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

doi:10.7523/j.ucas.2020.0041

Abstract

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

CLC Number:

P578.4
X513

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.

References

[1] Choo G H, Seo J, Yoon J, et al. Analysis of long-term (2005-2018) trends in tropospheric NO₂ percentiles over Northeast Asia[J]. Atmospheric Pollution Research, 2020, 11(8): 1429-1440.DOI:10.1016/j.apr.2020.05.012.
[2] Yu Y, Liu H R. Economic growth, industrial structure and nitrogen oxide emissions reduction and prediction in China[J]. Atmospheric Pollution Research, 2020, 11(7): 1042-1050.DOI:10.1016/j.apr.2020.03.011.
[3] Ren H J, Koshy P, Chen W F, et al. Photocatalytic materials and technologies for air purification[J]. Journal of Hazardous Materials, 2017, 325: 340-366.DOI:10.1016/j.jhazmat.2016.08.072.
[4] Wang X C, Anpo M, Fu X Z. Current developments in photocatalysis and photocatalytic materials[M]. Amsterdam: Elsevier, 2020:1-6.DOI:10.1016/b978-0-12-819000-5.00001-1.
[5] Chen H H, Nanayakkara C E, Grassian V H. Titanium dioxide photocatalysis in atmospheric chemistry[J]. Chemical Reviews, 2012, 112(11): 5919-5948.DOI:10.1021/cr3002092.
[6] Pelaez M, Nolan N T, Pillai S C, et al. A review on the visible light active titanium dioxide photocatalysts for environmental applications[J]. Applied Catalysis B: Environmental, 2012, 125: 331-349.DOI:10.1016/j.apcatb.2012.05.036.
[7] Sugrañez R, Balbuena J, Cruz-Yusta M, et al. Efficient behaviour of hematite towards the photocatalytic degradation of NO_x gases[J]. Applied Catalysis B: Environmental, 2015, 165: 529-536.DOI:10.1016/j.apcatb.2014.10.025.
[8] Balbuena J, Cruz-Yusta M, Pastor A, et al. A-Fe₂O₃/SiO₂ composites for the enhanced photocatalytic NO oxidation[J]. Journal of Alloys and Compounds, 2018, 735: 1553-1561.DOI:10.1016/j.jallcom.2017.11.259.
[9] Balbuena J, Cruz-Yusta M, Cuevas A L, et al. Hematite porous architectures as enhanced air purification photocatalyst[J]. Journal of Alloys and Compounds, 2019, 797: 166-173.DOI:10.1016/j.jallcom.2019.05.113.
[10] Rodriguez J A, Jirsak T, Liu G, et al. Chemistry of NO₂ on oxide surfaces: formation of NO₃ on TiO₂(110) and NO₂?O vacancy interactions[J]. Journal of the American Chemical Society, 2001, 123(39): 9597-9605.DOI:10.1021/ja011131i.
[11] Liu Z M, Ma L L, Junaid A S M. NO and NO₂ adsorption on Al₂O₃ and Ga modified Al₂O₃ surfaces: a density functional theory study[J]. The Journal of Physical Chemistry C, 2010, 114(10): 4445-4450.DOI:10.1021/jp907925w.
[12] Yu Y Y, Diebold U, Gong X Q. NO adsorption and diffusion on hydroxylated rutile TiO₂(110)[J]. Physical Chemistry Chemical Physics:PCCP, 2015, 17(40): 26594-26598.DOI:10.1039/c5cp04584c.
[13] Xie X Y, Wang Q, Fang W H, et al. DFT study on reaction mechanism of nitric oxide to ammonia and water on a hydroxylated rutile TiO₂(110) surface[J]. The Journal of Physical Chemistry C, 2017, 121(30): 16373-16380.DOI:10.1021/acs.jpcc.7b04811.
[14] Pan J, Hu Z B. Simulation of CTAB bilayer adsorbed on Au(100), Au(110), and Au(111) surfaces: structure stability and dynamic properties[J]. Journal of University of Chinese Academy of Sciences, 2017, 34(1): 38-49.DOI:10.7523/j.issn.2095-6134.2017.01.006.
[15] Fang L C, Hao K R, Yan Q B, et al. Adsorption and migration of Li-ion in layered SnSe₂: a first principle study[J]. Journal of University of Chinese Academy of Sciences, 2018, 35(6): 735-742.DOI:10.7523/j.issn.2095-6134.2018.06.004.
[16] Song Z J, Wang B, Yu J, et al. Density functional study on the heterogeneous oxidation of NO over α-Fe₂O₃ catalyst by H₂O₂: effect of oxygen vacancy[J]. Applied Surface Science, 2017, 413: 292-301.DOI:10.1016/j.apsusc.2017.04.011.
[17] Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple[J]. Physical Review Letters, 1996, 77(18): 3865-3868.DOI:10.1103/PhysRevLett.77.3865.
[18] Li F F, Shi C M, Wang X F, et al. The important role of oxygen defect for NO gas-sensing behavior of α-Fe₂O₃ (001) surface: predicted by density functional theory[J]. Computational Materials Science, 2018, 146: 1-8.DOI:10.1016/j.commatsci.2017.12.065.
[19] Rohrbach A, Hafner J, Kresse G. Ab initio study of the (0001) surfaces of hematite and chromia: influence of strong electronic correlations[J]. Physcial Review B, 2004, 70(12): 1-17.DOI:10.1103/physrevb.70.125426.
[20] Von Rudorff G F, Jakobsen R, Rosso K M, et al. Hematite(001)-liquid water interface from hybrid density functional-based molecular dynamics[J]. Journal of Physics: Condensed Matter, 2016, 28(39): 394001.DOI:10.1088/0953-8984/28/39/394001.
[21] Giannozzi P, Baroni S, Bonini N, et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials[J]. Journal of Physics: Condensed Matter, 2009, 21(39): 395502.DOI:10.1088/0953-8984/21/39/395502.
[22] Vanderbilt D. Soft self-consistent pseudopotentials in a generalized eigenvalue formalism[J]. Physical Review B:Condensed Matter, 1990, 41(1): 7892-7895.DOI:10.1103/physrevb.41.7892.
[23] Liao P L, Keith J A, Carter E A. Water oxidation on pure and doped hematite (0001) surfaces: prediction of Co and Ni as effective dopants for electrocatalysis[J]. Journal of the American Chemical Society, 2012, 134(32): 13296-13309.DOI:10.1021/ja301567f.
[24] Nguyen M T, Seriani N, Gebauer R. Water adsorption and dissociation on α-Fe₂O₃ (0001): PBE+U calculations[J]. The Journal of Chemical Physics, 2013, 138(19):194709.DOI:10.1063/1.4804999.
[25] Nguyen M T, Seriani N, Piccinin S, et al. Photo-driven oxidation of water on α-Fe₂O₃ surfaces: an ab initio study[J]. The Journal of Chemical Physics, 2014, 140(6): 064703.DOI:10.1063/1.4865103.
[26] Nguyen M T, Piccinin S, Seriani N, et al. Photo-oxidation of water on defective hematite(0001)[J]. ACS Catalysis, 2015, 5(2): 715-721.DOI:10.1021/cs5017326.
[27] Zhao H L, Sheng X, Fabris S, et al. Heterogeneous reactions of SO₂ on the hematite(0001) surface[J]. The Journal of Chemical Physics, 2018, 149(19): 194703.DOI:10.1063/1.5037847.
[28] Grimme S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction[J]. Journal of Computational Chemistry, 2006, 27(15): 1787-1799.DOI:10.1002/jcc.20495.
[29] Rohrbach A, Hafner J. Molecular adsorption of NO on NiO(100): DFT and DFT+U calculations[J]. Physical Review B, 2005, 71(4): 1-7.DOI:10.1103/physrevb.71.045405.
[30] Souvi S M O, Badawi M, Paul J F, et al. A DFT study of the hematite surface state in the presence of H₂, H₂O and O₂[J]. Surface Science, 2013, 610: 7-15.DOI:10.1016/j.susc.2021.12.012.
[31] Bergermayer W, Schweiger H, Wimmer E. Ab initio thermodynamics of oxide surfaces: O₂ on Fe₂O₃ (0001)[J]. Physical Review B, 2004, 69(19): 195409.DOI:10.1103/physrevb.69.195409.
[32] Atkins P, Paula J. Physical chemistry[M]. Oxford: Oxford University Press, 2010.
[33] National Institute of Standards and Technology, U.S. Department of Commerce. NIST standard reference database 13. NIST-JANAF thermochemical tables [EB/OL]. (2019-06-11) [2020-05-08]. https://janaf.nist.gov/.
[34] Busca G, Lorenzelli V. Infrared study of the adsorption of nitrogen dioxide, nitric oxide and nitrous oxide on hematite[J]. Journal of Catalysis, 1981, 72(2): 303-313.DOI:10.1016/0021-9517(81)90013-0.