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Received February 19, 2002
Accepted April 3, 2002
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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
Department of Environmental & Applied Chemical Engineering, Kangnung National University, Kangnung 210-702, Korea 1Center for Catalytic Science and Technology, Department of Chemical Engineering, University of Delaware, Newark, Delaware 19716, USA
inksong@kangnung.ac.kr
Korean Journal of Chemical Engineering, July 2002, 19(4), 567-573(7), 10.1007/BF02699297
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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 Å. Exposure to pyridine also shifted NDR peak voltages of HPA samples_x000D_
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
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Eguchi K, Seiyama T, Yamazoe N, Katsuki S, Taketa H, J. Catal., 111, 336 (1988)
Hashimoto M, Misono M, Acta Cryst. C, 50, 231 (1994)
Hill CL, Prosser-McCartha CM, Coord. Chem. Rev., 143, 407 (1995)
Hipps KW, Lu X, Wang XD, Mazur U, J. Phys. Chem., 100(27), 11207 (1996)
Johansson MK, Gray SM, Johansson LS, J. Vac. Sci. Technol. B, 14(2), 1015 (1996)
Kaba MS, Song IK, Barteau MA, J. Phys. Chem., 100(50), 19577 (1996)
Kaba MS, Song IK, Barteau MA, J. Vac. Sci. Technol. A, 15(3), 1299 (1997)
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Keggin JF, Nature, 131, 908 (1933)
Kim HC, Moon SH, Lee WY, Chem. Lett., 447 (1991)
Kinne M, Barteau MA, Surf. Sci., 447, 105 (2000)
Kozhevnikov IV, Catal. Rev.-Sci. Eng., 37(2), 311 (1995)
Lee HJ, Ho W, Phys. Rev., B, Condens. Matter, 61, R16347 (2000)
Lee JK, Song IK, Lee WY, Korean J. Chem. Eng., 12(3), 384 (1995)
Lee WY, Song IK, Lee JK, Park GI, Lim SS, Korean J. Chem. Eng., 14(6), 432 (1997)
Lee WY, Song IK, HWAHAK KONGHAK, 38(3), 317 (2000)
Maboudian R, Carraro C, Weinberg WH, Surf. Sci. Lett., 280, L263 (1993)
Misono M, Catal. Rev.-Sci. Eng., 29, 269 (1987)
Okuhara T, Hu C, Hashimoto M, Misono M, Bull. Chem. Soc. Jpn., 67, 1186 (1994)
Okuhara T, Mizuno N, Misono M, Adv. Catal., 41, 113 (1996)
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Silva SL, Patel AA, Pham TM, Leibsle FM, Surf. Sci., 441, 351 (1999)
Song IK, Moon SH, Lee WY, Korean J. Chem. Eng., 8(1), 33 (1991)
Song IK, Kaba MS, Barteau MA, J. Phys. Chem., 100(44), 17528 (1996)
Song IK, Kaba MS, Barteau MA, Lee WY, HWAHAK KONGHAK, 35(3), 407 (1997)
Song IK, Kaba MS, Barteau MA, Lee WY, Catal. Today, 44(1-4), 285 (1998)
Song IK, Barteau MA, J. Mol. Catal. A-Chem., 182-183, 185 (2002)
Song IK, Shnitser RB, Cowan JJ, Hill CL, Barteau MA, Inorg. Chem., 41(5), 1292 (2002)
Steltenpohl A, Memmel N, Surf. Sci., 443, 13 (1999)
Stipe BC, Rezaei MA, Ho W, Gao S, Persson M, Lundqvist BI, Phys. Rev. Lett., 78, 4410 (1997)
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Strandberg R, Acta Chem. Scand A, 29, 359 (1975)
Tanaka K, Ozami A, J. Catal., 8, 1 (1967)
Watson BA, Barteau MA, Haggerty L, Lenhoff AM, Weber RS, Langmuir, 8, 1145 (1992)
Weber RS, J. Phys. Chem., 98(11), 2999 (1994)
Wouda PT, Nieuwenhuys BE, Schmid M, Varge P, Surf. Sci., 359, 17 (1996)
