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The Interaction of Formic Acid with Zinc Oxide: A Combined Experimental and Theoretical Study on Single Crystal and Powder Samples

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Abstract

We present azimuth- and polarization-dependent infrared spectroscopy results obtained under ultra-high vacuum conditions on surface species formed by the interaction of formic acid with the mixed-terminated ZnO(10\(\bar{1}\)0) surface. Since there are no previous IRRAS data for formic-acid derived species on any ZnO single crystal surfaces, we have carried out calculations using density function theory to aid the interpretation of the results. From our combined experimental and theoretical data we conclude that two different formate species are formed. The more strongly bound species is a bidentate with the formate molecular plane oriented along the [1\(\bar{2}\)10] direction. The less strongly bound species is a quasi-bidentate with its molecular plane oriented along the [0001] direction. This second species is characterized by a strong hydrogen bond between a surface OH species and the formate. In addition, IR data were recorded for the same molecule adsorbed on commercial ZnO nanoparticles. The different bands of the powder IR-data are assigned on the basis of the experimental and theoretical results obtained for the single crystal surface. This study demonstrates the importance of the Surface Science approach to heterogeneous catalysis also for ZnO, an important catalyst for the conversion of syngas to methanol.

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Acknowledgements

M.B. and Q. L. thank the financial support from the Helmholtz Research School “Energy-related catalysis”. We thank S. Heißler (IFG) for his support and F. Bebensee for helpful discussions.

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Authors and Affiliations

  1. Institute of Functional Interfaces, Karlsruhe Institute of Technology, 76021, Karlsruhe, Germany

    Maria Buchholz, Alexei Nefedov & Christof Wöll

  2. Institute of Nanotechnology, Karlsruhe Institute of Technology, 76021, Karlsruhe, Germany

    Qiang Li & Karin Fink

  3. Laboratory of Industrial Chemistry, Ruhr-University Bochum, 44780, Bochum, Germany

    Heshmat Noei, Yuemin Wang & Martin Muhler

  4. Deutsches Elektronen-Synchrotron (DESY), 22607, Hamburg, Germany

    Heshmat Noei

  5. Department of Physical Chemistry I, Ruhr-University Bochum, 44780, Bochum, Germany

    Yuemin Wang

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  1. Maria Buchholz
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  2. Qiang Li
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  3. Heshmat Noei
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  4. Alexei Nefedov
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  8. Christof Wöll
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Correspondence to Christof Wöll.

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Buchholz, M., Li, Q., Noei, H. et al. The Interaction of Formic Acid with Zinc Oxide: A Combined Experimental and Theoretical Study on Single Crystal and Powder Samples. Top Catal 58, 174–183 (2015). https://doi.org/10.1007/s11244-014-0356-7

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