First-principles calculations based on density functional theory （DFr） and the generalized gradient approximation （GGA） have been used to study the adsorption of CO molecule on the Cu2O（111） oxygen-vacancy surfa...First-principles calculations based on density functional theory （DFr） and the generalized gradient approximation （GGA） have been used to study the adsorption of CO molecule on the Cu2O（111） oxygen-vacancy surface. Calculations indicate that the C-O bond is weakened upon adsorption compared with that over perfect surface. In addition, with the density increase of the defective sites, the adsorption energies of the defect-CO configuration increase whereas the C-O bond nearly remains constant.展开更多
The adsorptions of CO and 02 molecules individually on the stoichiometric Cu-terminatcd Cu20 （111） surface are investigated by first-principles calculations on the basis of the density functional theory. The calcula...The adsorptions of CO and 02 molecules individually on the stoichiometric Cu-terminatcd Cu20 （111） surface are investigated by first-principles calculations on the basis of the density functional theory. The calculated results indicate that the CO molecule preferably coordinates to the Cu2 site through its C atom with an adsorption energy of-1.69 eV, whereas the 02 molecule is most stably adsorbed in a tilt type with one O atom coordinating to the Cu2 site and the other O atom coordinating to the Cul site, and has an adsorption energy of -1.97 eV. From the analysis of density of states, it is observed that Cu 3d transfers electrons to 2π orbital of the CO molecule and the highest occupied 5σ orbital of the CO molecule transfers electrons to the substrate. The sharp band of Cu 4s is delocalized when compared to that before the CO molecule adsorption, and overlaps substantially with bands of the adsorbed CO molecule. There is a broadening of the 2π orbital of the 02 molecule because of its overlapping with the Cu 3d orbital, indicating that strong 3d-2π interactions are involved in the chemisorption of the 02 molecule on the surface.展开更多
H_(2)O吸附引起的二次电子发射增强是导致真空微波器件与设备异常放电的关键因素。为了研究H_(2)O吸附对金属表面二次电子发射特性的影响规律,该文考虑电子−H_(2)O分子碰撞的7种散射类型,采用Monte Carlo方法模拟电子−H_(2)O吸附分子的...H_(2)O吸附引起的二次电子发射增强是导致真空微波器件与设备异常放电的关键因素。为了研究H_(2)O吸附对金属表面二次电子发射特性的影响规律,该文考虑电子−H_(2)O分子碰撞的7种散射类型,采用Monte Carlo方法模拟电子−H_(2)O吸附分子的散射过程,同时考虑功函数变化对电子出射概率的影响,建立了一种H_(2)O吸附Cu表面的二次电子发射模型,统计二次电子的最终状态,并对二次电子发射系数(secondary electron yield,SEY)和二次电子能谱(secondary electron spectrum,SES)的变化规律进行分析。结果表明,H_(2)O吸附能够降低表面功函数,且产生更多电离电子,导致SEY增大;但当吸附厚度大于100 nm时,SEY不再继续增大,这是由于吸附层较厚时,电子无法进入Cu基底,仅在吸附层内散射。SES的谱峰随着吸附厚度的增加而增强,表明H_(2)O能够促使更多的低能电子出射,这是造成二次电子发射增强的重要因素。该文的模型为研究复杂表面状态的二次电子发射提供了可靠的分析方法,相关结果能够用于分析解释真空微波器件与设备放电形成机理,优化设备部件的设计参数。展开更多
Two Al2O3/Cu composites containing 0.24 wt.% Al2O3 and 0.60 wt.% Al2O3 separately are prepared by internal oxidation. Effects of sliding speed and pressure on the frictional characteristics of the composites and coppe...Two Al2O3/Cu composites containing 0.24 wt.% Al2O3 and 0.60 wt.% Al2O3 separately are prepared by internal oxidation. Effects of sliding speed and pressure on the frictional characteristics of the composites and copper against brass are investigated and compared. The changes in morphology of the sliding surface and subsurface are examined with scanning electron microscope （SEM） and energy dispersive X-ray spectrum （EDS）. The results show that the wear resistance of the Al2O3/Cu composites is superior to that of copper under the same conditions, Under a given electrical current, the wear rate of Al2O3/Cu composites decreases as the Al2O3-content increases, However, the wear rates of the Al2O3/Cu composites and copper increase as the sliding speed and pressure increase under dry sliding condition. The main wear mechanisms for Al2O3/Cu composites are of abrasion and adhesion; for copper, it is adhesion, although wear by oxidation and electrical erosion can also be observed as the speed and pressure rise.展开更多
A series of CuO/ZnO/Al_2O_3, CuO/ZnO/ZrO_2/Al_2O_3 and CuO/ZnO/CeO_2/Al_2O_3 catalysts were prepared by coprecipitation and characterized by N_2 adsorption, XRD, TPR, N_2O titration and HRTEM. The catalytic performanc...A series of CuO/ZnO/Al_2O_3, CuO/ZnO/ZrO_2/Al_2O_3 and CuO/ZnO/CeO_2/Al_2O_3 catalysts were prepared by coprecipitation and characterized by N_2 adsorption, XRD, TPR, N_2O titration and HRTEM. The catalytic performances of these catalysts for the steam reforming of methanol were evaluated in a laboratory-scale fixed-bed reactor at 0.1 MPa and temperatures between 473 and 543 K. The results showed that the catalytic activity depended greatly on the catalyst reducibility and the specific surface area of Cu. An approximate linear correlation between the catalytic activity and the Cu surface area was found for all catalysts investigated in this study.Compared to CuO/ZnO/Al_2O_3, the ZrO_2-doped CuO/ZnO/Al_2O_3 exhibited higher activity and selectivity to CO,while the CeO_2-doped catalyst displayed lower activity and selectivity. Finally, an intrinsic kinetic study was carried out over a screened CuO/ZnO/CeO_2/Al_2O_3 catalyst in the absence of internal and external mass transfer effects. A good agreement was observed between the model-derived effluent concentrations of CO(CO_2) and the experimental data. The activation energies for the reactions of methanol-steam reforming, water-gas shift and methanol decomposition over CuO/ZnO/CeO_2/Al_2O_3 were 93.1, 85.1 and 116.5 k J·mol^(-1), respectively.展开更多
Control of surface structure at the atomic level can effectively tune catalytic properties of nanomaterials.Tuning surface strain is an effective strategy for enhancing catalytic activity;however,the correlation studi...Control of surface structure at the atomic level can effectively tune catalytic properties of nanomaterials.Tuning surface strain is an effective strategy for enhancing catalytic activity;however,the correlation studies between the surface strain with catalytic performance are scant because such mechanistic studies require the precise control of surface strain on catalysts.In this work,a simple strategy of precisely tuning compressive surface strain of atomic-layer Cu2O on Cu@Ag (AL-Cu2O/Cu@Ag) nanoparticles (NPs) is demonstrated.The AL-Cu2O is synthesized by structure evolution of Cu@Ag core-shell nanoparticles,and the precise thickness-control of AL-Cu2O is achieved by tuning the molar ratio of Cu/Ag of the starting material.Aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM) and EELS elemental mapping characterization showed that the compressive surface strain of AL-Cu2O along the [111] and [200] directions can be precisely tuned from 6.5% to 1.6% and 6.6% to 4.7%,respectively,by changing the number of AL-Cu2O layer from 3 to 6.The as-prepared AL-Cu2O/Cu@Ag NPs exhibited excellent catalytic property in the synthesis of azobenzene from aniline,in which the strained 4-layers Cu2O (4.5% along the [111] direction,6.1% along the [200] direction) exhibits the best catalytic performance.This work may be beneficial for the design and surface engineering of catalysts toward specific applications.展开更多
LaMnO<sub>3</sub> (LMO) cap layers with different surface roughness were prepared on epi-MgO/ion-beam-assisted deposition (IBAD) MgO/solution deposition planarized (SDP) Y<sub>2</sub>O<sub&g...LaMnO<sub>3</sub> (LMO) cap layers with different surface roughness were prepared on epi-MgO/ion-beam-assisted deposition (IBAD) MgO/solution deposition planarized (SDP) Y<sub>2</sub>O<sub>3</sub>/Hastelloy tape. The effects of the surface roughness of LMO on the crystallization, texture and superconducting properties of YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7?δ </sub> (YBCO) films were systematically investigated. The crystallization and epitaxial texture of resulting YBCO film are significantly improved with the surface roughness of LMO decreasing from 7.0 to 1.3nm. High-performance YBCO-coated conductors could be achieved if surface roughness of LMO cap layer is well controlled.展开更多
Using DFT method, the stable adsorption configurations of Cu4 cluster on Cr2O3 （0001） surface were investi- gated. The regular tetrahedron structure and the planar structures were considered as the initial adsorptio...Using DFT method, the stable adsorption configurations of Cu4 cluster on Cr2O3 （0001） surface were investi- gated. The regular tetrahedron structure and the planar structures were considered as the initial adsorption configu- ration of Cu4 cluster, respectively. The adsorption energies of the two structures were also calculated. The simulation result indicated that the adsorption energy of the regular tetrahedron structure was higher than that of the planar structure, and thus the regular tetrahedron structure was confirmed to be the stable adsorption configuration for Cu4 cluster on Cr2O3 （0001） surface. Moreover, it was observed that the Cu4 cluster showed the definite stable adsorption sites on Cr2O3 （0001） surface, namely 3-fold O sites. During the adsorption process of Cu4 cluster onto Cr2O3 （0001） surface, the Cu4 cluster could bond with more Cr or O atoms on the surface, and the apparent charge transfer also occurred correspondingly. Meanwhile, the Cu4 cluster and Cr2O3 （0001） surface would bond in the form of local polarization to enhance the stability of adsorption configuration.展开更多
基金Supported by the National Natural Science Foundation of China (No. 10676007) and NCETFJ
文摘First-principles calculations based on density functional theory （DFr） and the generalized gradient approximation （GGA） have been used to study the adsorption of CO molecule on the Cu2O（111） oxygen-vacancy surface. Calculations indicate that the C-O bond is weakened upon adsorption compared with that over perfect surface. In addition, with the density increase of the defective sites, the adsorption energies of the defect-CO configuration increase whereas the C-O bond nearly remains constant.
基金Project supported by the National High Technology Research and Development Program of China (Grant No. 2009AA03 Z428)the National Natural Science Foundation of China (Grant No. 50872005)+1 种基金the National Basic Research Program of China (Grant No. 2007CB613306)the Innovation Foundation of BUAA for Ph. D. Graduates
文摘The adsorptions of CO and 02 molecules individually on the stoichiometric Cu-terminatcd Cu20 （111） surface are investigated by first-principles calculations on the basis of the density functional theory. The calculated results indicate that the CO molecule preferably coordinates to the Cu2 site through its C atom with an adsorption energy of-1.69 eV, whereas the 02 molecule is most stably adsorbed in a tilt type with one O atom coordinating to the Cu2 site and the other O atom coordinating to the Cul site, and has an adsorption energy of -1.97 eV. From the analysis of density of states, it is observed that Cu 3d transfers electrons to 2π orbital of the CO molecule and the highest occupied 5σ orbital of the CO molecule transfers electrons to the substrate. The sharp band of Cu 4s is delocalized when compared to that before the CO molecule adsorption, and overlaps substantially with bands of the adsorbed CO molecule. There is a broadening of the 2π orbital of the 02 molecule because of its overlapping with the Cu 3d orbital, indicating that strong 3d-2π interactions are involved in the chemisorption of the 02 molecule on the surface.
文摘H_(2)O吸附引起的二次电子发射增强是导致真空微波器件与设备异常放电的关键因素。为了研究H_(2)O吸附对金属表面二次电子发射特性的影响规律,该文考虑电子−H_(2)O分子碰撞的7种散射类型,采用Monte Carlo方法模拟电子−H_(2)O吸附分子的散射过程,同时考虑功函数变化对电子出射概率的影响,建立了一种H_(2)O吸附Cu表面的二次电子发射模型,统计二次电子的最终状态,并对二次电子发射系数(secondary electron yield,SEY)和二次电子能谱(secondary electron spectrum,SES)的变化规律进行分析。结果表明,H_(2)O吸附能够降低表面功函数,且产生更多电离电子,导致SEY增大;但当吸附厚度大于100 nm时,SEY不再继续增大,这是由于吸附层较厚时,电子无法进入Cu基底,仅在吸附层内散射。SES的谱峰随着吸附厚度的增加而增强,表明H_(2)O能够促使更多的低能电子出射,这是造成二次电子发射增强的重要因素。该文的模型为研究复杂表面状态的二次电子发射提供了可靠的分析方法,相关结果能够用于分析解释真空微波器件与设备放电形成机理,优化设备部件的设计参数。
基金National Natural Science Foundation of China (50432020)Henan Innovation Project for University Prominent Re- search Talents (2007KYCX008)+3 种基金Henan Education Department Science and Technology Project (2007430004)Henan Plan Project for College Youth Backbone TeacherHenan University of Science and Technology Major Pre-research Foundation (2005ZD003)Henan University of Science and Technology Personnel Scientific Research Foundation (of023)
文摘Two Al2O3/Cu composites containing 0.24 wt.% Al2O3 and 0.60 wt.% Al2O3 separately are prepared by internal oxidation. Effects of sliding speed and pressure on the frictional characteristics of the composites and copper against brass are investigated and compared. The changes in morphology of the sliding surface and subsurface are examined with scanning electron microscope （SEM） and energy dispersive X-ray spectrum （EDS）. The results show that the wear resistance of the Al2O3/Cu composites is superior to that of copper under the same conditions, Under a given electrical current, the wear rate of Al2O3/Cu composites decreases as the Al2O3-content increases, However, the wear rates of the Al2O3/Cu composites and copper increase as the sliding speed and pressure increase under dry sliding condition. The main wear mechanisms for Al2O3/Cu composites are of abrasion and adhesion; for copper, it is adhesion, although wear by oxidation and electrical erosion can also be observed as the speed and pressure rise.
基金Supported by the National Natural Science Foundation of China(21276076)the Program for New Century Excellent Talents in University(NCET-13-0801)the"111"Project(B08021)
文摘A series of CuO/ZnO/Al_2O_3, CuO/ZnO/ZrO_2/Al_2O_3 and CuO/ZnO/CeO_2/Al_2O_3 catalysts were prepared by coprecipitation and characterized by N_2 adsorption, XRD, TPR, N_2O titration and HRTEM. The catalytic performances of these catalysts for the steam reforming of methanol were evaluated in a laboratory-scale fixed-bed reactor at 0.1 MPa and temperatures between 473 and 543 K. The results showed that the catalytic activity depended greatly on the catalyst reducibility and the specific surface area of Cu. An approximate linear correlation between the catalytic activity and the Cu surface area was found for all catalysts investigated in this study.Compared to CuO/ZnO/Al_2O_3, the ZrO_2-doped CuO/ZnO/Al_2O_3 exhibited higher activity and selectivity to CO,while the CeO_2-doped catalyst displayed lower activity and selectivity. Finally, an intrinsic kinetic study was carried out over a screened CuO/ZnO/CeO_2/Al_2O_3 catalyst in the absence of internal and external mass transfer effects. A good agreement was observed between the model-derived effluent concentrations of CO(CO_2) and the experimental data. The activation energies for the reactions of methanol-steam reforming, water-gas shift and methanol decomposition over CuO/ZnO/CeO_2/Al_2O_3 were 93.1, 85.1 and 116.5 k J·mol^(-1), respectively.
基金the National Natural Science Foundation of China (Nos.51631001,21643003,51872030,51702016,and 51501010)Fundamental Research Funds for the Central Universities, Beijing Institute of Technology Research Fund Program for Young Scholars and ZDKT18-01 from State Key Laboratory of Explosion Science and Technology (Beijing Institute of Technology).
文摘Control of surface structure at the atomic level can effectively tune catalytic properties of nanomaterials.Tuning surface strain is an effective strategy for enhancing catalytic activity;however,the correlation studies between the surface strain with catalytic performance are scant because such mechanistic studies require the precise control of surface strain on catalysts.In this work,a simple strategy of precisely tuning compressive surface strain of atomic-layer Cu2O on Cu@Ag (AL-Cu2O/Cu@Ag) nanoparticles (NPs) is demonstrated.The AL-Cu2O is synthesized by structure evolution of Cu@Ag core-shell nanoparticles,and the precise thickness-control of AL-Cu2O is achieved by tuning the molar ratio of Cu/Ag of the starting material.Aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM) and EELS elemental mapping characterization showed that the compressive surface strain of AL-Cu2O along the [111] and [200] directions can be precisely tuned from 6.5% to 1.6% and 6.6% to 4.7%,respectively,by changing the number of AL-Cu2O layer from 3 to 6.The as-prepared AL-Cu2O/Cu@Ag NPs exhibited excellent catalytic property in the synthesis of azobenzene from aniline,in which the strained 4-layers Cu2O (4.5% along the [111] direction,6.1% along the [200] direction) exhibits the best catalytic performance.This work may be beneficial for the design and surface engineering of catalysts toward specific applications.
基金financially supported by the National Science Foundation of China(No.91421110)the National High Technology Research and Development Program of China(No.2014AA032702)+2 种基金the National Basic Research Program of China(No.2015CB358600)Sichuan Youth Science and Technology Innovation Research Team Fund(No.2011JTD0006)Sichuan Provincial Fund for Distinguished Young Academic and Technology Leaders(No.2014JQ0011)
文摘LaMnO<sub>3</sub> (LMO) cap layers with different surface roughness were prepared on epi-MgO/ion-beam-assisted deposition (IBAD) MgO/solution deposition planarized (SDP) Y<sub>2</sub>O<sub>3</sub>/Hastelloy tape. The effects of the surface roughness of LMO on the crystallization, texture and superconducting properties of YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7?δ </sub> (YBCO) films were systematically investigated. The crystallization and epitaxial texture of resulting YBCO film are significantly improved with the surface roughness of LMO decreasing from 7.0 to 1.3nm. High-performance YBCO-coated conductors could be achieved if surface roughness of LMO cap layer is well controlled.
文摘Using DFT method, the stable adsorption configurations of Cu4 cluster on Cr2O3 （0001） surface were investi- gated. The regular tetrahedron structure and the planar structures were considered as the initial adsorption configu- ration of Cu4 cluster, respectively. The adsorption energies of the two structures were also calculated. The simulation result indicated that the adsorption energy of the regular tetrahedron structure was higher than that of the planar structure, and thus the regular tetrahedron structure was confirmed to be the stable adsorption configuration for Cu4 cluster on Cr2O3 （0001） surface. Moreover, it was observed that the Cu4 cluster showed the definite stable adsorption sites on Cr2O3 （0001） surface, namely 3-fold O sites. During the adsorption process of Cu4 cluster onto Cr2O3 （0001） surface, the Cu4 cluster could bond with more Cr or O atoms on the surface, and the apparent charge transfer also occurred correspondingly. Meanwhile, the Cu4 cluster and Cr2O3 （0001） surface would bond in the form of local polarization to enhance the stability of adsorption configuration.
