skip to main content

Title: Reconciling structure prediction of alloyed, ultrathin nanowires with spectroscopy
A number of complementary, synergistic advances are reported herein. First, we describe the ‘first-time’ synthesis of ultrathin Ru 2 Co 1 nanowires (NWs) possessing average diameters of 2.3 ± 0.5 nm using a modified surfactant-mediated protocol. Second, we utilize a combination of quantitative EDS, EDS mapping (along with accompanying line-scan profiles), and EXAFS spectroscopy results to probe the local atomic structure of not only novel Ru 2 Co 1 NWs but also ‘control’ samples of analogous ultrathin Ru 1 Pt 1 , Au 1 Ag 1 , Pd 1 Pt 1 , and Pd 1 Pt 9 NWs. We demonstrate that ultrathin NWs possess an atomic-level geometry that is fundamentally dependent upon their intrinsic chemical composition. In the case of the PdPt NW series, EDS mapping data are consistent with the formation of a homogeneous alloy, a finding further corroborated by EXAFS analysis. By contrast, EXAFS analysis results for both Ru 1 Pt 1 and Ru 2 Co 1 imply the generation of homophilic structures in which there is a strong tendency for the clustering of ‘like’ atoms; associated EDS results for Ru 1 Pt 1 convey the same conclusion, namely the production of a heterogeneous structure. Conversely, EDS mapping more » data for Ru 2 Co 1 suggests a uniform distribution of both elements. In the singular case of Au 1 Ag 1 , EDS mapping results are suggestive of a homogeneous alloy, whereas EXAFS analysis pointed to Ag segregation at the surface and an Au-rich core, within the context of a core–shell structure. These cumulative outcomes indicate that only a combined consideration of both EDS and EXAFS results can provide for an accurate representation of the local atomic structure of ultrathin NW motifs. « less
Authors:
; ; ; ; ;
Award ID(s):
1807640
Publication Date:
NSF-PAR ID:
10223801
Journal Name:
Chemical Science
ISSN:
2041-6520
Sponsoring Org:
National Science Foundation
More Like this
  1. Conducting probe atomic force microscopy (CP-AFM) was employed to examine electron tunneling in self-assembled monolayer (SAM) junctions. A 2.3 nm long perylene tetracarboxylic acid diimide (PDI) acceptor molecule equipped with isocyanide linker groups was synthesized, adsorbed onto Ag, Au and Pt substrates, and the current–voltage ( I – V ) properties were measured by CP-AFM. The dependence of the low-bias resistance ( R ) on contact work function indicates that transport is LUMO-assisted (‘n-type behavior’). A single-level tunneling model combined with transition voltage spectroscopy (TVS) was employed to analyze the experimental I – V curves and to extract the effective LUMO position ε l = E LUMO − E F and the effective electronic coupling ( Γ ) between the PDI redox core and the contacts. This analysis revealed a strong Fermi level ( E F ) pinning effect in all the junctions, likely due to interface dipoles that significantly increased with increasing contact work function, as revealed by scanning Kelvin probe microscopy (SKPM). Furthermore, the temperature ( T ) dependence of R was found to be substantial. For Pt/Pt junctions, R varied more than two orders of magnitude in the range 248 K < T < 338 K. Importantly,more »the R ( T ) data are consistent with a single step electron tunneling mechanism and allow independent determination of ε l , giving values compatible with estimates of ε l based on analysis of the full I – V data. Theoretical analysis revealed a general criterion to unambiguously rule out a two-step transport mechanism: namely, if measured resistance data exhibit a pronounced Arrhenius-type temperature dependence, a two-step electron transfer scenario should be excluded in cases where the activation energy depends on contact metallurgy. Overall, our results indicate (1) the generality of the Fermi level pinning phenomenon in molecular junctions, (2) the utility of employing the single level tunneling model for determining essential electronic structure parameters ( ε l and Γ ), and (3) the importance of changing the nature of the contacts to verify transport mechanisms.« less
  2. Recently, we found that the atomic ensemble effect is the dominant effect influencing catalysis on surfaces alloyed with strong- and weak-binding elements, determining the activity and selectivity of many reactions on the alloy surface. In this study we design single-atom alloys that possess unique dehydrogenation selectivity towards ethanol (EtOH) partial oxidation, using knowledge of the alloying effects from density functional theory calculations. We found that doping of a strong-binding single-atom element ( e.g. , Ir, Pd, Pt, and Rh) into weak-binding inert close-packed substrates ( e.g. , Au, Ag, and Cu) leads to a highly active and selective initial dehydrogenation at the α-C–H site of adsorbed EtOH. We show that many of these stable single-atom alloy surfaces not only have tunable hydrogen binding, which allows for facile hydrogen desorption, but are also resistant to carbon coking. More importantly, we show that a rational design of the ensemble geometry can tune the selectivity of a catalytic reaction.
  3. Stability is an important aspect of alloys, and proposed alloys may be unstable due to unfavorable atomic interactions. Segregation of an alloy may occur preferentially at specific exposed surfaces, which could affect the alloy's structure since certain surfaces may become enriched in certain elements. Using density functional theory (DFT), we modeled surface segregation in bimetallic alloys involving all transition metals doped in Pt, Pd, Ir, and Rh. We not only modeled common (111) surfaces of such alloys, but we also modeled (100), (110), and (210) facets of such alloys. Segregation is more preferred for early and late transition metals, with middle transition metals being most stable within the parent metal. We find these general trends in segregation energies for the parent metals: Pt > Rh > Pd > Ir. A comparison of different surfaces suggests no consistent trends across the different parent hosts, but segregation energies can vary up to 2 eV depending on the exposed surface. We also developed a statistical model to predict surface-dependent segregation energies. Our model is able to distinguish segregation at different surfaces (as opposed to generic segregation common in previous models), and agrees well with the DFT data. The present study provides valuable informationmore »about surface-dependent segregation and helps explain why certain alloy structures occur ( e.g. core–shell).« less
  4. Surface segregation in bimetallic nanoparticles (NPs) is critically important for their catalytic activity because the activity is largely determined by the surface composition. Little, however, is known about the atomic scale mechanisms and kinetics of surface segregation. One reason is that it is hard to resolve atomic rearrangements experimentally. It is also difficult to model surface segregation at the atomic scale because the atomic rearrangements can take place on time scales of seconds or minutes – much longer than can be modeled with molecular dynamics. Here we use the adaptive kinetic Monte Carlo (AKMC) method to model the segregation dynamics in PdAu NPs over experimentally relevant time scales, and reveal the origin of kinetic stability of the core@shell and random alloy NPs at the atomic level. Our focus on PdAu NPs is motivated by experimental work showing that both core@shell and random alloy PdAu NPs with diameters of less than 2 nm are stable, indicating that one of these structures must be metastable and kinetically trapped. Our simulations show that both the Au@Pd and the PdAu random alloy NPs are metastable and kinetically trapped below 400 K over time scales of hours. These AKMC simulations provide insight into the energymore »landscape of the two NP structures, and the diffusion mechanisms that lead to segregation. In the core–shell NP, surface segregation occurs primarily on the (100) facet through both a vacancy-mediated and a concerted mechanism. The system becomes kinetically trapped when all corner sites in the core of the NP are occupied by Pd atoms. Higher energy barriers are required for further segregation, so that the metastable NP has a partially alloyed shell. In contrast, surface segregation in the random alloy PdAu NP is suppressed because the random alloy NP has reduced strain as compared to the Au@Pd NP, and the segregation mechanisms in the alloy require more elastic energy for exchange of Pd and Au and between the surface and subsurface.« less
  5. The most characteristic feature of planar π-aromatics is the ability to sustain a long-range shielding cone under a magnetic field oriented in a specific direction. In this article, we showed that similar magnetic responses can be found in σ-aromatic and spherical aromatic systems. For [Au 13 ] 5+ , long-range characteristics of the induced magnetic field in the bare icosahedral core are revealed, which are also found in the ligand protected [Au 25 (SH) 18 ] − model, proving its spherical aromatic properties, also supported by the AdNDP analysis. Such properties are given by the 8-ve of the structural core satisfying the Hirsch 2( N + 1) 2 rule, which is also found in the isoelectronic [M@Au 12 ] 4+ core, a part of the [MAu 24 (SR) 18 ] 2− (M = Pd, Pt) cluster. This contrasts with the [M@Au 12 ] 6+ core in [MAu 24 (SR) 18 ] 0 (M = Pd, Pt), representing 6-ve superatoms, which exhibit characteristics of planar σ-aromatics. Our results support the spherical aromatic character of stable superatoms, whereas the 6-ve intermediate electron counts satisfy the 4 N + 2 rule (applicable for both π- and σ-aromatics), showing the reversable and controlled interplaymore »between 3D spherical and 2D σ-aromatic clusters.« less