In this work, to understand how an amorphous surface influences the dynamics of surface photoinduced reactions, pump–probe spectroscopy in conjunction with mass spectrometry is employed to track the ultrafast evolution of intermediates and final products with time, mass, and energy resolution. As a model system, the photoinduced reaction of CD3I adsorbed on amorphous cerium oxide films is investigated. A fraction of the first intermediates produced on a freshly prepared surface is trapped to passivate the surface. After the A-band excitation, the minimum dissociation time of CD3I indicates that CD3I adsorption geometries with either CD3 or I facing the gas phase exist; however, the transient data suggest that most molecules are adsorbed with the I atom facing the surface. CD3 and I are consumed to form I2 and reform CD3I, which are produced at a steady rate only after the intermediates have lost the excess translational energy released from photodissociation.

Rational design of novel catalytic materials used to synthesize storable fuels via the CO hydrogenation reaction has recently received considerable attention. In this work, defect poor and defect rich 2D-MoS2 as well as 2D-MoS2 decorated with Mo clusters are employed as catalysts for the generation of acetylene (C2H2) via the CO hydrogenation reaction. Temperature programmed desorption is used to study the interaction of CO and H2 molecules with the MoS2 surface as well as the formation of reaction products. The experiments indicate the presence of four CO adsorption sites below room temperature and a competitive adsorption between the CO and H2 molecules. The investigations show that CO hydrogenation is not possible on defect poor MoS2 at low temperatures. However, on defect rich 2D-MoS2, small amounts of C2H2 are produced, which desorb from the surface at temperatures between 170 K and 250 K. A similar C2H2 signal is detected from defect poor 2D-MoS2 decorated with Mo clusters, which indicates that low coordinated Mo atoms on 2D-MoS2 are responsible for the formation of C2H2. Density functional theory investigations are performed to explore possible adsorption sites of CO and understand the formation mechanism of C2H2 on MoS2 and Mo7/MoS2. The theoretical investigation indicates a strong binding of C2H2 on the Mo sites of MoS2 preventing the direct desorption of C2H2 at low temperatures as observed experimentally. Instead, the theoretical results suggest that the experimental data are consistent with a mechanism in which CHO radical dimers lead to the formation of C2H2 that presents an exothermic desorption.

In this work, the growth and stability towards O 2 exposure of two dimensional (2D) TaS 2 on a Cu (111) substrate is investigated. Large area (∼1 cm 2 ) crystalline 2D-TaS 2 films with a metallic character are prepared on a single crystal Cu(111) substrate via a multistep approach based on physical vapor deposition. Analytical techniques such as Auger electron spectroscopy, low energy electron diffraction, and photoemission spectroscopy are used to characterize the composition, crystallinity, and electronic structure of the surface. At coverages below one monolayer equivalent (ML), misoriented TaS 2 domains are formed, which are rotated up to 13 o relative to the Cu(111) crystallographic directions. The TaS 2 domains misorientation decreases as the film thickness approaches 1 ML, at which the crystallographic directions of TaS 2 and Cu(111) are aligned. The TaS 2 film is found to grow epitaxially on Cu(111). As revealed by low energy electron diffraction in conjunction with an atomic model simulation, the (3×3) unit cells of TaS 2 match the (4×4) supercell of Cu(111). Furthermore, the exposure of TaS 2 to O 2 , does not lead to the formation of a robust tantalum oxide film, only minor amounts of stable oxides being detected on the surface. Instead, the exposure of TaS 2 films to O 2 leads predominantly to a reduction of the film thickness, evidenced by a decrease in the content of both Ta and S atoms of the film. This is attributed to the formation of oxide species that are unstable and mainly desorb from the surface below room temperature. Temperature programmed desorption spectroscopy confirms the formation of SO 2 , which desorbs from the surface between 100 and 500 K. These results provide new insights into the oxidative degradation of 2D-TaS 2 on Cu(111).

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In this work, to understand how an amorphous surface influence the dynamics of surface photoinduced reactions, pump-probe spectroscopy in conjunction with mass spectrometry is employed to track the ultrafast evolution of intermediates and final products with time, mass, and energy resolution. As a model system, the photoinduced reaction of CD3I adsorbed on amorphous cerium oxide films is investigated. A fraction of the first intermediates produced on a freshly prepared surface are trapped to passivate the surface. After the A-band excitation, the minimum dissociation time of CD3I, indicate that CD3I adsorption geometries with either CD3 or I facing the gas-phase exist, however the transient data suggest that most molecules are adsorbed with the I atom facing the surface. CD3 and I are consumed to form I2 and reform CD3I, which are produced with a steady rate only after the intermediates are losing the excess translational energy released from photodissociation.