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

Abstract

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

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

Sponsoring Org.:: USDOE

OSTI Identifier:: 1417300

Grant/Contract Number:: AC02-76SF00515

Resource 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

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

Citation Formats


                    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., 2017. 
        Web.  doi:10.1007/s11244-017-0850-9.

Copy to clipboard


                    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.

Copy to clipboard


                    Schumann, Julia, Kröhnert, Jutta, Frei, Elias, Schlögl, Robert, and Trunschke, Annette. Mon .  
        "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.

Copy to clipboard


                    
@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}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1007/s11244-017-0850-9

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 3 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

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

Similar Records in DOE PAGES and OSTI.GOV collections:

Hydrogenation of CO ₂ on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis

Journal Article Palomino, Robert M. ; Ramirez, Pedro J. ; Liu, Zongyuan ; ... - Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

The results of kinetic tests and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) show the important role played by a ZnO–copper interface in the generation of CO and the synthesis of methanol from CO ₂ hydrogenation. The deposition of nanoparticles of ZnO on Cu(100) and Cu(111), θ _oxi < 0.3 monolayer, produces highly active catalysts. The catalytic activity of these systems increases in the sequence: Cu(111) < Cu(100) < ZnO/Cu(111) < ZnO/Cu(100). The structure of the copper substrate influences the catalytic performance of a ZnO–copper interface. Furthermore, size and metal–oxide interactions affect the chemical and catalytic properties of the oxide making themore »« less
Cited by 2
DOI: 10.1021/acs.jpcb.7b06901

Full Text Available
Hydrogenation of CO ₂ to methanol on CeO _x/Cu(111) and ZnO/Cu(111) catalysts: Role of the metal-oxide interface and importance of Ce ³⁺ sites

Journal Article Senanayake, Sanjaya D. ; Ramirez, Pedro J. ; Waluyo, Iradwikanari ; ... - Journal of Physical Chemistry. C

The role of the interface between a metal and oxide (CeO _x–Cu and ZnO–Cu) is critical to the production of methanol through the hydrogenation of CO ₂ (CO ₂ + 3H ₂ → CH ₃OH + H ₂O). The deposition of nanoparticles of CeO _x or ZnO on Cu(111), θ _oxi < 0.3 monolayer, produces highly active catalysts for methanol synthesis. The catalytic activity of these systems increases in the sequence: Cu(111) < ZnO/Cu(111) < CeO _x/Cu(111). The apparent activation energy for the CO ₂ → CH ₃OH conversion decreases from 25 kcal/mol on Cu(111) to 16 kcal/mol on ZnO/Cu(111)more »« less
Cited by 28
DOI: 10.1021/acs.jpcc.5b12012

Full Text Available
Hydrogenation of CO ₂ to Methanol on CeO _x /Cu(111) and ZnO/Cu(111) Catalysts: Role of the Metal–Oxide Interface and Importance of Ce ³⁺ Sites

Journal Article Senanayake, Sanjaya D. ; Ramírez, Pedro J. ; Waluyo, Iradwikanari ; ... - Journal of Physical Chemistry. C

The role of the interface between a metal and oxide (CeO _x-Cu and ZnO-Cu) is critical to the production of methanol through the hydrogenation of CO ₂(CO ₂+ 3H ₂→ CH ₃OH + H ₂O). The deposition of nanoparticles of CeO _x or ZnO on Cu(111), Θ _oxi< 0.3 monolayer, produces highly active catalysts for methanol synthesis. The catalytic activity of these systems increases in the sequence: Cu(111) < ZnO/Cu(111) < CeO _x/Cu(111). The apparent activation energy for the CO ₂→ CH ₃OH conversion decreases from 25 kcal/mol on Cu(111) to 16 kcal/mol on ZnO/Cu(111) and 13 kcal/mol on CeOmore »« less
Cited by 28
DOI: 10.1021/acs.jpcc.5b12012

Full Text Available
Methanol and C sub 2 oxygenate synthesis over cesium doped Cu/ZnO and Cu/ZnO/Al sub 2 O sub 3 catalysts: A study of selectivity and sup 13 C incorporation patterns

Journal Article Nunan, J.G. ; Bogdan, C.E. ; Klier, K. ; ... - Journal of Catalysis; (USA)

Cesium formate significantly promotes methanol and C{sub 2} oxygenate (methyl formate MF and ethanol EtOH) synthesis over the Cu/ZnO catalyst. {sup 13}C NMR analysis of the product obtained from {sup 13}CH{sub 3}OH and {sup 12}CO/H{sub 2} shows that MF is formed by direct carbonylation of methanol and EtOH is formed by coupling of oxygenated C{sub 1} intermediates originating from methanol. The C{sub 1} coupling mechanism overrides various CO insertion paths to ethanol over the present Cs/Cu/ZnO catalyst. The kinetic significance of C{sub 1} aldehydic species such as adsorbed formyl and formaldehyde is supported by experimental evidence and theoretical calculations. 71more » refs.« less
DOI: 10.1016/0021-9517(88)90268-0
Infrared spectroscopic study of methanol synthesis on CuO-ZnO-SiO/sub 2/ catalysts

Journal Article Visser-Luirink, G. ; Matulewicz, E.R. ; Mol, J.C. - J. Phys. Chem.; (United States)

In the synthesis of methanol on a CuO-ZnO-SiO/sub 2/ catalyst both the zinc oxide content in the catalyst and the presence of hydrogen influence the adsorption of CO on copper under reaction conditions; hydrogen adsorption on zinc probably inhibits the adsorption of CO. In a series of CuO-ZnO-SiO/sub 2/ catalysts with varying CuO/ZnO ratio, the maximum intensity of the infrared CO absorption band in a CO/H/sub 2/ atmosphere and the optimum activity for methanol synthesis coincide.
DOI: 10.1021/j100232a002

Similar Records

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

Abstract

Citation Formats

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

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