Adsorption and dehydrogenation of C₂–C₆n-alkanes over a Pt catalyst: a theoretical study on the size effects of alkane molecules and Pt substrates

Abstract

Adsorption and dehydrogenation of C2-C6 n-alkanes are investigated on Pt substrate using density functional theory (DFT) calculations, and size effects of alkane molecule and Pt substrate are discussed in detail....

Highly active Ru/TiO2 nanostructures for total catalytic oxidation of propane

“…The computed physisorption energy evidenced that propane adsorption on the catalyst interface is energetically favored based on the computed adsorption energy of − 0.33 eV. This value is consistent with those reported for different metal oxides in previous studies (Martin et al 2021 ; Ding et al 2020 ; Chang et al 2017 ; Liu et al 2016 ).…”

Benchmarking the Accuracy of Density Functional Theory against the Random Phase Approximation for the Ethane Dehydrogenation Network on Pt(111)

“…Over the last few decades, computational catalysis using Density Functional Theory (DFT) has been instrumental to understanding the chemical kinetics and reaction mechanisms of various heterogeneous reactions. − However, computational investigations using DFT include significant inaccuracies due to errors from functional approximations, especially regarding the exchange-correlation (XC) functional that is used to describe exchange effects and electron–electron correlation interactions. − The choice of functional can lead to either under- or overestimation of DFT energies for gas phase species, surface intermediates, and transition state species involved in the system of interest. − For the predominantly used Generalized Gradient Approximation (GGA) class of functionals, approximate errors of 0.2–0.3 and 0.4–0.7 eV have been reported for strongly chemisorbed and physiosorbed species, respectively. ,, These errors propagate to the calculation of elementary reaction rate and equilibrium constants utilized in microkinetic modeling (MKM) and, thus, can significantly alter kinetic predictions such as turnover frequency (TOF), selectivity, and reaction orders. ,− The major sources of the GGA-based functional error include failing to account for the tail of dispersion interactions and lacking the exact exchange energy density. − Therefore, correction schemes for dispersion, such as those outlined by Grimme et al, are widely applied to GGA-based functionals. , Newer functionals such as meta-GGAs, hybrid functionals, and machine-learning-inspired (ML) functionals have received attention due to better capturing dispersion effects and the exchange interaction more accurately. ,− Lastly, the currently conceptually most accurate computational method for the density functional approximation (DFA) is the Random-Phase Approximation (RPA). RPA methods compute the nonlocal interactions between nonoverlapped densities and incorporate exact exchange .…”

Zeolite catalysts for non-oxidative ethane dehydrogenation to ethylene

“…However, it also triggers the severe deep dehydrogenation of ethylene to form coke, which is considered an inherent disadvantage of Pt catalysts in nonoxidative dehydrogenation. [24][25][26] The competition between ethylene desorption and deep dehydrogenation is crucial to determine the reaction channels of efficient EDH and coke formation. The unsaturated CQC bond could interact with the Pt sites through di-s and/or p adsorption (Fig.…”