Growth of filamentous carbon from the surface of Ni/SiO2 doped with alkali metal bromides

J Colloid Interface Sci. 2002 Jun 1;250(1):37-48. doi: 10.1006/jcis.2002.8298.

Abstract

The growth of ordered filamentous carbon, catalytically generated from the decomposition of ethylene, has been studied over the temperature range 673-898 K using an 11% w/w Ni/SiO2 catalyst doped to varying degrees (0.1-9.3% w/w) with a range of alkali metal bromides. The effect of these alkali metal/halogen adatoms in promoting/inhibiting carbon growth has been assessed and variations in the associated carbon structural characteristics have been examined. The introduction of Li consistently promoted filamentous carbon growth (where 723 K<T<823 K) while the presence of Na, K, Rb, or Cs resulted in an equivalent or lower carbon yield. The degree of carbon deposition was strongly dependent on the nature and loading of the alkali metal, the Ni/Br ratio in the activated catalyst, and reaction temperature; conditions for optimum carbon growth are identified. The response of carbon yield and structural order to alkali bromide doping is discussed in terms of Ni particle electronic structure and metal/support interaction(s). High-resolution transmission electron microscopy (HRTEM) has been used to probe the filamentous carbon structure and the dispersion/morphology/size of the supported Ni crystallites. Highly curved and helical filaments predominated over the doped (particularly CsBr) samples and this is attributed to a disruption in carbon diffusion through the Ni particle caused by a spreading/coating of the particle by the alkali adatom. Temperature-programmed oxidation studies have highlighted the changes in the graphitic nature of the carbon due to catalyst doping; the results are consistent with the TEM analysis.