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1.
Yuhai Hu 《Surface science》2009,603(2):336-2840
Interactions between S18O2 and NO on the surface of stepped Pt(3 3 2) were studied using Fourier transform infra red reflection-absorption spectroscopy (FTIR-RAS) combined with thermal desorption spectroscopy (TDS). Adsorbed S18O2 does not seem to have a preference for step sites on Pt(3 3 2). As such, the presence of S18O2 molecules following exposures of ?1.6 L does not significantly block the subsequent adsorption of NO (?0.8 L) on these step sites. Adsorbed S18O2 molecules undergo dissociation (S18O2(a) → S18O(a) + 18O(a)) as the surface temperature is increased to 250 K and above, but the resultant 18O(a) further reacts with sulfur oxides (S18O2(a) and S18O(a)) to form S18Ox (x > 2) species at ∼400 K and above. The S18Ox species desorb as S18O2. Even though the presence of co-adsorbed S18O2 suppresses NO dissociation and subsequent N2 production, this effect is not significantly enhanced with increasing the exposures of S18O2 in the range ?1.6 L; N2 desorption is still detectable at an exposure of 1.6 L S18O2, at which a considerable amount of S18O2 desorption is detected.  相似文献   

2.
Yuhai Hu  Keith Griffiths   《Surface science》2008,602(17):2949-2954
Fourier transform infra red reflection–absorption spectroscopy (FTIR-RAS), thermal desorption spectroscopy (TDS), and auger electron spectroscopy (AES), were employed to explore the mechanism of NO reduction in the presence of C2H4 on the surface of stepped Pt(3 3 2). Both NO–Pt and C2H4–Pt interactions are enhanced when NO and C2H4 are co-adsorbed on Pt(3 3 2). As a result, C2H4 is dissociated at surface temperatures as low as 150 K, and the N–O stretch band is weakened. The presence of post-exposed C2H4 leads NO desorption from steps to decrease significantly, but the same effect on NO desorption from terraces becomes appreciable only at higher post-exposures of C2H4, e.g., 0.6 L and 1.2 L, and proceeds to a much slighter extent. Auger spectra indicate that as a result of the reaction with O from NO dissociation, the amount of surface C species is greatly reduced when NO is post-exposed to a C2H4 adlayer. It is concluded that reduction of NO in the presence of C2H4 proceeds very effectively on the surface of the Pt(3 3 2), through a mechanism of NO dissociation and subsequent O removal. Following this mechanism, the significant dissociation of adsorbed NO molecules on steps at surface temperatures below 400 K, and subsequent rapid reaction between the resultant O and C-related species, accounts for the considerable amount of N2 desorption at temperatures below 400 K.  相似文献   

3.
Yuhai Hu 《Surface science》2007,601(21):5002-5009
The influence of pre-dosed O2 on the catalytic reduction of NO with 13C2H5OH on the surface of stepped Pt(3 3 2) was investigated using Fourier transform infra red reflection-absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). We show that the oxidation of 13C2H5OH with O2 is a very effective reaction, occurring at 150 K and giving rise to acetate. The presence of NO does not lead to any evident oxidation of 13C2H5OH irrespective of the annealing temperature. For the case of O2 + 13C2H5OH + NO co-adlayers, oxidation of 13C2H5OH also takes place at 150 K. However, no new surface species that are supposed to be an intermediate for the production of N2 are detected.The influence of O2 on the production and desorption of N2 is intimately related to both O2 and 13C2H5OH coverage. The presence of pre-dosed O2 does not greatly promote N2 desorption. In fact, N2 desorption is suppressed quantitatively with increasing O2 coverage, after which unreacted, or left-over O atoms appear and remain on steps. It is concluded that the presence of pre-dosed O2 does not play a role of activating reactants in the catalytic reduction of NO with 13C2H5OH on the surface of Pt(3 3 2).  相似文献   

4.
Yuhai Hu 《Surface science》2007,601(12):2467-2472
The interaction between NO and CH3OH on the surface of stepped Pt(3 3 2) was investigated using Fourier transform infra red reflection-absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). At 90 K, pre-dosed CH3OH molecules preferentially adsorb on step sites, suppressing the adsorption of NO molecules on the same sites. However, due to a much stronger interaction with Pt, at 150 K and higher, the adsorption of NO molecules on step sites is restored, giving rise to peaks closely resembling those of NO molecules adsorbed on clean Pt(3 3 2) surface. Adsorbed CH3OH is very reactive on this surface, and is readily oxidized to formate in the presence of O2, even at 150 K. In contrast, reactions between CH3OH and co-adsorbed NO are slight to non-existent. There are no new peaks in association with intermediates resulting from CH3OH-NO interactions. It is concluded that the reduction of NO with CH3OH on Pt(3 3 2) does not proceed through a mechanism of forming intermediates.  相似文献   

5.
The influence of pre-dosed oxygen on NO–C2H4 interactions on the surface of stepped Pt(3 3 2) has been investigated using Fourier transform infrared reflection–absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). The presence of oxygen significantly suppresses the adsorption of NO on the steps of Pt(3 3 2), leading to a very specific adsorption state for NO molecules when oxygen–NO co-adlayers are annealed to 350 K (assigned as atop NO on step edges). An oxygen-exchange reaction also takes place between these two kinds of adsorbed molecules, but there appears to be no other chemical reaction, which can result in the formation of higher-valence NOx.

C2H4 molecules which are post-dosed at 250 K to adlayers consisting of 18O and NO do not have strong interactions with either the NO or the 18O atoms. In particular, interactions which may result in the formation of new surface species that are intermediates for N2 production appear to be absent. However, C2H4 is oxidized to C18O2 by 18O atoms at higher annealing temperature. This reaction scavenges surface 18O atoms quickly, and the adsorption of NO molecules on step sites is therefore quickly restored. As a consequence, NO dissociation on steps proceeds very effectively, giving rise to N2 desorption which closely resembles that following only NO exposure on a clean Pt(3 3 2), both in peak intensity and desorption temperature. It is concluded that the presence of 18O2 in the selective catalytic reduction (SCR) of NO with C2H4 on the surface of Pt(3 3 2) does not play a role of activating reactants.  相似文献   


6.
The conductivity and elastic modulus of (CeO2)1 − x(YO1.5)x for x values of 0.10, 0.15, 0.20, 0.30, and 0.40 were investigated by experiments and molecular dynamics simulations. The calculated conductivity exhibited a maximum value at approximately 15 mol% Y2O3; this trend agreed with that of the experimental results. In order to clarify the reason for the occurrence of the maximum conductivity, the paths for the transfer of oxygen vacancies were counted. The numerical result revealed that as the content of Y2O3 dopant increases, the number of paths for the transfer of oxygen vacancies decreases, whereas the number of oxygen vacancies for conductivity increases. Thus, the trade-off between the increase in the number of vacancy sites and the decrease in the vacancy transfer was considered to be the reason for the maximum conductivity occurring at the Y2O3 dopant content of approximately 15 mol%. The calculated elastic modulus also exhibited a minimum value at approximately 20 mol% Y2O3, which also agreed with the experimental results. It was shown that the Y–O–Y bonding energy increased with the increasing content of Y2O3 dopant. Thus, the trade-off between the increase in the number of vacancy sites and that in the Y–O–Y bonding energy was considered to be the reason for the minimum elastic modulus occurring at the Y2O3 dopant content of approximately 20 mol%.  相似文献   

7.
The catalytic reduction of NO in the presence of benzene on the surface of Pt(3 3 2) has been studied using Fourier transform infra red reflection-absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). IR spectra show that while the presence of benzene molecules at low coverage (e.g., following an exposure of just 0.25 L) promotes NO-Pt interaction, the adsorption of NO on Pt(3 3 2) at higher benzene coverages is suppressed. It is also shown that there are no strong interactions between the adsorbed NO molecules and the benzene itself or benzene-derived hydrocarbons, which can lead to the formation of intermediate species that are essential for N2 production.TDS results show that the adsorbed benzene molecules undergo dehydrogenation accompanied by hydrogen desorption starting at 300 K and achieving a maximum at 394 K. Subsequent dehydrogenation of the benzene-derived hydrocarbons then begins with hydrogen desorption starting at 500 K. N2 desorption from NO adlayers on clean Pt(3 3 2) surface becomes significant at temperatures higher than 400 K, giving rise to a peak at 465 K. This peak corresponds to N2 desorption from NO dissociation on step sites. The presence of benzene promotes N2 desorption, depending on the benzene coverage. When the benzene exposure is 0.25 L, the N2 desorption peak at 459 K is dramatically increased. Increasing benzene coverage also results in the intensification of N2 desorption at ∼410 K. At benzene exposures of 2.4 L, N2 desorption develops as a broad peak with a maximum at ∼439 K.It is concluded that the catalytic reduction of NO by platinum in the presence of benzene proceeds by NO decomposition and subsequent oxygen removal at temperatures lower than 500 K, and NO dissociation is a rate-limiting step. The contribution of benzene to N2 desorption is mainly attributed to providing a source of H, which quickly reacts with NO-derived atomic O, leaving the surface with more vacant sites for further NO dissociation.  相似文献   

8.
The surface chemistry of NO and NO2 on clean and oxygen-precovered Pt(1 1 0)-(1 × 2) surfaces were investigated by means of high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). At room temperature, NO molecularly adsorbs on Pt(1 1 0), forming linear NO(a) and bridged NO(a). Coverage-dependent repulsive interactions within NO(a) drive the reversible transformation between linear and bridged NO(a). Some NO(a) decomposes upon heating, producing both N2 and N2O. For NO adsorption on the oxygen-precovered surface, repulsive interactions exist between precovered oxygen adatoms and NO(a), resulting in more NO(a) desorbing from the surface in the form of linear NO(a). Bridged NO(a) experiences stronger repulsive interactions with precovered oxygen than linear NO(a). The desorption activation energy of bridged NO(a) from oxygen-precovered Pt(1 1 0) is lower than that from clean Pt(1 1 0), but the desorption activation energy of linear NO(a) is not affected by the precovered oxygen. NO2 decomposes on Pt(1 1 0)-(1 × 2) surface at room temperature. The resulted NO(a) (both linear NO(a) and bridged NO(a)) and O(a) repulsively interact each other. Comparing with NO/Pt(1 1 0), more NO(a) desorbs from NO2/Pt(1 1 0) as linear NO(a), and both linear NO(a) and bridged NO(a) exhibit lower desorption activation energies. The reaction pathways of NO(a) on Pt(1 1 0), desorption or decomposition, are affected by their repulsive interactions with coexisting oxygen adatoms.  相似文献   

9.
The microstructures and the microwave dielectric properties of the (1 − x)(Mg0.95Co0.05)TiO3x(Na0.5La0.5)TiO3 ceramic system were investigated. Two-phase system was confirmed by the XRD patterns and the EDX analysis. A co-existed second phase (Mg0.95Co0.05)Ti2O5 was also detected. The microwave dielectric properties are strongly related to the density and the matrix of the specimen. A new microwave dielectric material 0.88(Mg0.95Co0.05)TiO3–0.12(Na0.5La0.5)TiO3, possessing an excellent combination of dielectric properties: εr  22.36, Q × f  110,000 GHz (at 9 GHz), τf  2.9 ppm/°C), is proposed as a candidate dielectric for GPS patch antennas.  相似文献   

10.
The effect of N2 treatment on the photocatalytic activity of Pt0/TiO2 was investigated. The results showed that after treatment at 500 °C in N2, 70% of the photocatalytic activity of 1.0 wt.% Pt0/TiO2 was lost by the evaluation of photocatalytic oxidation reaction of C3H6. Transmission electron microscopy (TEM) and Ar+ ion sputtering tests revealed that in the course of high-temperature N2 treatment, the size of Pt0 particles on TiO2 increases and a strong interaction between metal and support, i.e. Pt0 particles encapsulated by TixOy, happens, which are the reasons for the deactivation of Pt0/TiO2 photocatalyst treated by high-temperature N2.  相似文献   

11.
The reactivity of the (0 0 0 1)-Cr–Cr2O3 surface towards water was studied by means of periodic DFT + U. Several water coverages were studied, from 1.2H2O/nm2 to 14.1H2O/nm2, corresponding to ¼, 1, 2 and 3 water/Cr at the (0 0 0 1)-Cr2O3 surface, respectively. With increasing coverage, water gradually completes the coordination sphere of the surface Cr atoms from 3 (dry surface) to 4 (1.2 and 4.7H2O/nm2), 5 (9.4H2O/nm2) and 6 (14.1H2O/nm2). For all studied coverages, water replaces an O atom from the missing above plane. At coverages 1.2 and 4.7H2O/nm2, the Cr–Os (surface oxygen) acid–base character and bond directionality govern the water adsorption. The adsorption is molecular at the lowest coverage. At 4.7H2O/nm2, molecular and dissociative states are isoenergetic. The activation energy barrier between the two states being as low as 12 kJ/mol, allowing protons exchanges between the OH groups, as evidenced by ab inito molecular dynamics at room temperature. At coverages of 9.4 and 14.1H2O/nm2, 1D- (respectively, 2D-) water networks are formed. The resulting surface terminations are –Cr(OH)2 and –Cr(OH)3– like, respectively. The increased stability of those terminations as compared to the previous ones are due to the stabilization of the adsorbed phase through a H-bond network and to the increase in the Cr coordination number, stabilizing the Cr (t2g) orbitals in the valence band. An atomistic thermodynamic approach allows us to specify the temperature and water pressure domains of prevalence for each surface termination. It is found that the –Cr(OH)3-like, –Cr(OH)2 and anhydrous surfaces may be stabilized depending on (TP) conditions. Calculated energies of adsorption and OH frequencies are in good agreement with published experimental data and support the full hydroxylation model, where the Cr achieves a 6-fold coordination, at saturation.  相似文献   

12.
Pb(Zr0.52Ti0.48)O3 (PZT) thin films with large remanent polarization and SrBi2Ta2O9 (SBT) thin films with excellent fatigue-resisting characteristic have been widely studied for non-volatile random access memories, respectively. To combine these two advantages, bilayered Pb(Zr0.52Ti0.48)O3/SrBi2Ta2O9 (PZT/SBT) thin films were fabricated on Pt/TiO2/SiO2/Si substrates by chemical solution deposition method. X-ray diffraction patterns revealed that the diffraction peaks of PZT/SBT thin films were completely composed of PZT and SBT, and no other secondary phase was observed. The electrical properties of the bilayered structure PZT/SBT films have been investigated in comparison with pure PZT and SBT films. PZT/SBT bilayered thin films showed larger remanent polarization (2Pr) of 18.37 μC/cm2 than pure SBT and less polarization fatigue up to 1 × 109 switching cycles than pure PZT. These results indicated that this bilayered structure of PZT/SBT is a promising material combination for ferroelectric memory applications.  相似文献   

13.
The promotion of sulfur oxides on the selective catalytic reduction (SCR) of NO by hydrocarbons in the presence of a low concentration of sulfur oxides over Ag/Al2O3 has been investigated by a flow reaction test and in situ infrared spectroscopy. When the C3H6 (or C10H22) + NO + O2 feed-flow reaction was tested, maximum NO reduction was below 30% over fresh Ag/Al2O3. After the addition of SO2 to the feed flow, conversion increased slightly. Conversion increased further after SO2 was cut-off from the feed flow. This demonstrated that the increase in NO reduction activity of the catalyst was related to SOx adsorbed on the catalyst. SOx adsorbed on the catalytic surface (1375 cm−1) was detected by IR spectroscopy and was stable within the temperature range. NCO species, as an intermediate in NO reduction, on SOx-adsorbed Ag/Al2O3 in a C3H6 + NO + O2 feed flow was observed in in situ IR spectra during the elevation of the reaction temperature from 473 to 673 K, while it was only observed at 673 K on fresh Ag/Al2O3 under the same experimental conditions. We suggest that SOx in low concentrations depressed the combustion of reductants by contaminating hydrocarbon combustion active sites on the catalyst, resulting in an increase in NO reduction efficiency of the reductants.  相似文献   

14.
Thermal stability, interfacial structures and electrical properties of amorphous (La2O3)0.5(SiO2)0.5 (LSO) films deposited by using pulsed laser deposition (PLD) on Si (1 0 0) and NH3 nitrided Si (1 0 0) substrates were comparatively investigated. The LSO films keep the amorphous state up to a high annealing temperature of 900 °C. HRTEM observations and XPS analyses showed that the surface nitridation of silicon wafer using NH3 can result in the formation of the passivation layer, which effectively suppresses the excessive growth of the interfacial layer between LSO film and silicon wafer after high-temperature annealing process. The Pt/LSO/nitrided Si capacitors annealed at high temperature exhibit smaller CET and EOT, a less flatband voltage shift, a negligible hysteresis loop, a smaller equivalent dielectric charge density, and a much lower gate leakage current density as compared with that of the Pt/LSO/Si capacitors without Si surface nitridation.  相似文献   

15.
纳元元  王聪  褚立华  丁磊  闫君 《物理学报》2012,61(3):36801-036801
采用对靶磁控溅射方法在单晶Si(100)基片上制备了反钙钛矿结构的Mn3CuNx薄膜.通过控制制备过程中的反应气体氮气(N2) 流量(N2/Ar+N2), 研究了氮含量对Mn3CuNx薄膜结构及物理性能的影响.分别利用X射线衍射仪、俄歇电子能谱、 原子力显微镜、X射线光电子能谱、物理性能测试系统和超导量子干涉仪, 对所制备薄膜的晶体结构、成分、表面形貌和电、磁输运性质进行了测试.结果表明:制备的薄膜均为反钙钛矿立方结构,且沿 (200) 晶面择优生长.随着氮含量的增大,薄膜表面粗糙度和颗粒度尺寸逐渐增大, 导致电阻率增加.氮含量对薄膜的电输运性质没有影响,所有薄膜电阻率均随着温度的降低逐渐增大, 呈现半导体型导电行为,这与对应的块体材料结果相反.Mn3CuNx薄膜随着测试温度的增大发生了 亚铁磁到顺磁的磁转变,且N含量的增大降低了磁有序转变温度,主要是由于N缺陷对Mn6N八面体结构中 磁交换作用的影响所致.  相似文献   

16.
We investigate the effects of varying the degree of burner stabilization on Fenimore NO formation in fuel-rich low-pressure flat CH4/O2/N2 flames. Towards this end, axial profiles of flame temperature and OH, NO and CH mole fractions are measured using laser-induced fluorescence (LIF). The experiments are performed at equivalence ratios between 1.3 and 1.5. The flame temperature is seen to decrease by 200-300 K, with a concomitant decrease in OH mole fraction, upon reducing the total flow rate from 5 to 3 L/min, thus increasing stabilization. At equivalence ratios between 1.3 and 1.5, this decrease in flow rate lowers the maximum CH mole fraction by a factor of 2, and the NO mole fraction by ∼40% in all flames studied. Integrating the reaction rate for CH + N2 to estimate Fenimore NO formation, using the rate coefficient in GRI-Mech 3.0, and the measured temperatures and CH profiles show very good agreement with the measured NO mole fraction for ? = 1.3 and 1.4, supporting the current choice for this rate. This agreement also shows that the increase in residence time caused by increased stabilization is an important factor in the ultimate impact of the changes in CH mole fraction on NO formation. The results at ? = 1.5 suggest that substantial quantities of fixed nitrogen species, e.g., HCN, are only slowly oxidized in the post-flame zone under these conditions, leading to a significant discrepancy between the measured NO mole fraction and that obtained by integrating over the CH profile. Detailed calculations using GRI-Mech 3.0 predict the experimental results at ? = 1.3 nearly quantitatively, but show increasing differences with the measurements for both CH and NO profiles with increasing equivalence ratio.  相似文献   

17.
We investigated the effects of added Tm2O3, Sc2O3, and Yb2O3 on the superconducting properties of sintered Er123 samples. Tm2O3 addition caused the least Tc degradation, exhibiting a Tc above 90 K even for 17 vol% addition. Samples with added Sc2O3 maintained a Tc at above 90 K up to an addition of 7.2 vol%, while Yb2O3-containing samples showed a monotonic decrease in Tc with increased vol% of added Yb2O3. Tm2O3-containing samples exhibited a slight increase in Jc(0.1 T)/Jc(0) and had constant Jc values even for 17 vol% addition. XRD and SEM results indicate that the Tm2O3 is very stable in the superconducting matrix.  相似文献   

18.
We have fabricated exchange-biased Co/Pt layers ((0.3 nm/1.5 nm)×3) on (0 0 1)-oriented Cr2O3 thin films. The multilayered films showed extremely smooth surfaces and interfaces with root mean square roughness of ≈0.3 nm for 10 μm×10 μm area. The Cr2O3 films display sufficient insulation with a relative low leakage current (1.17×10−2 A/cm2 at 380 MV/m) at room temperature which allowed us to apply electric field as high as 77 MV/m. We find that the sign of the exchange bias and the shape of the hysteresis loops of the out-of-plane magnetized Co/Pt layers can be delicately controlled by adjusting the magnetic field cooling process through the Néel temperature of Cr2O3. No clear evidence of the effect of electric field and the electric field cooling was detected on the exchange bias for fields as high as 77 MV/m. We place the upper bound of the shift in exchange bias field due to electric field cooling to be 5 Oe at 250 K.  相似文献   

19.
The remote plasma nitridation (RPN) of an HfO2 film using N2 and NH3 has been investigated comparatively. X-ray photoelectron spectroscopy and Auger electron spectroscopy analyses after post-deposition annealing (PDA) at 700 °C show that a large amount of nitrogen is present in the bulk film as well as in the interfacial layer for the HfO2 film nitrided with NH3-RPN. It is also shown that the interfacial layer formed during RPN and PDA is a nitrogen-rich Hf-silicate. The C-V characteristics of an HfOxNy gate dielectric nitrided with NH3-RPN have a smaller equivalent oxide thickness than that nitrided with N2-RPN in spite of its thicker interfacial layer.  相似文献   

20.
The structural properties and relaxation mechanisms of Li2KH(SO4)2 crystals were determined using the temperature dependences of NMR spectra and the spin-lattice relaxation times (T1) of their 1H, 7Li, and 39K nuclei. The results obtained were compared with the previously reported physical properties of LiKSO4 crystals. The substitution of the potassium ions with protons in the LiKSO4 crystals were variations in the phase transition temperatures, and the non-appearance of ferroelastic properties. The 7Li T1 for the Li2KH(SO4)2 crystals was much shorter than the 7Li T1 for the LiKSO4 crystals, and these findings indicate that the presence of the protons in Li2KH(SO4)2 causes the Li ions to move with greater freedom.  相似文献   

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