The delplot technique: a new method for reaction pathway analysis

Bhore, Nazeer A.; Klein, Michael T.; Bischoff, Kenneth B.

doi:10.1021/ie00098a025

Cited by 207 publications

(157 citation statements)

References 6 publications

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“…As previously observed (30,32,33), the TOF for neopentane conversion by Pt/H-LTL is much higher, approximately 150 times, based on CO chemisorption (90 times higher, based on H 2 chemisorption) than that of Pt/K-LTL. In addition, the isomerization selectivity of Pt/K-LTL is 0.39, slightly higher than that of Pt/H-LTL, 0.35.…”

Section: Catalytic Reaction Of Neopentanesupporting

confidence: 81%

“…Analysis of the reaction products of neopentane at conversions between 0.5 and 2.0% by the Delplot method (32) indicate that methane, isobutane (hydrogenolysis), and isopentane (isomerization) are primary reaction products. For Pt/K-LTL and Pt(S)/H-LTL there was no deactivation; however, significant deactivation occurs for Pt/H-LTL and Pt(S)/K-LTL.…”

Section: Catalytic Reaction Of Neopentanementioning

confidence: 99%

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The Origin of Sulfur Tolerance in Supported Platinum Catalysts: The Relationship between Structural and Catalytic Properties in Acidic and Alkaline Pt/LTL

Miller¹,

Koningsberger

1996

Journal of Catalysis

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The reactivity, structure, and sulfur tolerance is compared for platinum supported on acidic and alkaline LTL zeolite. In the absence of sulfur, EXAFS spectroscopy indicates that small metallic platinum particles of approximately 6 to 14 atoms/cluster are present. The TOF for neopentane hydrogenolysis and isomerization is ca 100 times higher on the acidic LTL due to the metalsupport interaction. Saturation of the platinum by H 2 S, results in the formation of surface Pt-S bonds with a bond length of 2.33Å. Comparison of the EXAFS results of the sulfur poisoned catalysts, indicates that the S to Pt ratio is lower for platinum on the acidic zeolite. Catalytically, the initial activity (per gram) of both catalysts is greatly reduced after sulfur poisoning due to the loss of exposed platinum, however, the initial neopentane TOFs are nearly unchanged. Because of its higher TOF, the catalytic activity (per gram) of sulfur poisoned, acidic Pt/LTL is comparable to that of nonsulfur poisoned alkaline Pt/LTL. In both sulfur poisoned catalysts the neopentane isomerization selectivity increases compared to the sulfur free catalyst. Although the initial TOFs of the nonsulfur poisoned and sulfur poisoned catalysts are the same, there is a rapid loss in activity due to coke formation in the sulfur poisoned, alkaline LTL, while rate of deactivation by coke in the sulfided, acidic LTL is much lower. The increased sulfur tolerance of acidic supported noble metal catalysts appears to result primarily from the higher intrinsic TOF. In addition, because of its resistance to coke deactivation, the acidic supported sulfur tolerant catalyst is able to maintain stable catalytic activity.

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Section: Catalytic Reaction Of Neopentanesupporting

confidence: 81%

Section: Catalytic Reaction Of Neopentanementioning

confidence: 99%

The Origin of Sulfur Tolerance in Supported Platinum Catalysts: The Relationship between Structural and Catalytic Properties in Acidic and Alkaline Pt/LTL

Miller¹,

Koningsberger

1996

Journal of Catalysis

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“…11A,B) was applied to support this statement. Extrapolation of selectivities to zero conversion, sometimes referred to as first-rank Delplot analysis [43,44], helps to distinguish primary and secondary products of complex reaction networks. Plot with 21 non-zero intercept shows that the corresponding species is primary product.…”

Section: Pa Hydroconversionmentioning

confidence: 99%

A study of the hydrodenitrogenation of propylamine over supported nickel phosphide catalysts using amorphous and nanostructured silica supports

Badari

Lónyi

Drotár

et al. 2015

Applied Catalysis B: Environmental

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Pyrolysis of animal by-products provides pyro-oil that contains about 10 wt% nitrogen mainly in aliphatic compounds and virtually no sulfur. The nitrogen should be removed from the oil preferably by hydrodenitrogenation (HDN) to obtain liquid fuel and ammonia. In order to understand the catalytic HDN processes of such bio-oils the HDN of propylamine (PA) was studied as model reaction over silica-supported Ni 2 P and Ni catalysts. Catalysts were prepared by H 2 -reduction of catalyst precursor NiO/phosphated silica gel and NiO/phosphated SBA-15 silica material and NiO/silica gel. The catalyst surface was characterized by Diffuse Reflectance Infrared Fourier Transform Spectroscopic (DRIFTS) examination of adsorbed CO. It was shown that the Ni 2 P particles had a highly defected structure in the initial reduced state of the catalyst but were rapidly converted to ordered crystals in contact with PA under reaction conditions. The HDN reaction of PA was studied using a flow-through tube reactor

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“…Analysis of the reaction products, by the Delplot method (27) for neopentane conversions between 0.5 and 2.0%, indicated that the primary reaction products are methane, isobutane (hydrogenolysis), and isopentane (isomerisation), typical of a monofunctional metal catalysed reaction (28, • C, atmospheric pressure, and 1.0 vol% neopentane in H 2 . Pt/SiO 2 : Neopentane TOF determined at 390…”

Section: Neopentane Hydrogenolysismentioning

confidence: 99%

A New Model Describing the Metal–Support Interaction in Noble Metal Catalysts

Mojet

Miller²,

Ramaker

et al. 1999

Journal of Catalysis

218

191

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The catalytic activity and spectroscopic properties of supported noble metal catalysts are strongly influenced by the acidity/ alkalinity of the support but are relatively independent of the metal (Pd or Pt) or the type of support (zeolite LTL or SiO 2 ). As the alkalinity of the support increases, the TOF of the metal particles for neopentane hydrogenolysis decreases. At the same time, there is a decrease in the XPS binding energy and a shift from linear to bridge bonded CO in the IR spectra. Analysis of the shape resonance in XANES spectra indicates that in the presence of chemisorbed hydrogen the difference in energy between the Pt-H antibonding orbital and the Fermi level decreases as the alkalinity of the support increases. Based on the results from the IR, XPS, and shape resonance data a new model is proposed in which the interaction between the metal and support leads to a shift in the energy of the metal valence orbitals. The EXAFS structural analysis indicates that the small metal particles are in contact only with the oxide ions of the support. Finally, a new spectroscopic characterisation, Atomic XAFS, is presented which provides new insights into the origin of the electronic changes in the metal. As the alkalinity of the support increases, there is decrease in the metal ionisation potential. The primary interaction is a Coulomb attraction between metal particle and support oxygen ions, which affects the metal interatomic potential. This model for the metal-support interaction explicitly excludes the need for electron transfer, and it can account for all observed changes in the catalytic, electronic, and structural properties of the supported metal particles induced by support acidity ranging from acidic to neutral to alkaline.

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The delplot technique: a new method for reaction pathway analysis

Cited by 207 publications

References 6 publications

The Origin of Sulfur Tolerance in Supported Platinum Catalysts: The Relationship between Structural and Catalytic Properties in Acidic and Alkaline Pt/LTL

The Origin of Sulfur Tolerance in Supported Platinum Catalysts: The Relationship between Structural and Catalytic Properties in Acidic and Alkaline Pt/LTL

A study of the hydrodenitrogenation of propylamine over supported nickel phosphide catalysts using amorphous and nanostructured silica supports

A New Model Describing the Metal–Support Interaction in Noble Metal Catalysts

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