Trichloromethanesulfenyl thiocyanate, CCl3SSCN, was generated and studied by photoelectron spectroscopy （PES）, photoionization mass spectroscopy （PIMS）, and theoretical calculations. This molecule exhibits a gauch...Trichloromethanesulfenyl thiocyanate, CCl3SSCN, was generated and studied by photoelectron spectroscopy （PES）, photoionization mass spectroscopy （PIMS）, and theoretical calculations. This molecule exhibits a gauche conformation, and the torsional angle around S-S bond is 91.4° due to the sulfur-sulfur lone pair interactions. After ionization, the ground-state cationic-radical form of CCl3SSCN＋ adopts a trans planar main-atom structure with Cs symmetry. The highest occupied molecular orbital （HOMO） of CC13SSCN corresponds to the electrons mainly localized on the sulfur 3p lone pair MO. The first ionization energy is determined to be 10.40 cV.展开更多
Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi- gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal- culations. The main fragment ions at m/z...Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi- gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal- culations. The main fragment ions at m/z=86, 75, 74, 69, 57, 46, 45, 44, 41, 30, 28, and 18 from isoleucine are observed in the mass spectrum at the photon energy of 13 eV. From the photoionization efficiency curves, appearance energies for the principal fragment ions CsH12N＋ （rn/z=86）, C2H5NO2＋ （m/z=75）, C5H9＋ （rn/z=-69）, C4H9＋ （m/z=57）, and CH4N＋ （m/z=30） are determined to be 8.844-0.07, 9.254-0.06, 10.20-4-0.12, 9.254-0.10, and 11.05＋0.07 eV, respectively, and possible formation pathways are established in detail by the calculations at the B3LYP/6-31＋＋G（d, p） levels. These proposed channels include simple bond cleavage reactions as well as reactions involving intermediates and transition structures. The experimental and computational appearance energies or barriers are in good agreement.展开更多
The effect of the modification of an alumina support with chloride on the structure and the catalytic performance of Ag/Al_(2)O_(3)catalysts(SA)was investigated for the selective catalytic reduction(SCR)of NO using C_...The effect of the modification of an alumina support with chloride on the structure and the catalytic performance of Ag/Al_(2)O_(3)catalysts(SA)was investigated for the selective catalytic reduction(SCR)of NO using C_(3)H_(6)or H_(2)/C_(3)H_(6)as reductants.The Ag/Al_(2)O_(3)catalyst and Cl^(–)-modified Ag/Al_(2)O_(3)catalysts(SA-Cl)were prepared by a conventional impregnation method and characterized by X-ray diffraction,Brunauer-Emmett-Teller isotherm analysis,electron probe microanalysis,transmission electron microscopy,UV-Vis diffuse reflectance spectroscopy,X-ray photoelectron spectroscopy,and hydrogen temperature-programmed reduction.The catalytic activities in the C3H6-SCR and H_(2)/C3H6-SCR reactions were evaluated,and the reaction mechanism was studied using in situ diffuse reflectance infrared Fourier transform spectroscopy and synchrotron vacuum ultraviolet photoionization mass spectroscopy(SVUV-PIMS).We found that Cl^(-)modification of the alumina-supported Ag/Al_(2)O_(3)catalysts facilitated the formation of oxidized silver species(Ag_(n)^(ᵟ+))that catalyze the moderate-temperature oxidation of hydrocarbons into partial oxidation products(mainly acetate species)capable of participating in the SCR reaction.The low-temperature promoting effect of H_(2)on the C3H6-SCR("hydrogen effect")was found to originate from the enhanced decomposition of strongly adsorbed nitrates on the catalyst surface and the conversion of these adsorbed species to–NCO and–CN species.This"H_(2)effect"occurs in the presence of Ag_(n)^(ᵟ+)species rather than the metallic Ag^(0)species.A gaseous intermediate,acrylonitrile(CH_(2)CHCN),was also identified in the H_(2)/C3H6-SCR reaction using SVUV-PIMS.These findings provide novel insights in the structure-activity relationship and reaction mechanisms of the SA-catalyzed HC-SCR reaction of NO.展开更多
基金This work was supported by the Knowledge Innovation Program of the Chinese Academy of Sciences （No.KZCX2-YW-205） and the Hundred Talents Fund, the 973 Program of Ministry of Science and Technology of China （No.2006CB403701）, and the National Natural Science Foundation of China （No.20577052, No.20673123, No.20473094, and No.20503035）.
文摘Trichloromethanesulfenyl thiocyanate, CCl3SSCN, was generated and studied by photoelectron spectroscopy （PES）, photoionization mass spectroscopy （PIMS）, and theoretical calculations. This molecule exhibits a gauche conformation, and the torsional angle around S-S bond is 91.4° due to the sulfur-sulfur lone pair interactions. After ionization, the ground-state cationic-radical form of CCl3SSCN＋ adopts a trans planar main-atom structure with Cs symmetry. The highest occupied molecular orbital （HOMO） of CC13SSCN corresponds to the electrons mainly localized on the sulfur 3p lone pair MO. The first ionization energy is determined to be 10.40 cV.
基金V. ACKNOWLEDGMENTS This work is supported by the National Natural Science Foundation of China （No.10875126 and No.10979048） and the Specialized Research Fund for the Doctoral Program of Higher Education, SRF for ROCS, SEM.
文摘Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi- gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal- culations. The main fragment ions at m/z=86, 75, 74, 69, 57, 46, 45, 44, 41, 30, 28, and 18 from isoleucine are observed in the mass spectrum at the photon energy of 13 eV. From the photoionization efficiency curves, appearance energies for the principal fragment ions CsH12N＋ （rn/z=86）, C2H5NO2＋ （m/z=75）, C5H9＋ （rn/z=-69）, C4H9＋ （m/z=57）, and CH4N＋ （m/z=30） are determined to be 8.844-0.07, 9.254-0.06, 10.20-4-0.12, 9.254-0.10, and 11.05＋0.07 eV, respectively, and possible formation pathways are established in detail by the calculations at the B3LYP/6-31＋＋G（d, p） levels. These proposed channels include simple bond cleavage reactions as well as reactions involving intermediates and transition structures. The experimental and computational appearance energies or barriers are in good agreement.
文摘The effect of the modification of an alumina support with chloride on the structure and the catalytic performance of Ag/Al_(2)O_(3)catalysts(SA)was investigated for the selective catalytic reduction(SCR)of NO using C_(3)H_(6)or H_(2)/C_(3)H_(6)as reductants.The Ag/Al_(2)O_(3)catalyst and Cl^(–)-modified Ag/Al_(2)O_(3)catalysts(SA-Cl)were prepared by a conventional impregnation method and characterized by X-ray diffraction,Brunauer-Emmett-Teller isotherm analysis,electron probe microanalysis,transmission electron microscopy,UV-Vis diffuse reflectance spectroscopy,X-ray photoelectron spectroscopy,and hydrogen temperature-programmed reduction.The catalytic activities in the C3H6-SCR and H_(2)/C3H6-SCR reactions were evaluated,and the reaction mechanism was studied using in situ diffuse reflectance infrared Fourier transform spectroscopy and synchrotron vacuum ultraviolet photoionization mass spectroscopy(SVUV-PIMS).We found that Cl^(-)modification of the alumina-supported Ag/Al_(2)O_(3)catalysts facilitated the formation of oxidized silver species(Ag_(n)^(ᵟ+))that catalyze the moderate-temperature oxidation of hydrocarbons into partial oxidation products(mainly acetate species)capable of participating in the SCR reaction.The low-temperature promoting effect of H_(2)on the C3H6-SCR("hydrogen effect")was found to originate from the enhanced decomposition of strongly adsorbed nitrates on the catalyst surface and the conversion of these adsorbed species to–NCO and–CN species.This"H_(2)effect"occurs in the presence of Ag_(n)^(ᵟ+)species rather than the metallic Ag^(0)species.A gaseous intermediate,acrylonitrile(CH_(2)CHCN),was also identified in the H_(2)/C3H6-SCR reaction using SVUV-PIMS.These findings provide novel insights in the structure-activity relationship and reaction mechanisms of the SA-catalyzed HC-SCR reaction of NO.
