Theoretical Parameter-Free Analysis Model for Temperature-Programmed Desorption (TPD) Spectra

Abstract

This paper proposes a parameter-free mathematical model of analyzing either monosite or multisite temperatureprogrammed desorption (TPD) spectra. By linearizing the integral function difference, the desorption kinetic parameters, such as the desorption order n, the desorption activation energy E d , and the preexponential factor ν, can be extracted simultaneously with promising accuracy. A custom "ant" is further established in the model to explore the spectra by a "prediction−correction" loop, and the kinetics and the coverage distribution of the individual peak in the spectra can be solved sequentially. Meanwhile, eight cases on spectrum analysis, including but not limited to the spectrum with coverage-dependent kinetics, the spectrum affected by the noise, the practical spectrum, are demonstrated to fully understand the model's principle, process, and application. Moreover, the model optimization and resolution limitation are further discussed to stimulate the future potential of the innovative parameter-free model.

Adsorption of CO2 on Terrace, Step, and Defect Sites on Pt Surfaces: A Combined TPD, XPS, and DFT Study

“…The thermal desorption characteristics of CO 2 on Pt surfaces can be modeled using the Polanyi–Wigner equation − …”

Thermokinetics of production of biochar from crop residues: an overview

“…A considerable number of methods were developed to estimate the kinetic parameters, but all of them are based on the Polanyi–Wigner equation. 96,100 The maximum desorption peak temperature is used by many authors to estimate the E a of thermodesorption processes. Redhead in his work developed methods to estimate the E a by the peak desorption temperature ( T max ), at which the desorption rate is maximized (for first-order reactions).…”

“…[92][93][94] The method of thermal programmed desorption mass spectrometry (TPD-MS) is a powerful method for studying the processes of direct and catalytic pyrolysis of biomass and model compounds of biomass. 95,96 The methodology to obtain kinetic parameters from TPD-MS data was widely reported in the literature. For these purposes, the Arrhenius equation in its linear formulation is often used.…”

“…For these purposes, the Arrhenius equation in its linear formulation is often used. [96][97][98][99]…”