Hydrogen on transition metals

Karlberg GS. 2006. Adsorption trends for water, hydroxyl, oxygen, and hydrogen on transition-metal and platinum-skin surfaces. Phys Rev B 74 153414. 

Comparison of the oxidation rates of carbon monoxide and hydrogen on transition metal carbides indicates that there is parallelism between both (Figure 16.1). It was found that the reactivity of hydrogen was higher than that of CO. This could be due to the formation mobile, reactive hydrogen atoms from hydrogen activation. 

Chemisorption measurements of either CO or hydrogen on transition metals mounted on zeolite substrates require considerable care for adequate interpretation. The zeolite lattices after high-temperature evacuation can adsorb large amounts of hydrogen, and divalent cations such as calcium can adsorb large amounts of CO. 

Figures 1 Specular and off-specular HREELS spectra of H adsorbed on Pd(100). The perpendicular mode is at 63 meV. The parallel mode is at 76 meV. Reprinted from Surface Science, 178, M.E. Kordesch, Surface resonances in vibrational spectroscopy of hydrogen on transition metal surfaces Pd(IOO) and Pd(111), 578-588,1986, with permission from Elsevier Science.

Figures 17 Surface reflectivity of Pd(111) and Pd(IOO) with and without adsorbed H. The reflectivity is on log scale. The addition of hydrogen shifts and intensifies the lowest energy surface resonance on Pd(111) (5.5 eV). The sharp drop in reflectivity at 8 eV corresponds to the emergence of a surface diffraction beam, and opens a new channel for electron interaction with the surface. The image potential states are just below this emergence threshold. On Pd(IOO) the curves are similar, but the energy scale is reduced due to the different crystal structure of the surface and different-sized surface Brillouin Zone. Reprinted from Surface Science, 178, M.E. Kordesch, Surface resonances in vibrational spectroscopy of hydrogen on transition metal surfaces Pd(IOO) and Pd(111), 578-588, 1986, with permission from Elsevier Science.

Hydrogen gas chemisorbs on the surface of many metals in an important step for many catalytic reactions. A method for estimating the heat of hydrogen chemisorption on transition metals has been developed (67). These values and metal—hydrogen bond energies for 21 transition metals are available (67). 

Fig. 5(a) contains the oxygen and hydrogen density profiles it demonstrates clearly the major differences between the water structure next to a metal surface and near a free or nonpolar surface (compare to Fig. 3). Due to the significant adsorption energy of water on transition metal surfaces (typically of the order of 20-50kJmoP see, e.g., [136]), strong density oscillations are observed next to the metal. Between three and four water layers have also been identified in most simulations near uncharged metal surfaces, depending on the model and on statistical accuracy. Beyond about...

The mechanism of the poisoning effect of nickel or palladium (and other metal) hydrides may be explained, generally, in terms of the electronic theory of catalysis on transition metals. Hydrogen when forming a hydride phase fills the empty energy levels in the nickel or palladium (or alloys) d band with its Is electron. In consequence the initially d transition metal transforms into an s-p metal and loses its great ability to chemisorb and properly activate catalytically the reactants involved. 

The Mechanism of the Hydrogenation of Unsaturated Hydrocarbons on Transition Metal Catalysts G. C. Bond and P. B. Wells... 

Stereochemistry and Mechanism of Hydrogenation of Naphthalenes on Transition Metal Catalysts and Conformational Analysis of the Products A. W. Weitkamp... 

The hydrogenation of CO and C02 on transition metal surfaces is a promising area for using NEMCA to affect rates and selectivities. In a recent study of C02 hydrogenation on Rh,59 where the products were mainly CH and CO, under atmospheric pressure and at temperatures 300 to 500°C it was found that CH4 formation is electrophobic (Fig. 8.54a) while CO formation is electrophilic (Fig. 8.54b). Enhancement factor A values up to 220 were... 

Although this type of reaction is symmetry forbidden in an unadsorbed molecule, theoretical calculations showed that in a molecule adsorbed on transition metals, such a shift is allowed [3-5], Later, other theoretical calculations suggested another type of 1,3-hydrogen shift, one in which the allylic cxo-hydrogen is abstracted by the surface fi-om an adsorbed alkene (either 1,2-diadsorbed or n-complexed) and the resulting 7i-allyl species moves over the abstracted hydrogen in such a way that it adds to the former vinylic position and causes, in effect, a stepwise intramolecular 1,3-hydrogen shift (bottom shift) [6],... 

In the electron transfer theories discussed so far, the metal has been treated as a structureless donor or acceptor of electrons—its electronic structure has not been considered. Mathematically, this view is expressed in the wide band approximation, in which A is considered as independent of the electronic energy e. For the. sp-metals, which near the Fermi level have just a wide, stmctureless band composed of. s- and p-states, this approximation is justified. However, these metals are generally bad catalysts for example, the hydrogen oxidation reaction proceeds very slowly on all. sp-metals, but rapidly on transition metals such as platinum and palladium [Trasatti, 1977]. Therefore, a theory of electrocatalysis must abandon the wide band approximation, and take account of the details of the electronic structure of the metal near the Fermi level [Santos and Schmickler, 2007a, b, c Santos and Schmickler, 2006]. 

Abild-Pedersen F, Greeley J, Studt F, Moses PG, Rossmeisl J, Munter T, Bligaard T, Ndrskov JK. 2007. Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces. Phys Rev Lett 99 016105. 

Greeley J, Mavrikakis M. 2005. Surface and subsurface hydrogen adsorption properties on transition metals and near-surface alloys. J Phys Chem B 109 3460-3471. 

We ivill discuss the reaction of hydrogen and oxygen on transition metals first. This reaction has been extensively studied in our laboratory 18-32) using evaporated metal films as a catalyst. From our previous considerations it follows that as a consequence of the choice of this particular system we must restrict ourselves to certain problems only. We cannot identify the surface species (we can indirectly indicate only some of them) nor understand completely their role in the reaction. Because of the polycrystalline character of the film, all the experimental results are averaged over all the surface. Several new problems thus arise, such as grain boundaries, and, consequently, the exact physical interpretation of these results is almost impossible it is more or less a speculative one. However, we can still get some valuable information concerning the chemical nature of the active chemisorption complex. The experimental method and the considerations will be shown in full detail for nickel only. For other metals studied in our laboratory, only the general conclusions will be presented here. 

Yildirim, T., J. Iniguez, S. Ciraci, Molecular and dissociative adsorption of multiple hydrogen molecules on transition metal decorated C60. Phys. Rev. B Condens. Matter Mater. Phys. 72(15), 153403 (4 pages), 2005. 

Weitkamp, A.W., Stereochemistry and mechanism of hydrogenation of naphthalene on transition metal catalysts and conformational analysis of the products. Adv. Catal., 18,1-110 (1968). 

Some general reviews on hydrogenation using transition metal complexes that have appeared within the last five years are listed (4-7), as well as general reviews on asymmetric hydrogenation (8-10) and some dealing specifically with chiral rhodium-phosphine catalysts (11-13). The topic of catalysis by supported transition metal complexes has also been well reviewed (6, 14-29), and reviews on molecular metal cluster systems, that include aspects of catalytic hydrogenations, have appeared (30-34). 

In hydrogenation, early transition-metal catalysts are mainly based on metallocene complexes, and particularly the Group IV metallocenes. Nonetheless, Group III, lanthanide and even actinide complexes as well as later metals (Groups V-VII) have also been used. The active species can be stabilized by other bulky ligands such as those derived from 2,6-disubstituted phenols (aryl-oxy) or silica (siloxy) (vide infra). Moreover, the catalytic activity of these systems is not limited to the hydrogenation of alkenes, but can be used for the hydrogenation of aromatics, alkynes and imines. These systems have also been developed very successfully into their enantioselective versions. 

The diversity of the substrates, catalysts, and reducing methods made it difficult to organize the material of this chapter. Thus, we have chosen an arrangement related to that used by Kaesz and Saillant [3] in their review on transition-metal hydrides - that is, we have classified the subject according to the applied reducing agents. Additional sections were devoted to the newer biomimetic and electrochemical reductions. Special attention was paid mainly to those methods which are of preparative value. Stoichiometric hydrogenations and model reactions will be discussed only in connection with the mechanisms. 

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