Nickel catalyst adsorption

Fig. 8. The adsorption of hydrogen on copper-nickel catalysts as a function of the copper content. The circles represent the total amount of hydrogen adsorbed at room temperature at 10-cm pressure. The triangles represent the amount of strongly adsorbed hydrogen, i.e., the amount not removed by a 10-min evacuation at room temperature following the completion of the initial adsorption isotherm. The amount of strongly adsorbed hydrogen is determined as the difference between the initial isotherm and a subsequent isotherm obtained after a 10-min evacuation (74).

Surface modification of skeletal nickel with tartaric acid produced catalysts capable of enantiose-lective hydrogenation [85-89], The modification was carried out after the formation of the skeletal nickel catalyst and involved adsorption of tartaric acid on the surface of the nickel. Reaction conditions strongly influenced the enantioselectivity of the catalyst. Both Ni° and Ni2+ have been detected on the modified surface [89]. This technique has already been expanded to other modified skeletal catalysts for example, modification with oxazaborolidine compounds for reduction of ketones to chiral alcohols [90],... 

Butanol, reaction over reduced nickel oxide catalysts, 35 357-359 effect of ammonia, 35 343 effect of hydrogen, 35 345 effect of pyridine, 35 344 effect of sodium, 35 342, 351 effect of temperature, 35 339 over nickel-Kieselguhr, 35 348 over supported nickel catalysts, 35 350 Butanone, hydrogenation of, 25 103 Butene, 33 22, 104-128, 131, 135 adsorption on zinc oxide, 22 42-45 by butyl alcohol dehydration, 41 348 chemisorption, 27 285 dehydrogenation, 27 191 isomerization, 27 124, 31 122-123, 32 305-308, 311-313, 41 187, 188 isomerization of, 22 45, 46 isomers... 

Carbonates, diaryl, reactions with cyclohepta-amylose, 23 240 Carbon dioxide adsorption, 21 44 on chromia, 20 27 on gallium-doped NiO, 22 247-251 on nickel catalysts, 22 87-96 dissociative, 22 93-96... 

UHV surface analysis, apparatus designs, 36 4-14 see also Ultrahigh vacuum surface analysis mechanisms, 32 313, 319-320 Modified Raney nickel catalyst defined, 32 215-217 hydrogenation, 32 224-229 Modifying technique of catalysts, 32 262-264 Modulated-beam mass spectrometry, in detection of surface-generated gas-phase radicals, 35 148-149 MojFe S CpjfCOlj, 38 352 Molar integral entropy of adsorption, 38 158, 160-161... 

Wauquier and Jungers 110) have employed a similar treatment to abstract from kinetic data the relative adsorption constants of a number of aromatic compounds on a nickel catalyst. Rader and Smith 111) have extended the measurements to all the possible methyl-substituted benzenes on a platinum catalyst and Smith and Campbell 112) have. studied the same series on rhodium. 

The chapter Chiral Modification of Catalytic Surfaces [84] in Design of Heterogeneous Catalysts New Approaches based on Synthesis, Characterization and Modelling summarizes the fundamental research related to the chiral hydrogenation of a-ketoesters on cinchona-modified platinum catalysts and that of [3-ketoesters on tartaric acid-modified nickel catalysts. Emphasis is placed on the adsorption of chiral modifiers as well as on the interaction of the modifier and the organic reactant on catalytic surfaces. 

Figure 5 shows data for catalytic activity, CO adsorption at 23°, surface area by the B.E.T. method using krypton at —196°, and the fast hydrogen adsorption at —196° plotted against the temperature at which the various films were sintered. All quantities were taken as unity for films sintered at 23°C. These experiments clearly indicate that the previously observed slow adsorption of hydrogen on nickel catalysts is not adsorption but is sorption consisting of adsorption and... 

Fig. 9. Sorption isotherms on reduced nickel catalyst plotted from the data of Maxted and Hassid. (Catalyst was degassed at 250°C. before making measurements.) Hj adsorption at 10 3 ram. when catalyst was contacted with Hj at — 190°C. and then evacuated prior to raising the temperature.

In the last few decades, the study of adsorption phenomena at nickel electrodes by a radiotracer method has been the subject of several studies (see [34-40] and literature cited therein). M ost of these studies were carried out at smooth electrodes however, in some cases, nickel powder and Raney-nickel catalysts were used. 

Fig. 11. Changes in specific magnetization of a supported nickel catalyst during adsorption and desorption of hydrogen at room temperature. [Selwood, P. W., J. Am. Chem. Soc. 78. 3893 (1956).]...

It is clear that the influence of surface geometry upon catalytic activity is extremely complex and many more studies are required before any definitive relationship between catalytic activity and metal particle size can be established. Such studies will require to take cognisance of such factors as the perturbation of surface structure due to the formation of carbidic residues, as noted by Boudart [289] and by Thomson and Webb [95], and by the modification of catalytic properties on adsorption, as noted by Izumi et al. [296—298] and by Groenewegen and Sachtler [299] in studies of the modification of nickel catalysts for enantioselective hydrogenation. Possible effects of the support, as will be discussed in Sect. 6.3, must also be taken into account. 

In our own lab experiments with various cyano compounds and nickel catalysts, we concluded on a 2-site L.H type catalysis [67] but we had to introduce corrective parameters for substrate interactions, indicating failure of the basic assumption of surface ideality, i.e equal adsorption energy whichever coverage is reached. 

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