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Directed hydrogenation, in which product selectivity is dictated by the binding of an ancillary directing group on the substrate to the catalyst, is typically catalyzed by homogeneous Rh and Ir com...

Electronic doping of transition-metal oxides (TMOs) is typically accomplished through the synthesis of nonstoichiometric oxide compositions and the subsequent ionization of intrinsic lattice defects. As a result, ambipolar doping of wide-band-gap TMOs is difficult to achieve because the formation energies and stabilities of vacancy and interstitial defects vary widely as a function of the oxide composition and crystal structure. The facile formation of lattice defects for one carrier type is frequently paired with the high-energy and unstable generation of defects required for the opposite carrier polarity. Previous work from our group showed that the brucite (β-phase) layered metal hydroxides of Co and Ni, intrinsically p-type materials in their anhydrous three-dimensional forms, could be n-doped using a strong chemical reductant. In this work, we extend the electron-doping study to the α polymorph of Co(OH)2 and elucidate the defects responsible for n-type doping in these two-dimensional materials. Through structural and electronic comparisons between the α, β, and rock-salt structures within the cobalt (hydr)oxide family of materials, we show that both layered structures exhibit facile formation of anion vacancies, the necessary defect for n-type doping, that are not accessible in the cubic CoO structure. However, the brucite polymorph is much more stable to reductive decomposition in the presence of doped electrons because of its tighter layer-to-layer stacking and octahedral coordination geometry, which results in a maximum conductivity of 10-4 S/cm, 2 orders of magnitude higher than the maximum value attainable on the α-Co(OH)2 structure.

Cobalt sulfide nanomaterials are among the most active and stable catalysts for the electrocatalytic oxygen reduction reaction in pH 7 electrolyte. However, due to the complexity and dynamism of the catalytic surfaces in cobalt sulfide bulk materials, it is challenging to identify and tune the active site structure in order to achieve low overpotential oxygen reduction reactivity. In this work, we synthesize isolated Co sites supported on colloidal WS2 nanosheets and develop a synthetic strategy to rationally control the first-shell coordination environment surrounding the adsorbed Co active sites. By studying Co–WS2 materials with a range of Co–S coordination numbers, we are able to identify the optimal active site for pH 7 oxygen reduction catalysis, which comprises cobalt atoms bound to the WS2 support with a Co–S coordination number of 3–4. The optimized Co–WS2 material exhibits an oxygen reduction onset potential of 0.798 V vs. RHE, which is comparable to the most active bulk phases of cobalt sulfide in neutral electrolyte conditions.

Precise synthesis and characterization of bimetallic nanoparticles are critical toward understanding structure–activity relationships in alkane dehydrogenation catalysis. Traditional synthetic meth...

Single-atom functionalization of transition-metal dichalcogenide (TMD) nanosheets is a powerful strategy to tune the optical, magnetic, and catalytic properties of two-dimensional materials. In thi...

Incorporation of a metal oxide or hydroxide species into Pt-based electrocatalysts has been shown to lower the overpotential required to oxidatively remove carbon monoxide from the catalyst surface, a reaction that is critical to preventing catalyst poisoning and deactivation in fuel cell devices. In this work, we report a general synthetic method toward Pt-metal oxide composite nanoparticles via the adsorption of metal halide ligands onto 1–2 nm colloidal Pt nanoparticles. Pt-metal oxide composite nanoparticles spanning across the first-row transition metals and post-transition metals are synthesized and characterized with transmission electron microscopy and energy dispersive X-ray scattering. CO stripping and steady-state CO oxidation experiments reveal that Mn, Fe, Co, Ni, and In oxides are capable of participating in the catalysis as a bifunctional partner and reduce the overpotential required for CO electrooxidation by ∼200 mV relative to pure Pt.

Understanding the microstructural evolution of bimetallic Pt nanoparticles under electrochemical polarization is critical to developing durable fuel cell catalysts. In this work, we develop a colloidal synthetic method to generate core-shell Au@Pt nanoparticles of varying surface Pt coverages to understand how as-synthesized bimetallic microstructure influences nanoparticle structural evolution during formic acid oxidation. By comparing the electrochemical and structural properties of our Au@Pt core-shells with bimetallic AuPt alloys at various stages in catalytic cycling, we determine that these two structures evolve in divergent ways. In core-shell nanoparticles, Au atoms from the core migrate outward onto the surface, generating transient "single-atom" Pt active sites with high formic acid oxidation activity. Metal migration continues until Pt is completely encapsulated by Au, and catalytic reactivity ceases. In contrast, AuPt alloys undergo surface dealloying and significant leaching of Pt out of the nanoparticle. Elucidating the dynamic restructuring processes responsible for high electrocatalytic reactivity in Pt bimetallic structures will enable better design and predictive synthesis of nanoparticle catalysts that are both active and stable.

Core-shell nanoparticles of Au@Pd with precise submonolayer, monolayer, or multilayer structure were synthesized using ligand-exchange reactions of palladate ions onto colloidal Au nanocrystals. Decoupling the palladate adsorption step from the subsequent reduction enables excellent precision, uniformity, and tunability in the Pd shell thickness. The redox properties of the surface Pd are directly correlated to the thickness of the Pd shell with a+200 mV shift in the PdO reduction potential for submonolayer Au@Pd nanoparticles compared to pure Pd. Using these precisely controlled core-shell materials, the oxygen reduction catalytic activity can be directly correlated to PdO reduction potential and Pd surface coverage on Au. When the Pd oxide reduction peak is shifted by +240 mV compared to pure Pd, a 50 mV reduction in overpotential and a 4-fold increase in kinetic current density for oxygen reduction are observed. Colloidal ligand-exchange synthesis may be particularly useful for noble metal core-shell catalysts as a strategy to subtly tune the electronic properties of surface atoms in order to lower overpotential and increase catalytic turnover.