Adsorbent emission

While field ion microscopy has provided an effective means to visualize surface atoms and adsorbates, field emission is the preferred technique for measurement of the energetic properties of the surface. The effect of an applied field on the rate of electron emission was described by Fowler and Nordheim [65] and is shown schematically in Fig. Vlll 5. In the absence of a field, a barrier corresponding to the thermionic work function, prevents electrons from escaping from the Fermi level. An applied field, reduces this barrier to 4> - F, where the potential V decreases linearly with distance according to V = xF. Quantum-mechanical tunneling is now possible through this finite barrier, and the solufion for an electron in a finite potential box gives... 

Measuring the electron emission intensity from a particular atom as a function of V provides the work function for that atom its change in the presence of an adsorbate can also be measured. For example, the work function for the (100) plane of tungsten decreases from 4.71 to 4.21 V on adsorption of nitrogen. For more details, see Refs. 66 and 67 and Chapter XVII. Information about the surface tensions of various crystal planes can also be obtained by observing the development of facets in field ion microscopy [68]. 

IRE Infrared emission [110] Infrared emission from a metal surface is affected in angular distribution by adsorbed species Orientation of adsorbed molecules... 

OSEE Optically stimulated exoelectron emission [143] Light falling on a surface in a potential held produces electron emission Presence and nature of adsorbates... 

Surface heterogeneity may be inferred from emission studies such as those studies by de Schrijver and co-workers on P and on R adsorbed on clay minerals [197,198]. In the case of adsorbed pyrene and its derivatives, there is considerable evidence for surface mobility (on clays, metal oxides, sulfides), as from the work of Thomas [199], de Mayo and co-workers [200], Singer [201] and Stahlberg et al. [202]. There has also been evidence for ground-state bimolecular association of adsorbed pyrene [66,203]. The sensitivity of pyrene to the polarity of its environment allows its use as a probe of surface polarity [204,205]. Pyrene or ofter emitters may be used as probes to study the structure of an adsorbate film, as in the case of Triton X-100 on silica [206], sodium dodecyl sulfate at the alumina surface [207] and hexadecyltrimethylammonium chloride adsorbed onto silver electrodes from water and dimethylformamide [208]. In all cases progressive structural changes were concluded to occur with increasing surfactant adsorption. 

Many of the adsorbents used have rough surfaces they may consist of clusters of very small particles, for example. It appears that the concept of self-similarity or fractal geometry (see Section VII-4C) may be applicable [210,211]. In the case of quenching of emission by a coadsorbed species, Q, some fraction of Q may be hidden from the emitter if Q is a small molecule that can fit into surface regions not accessible to the emitter [211]. 

The ESDIAD pattern does, however, provide very usefril infomiation on the nature and synnnetry of an adsorbate. As an example, figure A1.7.13(a) shows the ESDIAD pattern of desorbed collected from a 0.25 ML coverage of PF on Ru(OOOl) [89]. The pattern displays a ring of emission, which indicates that the molecule adsorbs intact and is bonded tlirough the P end. It freely rotates about the P-Ru bond so that tlie emission occurs at all azimuthal angles, regardless of the substrate structure. In figure A1.7.13(b), the... 

Ultraviolet photoelectron spectroscopy (UPS) results have provided detailed infomiation about CO adsorption on many surfaces. Figure A3.10.24 shows UPS results for CO adsorption on Pd(l 10) [58] that are representative of molecular CO adsorption on platinum surfaces. The difference result in (c) between the clean surface and the CO-covered surface shows a strong negative feature just below the Femii level ( p), and two positive features at 8 and 11 eV below E. The negative feature is due to suppression of emission from the metal d states as a result of an anti-resonance phenomenon. The positive features can be attributed to the 4a molecular orbital of CO and the overlap of tire 5a and 1 k molecular orbitals. The observation of features due to CO molecular orbitals clearly indicates that CO molecularly adsorbs. The overlap of the 5a and 1 ti levels is caused by a stabilization of the 5 a molecular orbital as a consequence of fomiing the surface-CO chemisorption bond. 

One interesting new field in the area of optical spectroscopy is near-field scaiming optical microscopy, a teclmique that allows for the imaging of surfaces down to sub-micron resolution and for the detection and characterization of single molecules [, M]- Wlien applied to the study of surfaces, this approach is capable of identifying individual adsorbates, as in the case of oxazine molecules dispersed on a polymer film, illustrated in figure Bl.22,11 [82], Absorption and emission spectra of individual molecules can be obtamed with this teclmique as well, and time-dependent measurements can be used to follow the dynamics of surface processes. 

Spectroscopy is basically an experimental subject and is concerned with the absorption, emission or scattering of electromagnetic radiation by atoms or molecules. As we shall see in Chapter 3, electromagnetic radiation covers a wide wavelength range, from radio waves to y-rays, and the atoms or molecules may be in the gas, liquid or solid phase or, of great importance in surface chemistry, adsorbed on a solid surface. 

Applications. Both industrial emissions reduction and indoor air-poUution abatement uses will grow. For example, the development of adsorbents with higher capacity for removal of radon from humid air could allow the development of a one-bed, delay-for-decay system in which radon adsorbs, decays to lead, and is precipitated onto the adsorbent. 

A U.S. EPA study (41) showed that soil vapor extraction (SVE) is an effective treatment for removing volatile contaminants from the vadose zone. Sandy soils are more effectively treated than clay or soils with higher organic content because higher air flows are possible in sand and clays—organic soils tend to adsorb or retain more contaminants. Removal of volatiles is rapid in the initial phase of treatment and thereafter decreases rapidly thereafter-an important consideration in the design of air emissions control over the life of the project. 

B. H. Engler and co-workers. Reduction of Exhaust Gas Emission by Using IPydrocarbon Adsorber Systems, SAE 930738, Society of Automotive Engineers, Warrendale, Pa., 1993. 

Once an undesirable material is created, the most widely used approach to exhaust emission control is the appHcation of add-on control devices (6). Eor organic vapors, these devices can be one of two types, combustion or capture. AppHcable combustion devices include thermal iaciaerators (qv), ie, rotary kilns, Hquid injection combusters, fixed hearths, and uidi2ed-bed combustors catalytic oxidi2ation devices flares or boilers/process heaters. Primary appHcable capture devices include condensers, adsorbers, and absorbers, although such techniques as precipitation and membrane filtration ate finding increased appHcation. A comparison of the primary control alternatives is shown in Table 1 (see also Absorption Adsorption Membrane technology). 

Gaseous and particulate pollutants are withdrawn isoldnetically from an emission source and collected in a multicomponent sampling train. Principal components of the train include a high-efficiency glass- or quartz-fiber filter and a packed bed of porous polymeric adsorbent resin (typically XAD-2 or polyurethane foam for PCBs). The filter is used to collect organic-laden particulate materials and the porous polymeric resin to adsorb semivolatile organic species (com-... 

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