6 research outputs found
<i>In Situ</i> Study of Atomic Structure Transformations of PtâNi Nanoparticle Catalysts during Electrochemical Potential Cycling
When exposed to corrosive anodic electrochemical environments, Pt alloy nanoparticles (NPs) undergo selective dissolution of the less noble component, resulting in catalytically active bimetallic Pt-rich coreâshell structures. Structural evolution of PtNi<sub>6</sub> and PtNi<sub>3</sub> NP catalysts during their electrochemical activation and catalysis was studied by <i>in situ</i> anomalous small-angle X-ray scattering to obtain insight in element-specific particle size evolution and time-resolved insight in the intraparticle structure evolution. <i>Ex situ</i> high-energy X-ray diffraction coupled with pair distribution function analysis was employed to obtain detailed information on the atomic-scale ordering, particle phases, structural coherence lengths, and particle segregation. Our studies reveal a spontaneous electrochemically induced formation of PtNi particles of ordered Au<sub>3</sub>Cu-type alloy structures from disordered alloy phases (solid solutions) concomitant with surface Ni dissolution, which is coupled to spontaneous residual Ni metal segregation during the activation of PtNi<sub>6</sub>. Pt-enriched coreâshell structures were not formed using the studied Ni-rich nanoparticle precursors. In contrast, disordered PtNi<sub>3</sub> alloy nanoparticles lose Ni more rapidly, forming Pt-enriched coreâshell structures with superior catalytic activity. Our X-ray scattering results are confirmed by STEM/EELS results on similar nanoparticles
Deep Eutectic Solvents for the Self-Assembly of Gold Nanoparticles: A SAXS, UVâVis, and TEM Investigation
In this work, we report the formation
and growth mechanisms of
gold nanoparticles (AuNPs) in eco-friendly deep eutectic solvents
(DES; choline chloride and urea). AuNPs are synthesized on the DES
surface via a low-energy sputter deposition method. Detailed small
angle X-ray scattering (SAXS), UVâVis, and cryogenic transmission
electron microscopy (cryo-TEM) investigations show the formation of
AuNPs of 5 nm diameter. Data analysis reveals that for a prolonged
gold-sputtering time there is no change in the size of the particles.
Only the concentration of AuNPs increases linearly in time. More surprisingly,
the self-assembly of AuNPs into a first and second shell ordered system
is observed directly by in situ SAXS for prolonged gold-sputtering
times. The self-assembly mechanism is explained by the templating
nature of DES combined with the equilibrium between specific physical
interaction forces between the AuNPs. A disulfide-based stabilizer,
bisÂ((2-mercaptoethyl)Âtrimethylammonium) disulfide dichloride, was
applied to suppress the self-assembly. Moreover, the stabilizer even
reverses the self-assembled or agglomerated AuNPs back to stable 5
nm individual particles as directly evidenced by UVâVis. The
template behavior of DES is compared to that of nontemplating solvent
castor oil. Our results will also pave the way to understand and control
the self-assembly of metallic and bimetallic nanoparticles
Nonaqueous Microemulsions Based on <i>N</i>,<i>N</i>â˛âAlkylimidazolium Alkylsulfate Ionic Liquids
The ternary system composed of the
ionic liquid surfactant (IL-S) 1-butyl-3-methylimidazolium dodecylsulfate
([Bmim]Â[DodSO<sub>4</sub>]), the room temperature ionic liquid (RTIL)
1-ethyl-3-methylimidazolium ethylsulfate ([Emim]Â[EtSO<sub>4</sub>]),
and toluene has been investigated. Three major mechanisms guiding
the structure of the isotropic phase were identified by means of conductometric
experiments, which have been correlated to the presence of oil-in-IL,
bicontinuous, and IL-in-oil microemulsions. IL-S forms micelles in
toluene, which swell by adding RTIL as to be shown by dynamic light
scattering (DLS) and small-angle X-ray scattering (SAXS) experiments.
Therefore, it is possible to form water-free IL-in-oil reverse microemulsions
â¤10 nm in size as a new type of nanoreactor
Distribution of Counterions around Lignosulfonate Macromolecules in Different Polar Solvent Mixtures
Lignosulfonate is a colloidal polyelectrolyte that is
obtained
as a side product in sulfite pulping. In this work we wanted to study
the noncovalent association of the colloids in different solvents,
as well as to find out how the charged sulfonate groups are organized
on the colloid surface. We studied sodium and rubidium lignosulfonate
in waterâmethanol mixtures and in dimethyl formamide. The number
average molecular weights of the Na- and Rb-lignosulfonate fractions
were 7600 g/mol and 9100 g/mol, respectively, and the polydispersity
index for both was 2. Anomalous small-angle X-ray scattering (ASAXS)
was used for determining the distribution of counterions around the
Rb-lignosulfonate macromolecules. The scattering curves were fitted
with a model constructed from ellipsoids of revolution of different
sizes. Counterions were taken into account by deriving an approximative
formula for the scattering intensity of the PoissonâBoltzmann
diffuse double layer model. The interaction term between the spheroidal
particles was estimated using the local monodisperse approximation
and the improved HayterâPenfold structure factor given by the
rescaled mean spherical approximation. Effective charge of the polyelectrolyte
and the local dielectric constant of the solvent close to the globular
polyelectrolyte were followed as a function of the methanol content
in the solvent and lignosulfonate concentration. The lignosulfonate
macromolecules were found to aggregate noncovalently in waterâmethanol
mixtures with increasing methanol or lignosulfonate content in a specific
directional manner. The flat macromolecule aggregates had a nearly
constant thickness of 1â1.4 nm, while their diameter grew when
counterion association onto the polyelectrolyte increased. These results
indicate that the charged groups in lignosulfonate are mostly at the
flat surfaces of the colloid, allowing the associated lignosulfonate
complexes to grow further at the edges of the complex
Crystal Phase Transitions in the Shell of PbS/CdS Core/Shell Nanocrystals Influences Photoluminescence Intensity
We reveal the existence of two different
crystalline phases, i.e.,
the metastable <i>rock salt</i> and the equilibrium <i>zinc blende</i> phase within the CdS-shell of PbS/CdS core/shell
nanocrystals formed by cationic exchange. The chemical composition
profile of the core/shell nanocrystals with different dimensions is
determined by means of anomalous small-angle X-ray scattering with
subnanometer resolution and is compared to X-ray diffraction analysis.
We demonstrate that the photoluminescence emission of PbS nanocrystals
can be drastically enhanced by the formation of a CdS shell. Especially,
the ratio of the two crystalline phases in the shell significantly
influences the photoluminescence enhancement. The highest emission
was achieved for chemically pure CdS shells below 1 nm thickness with
a dominant metastable <i>rock salt</i> phase fraction matching
the crystal structure of the PbS core. The metastable phase fraction
decreases with increasing shell thickness and increasing exchange
times. The photoluminescence intensity depicts a constant decrease
with decreasing metastable <i>rock salt</i> phase fraction
but shows an abrupt drop for shells above 1.3 nm thickness. We relate
this effect to two different transition mechanisms for changing from
the metastable <i>rock salt</i> phase to the equilibrium <i>zinc blende</i> phase depending on the shell thickness
Design of a Nanometric AlTi Additive for MgB<sub>2</sub>âBased Reactive Hydride Composites with Superior Kinetic Properties
Solid-state hydride compounds are
a promising option for efficient
and safe hydrogen-storage systems. Lithium reactive hydride composite
system 2LiBH<sub>4</sub> + MgH<sub>2</sub>/2LiH + MgB<sub>2</sub> (Li-RHC)
has been widely investigated owing to its high theoretical hydrogen-storage
capacity and low calculated reaction enthalpy (11.5 wt % H<sub>2</sub> and 45.9 kJ/mol H<sub>2</sub>). In this paper, a thorough investigation
into the effect of the formation of nano-TiAl alloys on the hydrogen-storage
properties of Li-RHC is presented. The additive 3TiCl<sub>3</sub>¡AlCl<sub>3</sub> is used as the nanoparticle precursor. For the investigated
temperatures and hydrogen pressures, the addition of âź5 wt
% 3TiCl<sub>3</sub>¡AlCl<sub>3</sub> leads to hydrogenation/dehydrogenation
times of only 30 min and a reversible hydrogen-storage capacity of
9.5 wt %. The material containing 3TiCl<sub>3</sub>¡AlCl<sub>3</sub> possesses superior hydrogen-storage properties in terms of
rates and a stable hydrogen capacity during several hydrogenation/dehydrogenation
cycles. These enhancements are attributed to an in situ nanostructure
and a hexagonal AlTi<sub>3</sub> phase observed by high-resolution
transmission electron microscopy. This phase acts in a 2-fold manner,
first promoting the nucleation of MgB<sub>2</sub> upon dehydrogenation
and second suppressing the formation of Li<sub>2</sub>B<sub>12</sub>H<sub>12</sub> upon hydrogenation/dehydrogenation cycling