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  1. Applicability of the Delplot method for the determination of catalytic reaction sequences: Hydrodeoxygenation of $$\gamma$$-valerolactone on Ni2P/MCM-41

    Contact-time measurements based on sites are used to investigate the reaction sequence of the hydrodeoxygenation of γ-valerolactone (GVL) on Ni2P/MCM-41. Here the study is carried out at 300 °C and 0.5 MPa with site times of 0.29–6.1 s. A reaction network is proposed in which pentanoic acid and 2-methyltetrahydrofuran (2-MTHF) are formed in parallel initially and pentanal, butane and pentane are formed subsequently. A first-rank Delplot analysis (selectivity) gives a good fit, but higher-rank Delplots do not. The lack of applicability is explained by the magnitude of the rate constants, in which the rate constant for one of the latermore » steps (the consumption of pentanal) is substantially larger than those for the preceding steps. For this reason, pentanal demonstrated the characteristics of a primary product and consequently affected the discrimination of higher rank products. A simulation of a model sequence with assumed rate constants confirms the reason why the Delplot method does not work for this reaction. Since the rate constants cannot be determined a priori to be of close magnitude, the Delplot method cannot be generally used to ascertain reaction sequences.« less
  2. A New One-Pot Sequential Reduction-Deposition Method for the synthesis of Silica-supported NiPt and CuPt Bimetallic Catalysts

    A one-pot redox deposition method is described to prepare silica-supported bimetallic NiPt and CuPt catalysts using differences in standard reduction potentials. The synthesis involved the initial reduction of non-noble metal ions (Ni2+ and Cu2+) by NaBH4, followed by reduction of Pt ions by these reduced metals. Alloy formation and phase purity were established by X-ray diffraction (XRD), bulk composition by X-ray fluorescence (XRF), and surface composition by X-ray photoelectron spectroscopy (XPS). Alloy formation was enhanced by increase in the amount of base metals available to reduce Pt, or through the use of excess NaBH4 after redox deposition. The catalysts weremore » evaluated for methane oxidation at 300-400 °C and atmospheric pressure. Reference samples prepared using the incipient wetness impregnation (IW) method had inferior performance and characteristics. The redox deposition method provides a simple and versatile protocol for the preparation of bimetallic alloys between noble metals and base metals.« less
  3. Upgrading of pyrolysis bio-oil using nickel phosphide catalysts

  4. Nature of active sites in Ni2P hydrotreating catalysts as probed by iron substitution


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