Twenty kinds of adsorptions of HCN on the Fe（100）, Fe（111） and Fe（110） surfaces at the 1/4 monolayer coverage are found using the density functional theory. For Fe（100）, the adsorption energy of the most stabl...Twenty kinds of adsorptions of HCN on the Fe（100）, Fe（111） and Fe（110） surfaces at the 1/4 monolayer coverage are found using the density functional theory. For Fe（100）, the adsorption energy of the most stable configuration where the HCN locates at the fourfold site with the C-N bonded to four Fe atoms is 1.928 eV. The most favored adsorption structure for HCN on Fe（111） is f-η3（N）-h-η3（C）, in which the C-N bond is almost parallel to the surface, and the adsorption energy is 1.347 eV. On Fe（110）, the adsorption energy in the most stable configuration in which HCN locates at the two long-bridge sites is 1.777 eV. The adsorption energy of the parallel orientation for HCN is larger than that of the perpendicular configuration. The binding mechanism of HCN on the Fe（100）, Fe（111） and Fe（110） surfaces is also analyzed by Mulliken charge population and the density of states in HCN. The result indicates that the configurations in which the adsorbed HCN becomes the non-linear are beneficial to the formation of the addition reaction for hydrogen. The nature that the introduction of Fe into the catalyst could increase the catalytic activity of the bimetallic catalyst in the addition reaction of hydrogen for nitriles is revealed.展开更多
Adsorption behavior of Fe atoms on a metal-free naphthalocyanine（H2Nc） monolayer on Ag（111） surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional th...Adsorption behavior of Fe atoms on a metal-free naphthalocyanine（H2Nc） monolayer on Ag（111） surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional theory（DFT）based calculations. We found that the Fe atoms were adsorbed on the centers of H2Nc molecules and formed Fe–H2Nc complexes at low coverage. DFT calculations show that Fe sited in the center of the molecule is the most stable configuration, in good agreement with the experimental observations. After an Fe–H2Nc complex monolayer was formed, the extra Fe atoms self-assembled to Fe clusters of uniform size and adsorbed dispersively at the interstitial positions of Fe–H2Nc complex monolayer. Therefore, the H2Nc monolayer grown on Ag（111） could be a good template to grow dispersed magnetic metal atoms and clusters at room temperature for further investigation of their magnetism-related properties.展开更多
The Zn and Fe modified /ZrO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> catalyst (Zn-Fe-SZA) was prepared and mechanisms of deactivation and methods for regeneration of as-prepared cata...The Zn and Fe modified /ZrO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> catalyst (Zn-Fe-SZA) was prepared and mechanisms of deactivation and methods for regeneration of as-prepared catalyst were explored with n-pentane isomerization as a probe reaction. The results indicated that the isopentane yield of the fresh Zn-Fe-SZA-F catalyst was about 57% at the beginning of the run, and declined gradually to 50% within 1500 min, then fell rapidly from 50% to 40% between 1500 and 2500 minutes. The deactivation of Zn-Fe-SZA catalyst may be caused by carbon formation on surface of the catalyst, sulfate group attenuation owing to reduction by hydrogen, removal of sulfur species and the loss of strong acid sites. It was found that the initial catalytic activity over Zn-Fe-SZA-T catalyst was 48%, which recovered by 84.3% as compared to that of fresh catalyst (57%). However, it showed a sharp decrease in isopentane yield from 48% to 29% within 1500 minutes, showing poor stability. This is associated to the loss of acidity caused by removal of sulfur species cannot be basically restored by thermal treatment. Resulfating the calcined catalyst could improve the acidity of catalyst significantly, especially strong acid sites, as compared with the calcined sample. The improved stability of the resulfated catalyst can be explained by: 1) eliminaton of carbon deposition to some extent by calcination process, 2) formation of improved acidic nature by re-sulfation, favoring isomerization on acidic sites, 3) restructuring of the acid and metal sites via the calcination-re-sulfation procedure.展开更多
低温(110～130K)下,将次表层Fe结构的Pt-Fe模型催化剂(即Pt/Fe/Pt(111)结构)暴露于不同量CO气体,经不同温度退火后,采用高分辨电子能量损失谱(HREELS)研究催化剂表面CO分子的振动谱。结果表明,当CO的暴露量低于0.2 L (Langmuir)时,Pt/Fe...低温(110～130K)下,将次表层Fe结构的Pt-Fe模型催化剂(即Pt/Fe/Pt(111)结构)暴露于不同量CO气体,经不同温度退火后,采用高分辨电子能量损失谱(HREELS)研究催化剂表面CO分子的振动谱。结果表明,当CO的暴露量低于0.2 L (Langmuir)时,Pt/Fe/Pt(111)表面只存在顶位吸附;当暴露量大于0.4L,除了顶位吸附外,桥位吸附开始出现;顶位吸附分子的C-O键振动峰随着暴露量的增加不断向高波数方向偏移。退火温度影响Pt/Fe/Pt(111)表面CO的吸附形式,低于255K时,顶位吸附分子的脱附速率大于桥位吸附分子;高于255 K时,桥位吸附分子的脱附速率较大,并先于顶位吸附的CO从表面完全脱附,其完全脱附温度比Pt(111)表面低50 K。展开更多
To reveal the relative contribution of the components, Fe, Mn oxides or organic materials（OMs） in the surficial sediments（SSs）, and the natural surface coating samples（NSCSs） to adsorbing atrazine（AT）, a selec...To reveal the relative contribution of the components, Fe, Mn oxides or organic materials（OMs） in the surficial sediments（SSs）, and the natural surface coating samples（NSCSs） to adsorbing atrazine（AT）, a selective chemical extraction technique was employed, to remove the different components, and the adsorption characteristics of AT on the SSs and the NSCSs were investigated. The observed adsorptions of AT on the original and extracted SSs and NSCSs were analyzed by nonlinear least squares fitting（NLSF） to estimate the relative contribution of the components. The results showed that the maximum adsorption of AT on the NSCSs was greater than that in the SSs, before and after extraction treatments, implying that the NSCSs were more dominant than the SSs for organic pollutant adsorption. It was also found that the Fe oxides, OMs, and residues in SSs（NSCSs） facilitated the adsorption of AT, but Mn oxides directly or indirectly restrained the interaction of AT with SSs（NSCSs） particles. The contribution of the Fe oxides to AT adsorption was more than that of OMs; the greatest contribution to AT adsorption on a molar basis was from the Fe oxides in the nonresidual fractions, indicating that the Fe oxides played an important role in controlling the environmental behavior of AT in an aquatic environment.展开更多
The adsorption behavior of methyl nitrite （MN） on the closed-packed Pd（111） sur- face has been investigated in detail by using density functional theory （DFT）. MN binds to the surface in two alternative forms, u...The adsorption behavior of methyl nitrite （MN） on the closed-packed Pd（111） sur- face has been investigated in detail by using density functional theory （DFT）. MN binds to the surface in two alternative forms, using the nitrogen atom attached to the surface. An overall net charge transfer from the substrate to the cis-MN molecule is also confirmed. In addition, the reaction mechanism for the dissociation of MN on the Pd（111） surface has been identified and compared with the methanol decomposition via O-H scission. The results demonstrate that MN is a more active reactant than methanol for the oxidative addition to the Pd catalyst. The possible reason has been analyzed from the adsorption behaviors and reaction barriers, that is, MN is chemically absorbed on the Pd（111） surface; the CHaO-NO bond scission, leading to the formation of adsorbed methoxy species, is much more favorable than that of the O-H bond scission and has a large exothermic behavior.展开更多
T shaped skin-stiffener joint are one of the most commonly used structures in aerospace components.It has been proven in various studies that these joints are susceptible to failure when loaded in pull out conditions ...T shaped skin-stiffener joint are one of the most commonly used structures in aerospace components.It has been proven in various studies that these joints are susceptible to failure when loaded in pull out conditions however,in specific applications these joints undergo pull loading.De-lamination/de-bond nucleation and its growth is one of the most common failure mechanisms in a fiber reinforced composite structure.Crack growth takes place due to the induced interlaminar normal and shear stresses between different structural constituents when a load is applied.In this study,Finite Element Analysis has been performed using cohesive contact interactions on a composite T-joint to simulate the pull out test conditions.A simplified shell based model coupled with CZM is proposed,which can evaluate the failure initiation and progression accurately with lesser computational efforts.The final failure occurred at a displacement of 4.71 mm at the computed failure load of 472.57 kgf for basic configuration.Computed Failure load for the padded configuration is 672.8 kgf and corresponding displacement is 4.6 mm.The results obtained by the proposed numerical model are validated by experimental results and it is observed that predicted failure displacements and failure load calculated were correlating reasonably well with the experiment.展开更多
文摘Twenty kinds of adsorptions of HCN on the Fe（100）, Fe（111） and Fe（110） surfaces at the 1/4 monolayer coverage are found using the density functional theory. For Fe（100）, the adsorption energy of the most stable configuration where the HCN locates at the fourfold site with the C-N bonded to four Fe atoms is 1.928 eV. The most favored adsorption structure for HCN on Fe（111） is f-η3（N）-h-η3（C）, in which the C-N bond is almost parallel to the surface, and the adsorption energy is 1.347 eV. On Fe（110）, the adsorption energy in the most stable configuration in which HCN locates at the two long-bridge sites is 1.777 eV. The adsorption energy of the parallel orientation for HCN is larger than that of the perpendicular configuration. The binding mechanism of HCN on the Fe（100）, Fe（111） and Fe（110） surfaces is also analyzed by Mulliken charge population and the density of states in HCN. The result indicates that the configurations in which the adsorbed HCN becomes the non-linear are beneficial to the formation of the addition reaction for hydrogen. The nature that the introduction of Fe into the catalyst could increase the catalytic activity of the bimetallic catalyst in the addition reaction of hydrogen for nitriles is revealed.
基金supported by the National Natural Science Foundation of China(Grant Nos.61390501,51325204,and 11204361)the National Basic Research Program of China(Grant Nos.2011CB808401 and 2011CB921702)+1 种基金the National Key Scientific Instrument and Equipment Development Project of China(Grant No.2013YQ1203451)the National Supercomputing Center in Tianjin,China,and the Chinese Academy of Sciences
文摘Adsorption behavior of Fe atoms on a metal-free naphthalocyanine（H2Nc） monolayer on Ag（111） surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional theory（DFT）based calculations. We found that the Fe atoms were adsorbed on the centers of H2Nc molecules and formed Fe–H2Nc complexes at low coverage. DFT calculations show that Fe sited in the center of the molecule is the most stable configuration, in good agreement with the experimental observations. After an Fe–H2Nc complex monolayer was formed, the extra Fe atoms self-assembled to Fe clusters of uniform size and adsorbed dispersively at the interstitial positions of Fe–H2Nc complex monolayer. Therefore, the H2Nc monolayer grown on Ag（111） could be a good template to grow dispersed magnetic metal atoms and clusters at room temperature for further investigation of their magnetism-related properties.
文摘The Zn and Fe modified /ZrO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> catalyst (Zn-Fe-SZA) was prepared and mechanisms of deactivation and methods for regeneration of as-prepared catalyst were explored with n-pentane isomerization as a probe reaction. The results indicated that the isopentane yield of the fresh Zn-Fe-SZA-F catalyst was about 57% at the beginning of the run, and declined gradually to 50% within 1500 min, then fell rapidly from 50% to 40% between 1500 and 2500 minutes. The deactivation of Zn-Fe-SZA catalyst may be caused by carbon formation on surface of the catalyst, sulfate group attenuation owing to reduction by hydrogen, removal of sulfur species and the loss of strong acid sites. It was found that the initial catalytic activity over Zn-Fe-SZA-T catalyst was 48%, which recovered by 84.3% as compared to that of fresh catalyst (57%). However, it showed a sharp decrease in isopentane yield from 48% to 29% within 1500 minutes, showing poor stability. This is associated to the loss of acidity caused by removal of sulfur species cannot be basically restored by thermal treatment. Resulfating the calcined catalyst could improve the acidity of catalyst significantly, especially strong acid sites, as compared with the calcined sample. The improved stability of the resulfated catalyst can be explained by: 1) eliminaton of carbon deposition to some extent by calcination process, 2) formation of improved acidic nature by re-sulfation, favoring isomerization on acidic sites, 3) restructuring of the acid and metal sites via the calcination-re-sulfation procedure.
文摘低温(110～130K)下,将次表层Fe结构的Pt-Fe模型催化剂(即Pt/Fe/Pt(111)结构)暴露于不同量CO气体,经不同温度退火后,采用高分辨电子能量损失谱(HREELS)研究催化剂表面CO分子的振动谱。结果表明,当CO的暴露量低于0.2 L (Langmuir)时,Pt/Fe/Pt(111)表面只存在顶位吸附;当暴露量大于0.4L,除了顶位吸附外,桥位吸附开始出现;顶位吸附分子的C-O键振动峰随着暴露量的增加不断向高波数方向偏移。退火温度影响Pt/Fe/Pt(111)表面CO的吸附形式,低于255K时,顶位吸附分子的脱附速率大于桥位吸附分子;高于255 K时,桥位吸附分子的脱附速率较大,并先于顶位吸附的CO从表面完全脱附,其完全脱附温度比Pt(111)表面低50 K。
基金Supported by the National Natural Science Foundation of China(No.50879025)the Scientific Start-up Fund from North China Electric Power University, China(No.X60218)the National Basic Research Program of China(No.2004CB3418501).
文摘To reveal the relative contribution of the components, Fe, Mn oxides or organic materials（OMs） in the surficial sediments（SSs）, and the natural surface coating samples（NSCSs） to adsorbing atrazine（AT）, a selective chemical extraction technique was employed, to remove the different components, and the adsorption characteristics of AT on the SSs and the NSCSs were investigated. The observed adsorptions of AT on the original and extracted SSs and NSCSs were analyzed by nonlinear least squares fitting（NLSF） to estimate the relative contribution of the components. The results showed that the maximum adsorption of AT on the NSCSs was greater than that in the SSs, before and after extraction treatments, implying that the NSCSs were more dominant than the SSs for organic pollutant adsorption. It was also found that the Fe oxides, OMs, and residues in SSs（NSCSs） facilitated the adsorption of AT, but Mn oxides directly or indirectly restrained the interaction of AT with SSs（NSCSs） particles. The contribution of the Fe oxides to AT adsorption was more than that of OMs; the greatest contribution to AT adsorption on a molar basis was from the Fe oxides in the nonresidual fractions, indicating that the Fe oxides played an important role in controlling the environmental behavior of AT in an aquatic environment.
基金supported by the National Natural Science Foundation of China (21171039)
文摘The adsorption behavior of methyl nitrite （MN） on the closed-packed Pd（111） sur- face has been investigated in detail by using density functional theory （DFT）. MN binds to the surface in two alternative forms, using the nitrogen atom attached to the surface. An overall net charge transfer from the substrate to the cis-MN molecule is also confirmed. In addition, the reaction mechanism for the dissociation of MN on the Pd（111） surface has been identified and compared with the methanol decomposition via O-H scission. The results demonstrate that MN is a more active reactant than methanol for the oxidative addition to the Pd catalyst. The possible reason has been analyzed from the adsorption behaviors and reaction barriers, that is, MN is chemically absorbed on the Pd（111） surface; the CHaO-NO bond scission, leading to the formation of adsorbed methoxy species, is much more favorable than that of the O-H bond scission and has a large exothermic behavior.
文摘T shaped skin-stiffener joint are one of the most commonly used structures in aerospace components.It has been proven in various studies that these joints are susceptible to failure when loaded in pull out conditions however,in specific applications these joints undergo pull loading.De-lamination/de-bond nucleation and its growth is one of the most common failure mechanisms in a fiber reinforced composite structure.Crack growth takes place due to the induced interlaminar normal and shear stresses between different structural constituents when a load is applied.In this study,Finite Element Analysis has been performed using cohesive contact interactions on a composite T-joint to simulate the pull out test conditions.A simplified shell based model coupled with CZM is proposed,which can evaluate the failure initiation and progression accurately with lesser computational efforts.The final failure occurred at a displacement of 4.71 mm at the computed failure load of 472.57 kgf for basic configuration.Computed Failure load for the padded configuration is 672.8 kgf and corresponding displacement is 4.6 mm.The results obtained by the proposed numerical model are validated by experimental results and it is observed that predicted failure displacements and failure load calculated were correlating reasonably well with the experiment.
