Stand-alone polarization-modulation infrared reflection absorption spectroscopy instrument optimized for the study of catalytic processes at elevated pressures.

This paper describes the design and construction of a compact, "user-friendly" polarization-modulation infrared reflection absorption spectroscopy (PM-IRRAS) instrument at the Center for Functional Nanomaterials (CFN) of Brookhaven National Laboratory, which allows studying surfaces at pressures ranging from ultra-high vacuum to 100 Torr. Surface infrared spectroscopy is ideally suited for studying these processes as the vibrational frequencies of the IR chromophores are sensitive to the nature of the bonding environment on the surface. Relying on the surface selection rules, by modulating the polarization of incident light, it is possible to separate the contributions from the isotropic gas or solution phase, from the surface bound species. A spectral frequency range between 1000 cm-1 and 4000 cm-1 can be acquired. While typical spectra with a good signal to noise ratio can be obtained at elevated pressures of gases in ∼2 min at 4 cm-1 resolution, we have also acquired higher resolution spectra at 0.25 cm-1 with longer acquisition times. By way of verification, CO uptake on a heavily oxidized Ru(0001) sample was studied. As part of this test study, the presence of CO adsorbed on Ru bridge sites was confirmed, in agreement with previous ambient pressure X ray photoelectron spectroscopy studies. In terms of instrument performance, it was also determined that the gas phase contribution from CO could be completely removed even up to pressures close to 100 Torr. A second test study demonstrated the use of the technique for studying morphological properties of a spin coated polymer on a conductive surface. Note that this is a novel application of this technique. In this experiment, the polarization of incident light was modulated manually (vs. through a photoelastic modulator). It was demonstrated, in good agreement with the literature, that the polymer chains preferentially lie parallel with the surface. This PM-IRRAS system is small, modular, and easily reconfigurable. It also features a "vacuum suitcase" that allows for the integration of the PM-IRRAS system with the rest of the suite of instrumentation at our laboratory available to external users through the CFN user proposal system.

Immobilization of single argon atoms in nano-cages of two-dimensional zeolite model systems.

The confinement of noble gases on nanostructured surfaces, in contrast to bulk materials, at non-cryogenic temperatures represents a formidable challenge. In this work, individual Ar atoms are trapped at 300 K in nano-cages consisting of (alumino)silicate hexagonal prisms forming a two-dimensional array on a planar surface. The trapping of Ar atoms is detected in situ using synchrotron-based ambient pressure X-ray photoelectron spectroscopy. The atoms remain in the cages upon heating to 400 K. The trapping and release of Ar is studied combining surface science methods and density functional theory calculations. While the frameworks stay intact with the inclusion of Ar atoms, the permeability of gasses (for example, CO) through them is significantly affected, making these structures also interesting candidates for tunable atomic and molecular sieves. These findings enable the study of individually confined noble gas atoms using surface science methods, opening up new opportunities for fundamental research.