imidazolate ([BH(Im)3]−, Im = imidazole), and Co2+ ions for lithium
polysulfide adsorption. The cobalt imidazolate framework (CoN6-BIF) contains octahedrally coordinated Co centers that form
two-dimensional layers in the a,b plane. Composite cathodes containing CoN6-BIF exhibited
high sulfur utilization and capacity retention, resulting in improved
specific capacity and cycle life compared to sulfur/carbon controls.
Density functional theory (DFT) calculations suggest that CoN6-BIF linkers are rotationally flexible, allowing the framework
to accommodate polysulfide in the expanded pores. This unusual property
of BIFs opens up new avenues for exploring flexible metal–organic
frameworks (MOFs) and their applications to energy storage
Flexible 2D Boron Imidazolate Framework for Polysulfide Adsorption in Lithium–Sulfur Batteries
The “polysulfide shuttle,” a process initiated
by
the dissolution of polysulfides, is recognized to be one of the major
failure mechanisms of lithium–sulfur (Li–S) batteries.
Much research effort has been dedicated toward efficient cathode additives
and host materials to suppress the leaching of polysulfide species.
Herein, we report a new 2D metal–organic framework constituted
by a tritopic ligand, boron imidazolate ([BH(Im)3]−, Im = imidazole), and Co2+ ions for lithium
polysulfide adsorption. The cobalt imidazolate framework (CoN6-BIF) contains octahedrally coordinated Co centers that form
two-dimensional layers in the a,b plane. Composite cathodes containing CoN6-BIF exhibited
high sulfur utilization and capacity retention, resulting in improved
specific capacity and cycle life compared to sulfur/carbon controls.
Density functional theory (DFT) calculations suggest that CoN6-BIF linkers are rotationally flexible, allowing the framework
to accommodate polysulfide in the expanded pores. This unusual property
of BIFs opens up new avenues for exploring flexible metal–organic
frameworks (MOFs) and their applications to energy storage
Exploiting Localized Surface Binding Effects to Enhance the Catalytic Reactivity of Peptide-Capped Nanoparticles
Peptide-based methods represent new
approaches to selectively produce
nanostructures with potentially important functionality. Unfortunately,
biocombinatorial methods can only select peptides with target affinity
and not for the properties of the final material. In this work, we
present evidence to demonstrate that materials-directing peptides
can be controllably modified to substantially enhance particle functionality
without significantly altering nanostructural morphology. To this
end, modification of selected residues to vary the site-specific binding
strength and biological recognition can be employed to increase the
catalytic efficiency of peptide-capped Pd nanoparticles. These results
represent a step toward the <i>de novo</i> design of materials-directing
peptides that control nanoparticle structure/function relationships
Direct Synthetic Control over the Size, Composition, and Photocatalytic Activity of Octahedral Copper Oxide Materials: Correlation Between Surface Structure and Catalytic Functionality
We
report a synthetic approach to form octahedral Cu<sub>2</sub>O microcrystals
with a tunable edge length and demonstrate their use as catalysts
for the photodegradation of aromatic organic compounds. In this particular
study, the effects of the Cu<sup>2+</sup> and reductant concentrations
and stoichiometric ratios were carefully examined to identify their
roles in controlling the final material composition and size under
sustainable reaction conditions. Varying the ratio and concentrations
of Cu<sup>2+</sup> and reductant added during the synthesis determined
the final morphology and composition of the structures. Octahedral
particles were prepared at selected Cu<sup>2+</sup>:glucose ratios
that demonstrated a range of photocatalytic reactivity. The results
indicate that material composition, surface area, and substrate charge
effects play important roles in controlling the overall reaction rate.
In addition, analysis of the post-reacted materials revealed photocorrosion
was inhibited and that surface etching had preferentially occurred
at the particle edges during the reaction, suggesting that the reaction
predominately occurred at these interfaces. Such results advance the
understanding of how size and composition affect the surface interface
and catalytic functionality of materials
Light-Activated Tandem Catalysis Driven by Multicomponent Nanomaterials
Transitioning
energy-intensive and environmentally intensive processes
toward sustainable conditions is necessary in light of the current
global condition. To this end, photocatalytic processes represent
new approaches for H<sub>2</sub> generation; however, their application
toward tandem catalytic reactivity remains challenging. Here, we demonstrate
that metal oxide materials decorated with noble metal nanoparticles
advance visible light photocatalytic activity toward new reactions
not typically driven by light. For this, Pd nanoparticles were deposited
onto Cu<sub>2</sub>O cubes to generate a composite structure. Once
characterized, their hydrodehalogenation activity was studied via
the reductive dechlorination of polychlorinated biphenyls. To this
end, tandem catalytic reactivity was observed with H<sub>2</sub> generation
via H<sub>2</sub>O reduction at the Cu<sub>2</sub>O surface, followed
by dehalogenation at the Pd using the <i>in situ</i> generated
H<sub>2</sub>. Such results present methods to achieve sustainable
catalytic technologies by advancing photocatalytic approaches toward
new reaction systems
Elucidation of Peptide-Directed Palladium Surface Structure for Biologically Tunable Nanocatalysts
Peptide-enabled synthesis of inorganic nanostructures represents an avenue to access catalytic materials with tunable and optimized properties. This is achieved <i>via</i> peptide complexity and programmability that is missing in traditional ligands for catalytic nanomaterials. Unfortunately, there is limited information available to correlate peptide sequence to particle structure and catalytic activity to date. As such, the application of peptide-enabled nanocatalysts remains limited to trial and error approaches. In this paper, a hybrid experimental and computational approach is introduced to systematically elucidate biomolecule-dependent structure/function relationships for peptide-capped Pd nanocatalysts. Synchrotron X-ray techniques were used to uncover substantial particle surface structural disorder, which was dependent upon the amino acid sequence of the peptide capping ligand. Nanocatalyst configurations were then determined directly from experimental data using reverse Monte Carlo methods and further refined using molecular dynamics simulation, obtaining thermodynamically stable peptide-Pd nanoparticle configurations. Sequence-dependent catalytic property differences for C–C coupling and olefin hydrogenation were then elucidated by identification of the catalytic active sites at the atomic level and quantitative prediction of relative reaction rates. This hybrid methodology provides a clear route to determine peptide-dependent structure/function relationships, enabling the generation of guidelines for catalyst design through rational tailoring of peptide sequences
Effects of Metal Composition and Ratio on Peptide-Templated Multimetallic PdPt Nanomaterials
It
can be difficult to simultaneously control the size, composition,
and morphology of metal nanomaterials under benign aqueous conditions.
For this, bioinspired approaches have become increasingly popular
due to their ability to stabilize a wide array of metal catalysts
under ambient conditions. In this regard, we used the R5 peptide as
a three-dimensional template for formation of PdPt bimetallic nanomaterials.
Monometallic Pd and Pt nanomaterials have been shown to be highly
reactive toward a variety of catalytic processes, but by forming bimetallic
species, increased catalytic activity may be realized. The optimal
metal-to-metal ratio was determined by varying the Pd:Pt ratio to
obtain the largest increase in catalytic activity. To better understand
the morphology and the local atomic structure of the materials, the
bimetallic PdPt nanomaterials were extensively studied by transmission
electron microscopy, extended X-ray absorption fine structure spectroscopy,
X-ray photoelectron spectroscopy, and pair distribution function analysis.
The resulting PdPt materials were determined to form multicomponent
nanostructures where the Pt component demonstrated varying degrees
of oxidation based upon the Pd:Pt ratio. To test the catalytic reactivity
of the materials, olefin hydrogenation was conducted, which indicated
a slight catalytic enhancement for the multicomponent materials. These
results suggest a strong correlation between the metal ratio and the
stabilizing biotemplate in controlling the final materials morphology,
composition, and the interactions between the two metal species