Surface carbon formation mechanism

Mechanism of Surface Carbon Formation During the Pyrolysis of Benzene in the Presence of Hydrogen... 

Bartholomew and coworkers32 described deactivation of cobalt catalysts supported on fumed silica and on silica gel. Rapid deactivation was linked with high conversions, and the activity was not recovered by oxidation and re-reduction of the catalysts, indicating that carbon deposition was not responsible for the loss of activity. Based on characterization of catalysts used in the FTS and steam-treated catalysts and supports the authors propose that the deactivation is due to support sintering in steam (loss of surface area and increased pore diameter) as well as loss of cobalt metal surface area. The mechanism of the latter is suggested to be due to the formation of cobalt silicates or encapsulation of the cobalt metal by the collapsing support. 

The morphology of the carbon on the surface can assume several forms a two-dimensional film or so-called whisker carbon, which is formed when the carbon dissolves in the supported metal catalyst, diffuses through the metal, and forms a growing filament that lifts the metal from the catalyst surface. Whisker carbon is typically associated with Ni-based catalysts because carbon is soluble in Ni at reforming conditions. Whisker carbon tends to form at higher temperatures, low steam to hydrocarbon ratios and higher aromatic content of the feeds. This type of carbon formation may be minimized by the use of precious metals as catalysts, because these metals do not dissolve carbon. On a nickel surface, the whisker mechanism can be controlled by sulfur passivation. 

In a study conducted by the Armour Research Foundation (Ref 41) a-Pb azide crystals wrapped in a thin A1 foil were subjected to fast and thermal neutrons in the heavy water pile at Argonne National Laboratory. With a thermal flux rate of about 10l4n/cm2/sec the crystals were irradiated for 8, 17 and 170 hours. The crystals decompd to a brown powder which was identified as Pb carbonate by X-ray techniques and infrared absorption spectra. From a mass spectrographic analysis of the isotopes of carbon and oxygen in the decompn products, it was determined that the mechanism of carbonate formation is a reaction with the atmosphere by broken surface bands produced by the neutrons. Subsequently, Raney (Ref 60) reported... 

Needless to say that a deep understanding of both the formation mechanism of the SEI layer and the underlaying question of carbon s surface chemistry in a particular electrolyte solution is of utmost importance for battery developers. Clearly, the surface chemistry of graphite electrodes plays a key role in their performance.259 312 325 343-352 A lot of work was devoted to decipher this very complicated surface chemistry. It is therefore not surprising that the advancement in the understanding of surface chemistry of carbon electrodes in nonaqueous electrolytes correlates well with the worldwide production rate of lithium-ion batteries. 

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