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J Phys Chem B ; 122(2): 855-863, 2018 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-29091455


The role of oxygen in the activation of C-H bonds in methane on clean and oxygen-precovered Cu(111) and Cu2O(111) surfaces was studied with combined in situ near-ambient-pressure scanning tunneling microscopy and X-ray photoelectron spectroscopy. Activation of methane at 300 K and "moderate pressures" was only observed on oxygen-precovered Cu(111) surfaces. Density functional theory calculations reveal that the lowest activation energy barrier of C-H on Cu(111) in the presence of chemisorbed oxygen is related to a two-active-site, four-centered mechanism, which stabilizes the required transition-state intermediate by dipole-dipole attraction of O-H and Cu-CH3 species. The C-H bond activation barriers on Cu2O(111) surfaces are large due to the weak stabilization of H and CH3 fragments.

Rev Sci Instrum ; 84(10): 104101, 2013 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-24182134


A novel recirculating loop microreactor coupled to an ultrahigh vacuum (UHV) chamber has been constructed for the kinetic evaluation of model catalysts, which can be fully characterized by UHV surface science techniques. The challenge for this reactor design is to attain sufficient sensitivity to detect reactions on model single-crystal surfaces, which have a low number of active sites compared to conventional catalysts of equivalent mass. To this end, the total dead volume of the reactor system is minimized (32 cm(3)), and the system is operated in recirculation mode so that product concentrations build up to detectable levels over time. The injection of gas samples into the gas chromatography column and the refilling of the recirculation loop with fresh feed gas are achieved with computer-controlled, automated switching valves. In this manner, product concentrations can be followed over short time intervals (15 min) for extended periods of time (24 h). A proof of principle study in this reactor for CO oxidation at 145-165 °C on Pt clusters supported on a rutile TiO2(110) single crystal yields kinetic parameters that are comparable to those reported in the literature for CO oxidation on Pt clusters on powdered oxide supports, as well as on Pt(100). The calculated activation energy is 16.4 ± 0.7 kcal/mol, the turnover frequency is 0.03-0.06 molecules/(site·s) over the entire temperature range, and the reaction orders in O2 and CO at 160 °C are 0.9 ± 0.2 and -0.82 ± 0.03, respectively.

Langmuir ; 25(1): 216-25, 2009 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-19053659


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.