Martin Johansson

Combined high-pressure cell–ultrahigh vacuum system for fast testing of model metal alloy catalysts using scanning mass spectrometry

An apparatus for fabrication, surface analysis in ultrahigh vacuum, and testing of the catalytic activity of model metal alloy catalysts is described. Arrays of model catalysts are produced by electron-beam deposition of up to four metals simultaneously onto a substrate. The surface analysis techniques available are scanning electron microscopy, x-ray photoemission spectroscopy, ion scattering spectroscopy, Auger electron spectroscopy, sputter profiling, and temperature programmed desorption. The catalytic activity of the model catalysts is tested individually by scanning a combined gas delivery and gas sampling device over the sample surface. The gas sampled is analyzed with mass spectrometry. Experiments can be made at pressures up to 1 bar and temperatures up to 500 °C. It is shown that the lateral resolution is better than 0.2 mm and that up to 20 circular spots, 1 mm in diameter, can be studied on a substrate 10 mm in diameter. A high pressure cell with an all-metal sealed ultrahigh vacuum lock is al...

The sticking probability for H2 on some transition metals at a hydrogen pressure of 1bar

The sticking probability for hydrogen on films of Co, Ni, Cu, Ru, Rh, Pd, Ir, and Pt supported on graphite has been measured at a hydrogen pressure of 1 bar in the temperature range 40-200 degrees C. The sticking probability is found to increase in the order Ni, Co, Ir, Pd, Pt, Rh, and Ru at temperatures below 150 degrees C, whereas at higher temperatures, the sticking probability for Pd is higher than for Pt. The sticking probability for Cu is below the detection limit of the measurement. The measured sticking probabilities are slightly lower than those obtained at high hydrogen coverage under ultrahigh vacuum conditions. This could be a consequence of the higher hydrogen pressure used here. The apparent desorption energies extracted from the steady-state desorption rate are found to agree reasonably well with published values for the heat of adsorption at high coverage. However, the sticking probability is not related in a simple way to published values for the heat of adsorption at low coverage, with Ru and Rh giving exceptionally high values for the sticking probability. It is suggested that this is due to the presence of adsorption sites with very low desorption energy on Ru and Rh.

Is the methanation reaction over Ru single crystals structure dependent

The influence of monoatomic steps and defects on the methanation reaction over ruthenium has been investigated. The experiments are performed on a Ru(0 1 54) ruthenium single crystal, which contains one monoatomic step atom for each 27 terrace atoms. The methanation activity is measured at one bar of hydrogen and CO in a high pressure cell, which enables simultaneous measurements of the local reactivity of the well defined single crystal surface and the global reactivity of the entire crystal and its auxiliary support. By adding sulfur we observe that the measured activity from the well defined stepped front-side of the crystal is poisoned faster than the entire crystal containing more defects. We also observe that additional sputtering of the well-defined front-side increases the reactivity measured on the surface. Based on this, we conclude that the methanation reaction takes place on undercoordinated sites, such as steps and kinks, and that the methanation reaction is extremely structure dependent. Simulations of the flow, temperature, and product distributions in the high pressure cell are furthermore presented as supplementary information.

Probing the crossover in CO desorption from single crystal to nanoparticulate Ru model catalysts

Using model catalysts, we demonstrate that CO desorption from Ru surfaces can be switched from that typical of single crystal surfaces to one more characteristic of supported nanoparticles. First, the CO desorption behaviour from Ru nanoparticles supported on highly oriented pyrolytic graphite was studied. Both mass-selected and thermally evaporated nanoparticles were deposited. TPD spectra from the mass-selected nanoparticles exhibit a desorption peak located around 410 K with a broad shoulder extending from around 480 K to 600 K, while spectra obtained from thermally evaporated nanoparticles exhibit a single broad feature from ∼350 K to ∼450 K. A room temperature deposited 50 Å thick Ru film displays a characteristic nanoparticle-like spectrum with a broad desorption feature at ∼420 K and a shoulder extending from ∼450 K to ∼600 K. Subsequent annealing of this film at 900 K produced a polycrystalline morphology of flat Ru(001) terraces separated by monatomic steps. The CO desorption spectrum from this surface resembles that obtained on single crystal Ru(001) with two large desorption features located at 390 K and 450 K due to molecular desorption from terrace sites, and a much smaller peak at ∼530 K due to desorption of dissociatively adsorbed CO at step sites. In a second experiment, ion sputtering was used to create surface defects on a Ru(0 1 54) single crystal surface. A gradual shift away from the desorption spectrum typical of a Ru(001) surface towards one resembling desorption from supported Ru nanoparticles was observed with increasing sputter time.

Electron emission from ultralarge area metal-oxide-semiconductor electron emitters

Ultralarge metal-oxide-semiconductor (MOS) devices with an active oxide area of 1cm2 have been fabricated for use as electron emitters. The MOS structures consist of a Si substrate, a SiO2 tunnel barrier (∼5nm), a Ti wetting layer (3–10A), and a Au top layer (5–60nm). Electron emission from the Au metal layer to vacuum is realized from these devices by applying bias voltages larger than the work function of the Au layer. The emission is characterized for Au layers with thicknesses ranging from 5to60nm nominally. The emission efficiency changes from close to 10−6 to 10−10. The Ti wetting layer is varied from 3to10A which changes the emission efficiency by more than one order of magnitude. The apparent mean free path of ∼5eV electrons in Au is found to be 52A. Deposition of Cs on the Au film increased the electron emission efficiency to 4.3% at 4V by lowering the work function. Electron emission under high pressures (up to 2bars) of Ar was observed.