Nickel catalysts single crystal studies

In view of the nonlinear decrease in H2 adsorption with sulfur coverage in the single-crystal studies, it is interesting that such well-defined linear decreases with mean sulfur coverage are observed in the studies of polycrystalline and supported nickel 111, 162). However, since the partially poisoned catalysts are thought 111, 162) to consist of completely poisoned... 

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 above described experiments over atomically clean single crystal catalysts have been extended to studies of the kinetics of various catalytic reactions over chemically modified catalysts. Examples are recent studies Into the nature of poisoning by sulfur of the catalytic activity of nickel, ruthenium, and rhodium toward methana-tlon of CO (11,12) and CO2 (15). ethane (12) and cyclopropane (20) hydrogenolysls, and ethylene hydrogenation (21). 

Characterization of the Surfaces of Catalysts Measurements of the Density of Surface Faces for High Surface Area Supports. - It has always been a tenet of theories of catalysis that certain reactions will proceed at different rates on different surface planes of the same crystal. Experiments with metal single crystals have vindicated this view by showing that the rate of hydrogenolysis of ethane on a nickel surface will vary from one plane to another. In contrast the rate of methanation remains constant for the same planes.4 Because of this structure sensitivity of catalytic processes there is a requirement for methods of determining the number of each of the different planes which a catalyst and its support may expose at their surfaces. Electron microscopy studies of 5nm Pt particles supported upon graphite show them to be cubo-octahedra with surfaces bound by (111) and (100) planes.5 Similar studies of Pd and Pt prepared by evaporation reveal square pyramids of size 60-200 A bounded by incomplete (111) faces.6... 

Supported nickel catalysts have been the focus of attention of a number of infrared (IR) spectroscopic studies adopting CO as a surface probe molecule. This research has been motivated by the pronounced hydrotreating activity of the catalysts in processes of industrial importance [1,2]. Results published before 1978, have been critically assessed and compared to results then available on Ni° metal thin films and single crystal surfaces by Sheppard and Nguyen [3]. 

Investigations into these topics are presented in this volume. Iron, nickel, copper, cobalt, and rhodium are among the metals studied as Fischer-Tropsch catalysts results are reported over several alloys as well as single-crystal and doped metals. Ruthenium zeolites and even meteo-ritic iron have been used to catalyze carbon monoxide hydrogenation, and these findings are also included. One chapter discusses the prediction of product distribution using a computer to simulate Fischer-Tropsch chain growth. 

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