Nitrogen-doped graphene sheets were prepared through a hydrothermal reduction of colloidal dispersions of graphite oxide in the presence of hydrazine and ammonia at pH of 10. The effect of hydrothermal temperature on the structure, morphology, and surface chemistry of as-prepared graphene sheets were investigated though XRD, N(2) adsorption, solid-state (13)C NMR, SEM, TEM, and XPS characterizations. Oxygen reduction and nitrogen doping were achieved simultaneously under the hydrothermal reaction. Up to 5% nitrogen-doped graphene sheets with slightly wrinkled and folded feature were obtained at the relative low hydrothermal temperature. With the increase of hydrothermal temperature, the nitrogen content decreased slightly and more pyridinic N incorporated into the graphene network. Meanwhile, a jellyfish-like graphene structure was formed by self-organization of graphene sheets at the hydrothermal temperature of 160 °C. Further increase of the temperature to 200 °C, graphene sheets could self-aggregate into agglomerate particles but still contained doping level of 4 wt % N. The unique hydrothermal environment should play an important role in the nitrogen doping and the jellyfish-like graphene formation. This simple hydrothermal method could provide the synthesis of nitrogen-doped graphene sheets in large scale for various practical applications.
The hydrodesulfurization (HDS) of a diesel oil was carried out in a batch autoclave reactor over the temperature range 280-420 °C for 0-90 min under a total pressure of 2.9 MPa, using CoMo and NiMo catalysts in both one and two stages. The HDS reactivities of benzothiophenes, dibenzothiophenes (DBTs), and their alkylated homologes existing in the diesel fuel were examined in detail by means of respective quantitative analyses. The sulfur compounds can be classified into four groups according to their HDS reactivities which were described by their pseudo-first-order rate constants. DBTs carrying two alkyl substituents at the 4-and 6-positions, respectively, were the most resistant to desulfurization. H2S produced from reactive sulfur compounds in the early stage of the reaction is one of the main inhibitors for HDS of the unreactive species. A second stage using fresh hydrogen solved this inhibition problem, with NiMo achieving deeper desulfurization.
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