New reactor dedicated to in operando studies of model catalysts by means of surface x-ray diffraction and grazing incidence small angle x-ray scattering.

A new experimental setup has been developed to enable in situ studies of catalyst surfaces during chemical reactions by means of surface x-ray diffraction (SXRD) and grazing incidence small angle x-ray scattering. The x-ray reactor chamber was designed for both ultrahigh-vacuum (UHV) and reactive gas environments. A laser beam heating of the sample was implemented; the sample temperature reaches 1100 K in UHV and 600 K in the presence of reactive gases. The reactor equipment allows dynamical observations of the surface with various, perfectly mixed gases at controlled partial pressures. It can run in two modes: as a bath reactor in the pressure range of 1-1000 mbars and as a continuous flow cell for pressure lower than 10(-3) mbar. The reactor is connected to an UHV preparation chamber also equipped with low energy electron diffraction and Auger spectroscopy. This setup is thus perfectly well suited to extend in situ studies to more complex surfaces, such as epitaxial films or supported nanoparticles. It offers the possibility to follow the chemically induced changes of the morphology, the structure, the composition, and growth processes of the model catalyst surface during exposure to reactive gases. As an example the Pd(8)Ni(92)(110) surface structure was followed by SXRD under a few millibars of hydrogen and during butadiene hydrogenation while the reaction was monitored by quadrupole mass spectrometry. This experiment evidenced the great sensitivity of the diffracted intensity to the subtle interaction between the surface atoms and the gas molecules.

Highly strained structure of a four-layer deposit of Pd on Ni(110): a coupled theoretical and experimental study.

The structure of a four monolayer deposit of Pd on Ni(110) has been determined by a combination of x-ray diffraction experiments and density-functional theory calculations. This Pd film presents, after annealing at 500 K, a (Nx2) reconstruction associated with a large enhancement of its catalytic activity. The N superstructure, along the dense [11;0] direction, comes from periodic edge dislocations initiated by a vacancy in the first Pd layer. In the perpendicular direction, the doubling of the period originates in a pairing-buckling displacement of the rows. This study evidences a new Pd atoms arrangement with quasi-four-fold hollow sites on the surface, which could play an important role in the exceptional catalytic activity.