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1.
J Phys Chem Lett ; 6(18): 3632-8, 2015 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-26722734

RESUMO

Photochemically activated reactions, despite being a powerful tool to covalently stabilize self-organized molecular structures on metallic surfaces, have struggled to take off due to several not yet well understood light-driven processes that can affect the final result. A thorough understanding of the photoinduced charge transfer mechanisms at the organic/metal interface would pave the way to controlling these processes and to developing on-surface photochemistry. Here, by time-resolved two-photon photoemission measurements, we track the relaxation processes of the first two excited molecular states at the interface between porphyrin, the essential chromophore in chlorophyll, and two different orientations of the silver surface. Due to the energy alignment of the porphyrin first excited state with the unoccupied sp-bands, an indirect charge transfer path, from the substrate to the molecule, opens in porphyrin/Ag(100) 250 fs after the laser pump excitation. The same time-resolved measurements carried out on porphyrin/Ag(111) show that in the latter case such an indirect path is not viable.

2.
Analyst ; 138(24): 7392-9, 2013 Nov 12.
Artigo em Inglês | MEDLINE | ID: mdl-24171188

RESUMO

The possibility of using novel architectures based on carbon nanotubes (CNTs) for a realistic monitoring of the air quality in an urban environment requires the capability to monitor concentrations of polluting gases in the low-ppb range. This limit has been so far virtually neglected, as most of the testing of new ammonia gas sensor devices based on CNTs is carried out above the ppm limit. In this paper, we present single-wall carbon nanotube (SWCNT) chemiresistor gas sensors operating at room temperature, displaying an enhanced sensitivity to NH3. Ammonia concentrations in air as low as 20 ppb have been measured, and a detection limit of 3 ppb is demonstrated, which is in the full range of the average NH3 concentration in an urban environment and well below the sensitivities so far reported for pristine, non-functionalized SWCNTs operating at room temperature. In addition to careful preparation of the SWCNT layers, through sonication and dielectrophoresis that improved the quality of the CNT bundle layers, the low-ppb limit is also attained by revealing and properly tracking a fast dynamics channel in the desorption process of the polluting gas molecules.

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