Peculiarities of a liquid phase hydrogenation, namely lower diffusivity of components influencing the reaction rate and deactivation of catalysts by leaching, are discussed. A focus is on hydrogenation of aromatic com...Peculiarities of a liquid phase hydrogenation, namely lower diffusivity of components influencing the reaction rate and deactivation of catalysts by leaching, are discussed. A focus is on hydrogenation of aromatic compounds, whereas the following processes are evaluated： （l） partial hydrogenation of benzene to cyclohexene; （2） hydrogenation of aniline; （3） hydrogenation of diphenylamine; （4） preparation of aniline from nitrobenzene; （5） hydrogenation of chloronitrobenzenes; （6） hydrogenation of 4-nitrosodiphenylamine and 4-nitrodiphenylamine mixture. Processes （1） and （6） are typically carried out in the water-oil system. Generally, this type of system allows reaching a higher selectivity to desired products. In the case of hydrogenation of 4-nitrosodiphenylamine and 4-nitrodiphenylamine mixture, the water phase extracts a water soluble catalyst; which is recycled and used for condensation of aniline and nitrobenzene. Problems of reaction kinetics, as well as catalysts deactivation are here discussed.展开更多
Nanoscale noble metals can exhibit excellent photochemical and photophysical properties, due to surface plasmon resonance(SPR) from specifically collective electronic excitations on these metal surfaces. The SPR effec...Nanoscale noble metals can exhibit excellent photochemical and photophysical properties, due to surface plasmon resonance(SPR) from specifically collective electronic excitations on these metal surfaces. The SPR effect triggers many new surface processes, including radiation and radiationless relaxations. As for the radiation process, the SPR effect causes the significant focus of light and enormous enhancement of the local surface optical electric field, as observed in surface-enhanced Raman spectroscopy(SERS) with very high detection sensitivity(to the single-molecule level). SERS is used to identify surface species and characterize molecular structures and chemical reactions. For the radiationless process, the SPR effect can generate hot carriers, such as hot electrons and hot holes, which can induce and enhance surface chemical reactions. Here, we review our recent work and related literature on surface catalytic-coupling reactions of aromatic amines and aromatic nitro compounds on nanostructured noble metal surfaces. Such reactions are a type of novel surface plasmon-enhanced chemical reaction. They could be simultaneously characterized by SERS when the SERS signals are assigned. By combining the density functional theory(DFT) calculations and SERS experimental spectra, our results indicate the possible pathways of the surface plasmonenhanced photochemical reactions on nanostructures of noble metals. To construct a stable and sustainable system in the conversion process of the light energy to the chemical energy on nanoscale metal surfaces, it is necessary to simultaneously consider the hot electrons and the hot holes as a whole chemical reaction system.展开更多
文摘Peculiarities of a liquid phase hydrogenation, namely lower diffusivity of components influencing the reaction rate and deactivation of catalysts by leaching, are discussed. A focus is on hydrogenation of aromatic compounds, whereas the following processes are evaluated： （l） partial hydrogenation of benzene to cyclohexene; （2） hydrogenation of aniline; （3） hydrogenation of diphenylamine; （4） preparation of aniline from nitrobenzene; （5） hydrogenation of chloronitrobenzenes; （6） hydrogenation of 4-nitrosodiphenylamine and 4-nitrodiphenylamine mixture. Processes （1） and （6） are typically carried out in the water-oil system. Generally, this type of system allows reaching a higher selectivity to desired products. In the case of hydrogenation of 4-nitrosodiphenylamine and 4-nitrodiphenylamine mixture, the water phase extracts a water soluble catalyst; which is recycled and used for condensation of aniline and nitrobenzene. Problems of reaction kinetics, as well as catalysts deactivation are here discussed.
基金financially supported by the National Natural Science Foundation of China(21321062,21373172)
文摘Nanoscale noble metals can exhibit excellent photochemical and photophysical properties, due to surface plasmon resonance(SPR) from specifically collective electronic excitations on these metal surfaces. The SPR effect triggers many new surface processes, including radiation and radiationless relaxations. As for the radiation process, the SPR effect causes the significant focus of light and enormous enhancement of the local surface optical electric field, as observed in surface-enhanced Raman spectroscopy(SERS) with very high detection sensitivity(to the single-molecule level). SERS is used to identify surface species and characterize molecular structures and chemical reactions. For the radiationless process, the SPR effect can generate hot carriers, such as hot electrons and hot holes, which can induce and enhance surface chemical reactions. Here, we review our recent work and related literature on surface catalytic-coupling reactions of aromatic amines and aromatic nitro compounds on nanostructured noble metal surfaces. Such reactions are a type of novel surface plasmon-enhanced chemical reaction. They could be simultaneously characterized by SERS when the SERS signals are assigned. By combining the density functional theory(DFT) calculations and SERS experimental spectra, our results indicate the possible pathways of the surface plasmonenhanced photochemical reactions on nanostructures of noble metals. To construct a stable and sustainable system in the conversion process of the light energy to the chemical energy on nanoscale metal surfaces, it is necessary to simultaneously consider the hot electrons and the hot holes as a whole chemical reaction system.
