Alkali Promoters on Metal Surfaces

Potassium is a well-known promoter in the ammonia synthesis and the Fischer-Tropsch synthesis, where it is thought to assist the dissociation of the reactants, 

N2 and CO, respectively [31,32], Empirical knowledge about the promoting effect of many elements has been available since the development of the iron ammonia synthesis catalyst, for which some 8000 different catalyst formulations were tested. Recent research in surface science and theoretical chemistry has led to a fairly complete understanding of how a promoter works [33,34], 

Promoters are generally divided in two classes. Structural promoters help to stabilize certain surface structures of the catalyst, or to prevent sintering. Structural promoters are not involved in the catalytic reaction itself and have no interaction with the reacting species. Chemical promoters, on the other hand, directly influence the reacting species on the surface of the catalyst. Obviously, alkali promoters fall into the latter category. 

The fact that evaporated potassium arrives at the surface as a neutral atom, whereas in real life it is applied as KOH, is not a real drawback, because atomically dispersed potassium is almost a K+ ion. The reason is that alkali metals have a low ionization potential (see Table A.3). Consequently, they tend to charge positively on many metal surfaces, as explained in the Appendix. A density-of-state calculation of a potassium atom adsorbed on the model metal jellium (see Appendix) reveals that the 4s orbital of adsorbed K, occupied with one electron in the free atom, falls largely above the Fermi level of the metal, such that it is about 80% empty. Thus adsorbed potassium is present as K, with 8close to one [35]. Calculations with a more realistic substrate such as nickel show a similar result. The K 4s orbital shifts largely above the Fermi level of the substrate and potassium becomes positive [36], Table 9.2 shows the charge of K on several metals. 

Experimental confirmation that alkali adsorbates form positive ions on metallic 

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Supported Rhodium Catalysts Alkali Promoters on Metal Surfaces Cobalt-Molybdenum Sulfide Hydrodesulfurization Catalysts Chromium Oxide Polymerization Catalysts... 

Supported rhodium catalysts Alkali promoters on metal surfaces... 

The effect of alkali presence on the adsorption of oxygen on metal surfaces has been extensively studied in the literature, as alkali promoters are used in catalytic reactions of technological interest where oxygen participates either directly as a reactant (e.g. ethylene epoxidation on silver) or as an intermediate (e.g. NO+CO reaction in automotive exhaust catalytic converters). A large number of model studies has addressed the oxygen interaction with alkali modified single crystal surfaces of Ag, Cu, Pt, Pd, Ni, Ru, Fe, Mo, W and Au.6... 

The effect of the presence of alkali promoters on ethylene adsorption on single crystal metal surfaces has been studied in the case ofPt (111).74 77 The same effect has been also studied for C6H6 and C4H8 on K-covered Pt(l 11).78,79 As ethylene and other unsaturated hydrocarbon molecules show net n- or o-donor behavior it is expected that alkalis will inhibit their adsorption on metal surfaces. The requirement of two free neighboring Pt atoms for adsorption of ethylene in the di-o state is also expected to allow for geometric (steric) hindrance of ethylene adsorption at high alkali coverages. 

It is obvious that one can use the basic ideas concerning the effect of alkali promoters on hydrogen and CO chemisorption (section 2.5.1) to explain their effect on the catalytic activity and selectivity of the CO hydrogenation reaction. For typical methanation catalysts, such as Ni, where the selectivity to CH4 can be as high as 95% or higher (at 500 to 550 K), the modification of the catalyst by alkali metals increases the rate of heavier hydrocarbon production and decreases the rate of methane formation.128 Promotion in this way makes the alkali promoted nickel surface to behave like an unpromoted iron surface for this catalytic action. The same behavior has been observed in model studies of the methanation reaction on Ni single crystals.129... 

The rate constants in table 4 for Ru/AlaOs should be considered as initial rate constants since it was not possible to achieve a higher coverage of N— than 0.25. Furthennorc, it was not possible to detect TPA peaks for Ru/AlaOs within the experimental detection limit of about 20 ppm. Ru/MgO is a heterogeneous system with respect to the adsorption and desorption of Na due to the presence of promoted active sites which dominate under NH3 synthesis conditions. The rate constant of desorption given in table 4 for Ru/MgO refers to the unpromoted sites [19]. The Na TPD, Na TPA and lER results thus demonstrate the enhancing influence of the alkali promoter on the rate of N3 dissociation and recombination as expected based on the principle of microscopic reversibility. Adding alkali renders the Ru metal surfaces more uniform towards the interaction with Na. 

One further example of a structural study of CO adsorption on Ni relates to the rather general issue of the role of coadsorbed CO and alkali metals on metal surfaces. Alkali atoms are known to be promoters of certain catalytic processes, improving turnover rates and/or selectivity in certain reactions, and are used as additives in some commercial catalysts. Indeed, in the specific case of CO on Ni, it... 

To determine the effect of alkali-metal promotion on the surface morphology, the catalysts were investigated by IR spectroscopy.9 DRIFT spectra revealed two intense reflectance bands at 760-680 cm-1 and 650-570 cm-1 for the sodium promoted sample. Moreover, an absorption band at 535 cm, which has previously been assigned to PdC>3,28 was observable in the DRIFT spectra of oxidized Na-PdO/Sn02. 

Abstract Metal-carbonyl bonds, as found for carbon monoxide either liganded to metalloporphyrins or chemisorbed onto metal surfaces, are discussed. These two classes of systems are compared with emphasis on short range vs. long range perturbations of the vibrational bands, and Vcq. It is concluded that metalloporphyrins serve as models for terminal bondi on metal surfaces and that data obtained for carbonyl-hemes enable the isolation of non-local electronic effects, which are much discussed in connection with alkali promoters coadsorbed with CO on metal catalysts. 

Non-metallic impurities in liquid alkali metals play a major role in the corrosion of materials either by affecting metal solubilities, f orming spalli-ble corrosion products on the metal surface, promoting liquid metal embrittlement or bulk embrittlement of the surface or by sensitising the structure for further attack by other impurities e.g. O2. As in other corrosive environments the direction and magnitude of these impurity reactions... 

Alkalis are the most important electropositive promoters of metal and metal oxide catalysts. They are used in many important industrial catalysts but are also quite suitable for fundamental studies since they can be easily introduced under vacuum conditions on well-characterized model metal surfaces. 

The last point is confirmed by measuring the work function changes upon CO chemisorption on clean and alkali-promoted metal surfaces. Figures 2.16 and 2.17 show the work function changes induced by CO adsorption on a K/Pt(lll) and on a Na/Ru(1010) surface respectively, for various alkali... 

The alkali promotion of CO dissociation is substrate-specific, in the sense that it has been observed only for a restricted number of substrates where CO does not dissociate on the clean surface, specifically on Na, K, Cs/Ni( 100),38,47,48 Na/Rh49 and K, Na/Al(100).43 This implies that the reactivity of the clean metal surface for CO dissociation plays a dominant role. The alkali induced increase in the heat of CO adsorption (not higher than 60 kJ/mol)50 and the decrease in the activation energy for dissociation of the molecular state (on the order of 30 kJ/mol)51 are usually not sufficient to induce dissociative adsorption of CO on surfaces which strongly favor molecular adsorption (e. g. Pd or Pt). 

J. Paul, and F.M. Hoffmann, Alkali promoted CO bond weakening on aluminum A comparison with transition metal surfaces,/. Chem Phys. 86(9), 5188-5195 (1987). 

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