Cyclohexane is a high-valued chemical receivingsignificant interest in liquid hydrogen storage technology.TiO_(2)-based catalysts show high performance in the photocatalytic dehydrogenation of cyclohexane under mild c...Cyclohexane is a high-valued chemical receivingsignificant interest in liquid hydrogen storage technology.TiO_(2)-based catalysts show high performance in the photocatalytic dehydrogenation of cyclohexane under mild conditions,but the detailed reaction mechanism is not well understood.With the surface science approaches,we have studied the adsorption and surface chemistry of cyclohexane on rutile TiO_(2)(110).The thermal desorption spectroscopy and X-ray photoelectron spectroscopy results both demonstrate the molecular adsorption of cyclohexane on rutile TiO_(2)(110).Upon the UV Hg light irradiation,photodesorption of cyclohexane occurs from both the chemisorbed monolayer and the multilayer.No decomposition nor dehydrogenation of cyclohexane occurs on rutile TiO_(2)(110).These results deepen the fundamental understanding of the surface chemistry of cyclohexane on the TiO_(2)surface.展开更多
Chloro-（5,10,15,20-tetraphenylporphinato）iron（Ⅲ）(TPPFeCl)（A） used as a model compound of cytochrome P-450 to catalyze the monooxyenation of alkane is known, but the oxygenation of alkane catalyzed by μ-oxo-bis...Chloro-（5,10,15,20-tetraphenylporphinato）iron（Ⅲ）(TPPFeCl)（A） used as a model compound of cytochrome P-450 to catalyze the monooxyenation of alkane is known, but the oxygenation of alkane catalyzed by μ-oxo-bis（5,10,15,20-tetraphenylporphinato）-iron（Ⅲ）(（TPPFe）;O)（B） has not been reported. The catalytic characteristics of B for the oxygenation of cyclohexane with PhIO in CH;Cl;and cyclohexane medium were studied. We found that B had a fairly good展开更多
The effect of N_(2)discharge products on cyclohexane degradation over a MnO_(2)/γ-Al_(2)O_(3)catalyst has been evaluated by feeding N_(2)discharge products to the catalyst using a specially designed dielectric barrie...The effect of N_(2)discharge products on cyclohexane degradation over a MnO_(2)/γ-Al_(2)O_(3)catalyst has been evaluated by feeding N_(2)discharge products to the catalyst using a specially designed dielectric barrier discharge reactor.At a reaction temperature of 100℃,the cyclohexane conversion increased from 2.46%(without N_(2)discharge products)to 26.3%(with N_(2)discharge products).N-and O-containing by-product(3,4-dehydroproline)was found on the catalyst surface using gas chromatograph-mass spectrometry identification,in which C=N–C and C=N–H bonds were also confirmed from x-ray photoelectron spectroscopy analysis results.Operando analysis results using diffuse reflectance infrared Fourier transform spectroscopy revealed that N atoms can react with surface H_(2)O possibly to NH and OH reactive species that have reactivities to promote CO oxidation to CO_(2).The mechanism of N-atom-driven cyclohexane degradation to CO and CO_(2)is proposed.展开更多
The hydrothermal reaction of Zn（NO3）2·4H2O, cyclohexane-1,2,3,4,5,6-hexacarboxylic acid hydrate （H6LI·H2O, cis-conformation LI： a,e,a,e,a,e） and 2,2＇-bpy yielded a new coordination polymer [Zn2（H2LII...The hydrothermal reaction of Zn（NO3）2·4H2O, cyclohexane-1,2,3,4,5,6-hexacarboxylic acid hydrate （H6LI·H2O, cis-conformation LI： a,e,a,e,a,e） and 2,2＇-bpy yielded a new coordination polymer [Zn2（H2LII）（2,2＇-bpy）]·2H2O（trans-conformation LII： e,e,e,e,e,e）, which was characterized by single-crystal X-ray diffraction, elemental analysis, IR and XRPD（X-ray powder diffraction）. This complex crystallized in the triclinic system, with P1 space group and parameters a=0.66922（5） nm, b=0.97291（8） nm, c=1.22184（9） nm, α=99.0020（10）°, β=99.1300（10）°, γ=99.1910（10）°, V= 0.76176（10） nm3 and Z=2. The structure is a three-dimensional supramolecular network based on linear coordination chains through π-π stacking and hydrogen bonding interactions. The confromation of the starting ligand H6LI transfromed to the H2LII. The complex emits strong luminescence at room temperature.展开更多
基金This work is supported by the National Natural Science Foundation of China(No.22202191).
文摘Cyclohexane is a high-valued chemical receivingsignificant interest in liquid hydrogen storage technology.TiO_(2)-based catalysts show high performance in the photocatalytic dehydrogenation of cyclohexane under mild conditions,but the detailed reaction mechanism is not well understood.With the surface science approaches,we have studied the adsorption and surface chemistry of cyclohexane on rutile TiO_(2)(110).The thermal desorption spectroscopy and X-ray photoelectron spectroscopy results both demonstrate the molecular adsorption of cyclohexane on rutile TiO_(2)(110).Upon the UV Hg light irradiation,photodesorption of cyclohexane occurs from both the chemisorbed monolayer and the multilayer.No decomposition nor dehydrogenation of cyclohexane occurs on rutile TiO_(2)(110).These results deepen the fundamental understanding of the surface chemistry of cyclohexane on the TiO_(2)surface.
基金Project supported by The Natural Science Foundation Committee of
文摘Chloro-（5,10,15,20-tetraphenylporphinato）iron（Ⅲ）(TPPFeCl)（A） used as a model compound of cytochrome P-450 to catalyze the monooxyenation of alkane is known, but the oxygenation of alkane catalyzed by μ-oxo-bis（5,10,15,20-tetraphenylporphinato）-iron（Ⅲ）(（TPPFe）;O)（B） has not been reported. The catalytic characteristics of B for the oxygenation of cyclohexane with PhIO in CH;Cl;and cyclohexane medium were studied. We found that B had a fairly good
基金National Natural Science Foundation of China(No.12075037)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX21_2873)Research and Application Service Platform Project of API Manufacturing Environmental Protection and Safety Technology in China(No.2020-0107-3-1).
文摘The effect of N_(2)discharge products on cyclohexane degradation over a MnO_(2)/γ-Al_(2)O_(3)catalyst has been evaluated by feeding N_(2)discharge products to the catalyst using a specially designed dielectric barrier discharge reactor.At a reaction temperature of 100℃,the cyclohexane conversion increased from 2.46%(without N_(2)discharge products)to 26.3%(with N_(2)discharge products).N-and O-containing by-product(3,4-dehydroproline)was found on the catalyst surface using gas chromatograph-mass spectrometry identification,in which C=N–C and C=N–H bonds were also confirmed from x-ray photoelectron spectroscopy analysis results.Operando analysis results using diffuse reflectance infrared Fourier transform spectroscopy revealed that N atoms can react with surface H_(2)O possibly to NH and OH reactive species that have reactivities to promote CO oxidation to CO_(2).The mechanism of N-atom-driven cyclohexane degradation to CO and CO_(2)is proposed.
基金Supported by the National Natural Science Foundation of China(No.20901018)the Natural Science Foundation of Guangdong Province, China(No.9451009101003177)
文摘The hydrothermal reaction of Zn（NO3）2·4H2O, cyclohexane-1,2,3,4,5,6-hexacarboxylic acid hydrate （H6LI·H2O, cis-conformation LI： a,e,a,e,a,e） and 2,2＇-bpy yielded a new coordination polymer [Zn2（H2LII）（2,2＇-bpy）]·2H2O（trans-conformation LII： e,e,e,e,e,e）, which was characterized by single-crystal X-ray diffraction, elemental analysis, IR and XRPD（X-ray powder diffraction）. This complex crystallized in the triclinic system, with P1 space group and parameters a=0.66922（5） nm, b=0.97291（8） nm, c=1.22184（9） nm, α=99.0020（10）°, β=99.1300（10）°, γ=99.1910（10）°, V= 0.76176（10） nm3 and Z=2. The structure is a three-dimensional supramolecular network based on linear coordination chains through π-π stacking and hydrogen bonding interactions. The confromation of the starting ligand H6LI transfromed to the H2LII. The complex emits strong luminescence at room temperature.
