The possibility of a graphene bilayer nanosensor for the detection of explosive molecules was modeled using computational chemistry. A pore was designed on a graphene bilayer structure with three strategically placed ...The possibility of a graphene bilayer nanosensor for the detection of explosive molecules was modeled using computational chemistry. A pore was designed on a graphene bilayer structure with three strategically placed perimeter hydroxyl (OH) groups built around the edge of an indented, two-dimensional hexagonal pore. This hydroxylated pore and models of various explosive molecules were optimized using MM2 molecular mechanics parameters. Values were calculated for the molecule-surface interaction energy (binding energy), E, for 22 explosive molecules on a flat graphene bilayer and on the specially designed hydroxylated pore within the bilayer. The molecule-surface binding energy for trinitrotoluene (TNT) increased from 17.9 kcal/mol on the flat graphene bilayer to 42.3 kcal/mol on the hydroxylated pore. Due to the common functionality of nitro groups that exist on many explosive molecules, the other explosive molecules studied gave similar enhancements based on the specific hydrogen bonding interactions formed within the pore. Each of the 22 explosive adsorbate molecules showed increased molecule-surface interaction on the bilayer hydroxylated pore as compared to the flat bilayer. For the 22 molecules, the average E for the flat graphite surface was 15.8 kcal/mol and for the hydroxylated pore E was 33.8 kcal/mol. An enhancement of adsorption should make a detection device more sensitive. Nanosensors based on a modified graphene surface may be useful for detecting extremely low concentrations of explosive molecules or explosive signature molecules.展开更多
A quantum dynamic calculation on a five-dimensional O2/LiF （001） model system is performed using themulti-configuration time-dependent Hartree method.The obtained results show that the mechanism of rotational anddif...A quantum dynamic calculation on a five-dimensional O2/LiF （001） model system is performed using themulti-configuration time-dependent Hartree method.The obtained results show that the mechanism of rotational anddiffractive excitation in details: Comparison with the rotational excited state, the initially non-rotational state is seento favor the inelastic scattering in the rotational excitation process.The surface corrugation can damp the quantuminterferences and produce a greater amount of rotational inelastic scattering at the expense of the elastic process inthe rotational excitation process.The diffraction process and the average energy transferred into the rotational anddiffractive mode are also discussed.展开更多
We report the activation energy, ΔEa, for the quantum yield in thermally assisted photoelectron emission(TAPE) under 210-nm-wavelength light irradiation, and the associated X-ray photoelectron spectroscopy(XPS) resul...We report the activation energy, ΔEa, for the quantum yield in thermally assisted photoelectron emission(TAPE) under 210-nm-wavelength light irradiation, and the associated X-ray photoelectron spectroscopy(XPS) results. Samples were cleaned only in acetone and scratched in air, water, methanol, ethanol, acetone, benzene, and cyclohexane. Glow curves, describing the temperature dependence of photoelectron emission(PE) quantum yield(emitted electrons/photon), Y, were obtained. A simple method of determining ΔEa using Y, called YGC, at seven temperatures up to 353 °C, for the same Y glow curve, was proposed. The ΔEa obtained using this method was almost the same as that obtained from Y for seven stationary temperatures(YST). For scratched samples, the TAPE was measured over two cycles of temperature increase and subsequent decrease(Up1, Down1 and Up2, Down2 scans) in the 25–339 °C range, and ΔE_a was obtained from YGC. The Arrhenius plot was approximated by a straight line, although a convex swelling peak appeared in the Up1 scan. ΔE_(aUp1) was in the 0.212–0.035 eV range, depending on the environment in which scratching was performed; ΔE_(aUp1) for water was much higher than that for acetone. This was explained in terms of the mode of the acid–base interaction between the liquid molecules and the hydroxyl group of Fe–OH. The values of ΔE_(aDown1), ΔEa Up2, and ΔE_(aDown2) were in the 0.038–0.012 eV range. The total count of electrons emitted during the Up1 and Up2 scans was found to decrease with increasing ΔE_(aUp1) and ΔE_(aUp2), respectively. ΔE_(aUp2) was found to increase with increasing presence of the FeO component in the analyzed Fe oxides. The convex swelling peak was attributed to the removal of carbon materials from the scratched surface and the effect of the increased electron density of the surface hydroxyl group of FeOH under the light irradiation.展开更多
文摘The possibility of a graphene bilayer nanosensor for the detection of explosive molecules was modeled using computational chemistry. A pore was designed on a graphene bilayer structure with three strategically placed perimeter hydroxyl (OH) groups built around the edge of an indented, two-dimensional hexagonal pore. This hydroxylated pore and models of various explosive molecules were optimized using MM2 molecular mechanics parameters. Values were calculated for the molecule-surface interaction energy (binding energy), E, for 22 explosive molecules on a flat graphene bilayer and on the specially designed hydroxylated pore within the bilayer. The molecule-surface binding energy for trinitrotoluene (TNT) increased from 17.9 kcal/mol on the flat graphene bilayer to 42.3 kcal/mol on the hydroxylated pore. Due to the common functionality of nitro groups that exist on many explosive molecules, the other explosive molecules studied gave similar enhancements based on the specific hydrogen bonding interactions formed within the pore. Each of the 22 explosive adsorbate molecules showed increased molecule-surface interaction on the bilayer hydroxylated pore as compared to the flat bilayer. For the 22 molecules, the average E for the flat graphite surface was 15.8 kcal/mol and for the hydroxylated pore E was 33.8 kcal/mol. An enhancement of adsorption should make a detection device more sensitive. Nanosensors based on a modified graphene surface may be useful for detecting extremely low concentrations of explosive molecules or explosive signature molecules.
基金Support by the National Natural Science Foundation of China under Grant No.10776022 the Specialized Research Fund for the Doctoral Program of Higher Education under Grant No.20090181110080
文摘A quantum dynamic calculation on a five-dimensional O2/LiF （001） model system is performed using themulti-configuration time-dependent Hartree method.The obtained results show that the mechanism of rotational anddiffractive excitation in details: Comparison with the rotational excited state, the initially non-rotational state is seento favor the inelastic scattering in the rotational excitation process.The surface corrugation can damp the quantuminterferences and produce a greater amount of rotational inelastic scattering at the expense of the elastic process inthe rotational excitation process.The diffraction process and the average energy transferred into the rotational anddiffractive mode are also discussed.
基金the Ministry of Education,Culture,Sports,Science and Technology of Japan for supporting this work
文摘We report the activation energy, ΔEa, for the quantum yield in thermally assisted photoelectron emission(TAPE) under 210-nm-wavelength light irradiation, and the associated X-ray photoelectron spectroscopy(XPS) results. Samples were cleaned only in acetone and scratched in air, water, methanol, ethanol, acetone, benzene, and cyclohexane. Glow curves, describing the temperature dependence of photoelectron emission(PE) quantum yield(emitted electrons/photon), Y, were obtained. A simple method of determining ΔEa using Y, called YGC, at seven temperatures up to 353 °C, for the same Y glow curve, was proposed. The ΔEa obtained using this method was almost the same as that obtained from Y for seven stationary temperatures(YST). For scratched samples, the TAPE was measured over two cycles of temperature increase and subsequent decrease(Up1, Down1 and Up2, Down2 scans) in the 25–339 °C range, and ΔE_a was obtained from YGC. The Arrhenius plot was approximated by a straight line, although a convex swelling peak appeared in the Up1 scan. ΔE_(aUp1) was in the 0.212–0.035 eV range, depending on the environment in which scratching was performed; ΔE_(aUp1) for water was much higher than that for acetone. This was explained in terms of the mode of the acid–base interaction between the liquid molecules and the hydroxyl group of Fe–OH. The values of ΔE_(aDown1), ΔEa Up2, and ΔE_(aDown2) were in the 0.038–0.012 eV range. The total count of electrons emitted during the Up1 and Up2 scans was found to decrease with increasing ΔE_(aUp1) and ΔE_(aUp2), respectively. ΔE_(aUp2) was found to increase with increasing presence of the FeO component in the analyzed Fe oxides. The convex swelling peak was attributed to the removal of carbon materials from the scratched surface and the effect of the increased electron density of the surface hydroxyl group of FeOH under the light irradiation.
