Reflection-absorption infrared and thermal desorption studies of carbon monoxide and hydrogen adsorbed on rhodium

Reflection-absorption infrared spectroscopic and thermal desorption techniques have been used to study the interaction of mixtures of carbon monoxide and hydrogen with evaporated rhodium films. For equimolar mixtures near 10^?9 Torr, hydrogen adsorbed much more rapidly, but long exposure times or increases in CO pressures to 10^?6 Torr led to its partial, but never complete, displacement by adsorbed carbon monoxide. Hydrogen desorption spectra taken during the displacement process showed two peaks which was consistent with a cooperative interaction between adsorbed CO and H species. In contrast to previous transmission studies of CO adsorption on small rhodium particles, the present reflection—absorption infrared study of the film system showed a single absorption band at 2075 ±10 cm^?1. While explanations for the discrepancy in terms of particle size effects are possible it is considered more likely that all CO molecules are linearly bound to individual Rh atoms in the present situation. In our work, increases in CO pressure (especially above 10^?6 Torr) were accompanied by an upward frequency shift (from 2065 cm^?1 to 2085 cm^?1) and a narrowing in half width (from 25 to 17 cm^?1). Several possible explanations for the latter unusual effect are discussed.     

Frequency shifts in the spectra of molecules adsorbed on metals,with emphasis on the infrared spectrum of adsorbed CO

Two processes are considered which cause the frequency of the band maximum in the infrared absorption spectrum of molecules adsorbed on metals to shift with increasing coverage. The first arises from the coverage-dependent modification of the local field acting on an adsorbed molecule while the second originates from vibrational coupling arising from a through-metal interaction between molecules adsorbed on different metal atoms. Infrared absorption strengths are discussed and the method used heretofore to obtain the extinction coefficients of adsorbed molecules is questioned. In particular, a factor of 2 which results from the constructive superposition of the incident and reflected electric fields is shown to be often ignored. We show that dipolar (through-space) coupling is too weak to account for the magnitudes of the shifts recently observed for CO on single-crystal Pt and Pd as coverage progressed from low to high values. Vibrational coupling is also shown to account for the disparity in the intensities of the two bands observed when ¹²CO and ¹³CO are coadsorbed on supported metals. Similar experiments on single-crystal surfaces are suggested to help determine to what extent the observed spectral frequency shifts are derived from adsorbate—adsorbate coupling as opposed to other mechanisms.     

A photoelectron study of palladium,nickel, and copper clusters on carbon surfaces

Ultraviolet photoelectron spectra show that even at the threshold of detectability, Pd, Ni, and Cu atoms deposited on the basal plane of cleaved graphite nucleate into clusters sufficiently large to exhibit valence band and core binding energies characteristics of bulk metals. However at very low coverage of these metals on amorphous carbon, the spectra show that the valence d-bands have decreased widths and larger binding energies than the bulk metals. Core binding energies show a similar increase at very low coverage. These effects occur because at low coverage on amorphous carbon these metals are present as isolated adatoms.     

Experimental development of reflection-absorption spectroscopy: Infrared spectrum of carbon monoxide adsorbed on copper and copper oxide

The reflection-adsorption technique is used to obtain the infrared spectrum of a monolayer or less of carbon monoxide adsorbed on an evaporated copper film. The band is located at 2105 cm⁻¹ and is obtained with a signal-to-noise ratio in the range 5 to 15. In this technique, the infrared beam is multiply reflected between two closely-spaced parallel metal surfaces covered with the adsorbed layer. The CO band is used to investigate the dependence of the signal-to-noise ratio on the spacing of the metal surfaces. The existence of an optimum value of the spacing is demonstrated. The contribution to the absorption band of infrared rays with different angles of incidence is investigated and explained in terms of an optimum number of reflections and its variations with angle of incidence. After the copper surface is progressively exposed to oxygen, a slight shifting of the CO band to 2113 cm⁻¹ is observed. Further exposure gives rise to a new band of adsorbed CO at 2135 cm⁻¹, interpreted as CO adsorbed on copper oxide.     

A photoemission and thermal desorption study of carbon monoxide and oxygen adsorbed on platinum

We have studied the changes in the photoelectron spectra of platinum (for photon energies of 21.2 and ? 10.2 eV), in conjunction with thermal desorption experiments, for coverages of carbon monoxide and oxygen of up to ~0.25 monolayer (saturation coverage at room temperature). Based on a comparison of the photoemission and thermal desorption results, we suggest that the less tightly bound of the two adsorption states observed in the thermal desorption data is due to adsorbate-adsorbate interactions. We further suggest that a relatively delocalized chemisorption bond plays an important role in this interaction.     

Coadsorption of carbon monoxide and hydrogen on polycrystalline rhodium

The coadsorption of carbon monoxide and hydrogen on polycrystalline rhodium filament has been studied by thermal desorption mass spectrometry. From a series of thermal desorption spectra of CO and H₂ from rhodium as a function of the exposure time to the gas mixture of CO and H₂, it is indicated that there are a single broad peak for CO and three peaks designated as β₁, β₂, β₃ for hydrogen. Thermal desorption of hydrogen is complex. CO and β₁-hydrogen coadsorb on the rhodium surface with their partial pressures in the initial stage of the exposure to the gas mixture and then the β₁ -hydrogen adsorbed on the surface is replaced by CO with the further exposure time. The kinetics for the replacement of β₁-hydrogen by CO may be discussed from the standpoint of the L-H reaction process. The β₂-and β₃-hydrogen are observed with a longer exposure time after the elimination of β₁ -hydrogen. It may be suggested that the β₃-hydrogen peak is attributed to the desorption of hydrogen absorbed in the bulk. The nature of β₂ -hydrogen is also briefly mentioned in possible implications.     

Chemisorption and dissociation of carbon monoxide on rhodium surfaces

The adsorption, desorption and decomposition of CO on Rh surfaces have been investigated using field emission microscopy and thermal desorption spectroscopy. Thermal dissociation of CO cannot be detected on clean Rh surfaces at pressures up to 10^?1 Torr and temperatures below 1000 K. This holds also for atomically rough surfaces like (210). CO dissociation can be promoted under the influence of an electron beam directed to the surface, a high electric field in the presence of CO in the gas phase and by means of discharge techniques. The growth of crystallites formed by CO dissociation and the diffusion of carbon into the bulk has been followed as a function of temperature and surface structure. The tip regions around (110) are very active in these processes. Carbon crystallites on these surfaces disappear around 1000 K by diffusion into the lattice whereas crystallites present around (311) surfaces persist up to 1150 K. The results are discussed in relation to the activity of Rh in CO/H₂ reactions.     

Angular resolved studies of the photoemission bands from carbon monoxide adsorbed on palladium single crystals,and the assignment of these bands

The photoemission from CO adsorbed on a Pd(111) surface has been studied as a function of electron exit angle and of photon incidence angle; some studies have also been made using Pd(100) and Pd(110). The variations of intensity of the two photoemission bands support the sequence of levels 1π > 5θ ? 4θ for adsorbed CO. The adsorption on some other metals is discussed briefly.     

Adsorption-desorption kinetics of carbon monoxide on rhodium polycrystalline surfaces

Adsorption isotherms, the absolute adsorption rate, and the absolute desorption rate of carbon monoxide on rhodium polycrystalline surfaces were measured in the same manner as in our previous work on palladium. The absolute adsorption rate was proportional to pressure, independent of temperature and was a slightly non-linear function of the coverage of CO. The absolute desorption rate was proportional to the coverage and was an increasing function of temperature and pressure. These results are similar to those of palladium.     

In situ infrared spectroelectrochemical studies of cyanide adsorbed on platinum and palladium

In situ FTIR difference spectra of adsorbed cyanide on polished platinum and palladium electrodes in perchlorate media are presented. A linear CN⁻_ads moiety is observed on Pt, while on Pd four surface cyanide species are seen: linear and bridge-bound CN⁻_ads, as well as two surface Pd-CN films.     

A RHEED study of oxygen adsorbed on copper

The effect of oxygen adsorption on various clean, stepped copper surfaces at 300°C was examined by the use of Reflection High Energy Electron Diffraction (RHEED). The stability of a few high index planes is considered and the idea of this enhanced stability being due to a “fit” between the adsorption structure and the terrace width was extended. The interpretation of RHEED patterns from faceted surfaces was discussed so as to account for such features as the curving of the rods and the apparent existence of extra rods.     

利用红外光谱吸收原理的CO浓度测量装置研究

介绍了一种基于红外光谱吸收原理 ,利用钽酸锂热释电探测器实现一氧化碳浓度测量的装置。该装置主要由探测器系统、信号放大与处理系统及显示报警系统三部分组成。介绍了该装置的工作原理、基本结构及主要技术指标。讨论了其中的技术难点及其相应的解决方法。     

Transformation of auger electron spectra of ytterbium nanofilms under the action of adsorbed carbon monoxide and oxygen molecules

The transformation of the Auger electron spectra of ytterbium nanofilms as a result of chemisorption of CO and O₂ molecules on their surface has been studied. It has been shown that the adsorption of these molecules is accompanied by a radical transformation of the electronic structure of nanofilms, during which the 5d level of ytterbium drops below the Fermi level. As a consequence, one electron can transfer from the 4f level to the 5d level. In turn, this provides the conditions for a giant resonance 4d → 4f and a subsequent Coster-Kronig supertransition 4d ⁹4f ¹⁴ → 4d ¹⁰4f ¹² + Auger electron, which is accompanied by emission of one 4f electron to vacuum. The results obtained have demonstrated that molecules chemisorbed on the surface of nanofilms can cause qualitative changes in the properties of the surface and in the bulk of these films. It is obvious that this offers a means for designing nanoobjects with controlled properties.     

Adsorption of carbon monoxide on silver/palladium alloys

The adsorption of carbon monoxide on epitaxial (100) and (111) planes of Ag/Pd alloys with definite surface compositions has been studied by means of LEED, Auger electron spectroscopy and work function measurements. The formation of ordered adsorbed structures is prevented by even small amounts of silver in the surfaces. The maximum variation of the work function with CO adsorption bears no simple relationship to the surface composition. From measured adsorption isotherms the isosteric heats of adsorption have been evaluated. For CO adsorption on pure Pd planes the adsorption energies E_ad are either constant or decrease slowly up to high coverages, whereas a continuous decrease was observed with the alloys indicating the energetical heterogeneity. The results are discussed on the basis of our knowledge about the nature of the CO chemisorption and about the electronic structure of Ag/Pd alloys.     

A reflection-absorption infrared study of carbon monoxide and nitric oxide adsorption on platinum (100)

The adsorption of NO, CO, and NO/CO mixtures, onto Pt(100), is studied by RAIRS. CO and NO are found to adsorb into islands at 300 K, but the islands breakup upon heating to 400 K. Dosing with a mixture of NO and CO at temperatures below 325 K is found to produce a mixed NO/CO island. There is a shift in the CO peak and NO peak during mixed island formation which is attributed to a strong chemical interaction between the adsorbed NO and CO. This interaction is found to produce an increase in the desorption temperature of CO. Autocatalytic behavior is found to arise because of an enhanced reactivity when CO enters a mobile state. The autocatalytic behavior could be responsible for the “surface explosion” reported by Lesly and Schmidt.     

All-welded low-temperature vacuum vessel for the study of infrared spectra of solids and adsorbed molecules

Journal of Applied Spectroscopy -     

Theory of carbon monoxide chemisorption on transition metals

An Anderson formalism including overlap is used to treat the chemisorption of carbon monoxide on the transition metals Cu, Ni and Pd. According to the generally accepted scheme only coupling of the 2π¹- and 5σ-orbitals of CO to the metallic d-states is regarded. The wave functions of the metal surface are approximated by a linear combination of atomic d-orbitals, which are oriented in such a manner that maximum overlap with the 2π¹-orbital of CO is achieved. The error involved in this procedure is absorbed into the only adjustable parameter B. Predictions are made for the electronic structure, i.e. the chemisorption levels and occupation numbers. Comparison with results of photoelectron spectroscopy, energy loss spectroscopy and infrared experiments is encouraging. The variation of adsorption energy with geometric location, crystallographic orientation and nature of the substrate metal is extensively treated and compared with experiment. It was possible for example to predict correctly the structure models derived from LEED data and the changes in adsorption energy associated with structural modifications due to varying coverage.     

Coupled harmonic oscillator models of carbon monoxide adsorbed on stepped,platinum surfaces

Harmonic oscillator models are used to explain recent experimental data on infrared absorption by CO molecules adsorbed on two stepped platinum surfaces. These data reveal only a lower frequency band at low coverage and only a higher frequency band at high coverage. Both bands exist over a range of intermediate coverages. The data are explained by a coupled-dipole model which includes the effects of electronic polarizability, the tilted orientation of CO molecules at step sites, and the electric field enhancement at step sites. The lower-frequency band is associated with CO molecules adsorbed on step sites and the higher-frequency band is associated with two-dimensional islands consisting of both step and terrace CO. The model explains the observed variation of frequency and intensity with coverage for CO adsorption on Pt(533) and Pt(432) surfaces. The model calculations indicate that the wavenumber for a single, linearly bonded CO molecule is about 9 cm⁻¹ higher on a terrace site than on a step site.