Origin of High Activity and Durability of Twisty Nanowire Alloy Catalysts under Oxygen Reduction and Fuel Cell Operating Conditions.

The ability to control the surface composition and morphology of alloy catalysts is critical for achieving high activity and durability of catalysts for oxygen reduction reaction (ORR) and fuel cells. This report describes an efficient surfactant-free synthesis route for producing a twisty nanowire (TNW) shaped platinum-iron (PtFe) alloy catalyst (denoted as PtFe TNWs) with controllable bimetallic compositions. PtFe TNWs with an optimal initial composition of ∼24% Pt are shown to exhibit the highest mass activity (3.4 A/mgPt, ∼20 times higher than that of commercial Pt catalyst) and the highest durability (<2% loss of activity after 40 000 cycles and <30% loss after 120 000 cycles) among all PtFe-based nanocatalysts under ORR or fuel cell operating conditions reported so far. Using ex situ and in situ synchrotron X-ray diffraction coupled with atomic pair distribution function (PDF) analysis and 3D modeling, the PtFe TNWs are shown to exhibit mixed face-centered cubic (fcc)-body-centered cubic (bcc) alloy structure and a significant lattice strain. A striking finding is that the activity strongly depends on the composition of the as-synthesized catalysts and this dependence remains unchanged despite the evolution of the composition of the different catalysts and their lattice constants under ORR or fuel cell operating conditions. Notably, dealloying under fuel cell operating condition starts at phase-segregated domain sites leading to a final fcc alloy structure with subtle differences in surface morphology. Due to a subsequent realloying and the morphology of TNWs, the surface lattice strain observed with the as-synthesized catalysts is largely preserved. This strain and the particular facets exhibited by the TNWs are believed to be responsible for the observed activity and durability enhancements. These findings provide new insights into the correlation between the structure, activity, and durability of nanoalloy catalysts and are expected to energize the ongoing effort to develop highly active and durable low-Pt-content nanowire catalysts by controlling their alloy structure and morphology.

Lattice Strain and Surface Activity of Ternary Nanoalloys under the Propane Oxidation Condition.

The ability to harness the catalytic oxidation of hydrocarbons is critical for both clean energy production and air pollutant elimination, which requires a detailed understanding of the dynamic role of the nanophase structure and surface reactivity under the reaction conditions. We report here findings of an in situ/operando study of such details of a ternary nanoalloy under the propane oxidation condition using high-energy synchrotron X-ray diffraction coupled to atomic pair distribution function (HE-XRD/PDF) analysis and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The catalysts are derived by alloying Pt with different combinations of second (Pd) and third (Ni) transition metals, showing a strong dependence of the catalytic activity on the Ni content. The evolution of the phase structure of the nanoalloy is characterized by HE-XRD/PDF probing of the lattice strain, whereas the surface activity is monitored by DRIFTS detection of the surface intermediate formation during the oxidation of propane by oxygen. The results reveal the dominance of the surface intermediate species featuring a lower degree of oxygenation upon the first C-C bond cleavage on the lower-Ni-content nanoalloy and a higher degree of oxygenation upon the second C-C bond cleavage on the higher-Ni-content nanoalloy. The face-centered-cubic-type phase structures of the nanoalloys under the oxidation condition are shown to exhibit Ni-content-dependent changes of lattice strains, featuring the strongest strain with little variation for the higher-Ni-content nanoalloy, in contrast to the weaker strains with oscillatory variation for the lower-Ni-content nanoalloys. This process is also accompanied by oxygenation of the metal components in the nanoalloy, showing a higher degree of oxygenation for the higher-Ni-content nanoalloy. These subtle differences in phase structure and surface activity changes correlate with the Ni-composition-dependent catalytic activity of the nanoalloys, which sheds a fresh light on the correlation between the dynamic change of atomic strains and the surface reactivity and has significant implications for the design of oxidation catalysts with enhanced activities.

Surface oxygenation of multicomponent nanoparticles toward active and stable oxidation catalysts.

The need for active and stable oxidation catalysts is driven by the demands in production of valuable chemicals, remediation of hydrocarbon pollutants and energy sustainability. Traditional approaches focus on oxygen-activating oxides as support which provides the oxygen activation at the catalyst-support peripheral interface. Here we report a new approach to oxidation catalysts for total oxidation of hydrocarbons (e.g., propane) by surface oxygenation of platinum (Pt)-alloyed multicomponent nanoparticles (e.g., platinum-nickel cobalt (Pt-NiCo)). The in-situ/operando time-resolved studies, including high-energy synchrotron X-ray diffraction and diffuse reflectance infrared Fourier transform spectroscopy, demonstrate the formation of oxygenated Pt-NiOCoO surface layer and disordered ternary alloy core. The results reveal largely-irregular oscillatory kinetics associated with the dynamic lattice expansion/shrinking, ordering/disordering, and formation of surface-oxygenated sites and intermediates. The catalytic synergy is responsible for reduction of the oxidation temperature by ~100 °C and the high stability under 800 °C hydrothermal aging in comparison with Pt, and may represent a paradigm shift in the design of self-supported catalysts.

Deviations from Vegard's law and evolution of the electrocatalytic activity and stability of Pt-based nanoalloys inside fuel cells by in operando X-ray spectroscopy and total scattering.

Catalysts for energy related applications, in particular metallic nanoalloys, readily undergo atomic-level changes during electrochemical reactions. The origin, dynamics and implications of the changes for the catalysts' activity inside fuel cells though are not well understood. This is largely because they are studied on model nanoalloy structures under controlled laboratory conditions. Here we use combined synchrotron X-ray spectroscopy and total scattering to study the dynamic behaviour of nanoalloys of Pt with 3d-transition metals as they function at the cathode of an operating proton exchange membrane fuel cell. Results show that the composition and atomic structure of the nanoalloys change profoundly, from the initial state to the active form and further along the cell operation. The electrocatalytic activity of the nanoalloys also changes. The rate and magnitude of the changes may be rationalized when the limits of traditional relationships used to connect the composition and structure of nanoalloys with their electrocatalytic activity and stability, such as Vegard's law, are recognized. In particular, deviations from the law inherent for Pt-3d metal nanoalloys can well explain their behaviour under operating conditions. Moreover, it appears that factors behind the remarkable electrocatalytic activity of Pt-3d metal nanoalloys, such as the large surface to unit volume ratio and "size misfit" of the constituent Pt and 3d-transition metal atoms, also contribute to their instability inside fuel cells. The new insight into the atomic-level evolution of nanoalloy electrocatalysts during their lifetime is likely to inspire new efforts to stabilize transient structure states beneficial to their activity and stability under operating conditions, if not synthesize them directly.

Evolution of Active Sites in Pt-Based Nanoalloy Catalysts for the Oxidation of Carbonaceous Species by Combined in Situ Infrared Spectroscopy and Total X-ray Scattering.

We present results from combined in situ infrared spectroscopy and total X-ray scattering studies on the evolution of catalytically active sites in exemplary binary and ternary Pt-based nanoalloys during a sequence of CO oxidation-reactivation-CO oxidation reactions. We find that when within a particular compositional range, the fresh nanoalloys may exhibit high catalytic activity for low-temperature CO oxidation. Using surface-specific atomic pair distribution functions (PDFs) extracted from the in situ total X-ray scattering data, we find that, regardless of their chemical composition and initial catalytic activity, the fresh nanoalloys suffer a significant surface structural disorder during CO oxidation. Upon reactivation in oxygen atmosphere, the surface of used nanoalloy catalysts both partially oxidizes and orders. Remarkably, it largely retains its structural state when the nanoalloys are reused as CO oxidation catalysts. The seemingly inverse structural changes of studied nanoalloy catalysts occurring under CO oxidation and reactivation conditions affect the active sites on their surface significantly. In particular, through different mechanisms, both appear to reduce the CO binding strength to the nanoalloy's surface and thus increase the catalytic stability of the nanoalloys. The findings provide clues for further optimization of nanoalloy catalysts for the oxidation of carbonaceous species through optimizing their composition, activation, and reactivation. Besides, the findings demonstrate the usefulness of combined in situ infrared spectroscopy and total X-ray scattering coupled to surface-specific atomic PDF analysis to the ongoing effort to produce advanced catalysts for environmentally and technologically important applications.

Evolution of surface catalytic sites on thermochemically-tuned gold-palladium nanoalloys.

Nanoscale alloying constitutes an increasingly-important pathway for design of catalysts for a wide range of technologically important reactions. A key challenge is the ability to control the surface catalytic sites in terms of the alloying composition, thermochemical treatment and phase in correlation with the catalytic properties. Herein we show novel findings of the nanoscale evolution of surface catalytic sites on thermochemically-tuned gold-palladium nanoalloys by probing CO adsorption and oxidation using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique. In addition to the bimetallic composition and the support, the surface sites are shown to depend strongly on the thermochemical treatment condition, demonstrating that the ratio of three-fold vs. bridge or atop Pd sites is greatly reduced by thermochemical treatment under hydrogen in comparison with that under oxygen. This type of surface reconstruction is further supported by synchrotron high-energy X-ray diffraction coupled to atomic pair distribution function (HE-XRD/PDF) analysis of the nanoalloy structure, revealing an enhanced degree of random alloying for the catalysts thermochemically treated under hydrogen. The nanoscale alloying and surface site evolution characteristics were found to correlate strongly with the catalytic activity of CO oxidation. These findings have significant implications for the nanoalloy-based design of catalytic synergy.