Low-energy electron diffraction,Auger electron spectroscopy,and thermal desorption studies of chemisorbed CO and O2 on the (111) and stepped [6(111) × (100)] iridium surfaces

The adsorption of CO, O₂, and H₂O was studied on both the (111) and [6(111) × (100)] crystal faces of iridium. The techniques used were LEED, AES, and thermal desorption. Marked differences were found in surface structures and heats of adsorption on these crystal faces. Oxygen is adsorbed in a single bonding state on the (111) face. On the stepped iridium surface an additional bonding state with a higher heat of adsorption was detected which can be attributed to oxygen adsorbed at steps. On both (111) and stepped iridium crystal faces the adsorption of oxygen at room temperature produced a (2 × 1) surface structure. Two surface structures were found for CO adsorbed on Ir(111); a (√3 × √3)R30° at an exposure of 1.5–2.5 L and a (2√3 × 2√3)R30° at higher coverage. No indication for ordering of adsorbed CO was found on the Ir(S)-[6(111) × (100)] surface. No significant differences in thermal desorption spectra of CO were found on these two faces. H₂O is not adsorbed at 300 K on either iridium crystal face. The reaction of CO with O₂ was studied on Ir(111) and the results are discussed. The influence of steps on the adsorption behaviour of CO and O₂ on iridium and the correlation with the results found previously on the same platinum crystal faces are discussed.     

Chemisorption of nitrogen on platinum {111}: Reflection-absorption infrared spectroscopy

Reflection-absorption infrared spectroscopy has been combined with thermal desorption and surface coverage measurements to study nitrogen adsorption on a {111}-oriented platinum ribbon under ultrahigh vacuum conditions. Desorption spectra show a single peak (at 180 K) after adsorption at 120 K, giving a coverage-independent activation energy for desorption'of ～40 kJmol^?1. The initial sticking probability at this temperature is 0.15, and the maximum uptake was ～1.1 × 10¹⁴ molecule cm^?2. The adsorbed nitrogen was readily displaced by CO, h₂ and O₂. An infrared absorption band was observed with a peak located at 2238 ± 1 cm^?1, and a halfwidth of 9 cm^?1, with a molecular intensity comparable to that reported for CO on Pt{111}. The results are compared with data for chemisorption on other group VIII metals. An earlier assignment of infrared active nitrogen to B₅ sites on these metals is brought into question by the present results.     

Crystal face specificity of xenon adsorption on iridium field emitters

Fundamental problems of the adsorption of noble gas atoms on metal surfaces are discussed on the basis of new data of xenon adsorption on well-defined crystal faces of iridium. These data include surface potentials ( = changes in work function), heats of adsorption and their decrease with increasing coverage; they have been obtained by using a field emitter probe-hole assembly. It is found that the heat of adsorption Q_hkl is not simply additive in the number of Ir atoms contacting a Xe atom on a given site; in particular for the close-packed faces, Q₁₁₁ and Q₁₀₀ are relatively too high. Apparently, strong bonding is favoured by high work function of the adsorbing crystal face. This proves a significant contribution of a charge-transfer no-bond interaction to the adsorption bond. A model of Xe polarization by an electric surface field is rejected, as it predicts the wrong sign for the adsorption dipole. While at low coverage adsorption is confined to sites determined by the atomic topography of the adsorbing surface, several possibilities exist for high coverages. Either a two-dimensional close-packed layer is formed with little or no epitaxial relation to surface topography, or adsorption remains confined to certain sites. The present data favour the former possibility for atomically smooth faces in agreement with recent LEED results. For atomically rough faces however, the smallness of the decrease of Q_hkl with coverage seems to favour site adsorption even at high coverage. The latter result is of relevance for surface area determinations by means of “physical” adsorption.     

Adsorption of nitrogen on single crystal faces of iridium,studied by field emission microscopy

The adsorption of nitrogen on iridium was studied with a field emission microscope equipped with a probe-hole assembly to enable emission experiments on individual emitter regions. The adsorption of nitrogen is markedly face-specific. Temperature programmed desorption reveals three binding states: γ₁ on the (100) face with a maximum heat of adsorption of 7–8 kcal/mole, γ₂ on the regions around (110) with a maximum heat of adsorption of 10–11 kcal/mole and γ₃ on the roughest tip regions (210), (320), (531) and (731) with a maximum heat of adsorption of 13–14 kcal/mole. Nitrogen adsorbed in the γ₁ and γ₃ states causes a decrease, but in the γ₂ state a small increase, in the work function. These results are discussed in relation with data on nickel, palladium, platinum and rhodium. While nitrogen is only weakly adsorbed on all these metals there is a marked difference in the nature of the pertinent adsorption complex.     

Thermionic emission properties of hexaborides

Thermionic emission properties of the single crystal hexaborides LaB₆, CeB₆, PrB₆, NdB₆, SmB₆, EuB₆, (La, Sr)B₆, (La, Ba)B₆, (La, Ce)B₆, (La, Pr)B₆, (La, Sm)B₆, and (La, Dy)B₆ are measured in the temperature range between 1250 and 1700°C. Of these, LaB₆ is shown to have the highest emission current density in the temperature range investigated. The LaB₆-based mixed hexaborides, (La, M)B₆, show current densities similar to LaB₆, but a little lower. Analyses by Auger electron spectroscopy indicate that the surface composition of (La, M)B₆ approaches that of LaB₆ at elevated temperatures and that the thickness of the surface layer whose composition is different from that of the bulk is typically several atomic layers. The formation of the surface layer is considered to be caused by a relatively slow evaporation rate of La compared to that of the other metal.     

The decomposition of ammonia on the flat (111) and stepped (557) platinum crystal surfaces

Ammonia adsorption, desorption and decomposition to H₂ and N₂ has been studied on the flat (111) and stepped (557) single crystal faces of platinum using molecular beam surface scattering techniques. Both surfaces show significant adsorption with sticking coefficients on the order of unity. The stepped (557) surface is 16 times more reactive for decomposition of ammonia to N₂ and H₂ than the flat (111) surface. Kinetic parameters have been determined for the ammonia desorption process from the Pt(111) surface. The mechanism of ammonia decomposition on the (557) face of platinum has been investigated.     

Field emission study of ammonia adsorption and catalytic decomposition on individual molybdenum planes

A probe-hole field emission microscope was used to investigate the crystallographic specificity of ammonia adsorption at 200 and 300 K on (110), (100), (211) and (111) molybdenum crystal planes. Chemisorbed NH₃ causes a large work function decrease, especially at 200 K in agreement with an associative adsorption model which can also explain that this decrease is more important on the crystal planes of highest work function (At 200 K, Δφ = ?2.25 eV on Mo(110) compared to Δφ = ?1.55 eV on Mo (111). The decomposition of NH₃ was followed by measuring the work function changes for stepwise heating of the Mo tip covered with NH₃ at 200 K. On the four studied planes NH₃ decomposition and H₂ desorption are completed at about 400 K. Δφ changes above 400 K depend on the crystal plane and have been related to two different nitrogen surface states. No inactive plane towards NH₃ adsorption and decomposition has been found but the noted crystallographic anisotropy in this low pressure study is relevant to the structure sensitive character of the NH₃ decomposition and synthesis reactions.     

The adsorption of CO,O2, and H2 on Pt: II. Ultraviolet photoelectron spectroscopy studies

Ultraviolet photoelectron spectroscopy (UPS) has been used to study the chemisorption of CO, O₂, and H₂ on platinum. Three single crystal surfaces ((111), 6(111) × (100), and 6(111) × (111)) and two polycrystalline surfaces were studied. These studies yielded three important results. First, the most dominant change in the Pt valence band upon gas adsorption was a decrease in the height of the peak immediately below the Fermi level. This decrease was nearly identical for all three gases studied. Second, CO adsorption resulted in the formation of a resonance state ～8 eV below the Fermi level which was attributed to CO molecular orbitals. In contrast, no dominant resonance states were observed for adsorbed O or H. The lack of an O resonance state on platinum is in contrast to the results observed for O adsorbed on Fe and Ni and suggests important differences between the OPt chemisorption bond and the OFe and ONi chemisorption bonds. Finally, adsorption of CO at steps or defects led to a decrease in work function while its adsorption on terraces led to an increase in work function. For H, adsorption at steps led to an increase in work function while adsorption on terraces led to a decrease in work function. The adsorption of O led to an increase in work function on all of the surfaces studied.     

Molecular beam study of the apparent activation barrier associated with adsorption and desorption of hydrogen on copper

Molecular beam techniques are employed to study the adsorption and desorption of H₂ on the (100), (110), and stepped (310) crystal faces of copper. Each crystal is exposed simultaneously to a supersonic molecular beam of H₂ (energy variable from 1.6 to 10.7 kcal/mole) and a highly dissociated beam of deuterium. The majority of the H₂ molecules are scattered from the surface (i.e., are not adsorbed), while a portion of the remaining molecules adsorb dissociatively and react catalytically with adsorbed deuterium atoms to form HD molecules. These HD molecules desorb, and their angular distribution is measured by a rotatable mass spectrometer. For all three crystal faces, the distributions of desorbed HD deviate significantly from diffuse emission and are in excellent agreement with the results of our previous permeation study. From the dependence of the HD signal on the energy and incident angle of the H₂ beam, it appears that there are substantial energy barriers to adsorption, with these barriers depending on crystallographic orientation and acting essentially perpendicular to the surfaces. Both the energy dependence of the dissociative adsorption probability and the shapes of the HD angular distributions are nearly identical for the stepped (310) and (100) surfaces, thereby suggesting that ledge sites are not the principal regions responsible for adsorption of hydrogen on copper. The estimated adsorption probabilities versus energy are “S” shaped curves which appear to level off at values considerably less than unity. A comparison of our results with a very simple model with a single energy barrier to adsorption is qualitatively but not quantitatively satisfactory. An interpretation which includes a distribution of energy barriers is suggested.     

Photoluminescence study in Ce activated M6B5AlO15 (M = Sr,Ca, Ba) and mixed host aluminoborate phosphors

In this paper we report the modified solid state synthesis of Ce³⁺ activated Sr₆B₅AlO₁₅, Ca₆B₅AlO₁₅ Ba₆B₅AlO₁₅ and mixed host aluminoborate phosphors. The prepared phosphors were characterized by photoluminescence technique. The PL excitation spectra showed the excitation peaks ranging from 300 to 400 nm and emission spectra are observed in UV-blue region of spectrum and it varied for different hosts. This kind of emission is due to 4f⁶5d → 4f⁷ transition of Ce³⁺ ion. Further PLE and PL emission spectra for various compositions Ca₅Sr₁B₅AlO₁₅, Ca₄Sr₂B₅AlO₁₅, Ca₃Sr₃B₅AlO₁₅, Ca₂Sr₄B₅AlO₁₅, CaSr₅B₅AlO₁₅ are also taken which shows Ce³⁺ emission at 428 nm, 425 nm, 432 nm, 427 nm, 438 nm respectively. The calculated ²F_J (J = 7/2, 5/2) energy gap of Ce³⁺ in all hosts have been calculated and obtained values for Sr₆B₅AlO₁₅, Ba₆B₅AlO₁₅ phosphors are 1888 cm⁻¹ and 1330 cm⁻¹ respectively. PL emission spectra of mixed host aluminoborates have shown slight variations in positions of emission peaks.     

Exohedral chemical functionalization of C48B6N6 with NH3: Binding energies and electronic structures of C48B6N6–(NH3)n=1−6

Theoretical study of exohedral chemical functionalization of C₄₈B₆N₆ with NH₃ molecules has been investigated using DFT. It was found that NH₃ molecule can be chemically adsorbed on boron sites of C₄₈B₆N₆, with a charge transfer from NH₃ to C₄₈B₆N₆. Adsorption energy and the quantity of electron charge transfer from latest adsorbed ammonia to C₄₈B₆N₆ decreased with increasing in the adsorbed NH₃ molecules. Despite the strong adsorption energies, electronic properties of C₄₈B₆N₆ is preserved after modification(s) with NH₃ molecule(s) and chemical modification of C₄₈B₆N₆ with NH₃ molecules can be viewed as some kind of safe modification.     

Influence of the surface structure on the adsorption of hydrogen on platinum,as studied by field emission probe-hole microscopy

The adsorption of hydrogen on platinum was investigated with a field emission microscope, equipped with a probe-hole assembly to enable adsorption studies on individual emitter regions. Adsorption of hydrogen is markedly face-specific. At 95 K and a hydrogen equilibrium pressure smaller than 2 × 10^?9 Torr the work function decreased strongly on the (111) face but increased on the (110) and (210) regions. Three different adsorption states were observed: β-hydrogen which desorbed above 300 K, α-hydrogen which desorbed around 230 K and a very weakly bound γ-state with a maximum heat of adsorption of 6 $\text{kcal}\text{mole}$. The α- and γ-states caused a decrease, the β-state an increase of the work function. The results show that the relative contribution of these three states and their heat of adsorption depend strongly on the crystal face. The β-state appeared to be absent on a smooth (111) plane. Hydrogen bound in the αstate has a relatively high heat of adsorption on the (111) region. A model has been proposed for the nature of the sites on the different surfaces involved in the adsorption of hydrogen.     

The adsorption of activated nitrogen on platinum single crystal faces

The adsorption of activated nitrogen on a stepped Pt(S)-[9(111) × (111)] face was investigated by LEED, AES and flash desorption. Nitrogen was supplied to the crystal from a high frequency discharge tube. For comparison some orienting measurements were also carried out on smooth (111) and (100) platinum faces. Activated nitrogen is adsorbed at room temperature on all three faces up to about half a monolayer coverage. No additional LEED patterns indicating long range order of the adsorbed layer were found. By flash heating a small desorption peak at 120°C and a large peak between 175 and 230°C depending on the initial coverage were observed on the (111) type faces. The desorption can be described approximately by a second order rate law with an energy of activation of 25± 3 kcal/mole. No influence of surface steps on the properties of the adsorbed layer was detected. On the (100) face two coverage independent desorption maxima at 120 and 170°C of about equal intensities were found.     

Can bowl-like B30 nanostructure sense toxic cyanogen gas in air?: a theoretical study

In this work, an attempt has been made to study sensing performance of bowl-like B₃₀ nanostructure towards toxic cyanogen gas using density functional theory (DFT) at B97D/6-31+G(d) computational level. The results reveal that B₃₀ nanostructure is a proper sensor for sensing of toxic cyanogen gas. The most favourite adsorption site of B₃₀ is the exterior boron atoms that lead to the adsorption energy of ?78.48 (kJ/mol) with the remarkable change in electronic properties of B₃₀. The competitive sensing of cyanogen gas in the presence of water, oxygen and nitrogen molecules is also considered. Significant changes in the electronic properties of B₃₀ due to adsorption of cyanogen in presence of O₂, H₂O and N₂ gases enable it to be used in the detection of toxic cyanogen gas in air.     

Vibration spectroscopy of benzene adsorbed on Pt(111) and Ni(111)

High resolution electron energy loss spectroscopy has been applied to study the adsorption of benzene (C₆H₆ and C₆D₆) on Pt(111) and Ni(111) single crystal surfaces between 140 and 320 K. The vibrational spectra provide evidence that benzene is chemisorbed with its ring parallel to the surface, predominantly π bonded to the platinum and nickel surface respectively. A significant frequency increase of the CH-out-of-plane bending mode, largest in the case of platinum, is observed compared to the free molecule. On both metals two phases of benzene exist simultaneously, characterized by a different frequency shift. The shifts are explained by electronic interaction between the metal d-orbitals and molecules adsorbed in on top and threefold hollow sites respectively. The vibrational spectra of the multilayer condensed phase of benzene exhibit the infrared active modes of the gasphase molecule as expected.     

Emission and excitation spectra of Bi2Ge3O9:Eu3+

The emission and excitation spectra of the Bi₂Ge₃O₉:Eu crystal are observed at 77 K and 297 K. The spectra contain groups of sharp lines which are attributed to the transitions within 4f⁶ (Eu³⁺) configuration. The numbers of Stark splitting of terminal levels of transitions from ⁵D₀ and ⁷F₀ multiplets indicate that Eu³⁺ substitutes for Bi³⁺ in Bi₂Ge₃O₉. Tentative assignment of Stark levels of ⁷F_0-4 multiplets is made to crystal quantum numbers of C₃ symmetry which represents the site symmetry of Bi³⁺ in Bi₂Ge₃O₉. The following set of values of crystal field parameters of the C₃ point group is found to give the best overall agreement between the observed energy levels and the calculated levels: B²₀ = -533.84 cm^-1, B⁴₀ = 1085.99 cm^-1, Re(B⁴₃) = 327.57 cm^-1, Im(B⁴₃) = 75.209 cm^-1, B⁶₀ = 185.02 cm^-1, Re(B⁶₃) = - 68.475 cm^-1, Im(B⁶₃) = - 300.45 cm^-1, Re(B⁶₆) = 137.24 cm^-1 and Im(B⁶₆) = 882.29 cm^-1.     

掺Bi钨酸镉单晶体发光特性的研究

用坩埚下降法(Bridgman)生长出了Bi离子掺杂的CdWO₄单晶.测定了晶体不同部位的吸收光谱、发射光谱和X射线电子能谱(XPS).Bi离子的掺入引起CdWO₄晶体的吸收边从345 nm红移到399 nm.在311 nm, 373 nm,808 nm和980 nm光的激发下,分别观测到中心波长为470 nm,528 nm,1078 nm和较弱的1504 nm四个不同发射带.Bi:CdWO₄单晶的XPS谱分别与Bi₂ 关键词： Bi离子 荧光光谱 X射线电子能谱 4单晶')" href="#">CdWO₄单晶     

The role of adsorbed sulfur in the H2D2 equilibration reaction on Pt single crystals

The H₂D₂ equilibration on Pt single crystals was investigated under intermediate pressure (100–400 Torr) and temperature (50–250°C), as a function of sulfur coverage. On Pt(110) and Pt(111), adsorbed sulfur modifies the kinetic parameters, activation energy and pre-exponential factor; the latter depends on the temperature on Pt(110) only. The clean Pt(110) face was found to be 5 times more active than the clean Pt(111). On both faces, adsorption of sulfur induces electronic effects on the neighbouring reactional sites. The difference in the behaviour of the two faces and a clear influence of the arrangement of the adsorbed sulfur atoms, deduced from LEED diagrams, tend to prove the structure dependency of the H₂D₂ reaction. A consistent reaction mechanism could be proposed, involving the dissociative adsorption and surface recombination of hydrogen and deuterium, and the reaction between adsorbed molecules for high sulfur coverages. The value of the sulfur coverage which makes the platinum inactive towards H₂D₂ is lower for the (111) than for the (110) orientation; this is in correlation with the roughness of the surface; the denser at atomic scale a surface is, the further is the extent of the lateral interactions due to adsorbed sulfur.     

LEED,AES and thermal desorption studies of chemisorbed Hydrogen and hydrocarbons (C2H2, C2H4, C6H6, C6H12) on the (111) and stepped [6(111) × (100)] iridium crystal surfaces; comparison with platinum

The adsorption of hydrogen, ethylene, acetylene, cyclohexane and benzene was studied on both the (111) and stepped [6(111) × (100)] crystal surfaces of iridium. The techniques used were low energy electron diffraction, Auger electron spectroscopy, and thermal desorption mass spectrometry. At 30°C, acetylene, ethylene and benzene are adsorbed with a sticking probability near unity. The sticking probability of cyclohexane is less than 0.1 on both surfaces. Heating the (111) surface above 800°C, in the presence of the hydrocarbons, results in the formation of an ordered carbonaceous overlayer with a diffraction pattern corresponding to a (9 × 9) surface structure. No indication for ordering of the carbonaceous residue was found on the stepped iridium surface in these experimental conditions. The hydrocarbon molecules form only poorly ordered surface structures on both iridium surfaces when the adsorption is carried out at 30°C. Benzene is the only gas that can be desorbed from the surfaces in large amounts by heating. Ethylene remains largely on the surface, only a few percent is removed by heating while acetylene and cyclohexane cannot be desorbed at all. When adsorption is carried out at 30°C and the crystal is subsequently flashed to high temperature, hydrogen is liberated from the surface. The hydrogen desorption spectra from the iridium surfaces exposed to C₂H₄, C₂H₂, or C₆H₆ exhibit two hydrogen desorption peaks, one around 200°C and the second around 350°C. The temperatures where these peaks appear vary slightly with the type of hydrocarbon. The relative intensities of these two peaks depend strongly on the surface used. Arguments are presented that decomposition of the hydrocarbon molecules (C-H bond breaking nd possibly also C-C bond breaking) occurs easier on the stepped iridium surface than on the (111) surface. Hydrogen is desorbed at a higher temperature from an iridium surface possessing a high density of surface imperfections than from a perfect iridium (111) surface. The results are compared with those obtained previously on similar crystal surfaces of platinum. It appears that C-H bond breaking occurs more easily on iridium than on platinum.     

Site-specific interaction of H2O with ZnO single-crystal surfaces studied by thermal desorption and UV photoelectron spectroscopy

The adsorption and condensation of H₂O(D₂O) on ZnO(101̄0), (0001)Zn and (0001̄)O surfaces was investigated by means of thermal desorption (TDS) and UV photoelectron spectroscopy (UPS). The clean ZnO single-crystal surfaces were prepared by Ar-ion sputtering and annealing and characterised by Auger electron spectroscopy, LEED, UPS and work-function measurements. On all three surfaces six different adsorption states were found. In the monolayer regime there is a stronger bonding to Zn sites (desorption temperature 340 K) than to O sites (190 K), The bonding to the Zn sites seems to be accompanied by some clustering. Before the chemisorption layer is completed a first ice state is found whose desorption temperature shifts from 162 to 168 K with increasing exposures. At higher exposures the multilayer ice state is found at 152 K. On the (0001̄)O face defect-induced features were identified. The water lone-pair orbital 1b₁, whose energy falls between the O p and the Zn 3d emission of the substrate and which is known to show bonding shifts, was analysed using angle-resolved UPS. In the monolayer, the main chemisorption states are found at E_B^V(1b₁) = ?9.6 eV for the (0001)Zn face and at ? 10.6 eV for the (0001̄)O face and are compared with the multilayer ice emission at 1̄1.1 eV. The difference in binding energies shows the same trend as the TDS data. For the (101̄0) face the 1b₁ emission is very broad, indicating some overlap between different states.