Ab initio simulations of NO adsorption on hematite (0001) surface: PBE versus PBE+U

WU Cuixia; SUN Tao; FABRIS Stefano; DU Lin

doi:10.7523/j.ucas.2020.0041

Journal of University of Chinese Academy of Sciences >

2022 , Vol. 39 >Issue 2: 193 - 200

DOI: https://doi.org/10.7523/j.ucas.2020.0041

Research Articles

Ab initio simulations of NO adsorption on hematite (0001) surface: PBE versus PBE+U

WU Cuixia ,
SUN Tao ,
FABRIS Stefano ,
DU Lin

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1 College of Earth and Planetary Sciences, University of Chinese Academy of Sciences, Beijing 100049, China;
2 CNR-IOM DEMOCRITOS, Istituto Officina dei Materiali, Consiglio Nazionale delle Ricerche, Trieste 34136, Italy;
3 Environment Research Institute, Shandong University, Qingdao 266237, Shandong, China

Received date: 2020-07-24

Revised date: 2020-08-10

Online published: 2020-08-10

Supported by

Supported by National Natural Science Foundation of China (41972044, 91644214) and Strategic Priority Research Program (B) of Chinese Academy of Sciences (XDB18000000)

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Abstract

NO_x(x=1,2) are major air-pollutants detrimental to human health and much effort has been devoted to find efficient photocatalysts capable of removing NO_x from air (de-NO_x). Recent experiments indicate that hematite (α-Fe₂O₃) is a promising de-NO_x photocatalyst. However some key features of the NO adsorption on the hematite surface remain unclear, hindering further comprehension of the photocatalytic process. Here we study the adsorption of NO on the hematite (0001) surface using the PBE+U method with a dispersion correction (vdw) in the framework of density functional theory (DFT). We find the addition of a Hubbard U term in the DFT Hamiltonian strongly affects the adsorption properties, with the adsorption energy (-0.64eV) decreased by 50% with respect to those of PBE (-1.31eV). This decrease is attributed to two factors:(i) the U term shifts the energy of Fe 3d orbitals away from the valence band maximum, making them chemically less active; (ii) the NO molecule has an unpaired π^* electron and is more sensitive to the electronic structure of the substrate. In contrast to the inclusion of U, the dispersion correction causes little change to the adsorption properties except increases the adsorption energy by about -0.18eV. We use the Langmuir formula to calculate the thermal equilibrium coverage of NO on the hematite (0001) surface and find predictions made with the PBE+U vdw are more consistent with experiments. These results highlight the importance of strong electronic correlations in describing the hematite surface reactions, and may serve as a starting point to unravel the complete photocatalytic mechanism.

Key words： hematite; NO; photocatalysis; Langmuir; air pollution

Cite this article

WU Cuixia , SUN Tao , FABRIS Stefano , DU Lin . Ab initio simulations of NO adsorption on hematite (0001) surface: PBE versus PBE+U[J]. Journal of University of Chinese Academy of Sciences, 2022 , 39(2) : 193 -200 . DOI: 10.7523/j.ucas.2020.0041

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