SCIENCE CHINA Chemistry, Volume 60, Issue 7: 912-919(2017) https://doi.org/10.1007/s11426-016-9063-2

Clarification of copper species over Cu-SAPO-34 catalyst by DRIFTS and DFT study of CO adsorption

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  • ReceivedNov 15, 2016
  • AcceptedApr 17, 2017
  • PublishedMay 6, 2017


In this work, the nature, location and evolution of Cu+ ions in Cu-SAPO-34 are investigated by diffuse reflectance infrared Fourier transform spectrum (DRIFTS) of CO adsorption and density functional theory (DFT) calculation. By combination with DFT results, characteristic Cu+–CO bands located at 2154 and 2136 cm−1 are attributed to CO adsorbed on Cu+ ions located at sites I (in the plane of six-membered ring connected to the large cages) and site II (in the eight-membered ring cages near the tilted four membered ring) in the framework of H-SAPO-34 zeolite. Subsequently, both the influences of Cu loading and preparation method are considered and discussed. By varying the Cu loading, the site-occupation preference of Cu+ ions on site I is confirmed, especially at low Cu loadings. Through elevating the desorption temperature, migration of Cu+ ions is revealed because of the adsorption-induced effect. Furthermore, a facile and more efficient approach to introduce Cu+ ions into CHA zeolite, compared with solid-state ion exchange with CuCl and conventional ion exchange in aqueous solution, and the different preparation methods also result in different occupations of Cu+ ions.

Funded by

National Natural Science Foundation of China(21325626,21406120)


This work was supported by the National Natural Science Foundation of China (21325626, 21406120).

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

These authors contributed equally to this work.


The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.


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  • Figure 1

    Chabazite type structure with cationic sites (red balls) according to the Refs. [28,29]. Site I is in the plane of 6-MR; site I’ is slightly away from the plane of 6-MR toward the 8-MR cage of the structure; site II is in the 8-MR near the tilted 4-MR (color online).

  • Figure 2

    DRIFT spectra of Cu-S-Ac-5 sample exposed to CO. (a) Adsorption; (b) He flush at 293 K (color online).

  • Figure 3

    DRIFT spectra of CO desorption over Cu-S-Ac-5 sample in different temperature ranges. (a) 293–413 K; (b) 413–593 K. The darker color of the line represents the higher desorption temperature.

  • Figure 4

    (a–d) The optimized structure of Cu+-SAPO-34. (a, b) Front view and top view of Cu+ located in site I; (c, d) front view and side view of Cu+ at site II. (e–h) The optimized structure of CO molecule interaction with Cu+ at different sites. (e, f) Front view and top view of Cu+ located in site I; (g, h) front view and side view of Cu+ at site II (color online).

  • Figure 5

    DRIFT spectra of CO adsorbed on Cu-S-Ac-x (x=0.25–5) samples with different Cu loadings at 293 K (color online).

  • Figure 6

    DRIFT spectra of Cu-S-Cl catalyst exposed to CO. (a) Adsorption; (b) He flush at 293 K (color online).

  • Figure 7

    DRIFT spectra of Cu-S-IE catalyst exposed to CO. (a) Adsorption; (b) He flush at 293 K (color online).

  • Table 1   Bond lengths (Å) and linear vibrational frequency shift of CO adsorbed on extra-framework Cu in different sites


    RCu−O (Å)

    RC−O (Å)

    νexp (cm−1)

    νcal (cm−1)

    Δνexp (cm−1)

    Δνcal (cm−1)


    2.0685, 2.0434







    2.0209, 2.0909






    Gas-phase CO







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