IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer

doi:10.1007/s11244-017-0850-9

Title: IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer

Carbon monoxide was applied as probe molecule to compare the surface of a ZnO-containing (Cu/ZnO:Al) and a ZnO-free (Cu/MgO) methanol synthesis catalyst (copper content 70 atomic %) after reduction in hydrogen at 523 K by DRIFT spectroscopy. Nano-structured, mainly metallic copper was detected on the surface of the Cu/MgO catalyst. In contrast, the high energy of the main peak in the spectrum of CO adsorbed on reduced Cu/ZnO:Al (2125 cm ^-1) proves that metallic copper is largely absent on the surface of this catalyst. The band is assigned to Zn ^δ+–CO. The presence of not completely reduced Cu ^δ+–CO species cannot be excluded. The results are interpreted in terms of a partial coverage of the copper nano-particles in the Cu/ZnO:Al catalyst by a thin layer of metastable, defective zinc oxide. Minor contributions in the spectrum at 2090 and 2112 cm ^-1 due to nano-structured Cu ⁰–CO and CO adsorbed on highly defective Cu ⁰, respectively, indicate that the coverage of metallic copper is not complete.

Authors:

Schumann, Julia ^[1] ; Kröhnert, Jutta ^[2] ; Frei, Elias ^[2] ; Schlögl, Robert ^[3] ; Trunschke, Annette ^[2]

Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Department of Inorganic Chemistry; Stanford Univ., CA (United States). Department of Chemical Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Department of Inorganic Chemistry
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Department of Inorganic Chemistry ; Max Planck Institute for Chemical Energy Conversion, Mulheim (Germany)

Publication Date:: 2017-08-28

Grant/Contract Number:: AC02-76SF00515

Type:: Accepted Manuscript

Journal Name:: Topics in Catalysis

Additional Journal Information:: Journal Volume: 60; Journal Issue: 19-20; Journal ID: ISSN 1022-5528

Publisher:: Springer

Research Org:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Org:: USDOE

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cu; Methanol synthesis catalyst; CO adsorption; DRIFTS

OSTI Identifier:: 1417300


                    Schumann, Julia, Kröhnert, Jutta, Frei, Elias, Schlögl, Robert, and Trunschke, Annette. IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer.  United States: N. p.,  
        Web.  doi:10.1007/s11244-017-0850-9.

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                    Schumann, Julia, Kröhnert, Jutta, Frei, Elias, Schlögl, Robert, & Trunschke, Annette. IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer.  United States.  doi:10.1007/s11244-017-0850-9.

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                    Schumann, Julia, Kröhnert, Jutta, Frei, Elias, Schlögl, Robert, and Trunschke, Annette. 2017.  
        "IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer".  United States.  
        doi:10.1007/s11244-017-0850-9.  https://www.osti.gov/servlets/purl/1417300.

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@article{osti_1417300,

  title        = {IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer},

  author       = {Schumann, Julia and Kröhnert, Jutta and Frei, Elias and Schlögl, Robert and Trunschke, Annette},

  abstractNote = {Carbon monoxide was applied as probe molecule to compare the surface of a ZnO-containing (Cu/ZnO:Al) and a ZnO-free (Cu/MgO) methanol synthesis catalyst (copper content 70 atomic %) after reduction in hydrogen at 523 K by DRIFT spectroscopy. Nano-structured, mainly metallic copper was detected on the surface of the Cu/MgO catalyst. In contrast, the high energy of the main peak in the spectrum of CO adsorbed on reduced Cu/ZnO:Al (2125 cm-1) proves that metallic copper is largely absent on the surface of this catalyst. The band is assigned to Znδ+–CO. The presence of not completely reduced Cuδ+–CO species cannot be excluded. The results are interpreted in terms of a partial coverage of the copper nano-particles in the Cu/ZnO:Al catalyst by a thin layer of metastable, defective zinc oxide. Minor contributions in the spectrum at 2090 and 2112 cm-1 due to nano-structured Cu0–CO and CO adsorbed on highly defective Cu0, respectively, indicate that the coverage of metallic copper is not complete.},

  doi          = {10.1007/s11244-017-0850-9},

  journal      = {Topics in Catalysis},

  number       = 19-20,

  volume       = 60,

  place        = {United States},

  year         = {2017},

  month        = {8}

}

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10.1007/s11244-017-0850-9
https://doi.org/10.1007/s11244-017-0850-9

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Works referenced in this record:

The Active Site of Methanol Synthesis over Cu/ZnO/Al₂O₃ Industrial Catalysts
journal, April 2012

Behrens, M.; Studt, F.; Kasatkin, I.
Science, Vol. 336, Issue 6083, p. 893-897
DOI: 10.1126/science.1219831

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Title: IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer

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