RESUMEN
The decomposition of dimethyl methylphosphonate (DMMP) was studied by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES) on TiO(2)-supported Pt, Au, and Au-Pt clusters as well as on TiO(2)(110) itself. In agreement with previous work, TPD experiments for DMMP on TiO(2)(110) showed that methyl and methane were the main gaseous products. Multiple DMMP adsorption-reaction cycles on TiO(2)(110) demonstrated that active sites for DMMP decomposition were blocked after a single cycle, but some activity for methyl production was sustained even after five cycles. Furthermore, the activity of the TiO(2) surface could be regenerated by heating in O(2) at 800 K or heating in vacuum to 965 K to remove surface carbon and phosphorus, which are byproducts of DMMP decomposition. On 0.5 ML Pt clusters deposited on TiO(2)(110), TPD studies of DMMP reaction showed that CO and H(2) were the main gas products, with methyl and methane as minor products. The Pt clusters were more active than TiO(2) both in terms of the total amount of DMMP reaction and the ability to break C-H, P-O, and P-OCH(3) bonds in DMMP. However, the Pt clusters had no sustained activity for DMMP decomposition, since the product yields dropped to zero after a single adsorption-reaction cycle. This loss of activity is attributed to a combination of poisoning of active sites by surface phosphorus species and encapsulation of the Pt clusters by reduced titania after heating above 600 K due to strong metal support interactions (SMSI). On 0.5 ML Au clusters, CO and H(2) were also the main products detected in TPD experiments, in addition to methane and methyl produced from reaction on the support. The Au clusters were less active for DMMP decomposition to CO and H(2) as well as P-O bond scission, but surface phosphorus was removed from the Au clusters by desorption at approximately 900 K. Au-Pt bimetallic clusters on TiO(2)(110) were prepared by depositing 0.25 ML of Pt followed by 0.25 ML of Au, and the bimetallic surfaces exhibited activity intermediate between that of pure Pt and pure Au in terms of CO and H(2) desorption yields. However, there is evidence that the production of methane from DMMP decomposition occurs at Au-Pt sites.
RESUMEN
We report studies on the modifications induced by the evaporation of copper overlayers on a self-assembled monolayer (SAM) of the oligo(phenylene-ethynyl) dithiol, 1-thio-4-[4'-[(4'-thio)phenylethynyl]-1'-ethynyl]-benzene (TTPEB). These SAMs were characterized after deposition from a tetrahydrofuran solution on polycrystalline gold substrates and after copper evaporation and its subsequent removal by nitric acid. Monolayers were studied via cyclic voltammetry (CV), UV-vis multiwavelength ellipsometry, external reflectance infrared (IR) spectroscopy, and ion scattering spectroscopy (ISS). The results obtained indicate that TTPEB SAMs display the same packing characteristics before and after copper evaporation and removal. However, as shown by IR spectroscopy, the monolayers undergo a reorganization process that involves an increase in tilt angle accompanied by rotation of aromatic rings that results in a decrease in the average molecular twist angle. ISS data suggest that copper diffuses through the monolayer after copper evaporation, a result that is significant for applications of this molecule in molecular electronic devices.
