The analysis of temperature programmed desorption experiments of systems with lateral interactions; implications of the compensation effect

Nieskens, Davy L. S.; Bavel, Alexander P. van; Niemantsverdriet, J.W.

doi:10.1016/j.susc.2003.09.035

Cited by 67 publications

(79 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The second possibility is commonly known as the compensation effect, 20,[23][24][25][26][27] in which E d (θ) and ν n (θ) may vary with θ, but the product ν n (θ) exp[-E d (θ)/kT] is nearly constant. It is not possible to know if such compensation effects will be present on a particular system a priori, and applying eq 5 to a single-TPD data set where this is not the case will result in erroneous E d and ν n values.…”

Section: Analysis Methodsmentioning

confidence: 99%

Size Effects on the Desorption of O₂ from Au₂O₃/Au⁰ Nanoparticles Supported on SiO₂: A TPD Study

Ono

Cuenya

2008

J. Phys. Chem. C

View full text Add to dashboard Cite

This article contains an in-depth study of the kinetics of O 2 desorption from preoxidized size-selected gold nanoparticles (NPs) of average size ∼1.5 and ∼5 nm synthesized by micelle encapsulation and supported on SiO 2 . Thanks to the narrow NP size distributions achieved using our preparation route, information on the effect of the nanoparticle size on the reaction kinetics could be obtained by temperature programmed desorption (TPD). In addition, the validity of different TPD analysis methods (Redhead, heating rate variation, Arrhenius plots, and the complete analysis) to extract meaningful kinetic parameters on supported NPs is discussed. From the different analysis methods, activation energies for O 2 desorption of E d ) 1.3 ( 0.2 eV and 1.7 ( 0.1 eV were obtained for the ∼5 and ∼1.5 nm Au NPs, respectively. These differences in the activation energies are directly related to the nanoparticle size and not to nanoparticle-support interactions.

show abstract

Section: Analysis Methodsmentioning

confidence: 99%

Size Effects on the Desorption of O₂ from Au₂O₃/Au⁰ Nanoparticles Supported on SiO₂: A TPD Study

Ono

Cuenya

2008

J. Phys. Chem. C

View full text Add to dashboard Cite

show abstract

“…More complex and accurate methods exist for TPD analysis, 52 but the complexity of the chemical systems and the overlap of peaks make the Redhead method more suitable.…”

Section: Figure 1 Xps Spectra Acquired At Different Temperatures Stamentioning

confidence: 99%

Decomposition Mechanism of Anisole on Pt(111): Combining Single-Crystal Experiments and First-Principles Calculations

Réocreux

Hamou²,

Michel

et al. 2016

ACS Catal.

View full text Add to dashboard Cite

To valorize lignin as a renewable source of aromatics, it is necessary to develop selective heterogeneous catalysts for the hydrodeoxygenation reaction of aromatic oxygenates such as anisole. Most of the metal supported catalysts tested so far exhibit a high conversion but a low selectivity towards valuable aromatic hydrocarbons, yielding mainly phenolic compounds. To gain insights into that catalytic system, we performed surface science experiments (X-ray Photoelectron Spectroscopy and Temperature Programmed Desorption)under Ultra-High Vacuum conditions (UHV). Dosing anisole on Pt(111) surprisingly gave benzene, carbon monoxide and hydrogen as the main desorbing products of decomposition.With the help of Density Functional Theory (DFT) we successfully explain the unexpected selectivity. In the present work we show in particular that phenoxy PhO stands as a key intermediate. Although the UHV conditions do not allow the hydrogenation of phenoxy into phenol, i.e. the catalytic product, they reveal the key role of both hydrogen and carbonaceous species. Under UHV conditions, anisole gets extensively dehydrogenated: it results in the formation of carbonaceous fragments, which can actually perform the deoxygenation of phenoxy into benzene, but also, more importantly, coke. This detailed study opens the door to a rational design of hydrodeoxygenation catalysts based on supported metals.

show abstract

“…The overall rate law for escape from the Knudsen cell can be approximated by Equation (6) and the apparent rate constant, :…”

Section: Ie-smentioning

confidence: 99%

“…Ordinary linear least squares provides a single set of rate parameters for each series of rate constants, and so does not provide information on time-varying effects such as lateral interactions between absorbed species [6], mass and heat transfer processes [7], shape selectivity [8], surface heterogeneity and restructuring [9]. Flexible least squares can exactly simulate each data set by varying each of the parameters at each temperature.…”

Section: Introductionmentioning

confidence: 99%

Rate Parameter Distributions for Isobutane Dehydrogenation and Isobutene Dimerization and Desorption over HZSM-5

et al. 2013

View full text Add to dashboard Cite

Deconvolution of the evolved isobutene data obtained from temperature-programmed, low-pressure steady-state conversion of isobutane over HZSM-5 has yielded apparent activation energies for isobutane dehydrogenation, isobutene dimerization and desorption. Intrinsic activation energies and associated isobutane collision frequencies are also estimated. A combination of wavelet shrinkage denoising, followed by time-varying flexible least squares of the evolved mass-spectral abundance data over the temperature range 150 to 450 °C, provides accurate, temperature-dependent, apparent rate parameters. Intrinsic activation energies for isobutane dehydrogenation range from 86 to 235.2 kJ mol ). These wide ranges reflect the heterogeneity and acidity of the zeolite surface and structure. Seven distinct locations and sites, including Lewis and Brønsted acid sites can be identified in the profiles. Isobutane collision frequencies range from 10 IA (g) and IE (g) gas-phase isobutane and isobutene S and S* non-specific sites and acidic sites on the zeolite surface IA-S and IE-S isobutane and isobutene adsorbed on non-specific sites IA-S*, IE-S* and IE 2 -S*

show abstract

The analysis of temperature programmed desorption experiments of systems with lateral interactions; implications of the compensation effect

Cited by 67 publications

References 24 publications

Size Effects on the Desorption of O₂ from Au₂O₃/Au⁰ Nanoparticles Supported on SiO₂: A TPD Study

Size Effects on the Desorption of O₂ from Au₂O₃/Au⁰ Nanoparticles Supported on SiO₂: A TPD Study

Decomposition Mechanism of Anisole on Pt(111): Combining Single-Crystal Experiments and First-Principles Calculations

Rate Parameter Distributions for Isobutane Dehydrogenation and Isobutene Dimerization and Desorption over HZSM-5

Contact Info

Product

Resources

About

The analysis of temperature programmed desorption experiments of systems with lateral interactions; implications of the compensation effect

Cited by 67 publications

References 24 publications

Size Effects on the Desorption of O2 from Au2O3/Au0 Nanoparticles Supported on SiO2: A TPD Study

Size Effects on the Desorption of O2 from Au2O3/Au0 Nanoparticles Supported on SiO2: A TPD Study

Decomposition Mechanism of Anisole on Pt(111): Combining Single-Crystal Experiments and First-Principles Calculations

Rate Parameter Distributions for Isobutane Dehydrogenation and Isobutene Dimerization and Desorption over HZSM-5

Contact Info

Product

Resources

About

Size Effects on the Desorption of O₂ from Au₂O₃/Au⁰ Nanoparticles Supported on SiO₂: A TPD Study

Size Effects on the Desorption of O₂ from Au₂O₃/Au⁰ Nanoparticles Supported on SiO₂: A TPD Study