An official website of the United States government
Abstract This article describes a systematic study of the oxidative etching and regrowth behaviors of Pd nanocrystals, including single‐crystal cubes bounded by {100} facets, single‐crystal octahedra and tetrahedra enclosed by {111} facets; and multiple‐twinned icosahedra covered by {111} facets and twin boundaries. During etching, Pd atoms are preferentially oxidized and removed from the corners regardless of the type of nanocrystal, and the resultant Pd2+ions are then reduced back to elemental Pd. For cubes and icosahedra, the newly formed Pd atoms are deposited on the {100} facets and twin boundaries, respectively, due to their relatively higher energies. For octahedra and tetrahedra, the Pd atoms self‐nucleate in the solution phase, followed by their growth into small particles. We can control the regrowth rate relative to etching rate by varying the concentration of HCl in the reaction solution. As the concentration of HCl is increased, 18‐nm Pd cubes are transformed into octahedra of 23, 18, and 13 nm, respectively, in edge length. Due to the absence of regrowth, however, Pd octahedra are transformed into truncated octahedra, cuboctahedra, and spheres with decreasing sizes whereas Pd tetrahedra evolve into truncated tetrahedra and spheres. In contrast, Pd icosahedra with twin boundaries on the surface are converted to asymmetric icosahedra, flower‐like icosahedra, and spheres. This work not only advances the understanding of etching and growth behaviors of metal nanocrystals with various shapes and twin structures but also offers an alternative method for controlling their shape and size.
more »
« less
Fast and Non‐equilibrium Uptake of Hydrogen by Pd Icosahedral Nanocrystals
Abstract We report for the first time that Pd nanocrystals can absorb H via a “single‐phase pathway” when particles with a proper combination of shape and size are used. Specifically, when Pd icosahedral nanocrystals of 7‐ and 12‐nm in size are exposed to H atoms, the H‐saturated twin boundaries can divide each particle into 20 smaller single‐crystal units in which the formation of phase boundaries is no longer favored. As such, absorption of H atoms is dominated by the single‐phase pathway and one can readily obtain PdHxwith anyx in the range of 0–0.7. When switched to Pd octahedral nanocrystals, the single‐phase pathway is only observed for particles of 7 nm in size. We also establish that the H‐absorption kinetics will be accelerated if there is a tensile strain in the nanocrystals due to the increase in lattice spacing. Besides the unique H‐absorption behaviors, the PdHx(x=0–0.7) icosahedral nanocrystals show remarkable thermal and catalytic stability toward the formic acid oxidation due tothe decrease in chemical potential for H atoms in a Pd lattice under tensile strain.
more »
« less
- Award ID(s):
- 2105602
- PAR ID:
- 10444110
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 62
- Issue:
- 42
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The synthesis of cone‐shaped Pt nanoparticles featuring compressively‐strained {111} facets by depositing Pt atoms on the vertices of Pd icosahedral nanocrystals, followed by selective removal of the Pd template via wet etching, is reported. By controlling the lateral dimensions down to ca. 3 nm, together with a thickness of ca. 2 nm, the Pt cones show greatly enhanced specific and mass activities toward oxygen reduction, with values being 2.8 and 6.4 times those of commercial Pt/C, respectively. Both the strain field and the observed activity trend are rationalized using density functional theory calculations. With the formation of ultrathin linkers among the Pt cones derived from the same Pd icosahedral seed, the interconnected Pt cones acquire stronger interactions with the carbon support, preventing them from detachment and aggregation during the catalytic reaction. Even after 20 000 cycles of accelerated durability test, the Pt cones still show a mass activity 5.3 times higher than the initial value of the Pt/C.more » « less
-
Abstract There is an urgent need to develop cost‐effective electrocatalysts based on Pt for a broad spectrum of applications, including those vital to the operation of fuel cells. Hollowing out the interior of Pt nanocrystals offers a simple and viable strategy for maximizing the utilization efficiency of this precious metal while enhancing the electrocatalytic performance. Herein, we report the synthesis and electrocatalytic evaluation of Pt−Ag icosahedral nanocages with an average wall thickness of 1.6 nm. The Pt atoms are coated on the surface of Ag icosahedral seeds, leading to the formation of Ag@PtnLcore‐shell icosahedral nanocrystals with tunable shell thicknesses. The core‐shell nanocrystals are then converted to icosahedral nanocages by selectively etching away the Ag in the core. The as‐obtained nanocages with a composition of Pt4.5Ag exhibit an almost 3‐fold enhancement in specific activity toward oxygen reduction relative to the commercial Pt/C in acid media.more » « less
-
We report our studies of the thickness dependence of electrical resistivity and lattice constants in strained epitaxial thin films of calcium manganese oxide. Our results indicate the potential of bi-axial lattice mismatch strain as a handle for modulating electrical resistivity. We observe thickness dependence of lattice constants consistent with what is expected for strain relaxation for films thicker than 400 Å. At lower thickness values, anomalies are observed suggestive of reduced oxygen stoichiometry. We observe a remarkable decrease in electrical resistivity with decreasing film thickness. The resistivity of our thinnest films (5–7 nm) is about three orders of magnitude lower than the resistivity of bulk CaMnO3. Resistivity increases as the film thickness increases, along with the progression of strain relaxation. It is noteworthy that the thickness dependence of resistivity we observe in CMO thin films is the opposite of what has been reported for their hole-doped rare earth manganite counterpart La0.67Ca0.33MnO3 (LCMO), where tensile lattice mismatch strain suppresses metallicity, leading to the increase in resistivity with film thickness. We believe that the enhanced conductivity in our thinnest films is related to the possible oxygen deficiency promoted by tensile strain. Recent x-ray absorption measurements have revealed reduced oxygen content and associated changes in Mn valence states in tensile-strained CMO thin films, as also predicted by density functional theory calculations. This report is the first observation of electrical transport behavior possibly indicative of strain–oxygen stoichiometry coupling.more » « less
-
Metastable phases of the photoswitchable molecular magnet K0.3Co[Fe(CN)6]0.77 ⋅ nH2O in sub-micrometer particles have been structurally investigated by synchrotron powder x-ray diffraction (PXRD) measurements. The K0.3Co[Fe(CN)6]0.77 ⋅ nH2O bulk compound (studied here with a sample having average particle size of 500 nm) undergoes a charge transfer coupled spin transition (CTCST), where spin configurations change between a paramagnetic CoII( S = 3/2) –FeIII( S = 1/2) high-temperature (HT) state and a diamagnetic CoIII( S = 0) –FeII( S = 0) low-temperature (LT) state. The bulk compound exhibits a unique intermediate (IM) phase, which corresponds to a mixture of HT and LT spin states that depend on the cooling rate. Several hidden metastable HT states emerge as a function of thermal and photo stimuli, namely: (1) a quench (Q) state generated from the HT state by flash cooling, (2) a LTPX state obtained by photoexcitation from the LT state derived by thermal relaxation from the Q state, and (3) an IMPX state accessed by photo-irradiation from the IM state. A sample with a smaller particle size, 135 nm, is investigated for which the particles are on the scale of the coherent LT domains in the IM phase within the larger 500 nm sample. PXRD studies under controlled thermal and/or optical excitations have clarified that the reduction of the particle size profoundly affects the structural changes associated with the CTCST. The unusual IM state is also observed as segregated domains in the 135 nm particle, but the collective structural transformations are more hindered in small particles. The volume change decreases to 2%–3%, almost half the value found for 500 nm particles (5%–8%), even though the linear thermal expansion coefficients are larger for the smaller particles. Furthermore, photoexcitation from the IM and LT states does not turn into single phases in the smaller particles, presumably because of the multiple interfaces and/or internal stress generated by the coexistence of small CoII–FeIIIand CoIII–FeIIdomains in the lattice. Since the reduced particle size limits cooperativity and domain growth in the lattice, CTCST in the small particle sample becomes less sensitive to external stimuli.more » « less
