The interaction of hydrogen and carbon monoxide with oxygen on Cu(111)-Fe Surfaces

The interaction of hydrogen and carbon monoxide with oxygen adsorbed on Cu(111)-Fe surfaces containing different amounts of iron has been studied with ellipsometry, Auger electron spectroscopy and low energy electron diffraction. With carbon monoxide copper can be reduced completely and if, at larger iron deposits, γ-Fe₂O₃ is present, γ-Fe₂O₃ can be reduced to Fe₃O₄. The maximum reaction rate is proportional to the square of the total copper surface. With hydrogen all oxygen can be removed. The reduction proceeds via a number of different stages. This is explained by the subsequent occurrence of γ-Fe₂O₃, Fe₃O₄ Fe_0.95O and Fe.     

On the structure of CO adlayers on Cu(100) and Cu(111)

Alternative models for the high coverage compressed overlayers of CO on copper (100) and (111) are proposed in which the LEED patterns previously attributed to out-of-registry, uniformly compressed structures are re-interpreted in terms of adsorption on linear and bridged sites. The models provide a simpler explanation for the small influence of compression on the frequency of the infrared adsorption bond near 2000 cm^?1 compared with the large change of surface potential.     

Interactions of CO molecules adsorbed on oxidised Cu(111) and Cu(110)

Reflection absorption infrared spectroscopy has been used in conjunction with LEED and surface potential measurements to study low temperature CO adsorption on the oxidised Cu surfaces Cu(111)O|$\text{3}\text{2}\text{?}\text{2}$|, Cu(110)O(2 × 1) and Cu(110)Oc(6 × 2). On all three surfaces adsorption at 80 K yields surface potential changes in excess of 0.6 V and does not lead to the formation of an ordered overlayer. At high coverages the adsorption enthalpy is lower than on the clean surfaces. Infrared spectra show the growth of a doublet band with components initially at 2100 and 2117 cm^?1 on the oxidised Cu(111) surface. Similar features seen on the oxidised Cu(110) surfaces are accompanied by a band at 2140 cm^?1: a very weak band at the same frequency on oxidised Cu(111) is attributed to defect sites. Studies of the temperature dependence of the spectrum from oxidised Cu(111) lead to the conclusion that two different binding sites are occupied. Spectra of ${}^{12}\text{CO}{}^{13}\text{CO}$ mixtures show that the molecules occupying these sites are in close proximity to each other, and that the spectrum is subject to large but opposing coverage-dependent frequency shifts.     

Carburization of Cu(110)-Fe alloys by CO excited by electrons

Carbon deposition due to electron excited carbon monoxide is observed on Cu(110)-Fe surfaces. This is studied with a filament specially mounted for this purpose. When copper is covered by more than a few carbon monolayers there is no evidence of a ceasing of the reaction. Iron is lifted from the surface or at least is not completely covered by carbon. The reaction proceeds fastest when a large amount of very small clusters or monomers of iron is present at the surface; the rate is observed to decrease with increasing iron fraction when more iron than a few percent is present at the surface as then only the number and size of the iron facets grow.     

Chemisorption of CO on differently prepared Cu(111) surfaces

The adsorption of CO on Cu(111) has been studied by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), electron energy loss spectroscopy (EELS), work function measurements and thermal desorption spectroscopy. Two LEED overlayers of CO on Cu(111) have been found: $\text{√3 × √3}\text{R}\text{30°}$ and $\text{√}\text{7}\text{3}\text{× √}\text{7}\text{3}\text{R}\text{49.1°}$. Two different heats of adsorption were derived from thermal desorption spectra: 44.2 and 35.1 kj/mole. The isosteric heat of adsorption evaluated from work function measurements corresponds to the thermal desorption results. Energy losses due to CO adsorption have been found by means of EELS at 4.7, 7.7, and 13.8 eV.     

Collective vibrational modes of isotopic mixtures of CO on Cu(111) and Cu(001)

Recent infrared absorption measurements of isotopic mixtures of CO on Cu(111) and Cu(001) are analyzed in terms of a dipole coupling theory for substitionally disordered overlayers. The variation of frequencies as well as intensities of the collective C–O stretching vibrational modes with composition are in excellent agreement with the dipole theory. The electronic and vibrational contributions to the molecular polarizability are consistent with those derived from a direct measurement of the normal mode dispersion using electron loss spectroscopy. The interaction of a vibrating dipole with its own image is discussed and it is shown that this effect should not be included explicitly in the dipole sum.     

CO adsorption studies on pure and Ni-covered Cu(111) surfaces

The adsorption of CO on pure and Ni-covered Cu(111) surfaces has been studied by means of LEED, TDS, UPS and work function measurements during adsorption and desorption. Different Ni-coverages between 0.1 and 2 monolayers were obtained by Ni-evaporation controlled by a quartz micro balance and by AES. Near room temperature Ni grows in a layer-by-layer mode on Cu(111). The island structure of the surfaces with submonolayer Ni-coverages is clearly demonstrated by TDS und LEED results obtained after CO adsorption. As with surfaces of bulk Cu-Ni alloys CO adsorption on Cu(111) with submonolayer Ni-coverage is dominated by a site effect. Cu-, Ni-, and mixed adsorption sites can be distinguished. The CO induced work function changes for Ni- and Cu-site adsorption show the same sign as observed with the pure metals. Mixed site adsorption has only a minor influence on the work function. A “ligand effect” observed only for the Ni-site adsorption, and only at small Ni-coverages is discussed in detail. Studies on the adsorption kinetics reveal that the Cu-sites may serve as precursor sites for Ni-site adsorption. Detailed UPS studies demonstrate that the CO-induced emission maxima observed on Cu surfaces with submonolayer Ni-coverages can be interpreted as a superposition of the respective adsorption features observed with the pure metals, roughly separated by their work function difference.     

Photoelectron spectroscopy from CO adsorbed on a Cu(111) surface

He II-ultraviolet photoelectron spectra (hv = 40.8 eV) from a carbon monoxide layer adsorbed on a Cu(111) surface exhibit two peaks at 8.5 and 11.6 eV below the Fermi level and a weaker maximum centered at about 13.5 eV. The emission from the Cu d-band is markedly suppressed after adsorption. The results are discussed in terms of the recent models for assigning the UPS peaks observed after adsorption of CO on transtion metals     

Interaction of HNCO with Au(111) surfaces

The surface chemistry of isocyanic acid, HNCO, and its dissociation product, NCO, was studied on clean, O-dosed and Ar ion bombarded Au(111) surfaces. The techniques used are high resolution energy loss spectroscopy (HREELS) and temperature-programmed desorption (TPD). The structure of Ar ion etched surface is explored by scanning tunneling microscopy (STM). HNCO adsorbs molecularly on Au(111) surface at 100 K yielding strong losses at 1390, 2270 and 3230 cm^? 1. The weakly adsorbed HNCO desorbs in two peaks characterized by T_p = 130 and 145 K. The dissociation of the chemisorbed HNCO occurs at 150 K to give NCO species characterized by a vibration at 2185 cm^? 1. The dissociation process is facilitated by the presence of preadsorbed O and by defect sites on Au(111) produced by Ar ion bombardment. In the latter case the loss feature of NCO appeared at 2130 cm^? 1. Isocyanate on Au(111) surface was found to be more stable than on the single crystal surfaces of Pt-group metals. Results are compared with those obtained on supported Au catalysts.     

Interaction of H2O,CO, and H2 with Pt(111) and Pt(111)+K surfaces

The potential energy and surface dipole were calculated as a function of the geometry of the coadsorbed systems using the cluster method and theoretical oscillation frequencies and work function changes were compared with experiment. It was found that the K fills unoccupied Pt 5d states and reduces the local polarizability of the metal. The H₂O molecule binds to the K atom, such that the H atoms point towards the surface inducing an increase in the work function. For the CO molecule a charge transfer (KCO) through the surface stabilizes the bond and induces a change of adsorption place (on-topbridge). The K increases the tendency to H₂ dissociation because of the local decrease of the work function. Zero-point energy effects add important dynamical features to the electronic H₂- surface interaction. Three examples for the Pt(111)-H₂ system are presented: (i) A virtual attractive potential well produced by the softening of the H-H bond near the surface, (ii) a virtual potential barrier for dissociation due to the hindering of molecular rotations at the surface, and (iii) a change in the apparent surface temperature in H₂ desorption processes.     

CO与K在Cu(111)面上共吸附的角分辨紫外光电子能谱

CO在有K沉积的Cu(111)面上吸附的角分辨紫外光电子能谱(ARUPS)测量结果表明:在室温下,有分子状态的CO吸附在该表面,CO分子的4σ态信号强度明显低于5σ/1π态的强度,这表明CO分子在该状态下是强烈倾斜的,低温下(～150K),有两种不同的CO吸附状态,一种只有在较高CO暴露量下才出现,而另一种则在任何暴露量下都存在,后者是一种类似于CO在室温时的吸附状态。 关键词：     

Surface state energy shifts by molecular adsorption: CO ON Cu(111)

Molecular adsorption induced energy shifts of a surface state is observed for the Cu(111)/CO system. Angle resolved photoelectron energy spectra show that a zone center surface state shifts to higher energy relative to the Cu bulk bands. The effects is discussed in terms of charge transfer, molecular interaction range and absorption site.     

局域功函数图像及其在Cu(111)-Au/Pd表面的应用

用扫描隧道显微镜（STM）对Cu(111)-Au和Cu(111)-Pd表面的局域功函数进行了研究.通过 测量隧道电流对针尖样品间距的响应，得到了与STM形貌图一一对应的表面局域功函数图像. 实验发现，Au/Pd覆盖层和Cu衬底间的功函数有明显的不同.Pd薄膜的功函数甚至超过了其体 本征值，且功函数在台阶处变小.用偶极子的形成解释了台阶处功函数的降低.这一工作表明 ，用测量局域功函数的方法容易区分表面上不同的元素，并具有纳米尺度的空间分辨率. 关键词： 扫描隧道显微镜 局域功函数 台阶     

被羰基镍污染的CO气体在Cu(111)表面的近常压吸附研究

本文利用近常压X射线光电子能谱和近常压扫描隧道显微镜研究了在超高真空(UHV)和近常压条件下,被羰基镍污染的CO气体在Cu(111)表面的吸附过程. 通过控制被污染CO的气体压力,可以在Cu(111)表面上形成Ni-Cu双金属催化剂. 此外,本文探索了CO在所形成的Ni-Cu双金属表面上的吸附和解离过程,并报道了几种CO的高压吸附相结构.     

Interaction of oxygen with a Mo(111) surface

Oxygen adsorption on a Mo(111) surface is investigated at low pressures (10^?7 to 10^?5 Pa) and room temperature by Auger electron spectroscopy (AES), low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS). In agreement with previous studies it is established that the surface is not reconstructed during adsorption and the oxygen forms no ordered structures. On the basis of kinetic and spectroscopy data, the formation of two adsorption states on the surface within 1 monolayer is established. The valence band of a clean surface is studied in detail. An attempt is made to ascribe the peaks obtained to definite d states. The interaction between O₂ and Mo(111) is discussed in terms of the results obtained and a comparison with the O₂/W(111) system is made.     

Interaction of NO with a Ni (111) surface

The interaction of NO with a Ni (111) surface was studied by means of LEED, AES, UPS and flash desorption spectroscopy. NO adsorbs with a high sticking probability and may form two ordered structures (c4 × 2 and hexagonal) from (undissociated) NO_ad. The mean adsorption energy is about 25 $\text{kcal}\text{mole}$. Dissociation of adsorbed NO starts already at ?120°C, but the activation energy for this process increases with increasing coverage (and even by the presence of preadsorbed oxygen) up to the value for the activation energy of NO desorption. The recombination of adsorbed nitrogen atoms and desorption of N₂ occurs around 600 °C with an activation energy of about 52 $\text{kcal}\text{mole}$. A chemisorbed oxygen layer converts upon further increase of the oxygen concentration into epitaxial NiO. A mixed layer consisting of N_ad + O_ad (after thermal decomposition of NO) exhibits a complex LEED pattern and can be stripped of adsorbed oxygen by reduction with H₂. This yields an N_ad overlayer exhibiting a 6 × 2 LEED pattern. A series of new maxima at ≈ ?2, ?8.8 and ?14.6 eV is observed in the UV photoelectron spectra from adsorbed NO which are identified with surface states derived from molecular orbitals of free NO. N_ad as well as O_ad causes a peak at ?5.6 eV which is derived from the 2p electrons of the adsorbate. The photoelectron spectrum from NiO agrees closely with a recent theoretical evaluation.     

Interaction of Co with an Fe(111) surface

Adsorption of CO on Fe(111) below 300 K causes the appearance of three different non-dissociated species as distinguished by their CO stretch frequencies of about 1530 cm^-1 (a), 1800 cm^-1 (b), and 2000 cm^-1 (c). At T ? 220 K the b-state is first filled up and saturates after 1.5 L exposure; upon increasing the temperature it partly desorbs around 400 K and partly dissociates. Recombination of the C and O atoms followed by CO desorption takes place at about 800 K. Above 1.5 L exposure the a- and c-states are occupied simultaneously; in the thermal desorption spectrum in turn they show up as a relatively broad shoulder at ～ 340 K, which indicates similar adsorption energies for these two species. Saturation of the surface is reached after about 6 L exposure, which is paralleled by a continuous work function increase of up to Δφ = 1.6 eV. A high background intensity in the LEED pattern suggests substantial disorder in the adlayer. Evaluation of the TDS data yields about 2:1 population of the b- and (c + a)-states. The unusual low CO frequency of the a-state finds its analogues in reports on CO adsorption at stepped surfaces, as well as with complex compounds where the π-orbitals of the ligand directly interact with a neighboring metal atom. This species is therefore identified with adsorption in the “deep hollow” sites on the rather open Fe(111) surface. The b-state is tentatively attributed to the “shallow hollow” sites, and the c-state to adsorption on the “on top” sites.     

Bromine adsorption on Cu(111)

The dissociative chemisorption of molecular bromine on Cu(111) at 300 K has been studied using ultraviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES), low energy electron diffraction (LEED) and work function change measurements. A (√3 × √3)R30° structure is formed initially at a bromine coverage of 0.33 ML. This then converts to a (9√3 × 9√3)R30° compression structure with a coverage of 0.41 ML. The coincidence distance of the compression structure is determined entirely by the van der Waals diameter of adsorbed bromine. The applicability of using the van der Waals diameters of the three halogens, Cl, Br and I, to predict the saturation compression structures on Cu(111), is discussed.