Chemical reactions at surfaces and interfaces from first principles: Theory and application

Abstract

Abstract:The last decade has seen rapid expansion and development in the field of density functional theory (DFT) simulation on the complex chemical processes that occur at surfaces and interfaces. The understanding of the phenomena in surface science and heterogeneous catalysis has benefited tremendously from these quantum mechanic calculations. This article reviews current progress in the theory of reactions on surfaces, in particular, those relevant to the barrier and the active site of surface reactions. Two representative reactions, namely, NO dissociation and CO oxidation, are selected to illustrate how these theoretical concepts are applied to understand catalytic reactions. Here, the pathways and energetics of these reactions under various catalytic conditions are described in detail, and the understanding of the reactions is generalized. It is concluded that DFT-based methods can be well applied to catalysis to understand the electronic structure of chemical processes and to elucidate mechanisms of complex surface reactions.

Recent Advances in Understanding CO Oxidation on Gold Nanoparticles Using Density Functional Theory

“…For reviews of CO oxidation on metal surface see references [70] and [71]. It has been generally accepted that CO oxidation over a metal surface follows the Langmuir-Hinshelwood mechanism.…”

Catalyst screening: Refinement of the origin of the volcano curve and its implication in heterogeneous catalysis

“…Fortunately, the use of DFT calculations and quantum chemical softwares with massively parallel computing techniques facilitates the accumulation of relevant information. Firstly, DFT calculations have become a powerful tool to investigate catalytic processes [12,13]. The binding energies of intermediates, reaction barriers, surface structures, and so on can be routinely obtained with reasonable accuracy.…”

The Impact of the Surface Modification on Tin-Doped Indium Oxide Nanocomposite Properties

“…Due to the exponential increase in the computational time by increasing the number of atoms, a limit of 3 nm for the thickness is used. Finally, to have a proper convergence for the structure, a cut-off energy between 300 to 500 eV is considered [ 23 , 30 , 52 , 62 , 69 , 86 , 87 , 114 ]. Using the above parameters, the geometry and crystallographic parameters would be in good agreement with the experimental data.…”

“…The first principle calculations have been applied to provide molecular-level insights about the interface of metal oxides and molecules [ 28 ] and to study the chemical reactions on the surface for close to three decades [ 29 ]. Recently, with new developments in computing power, software and computational algorithms, using the density functional theory (DFT), made these simulations applicable for the study of interface properties [ 30 , 31 , 32 ]. In recent years, the DFT has also been used to investigate the physical properties of alloys, especially the thermal conductivity of different alloys [ 33 , 34 , 35 , 36 , 37 ].…”

“…Modification of conducting metal oxides and the concept of doping are of wide interest [ 38 , 39 , 40 , 41 , 42 , 43 ]. There are several reports on investigating the interface of biomolecules and metal oxides [ 29 , 30 , 31 , 32 , 33 , 34 , 35 ], in particular indium oxide [ 44 , 45 , 46 ] and titania [ 47 , 48 ]. Recently, studies have been performed on surface treatment of ITO using biomolecules for investigating its electrochemical properties and electronic properties for biosensing, including even faster biosensors, to help fight the current pandemic [ 6 , 17 , 49 , 50 ].…”