"Intelligent" reforming catalysts: Trace noble metal-doped Ni/Mg(Al)O derived from hydrota

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Trace amounts of noble metal-doped Ni/Mg(Al)O catalysts were pre-pared starting from Mg-Al hydrotalcites (HTs) and tested in daily start-up and shut-down (DSS) operation of steam reforming (SR) of methane or partial oxidation (PO) of propane. Although Ni/Mg(Al)O catalysts prepared from Mg(Ni)-Al HT exhibited high and stable activity in stationary SR,PO and dry reforming of methane and propane,the Ni/Mg(Al)O catalysts were drastically deactivated due to Ni oxidation by steam as purge gas when they were applied in DSS SR of methane. Such deactivation was effectively suppressed by dop-ing trace amounts of noble metal on the catalysts by using a memory effect of HTs. Moreover,the noble metal-doped Ni/Mg(Al)O cat-alysts exhibited intelligent catalytic behaviors,i.e.,self-activation and self-regenerative activity,leading to high and sustainable activity during DSS operation. Pt was the most effective among noble met-als tested. The self-activation occurred by the reduction of Ni2+ in Mg(Ni,Al)O periclase to Ni~0 assisted by hydrogen spillover from Pt (or Pt-Ni alloy). The self-regenerative activity was accomplished by self-redispersion of active Ni~0 particles due to a reversible reduction-oxidation movement of Ni between the outside and the inside of the Mg(Al)O periclase crystal;surface Ni~0 was oxidized to Ni~(2+) by steam and incorporated into Mg(Ni~(2+),Al)O periclase,whereas the Ni~(2+) in the periclase was reduced to Ni~0 by the hydrogen spillover and appeared as the fine Ni~0 particles on the catalyst surface. Fur-ther a green preparation of the Pt/Ni/[Mg3.5Al]O catalysts was ac-complished starting from commercial Mg3.5-Al HT by calcination,followed by sequential impregnation of Ni and Pt.
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