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Journal of Chemical Physics / Volume 136 / Issue 6 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation
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J. Chem. Phys. 136, 064501 (2012); http://dx.doi.org/10.1063/1.3676408 (17 pages)

Structure and properties of metal-exchanged zeolites studied using gradient-corrected and hybrid functionals. I. Structure and energetics

Florian Göltl and Jürgen Hafner

Fakultät für Physik and Center for Computational Materials Science, Universität Wien, Sensengasse 8/12, A-1090 Wien, Austria

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(Received 10 October 2011; accepted 21 December 2011; published online 8 February 2012)

The structural and energetic properties of purely siliceous, proton-, and Cu- and Co-exchanged chabazite have been studied using periodic density-functional (DFT) calculations with both conventional gradient-corrected exchange-correlation functionals and hybrid functionals mixing exact (i.e., Hartree-Fock) and DFT exchange. Spin-polarized and fixed-moment calculations have been performed to determine the equilibrium and excited spin-configurations of the metal-exchanged chabazites. For the purely siliceous chabazite, hybrid functionals predict a slightly more accurate cell volume and lattice geometry. For isolated Al/Si substitution sites, gradient-corrected functionals predict that the lattice distortion induced by the substitution preserves the local tetrahedral symmetry, whereas hybrid functionals lead to a distorted Al coordination with two short and two long Al-O bonds. Hybrid functionals yield a stronger cation-framework binding that conventional functionals in metal-exchanged zeolites, they favor shorter cation-oxygen bonds and eventually also a higher coordination of the cation. Both types of functionals predict the same spin in the ground-state. The structural optimization of the excited spin-states shows that the formation of a high-spin configuration leads to a strong lattice relaxation and a weaker cation-framework bonding. For both Cu- and Co-exchanged chabazite, the prediction of a preferred location of the cation in a six-membered ring of the zeolite agrees with experiment, but the energy differences between possible cation locations and the lattice distortion induced by the Al/Si substitution and the bonding of the cation depends quite significantly on the choice of the functional. All functionals predict similar energy differences for excited spin states. Spin-excitations are shown to be accompanied by significant changes in the cation coordination, which are more pronounced with hybrid functionals. The consequences of electronic spectra and chemical reactivity are analyzed in the following papers.

© 2012 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. FUNCTIONALS
    1. Computational setup
  3. STRUCTURES
  4. PURELY SILICEOUS AND AL-DOPED CHABAZITE
    1. SiO 2 chabazite
    2. Al→Si substitution and protonated chabazite
  5. EXTRA-FRAMEWORK SITES IN METAL-EXCHANGED CHABAZITE
    1. Cu-exchanged chabazite
      1. Structure of Cu(I) Lewis-sites in chabazite
      2. Energies of Cu(I) Lewis-sites in chabazite
      3. Structure and energies of Cu(I) Lewis-sites in excited spin-states
      4. Structure of the Lewis site in Cu(II) chabazite
      5. Energies of the Lewis site in Cu(II) chabazite
      6. Structure and energy of Cu(II) Lewis-sites in excited spin-states
    2. Co(II)-exchanged chabazite
      1. Structure of the Lewis site in Co(II) chabazite
      2. Energies of Co(II) Lewis sites in chabazite
      3. Structure and energies of excited spin-states
  6. COMPARISON WITH EXPERIMENT
    1. Structure of purely siliceous chabazite
    2. Structure of Lewis sites: Comparisons with XRD and EXAFS data
  7. CONCLUSIONS

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  2. Structure and properties of metal-exchanged zeolites studied using gradient-corrected and hybrid functionals. III. Energetics and vibrational spectroscopy of adsorbates
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KEYWORDS, PACS, and IPC

Keywords

density functional theory, ion exchange, organic compounds, spin polarised transport, zeolites

PACS

  • 82.30.Vy

    Homogeneous catalysis in solution, polymers and zeolites

  • 82.33.Jx

    Reactions in zeolites

  • 82.39.Wj

    Ion exchange, dialysis, osmosis, electro-osmosis, membrane processes

  • 71.15.Mb

    Density functional theory, local density approximation, gradient and other corrections

  • 82.30.Hk

    Chemical exchanges (substitution, atom transfer, abstraction, disproportionation, and group exchange)

International Patent Classification (IPC)

  • B01J47/00

    Ion-exchange processes in general; Apparatus therefor

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3676408

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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Figures (click on thumbnails to view enlargements)

FIG.1
Crystal structure of chabazite. Four unit-cells with different Al occupancy are shown: The purely siliceous unit cell with the four different O-positions around a tetrahedral site occupied by Si (a), a cell with one Al-Si substitution per cell (b), two Al-Si substitutions in the same six-membered ring (c), and two Al-Si substitutions in different rings (d). O atoms are displayed in red, Si atoms in yellow, and Al atoms in grey color. Possible locations of extra-framework cations are marked in blue. At site (I), the transition metal atom is located in the center of a six-membered ring, bonding to O(2) and O(3) atoms. At sites (IIa) and (IIb), the atom lies in the center of different eight-membered rings, bonding to O(1) and O(4), and to O(2) and O(4) atoms, respectively. see text for details.

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FIG.2
Coordination of a Cu(I) cation in a 6MR of chabazite [configuration (1)]. The extra-framework cation forms three (four) strong bonds to framework oxygen atoms if GGA (hybrid) functionals are used: two to activated O(2) and O(3) activated atoms closest to the Al-atom, one to a non-activated O(2). The fourth bond to the O(3) atom on the opposite side of the ring is formed only if hybrid functionals are used. The color-coding is the same as in Fig. 1. Only bonds around Cu(I) that are shorter than 3 Å are drawn, bonds drawn in light shading are formed only if hybrid functionals are used. See text for details.

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FIG.3
Three-fold coordination of a Cu(I) cation in a 8MR of chabazite [configuration (2)] to O(1), O(4), and O(2) framework atoms. See Fig. 2 and text for details.

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FIG.4
Twofold coordination of a Cu(I) cation in a 8MR of chabazite [configuration (3)], binding to activated O(2) and O(2) framework atoms. See Fig. 2 and text for details.

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FIG.5
Triplet-optimized coordination of a Cu(I) cation in a 6MR of chabazite [configuration (1)]. The extra-framework cation forms only two strong bonds to activated framework oxygen atoms O(2) and O(3). See Fig. 2 for the singlet GS-configurations and text for details.

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FIG.6
(a) and (b) Fourfold coordination of a Cu(II) cation in a 6MR of chabazite, with two Al atoms (a) and only one Al atom (b) in the 6MR [configurations (1) and (2)], respectively. (c) and (d) Threefold coordination of a Cu(II) cation in extra-framework site IIa [configurations (3) and (4) differ only in the location of the Al atoms]. (e) and (f) Threefold coordination of a Cu(II) cation in extra-framework site IIb [configurations (5) and (6)]. See Fig. 2, and text for details.

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FIG.7
Quadruplet-optimized coordination of a Cu(II) cation in a 6MR of chabazite [configuration (1)]. The extra-framework cation forms only two strong bonds to activated framework oxygen atoms O(2) and O(3). See Fig. 2 for the singlet GS-configuration, and text for details.

FIG.7 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

Supplemental Files (EPAPS)

Tables

Table I. Geometric data and energy gap of purely siliceous chabazite, calculated with different functionals. Lattice constants and interatomic distances are given in Å, the cell volume in Å3, angles in degrees, and the width of the bandgap in eV.

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Table II. Structural data for extra-framework cations Cu(I), Cu(II), and Co(II) in chabazite, calculated for different configurations and using both GGA (PW91, PBE) and hybrid (PBE0, HSE03, HSE06) functionals. All distances are given in Å.

View Table
Table III. Binding energy E of the extra-framework Cu-atom, energy difference ΔEspin of the relaxed first excited spin-state relative to the ground state, and energy difference ΔEsite with respect to the most stable configuration, calculated with different exchange-correlation functionals. All energies are given in eV.

View Table
Table IV. Binding energy E of extra-framework Co-atoms, energy difference ΔEspin between the relaxed spin ground sate and the relaxed first excited spin-state, and energy difference ΔEsite with respect to the most stable configuration, calculated with different exchange-correlation functionals. All energies are given in eV.

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