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Scanning tunneling microscopy (STM) and tunneling spectroscopy (TS) of heteropolyacid (HPA) self-assembled monolayers (SAMS): connecting nano properties to bulk properties

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Abstract

Nanoscale investigation of Keggin-type heteropolyacid (HPA) self-assembled monolayers (SAMs) was performed by scanning tunneling microscopy (STM) and tunneling spectroscopy (TS) in order to relate surface properties of nanostructured HPA monolayers to bulk redox and acid properties of HPAs. Cation-exchanged, polyatomsubstituted, and heteroatom-substituted HPAs were examined to see the effect of different substitutions. HPA samples were deposited on HOPG surfaces in order to obtain images and tunneling spectra by STM before and after pyridine adsorption. All HPA samples formed well-ordered monolayer arrays, and exhibited negative difference resistance (NDR) behavior in their tunneling spectra. NDR peaks measured for fresh HPA samples appeared at less negative potentials for higher reduction potentials of the HPAs. These changes could also be correlated with the electronegativities of the substituted atoms. Introduction of pyridine into the HPA arrays increased the lattice constants of the two-dimensional HPA arrays by ca. 6 A. Exposure to pyridine also shifted NDR peak voltages of HPA samples to less negative values in the tunneling spectroscopy measurements. The NDR shifts of HPAs obtained before and after pyridine adsorption were correlated with the acid strengths of the HPAs. This work demonstrates that tunneling spectra measured by STM can fingerprint acid and redox properties of HPA monolayers on the nanometer scale.

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References

  • Ai, M., “Effects of Cations Introduced into 12-Molybdophosphoric Acid on the Catalyst Properties,”Appl. Catal.,4, 245 (1982).

    Article  CAS  Google Scholar 

  • Altenau, J. J., Pope, M. T., Prados, R.A. and So, H., “Models for Heteropoly Blues. Degree of Valence Trapping in Vanadium(IV)-and Molybdenum(V)-substituted Keggin Anions,”Inorg. Chem.,14, 417 (1975).

    Article  CAS  Google Scholar 

  • Brown, G. M., Noe-Spirlet, M. R., Busing, W. R. and Levy, H.A., “Dodecatungstophosphoric Acid Hexahydrate, (H5O2/+)3(PW12O40/3-). The True Structure of Keggin’s Pentahydrate from Single-crystal X-ray and Neutron Diffraction Data,”Acta. Cryst. B,33, 1038 (1977).

    Article  Google Scholar 

  • Carroll, D. L., Czerw, R., Tekeleab, D. and Smith, Jr., D.W., “Anomalous Periodic Structure of Polypropylene Chains Observed with Scanning Tunneling Microscopy,”Langmuir,16, 3574 (2000).

    Article  CAS  Google Scholar 

  • Cernota, P., Yoon, H.A., Salmeron, M. and Somorjai, G.A., “The Structure of para-Xylene and meta-Xylene Adsorbed on Rh(111) Studied by Scanning Tunneling Microscopy,”Surf. Sci.,415, 351 (1998).

    Article  CAS  Google Scholar 

  • Cernota, P., Rider, K., Yoon, H.A., Salmeron, M. and Somorjai, G.A., “Dense Structures Formed by CO on Rh(111) Studied by Scanning Tunneling Microscopy,”Surf. Sci.,445, 249 (2000).

    Article  CAS  Google Scholar 

  • Chen, Q., Perry, C. C., Frederick, B.G., Murray, P.W., Haq, S. and Richardson, N.V., “Structural Aspects of the Low-temperature Deprotonation of Benzoic Acid on Cu(110) Surfaces,”Surf. Sci.,446, 63 (2000).

    Article  CAS  Google Scholar 

  • Chiang, S., “Scanning Tunneling Microscopy Imaging of Small Adsorbed Molecules on Metal Surfaces in an Ultrahigh Vacuum Environment,”Chem. Rev.,97, 1083 (1997).

    Article  CAS  Google Scholar 

  • Choi, J. S., Song, I.K. and Lee, W.Y., “A Composite Catalytic Membrane Reactor Using Heteropolyacid-blended Polymer Membrane,”Korean J. Chem. Eng.,17, 280 (2000).

    Article  CAS  Google Scholar 

  • Eguchi, K., Seiyama, T., Yamazoe, N., Katsuki, S. and Taketa, H., “Electronic Structures of XMo12O40 Heteropolyanions (X=P, As, Si, and Ge) and Their Reduction Behavior,”J. Catal.,111, 336 (1988).

    Article  CAS  Google Scholar 

  • Hashimoto, M. and Misono, M., “[(C5H5N)2H]3[PW12O40],”Acta Cryst. C,50, 231 (1994).

    Article  Google Scholar 

  • Hill, C. L. and Prosser-McCartha, C. M., “Homogeneous Catalysis by Transition Metal Oxygen Anion Clusters,”Coord. Chem. Rev.,143, 407 (1995).

    Article  CAS  Google Scholar 

  • Hipps, K.W., Lu, X., Wang, X. D. and Mazur, U., “Metal d-Orbital Occupation-Dependent Images in the Scanning Tunneling Microscopy of Metal Phthalocyanines,”J. Phys. Chem.,100, 11207 (1996).

    Article  CAS  Google Scholar 

  • Johansson, M.K.-J., Gray, S.M. and Johansson, L. S.O., “Studies of Low Coverage Adsorption of Li on Si(001): Observation of Negative Differential Resistance and Electron Trapping,”J. Vac. Sci. Technol. B,14, 1015 (1996).

    Article  CAS  Google Scholar 

  • Kaba, M. S., Song, I. K. and Barteau, M.A., “Ordered Array Formation and Negative Differential Resistance Behavior of Cation-exchanged Heteropoly Acids Probed by Scanning Tunneling Microscopy,”J. Phys. Chem.,100, 19577 (1996).

    Article  CAS  Google Scholar 

  • Kaba, M. S., Song, I.K. and Barteau, M.A., “Investigation of Framework and Cation Substitutions in Keggin-type Heteropoly Acids Probed by Scanning Tunneling Microscopy and Tunneling Spectroscopy,”J. Vac. Sci. Technol. A,15, 1299 (1997).

    Article  CAS  Google Scholar 

  • Kaba, M. S., Song, I.K., Duncan, D. C., Hill, C. L. and Barteau, M.A., “Molecular Shapes, Orientation, and Packing of Polyoxometalate Arrays Imaged by Scanning Tunneling Microscopy,”Inorg. Chem.,37, 398 (1998).

    Article  CAS  Google Scholar 

  • Kaba, M. S., Barteau, M. A., Lee, W.Y. and Song, I.K., “Nanoscale Characterization of Acid Properties of Heteropolyacids by Scanning Tunneling Microscopy and Tunneling Spectroscopy,”Appl. Catal. A,194, 129 (2000).

    Article  Google Scholar 

  • Kaba, M. S., Song, I.K. and Barteau, M.A., “Site Identification of Mixed Arrays of Keggin-type Heteropolyacids (HPAs) by Scanning Tunneling Microscopy and Tunneling Spectroscopy,”J. Phys. Chem. B,106, 2337 (2002).

    Article  CAS  Google Scholar 

  • Keggin, J. F., “Structure of the Molecule of 12-Phosphotungstic Acid,”Nature,131, 908 (1933).

    CAS  Google Scholar 

  • Kim, H.C., Moon, S.H. and Lee, W.Y., “Nature of the Effect of Counter Cations on the Redox Property of 12-Molybdophosphates,” Chem. Lett., 447 (1991).

  • Kinne, M. and Barteau, M.A., “STM and TS Investigations of Silver Polyoxometalate Monolayers: Model Compounds and Potential Multifunctional Oxidation Catalysts,”Surf. Sci.,447, 105 (2000).

    Article  CAS  Google Scholar 

  • Kozhevnikov, I. V., “Heteropoly Acids and Related Compounds as Catalysts for Fine Chemical Synthesis,”Catal. Rev.-Sci. Eng.,37, 311 (1995).

    Article  CAS  Google Scholar 

  • Lee, H. J. and Ho, W., “Structure Determination by Single-molecule Vibrational Spectroscopy and Microscopy: Contrast between Copper and Iron Carbonyls,”Phy. Rev. B,61, R16347 (2000).

    Article  CAS  Google Scholar 

  • Lee, J.K., Song, I.K. and Lee, W.Y., “Separation of H2/CO by the Selective Sorption Property of H3PMo12O40 Embedded in PVA Membrane,”Korean J. Chem. Eng.,12, 384 (1995).

    CAS  Google Scholar 

  • Lee, W.Y., Song, I. K., Lee, J. K., Park, G. I. and Lim, S. S., “Design of Heteropoly Compound-imbedded Polymer Film Catalysts and Their Application,”Korean J. Chem. Eng.,14, 432 (1997).

    CAS  Google Scholar 

  • Lee, W.Y. and Song, I.K., “Design of Heteropolyacid-imbedded Polymer Films and Catalytic Membranes,”HWAHAK KONGHAK,38, 317 (2000).

    CAS  Google Scholar 

  • Maboudian, R., Carraro, C. and Weinberg, W. H., “Resonant Scanning Tunneling Spectroscopy of a Quantum-well Heterostructure,”Surf. Sci. Lett.,280, L263 (1993).

    Article  Google Scholar 

  • Misono, M., “Heterogeneous Catalysis by Heteropoly Compounds of Molybdenum and Tungsten,”Catal. Rev.-Sci. Eng.,29, 269 (1987).

    Article  CAS  Google Scholar 

  • Okuhara, T., Hu, C., Hashimoto, M. and Misono, M., “Acid Strength of Heteropolyacids and Its Correlation with Catalytic Activity,”Bull. Chem. Soc. Jpn.,67, 1186 (1994).

    Article  CAS  Google Scholar 

  • Okuhara, T., Mizuno, N. and Misono, M., “Catalytic Chemistry of Heteropoly Compounds,”Adv. Catal.,41, 113 (1996).

    CAS  Google Scholar 

  • Park, G. I., Lee, W.Y. and Song, I.K., “MTBE Synthesis by Keggintype and Dawson-type Heteropolyacids,”HWAHAK KONGHAK,38, 155 (2000).

    CAS  Google Scholar 

  • Pope, M. T. and Müller, A. (Eds.), “Polyoxometalates: from Platonic Solids to Anti-retroviral Activity,” Kluwer Academic Publishers, Dordrecht, The Netherlands (1994).

    Google Scholar 

  • Sadakane, M. and Steckhan, E., “Electrochemical Properties of Polyoxometalates as Electrocatalysts,”Chem. Rev.,98, 219 (1998).

    Article  CAS  Google Scholar 

  • Silva, S. L., Patel, A.A., Pham, T. M. and Leibsle, F. M., “Scanning Tunneling Microscopy Studies of Methoxy and Formate on Cu(110) Surfaces Resulting from Reactions with Methyl Formate, Methanol, and Formic Acid,”Surf. Sci.,441, 351 (1999).

    Article  CAS  Google Scholar 

  • Song, I.K., Moon, S.H. and Lee, W.Y., “Catalytic Properties of Thermally Decomposed 12-Molybdophosphoric and 10-Molybdo-2-vanadophosphoric Acids,”Korean J. Chem. Eng.,8, 33 (1991).

    Article  CAS  Google Scholar 

  • Song, I.K., Kaba, M. S. and Barteau, M.A., “STM Investigation of Pyridine Interaction with Heteropoly Acid Monolayers,”J. Phys. Chem.,100, 17528 (1996).

    Article  CAS  Google Scholar 

  • Song, I. K., Kaba, M. S., Barteau, M. A. and Lee, W. Y., “Scanning Tunneling Microscopy of Self-assembled Heteropoly Acid Monolayers Deposited on Graphite Surface: NDR Behavior and Redox Activity,”HWAHAK KONGHAK,35, 407 (1997).

    CAS  Google Scholar 

  • Song, I.K., Kaba, M. S., Barteau, M.A. and Lee, W.Y., “Investigation of Redox Potential and Negative Differential Resistance Behavior of Heteropolyacids by Scanning Tunneling Microscopy,”Catal. Today,44, 285 (1998).

    Article  CAS  Google Scholar 

  • Song, I.K. and Barteau, M.A., “Bulk Redox Properties of Heteropolyacids (HPAs) Determined from Surface Properties of Nanostructured Heteropolyacid Monolayers,”J. Mol. Catal. A,182-183, 185 (2002).

    Article  CAS  Google Scholar 

  • Song, I. K., Shnitser, R. B., Cowan, J. J., Hill, C. L. and Barteau, M.A., “Nanoscale Characterization of Redox and Acid Properties of Keggin-type Heteropolyacids by Scanning Tunneling Microscopy and Tunneling Spectroscopy: Effect of Heteroatom Substitution,”Inorg. Chem.,41, 1292 (2002).

    Article  CAS  Google Scholar 

  • Steltenpohl, A. and Memmel, N., “Adsorption Site of Oxygen on Pd (111),”Surf. Sci.,443, 13 (1999).

    Article  CAS  Google Scholar 

  • Stipe, B. C., Rezaei, M.A., Ho, W., Gao, S., Persson, M. and Lundqvist, B. I., “Single-Molecule Dissociation by Tunneling Electrons,”Phy. Rev. Lett.,78, 4410 (1997).

    Article  CAS  Google Scholar 

  • Stipe, B. C., Rezaei, M. A. and Ho, W., “Single-molecule Vibrational Spectroscopy and Microscopy,”Science,280, 1732 (1998).

    Article  CAS  Google Scholar 

  • Strandberg, R., “Multicomponent Polyanions. 13. The Crystal Structure of a Hydrated Dodecamolybdophosphoric Acid, H3Mo12PO40 (H2O)29-31,”Acta Chem. Scand. A,29, 359 (1975).

    Article  Google Scholar 

  • Tanaka, K. and Ozami, A., “Acid-Base Properties and Catalytic Activity of Solid Surfaces,”J. Catal.,8, 1 (1967).

    Article  CAS  Google Scholar 

  • Watson, B.A., Barteau, M.A., Haggerty, L., Lenhoff, A. M. and Weber, R. S., “Scanning Tunneling Microscopy and Tunneling Spectroscopy of Ordered Hetero-and Iso-polyacid Arrays on Graphite,”Langmuir,8, 1145 (1992).

    Article  CAS  Google Scholar 

  • Weber, R. S., “Molecular Orbital Study of C-H Bond Breaking during the Oxidative Dehydrogenation of Methanol Catalyzed by Metal Oxide Surfaces,”J. Phys. Chem.,98, 2999 (1994).

    Article  CAS  Google Scholar 

  • Wouda, P. T., Nieuwenhuys, B. E., Schmid, M. and Varge, P., “Chemically Resolved STM on a PtRh(100) Surface,”Surf. Sci.,359, 17 (1996).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Environmental & Applied Chemical Engineering, Kangnung National University, 210-702, Kangnung, Korea

    In Kyu Song & Mark A. Barteau

  2. Center for Catalytic Science and Technology, Department of Chemical Engineering, University of Delaware, 19716, Newark, Delaware, USA

    Mark A. Barteau

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  1. In Kyu Song
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  2. Mark A. Barteau
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Correspondence to In Kyu Song.

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This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University.

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Song, I.K., Barteau, M.A. Scanning tunneling microscopy (STM) and tunneling spectroscopy (TS) of heteropolyacid (HPA) self-assembled monolayers (SAMS): connecting nano properties to bulk properties. Korean J. Chem. Eng. 19, 567–573 (2002). https://doi.org/10.1007/BF02699297

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