Abstract

The heterogeneity of metal island films electrodeposited on conductive metal oxide modified internal reflection elements is shown to provide a variable attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) response. A self-assembled monolayer of a ferrocene-terminated thiol monolayer (FcC11SH) was formed on the gold islands covering a single substrate, which was measured using both a conventional spectrometer and a custom-built horizontal microscope. Cyclic voltammetry and ATR-SEIRAS results reveal that the FcC11SH-modified substrate undergoes a reversible electron transfer and an associated re-orientation of both the ferrocene/ferrocenium headgroup and the hydrocarbon backbone. The magnitude of the absorption signal arising from the redox changes in the monolayer, as well as the IR signature arising from the ingress/egress of the perchlorate counterions, is shown to depend significantly on the size of the infrared beam spot when using a conventional Fourier transform infrared spectrometer. By performing equivalent measurements on a horizontal microscope, the primary cause of the differences in the signal level is found to be the heterogeneity in the density of gold islands on the conductive metal oxide.

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2020 (3)

O.Q. Carvalho, P. Adiga, S.K. Murthy, J.L. Fulton, et al. “Understanding the Role of Surface Heterogeneities in Electrosynthesis Reactions”. iScience. 2020; 23(12): 101814.

X.-Y. Ma, C. Ding, H. Li, K. Jiang, et al. “Revisiting the Acetaldehyde Oxidation Reaction on a Pt Electrode by High-Sensitivity and Wide-Frequency Infrared Spectroscopy”. J. Phys. Chem. Lett. 2020; 11(20): 8727–8734.

E. Strelcov, C. Arble, H. Guo, B.D. Hoskins, et al. “Nanoscale Mapping of the Double Layer Potential at the Graphene–Electrolyte Interface”. Nano Lett. 2020; 20(2): 1336–1344.

2019 (6)

Y.-H. Lu, J.M. Larson, A. Baskin, X. Zhao, et al. “Infrared Nanospectroscopy at the Graphene–Electrolyte Interface”. Nano Lett. 2019; 19(8): 5388–5393.

I.R. Andvaag, T.A. Morhart, O.J.R. Clarke, I.J. Burgess. “Hybrid Gold–Conductive Metal Oxide Films for Attenuated Total Reflectance Surface Enhanced Infrared Absorption Spectroscopy”. ACS Appl. Nano Mater. 2019; 2(3): 1274–1284.

C. Zhu, B. Lan, R.-L. Wei, et al. “Potential-Dependent Selectivity of Ethanol Complete Oxidation on Rh Electrode in Alkaline Media: A Synergistic Study of Electrochemical ATR SEIRAS and IRAS”. ACS Catal. 2019; 9(5): 4046–4053.

M.J.S. Farias, J.M. Feliu. “Determination of Specific Electrocatalytic Sites in the Oxidation of Small Molecules on Crystalline Metal Surfaces”. Top. Curr. Chem. 2019; 377(1): 5.

J.A. Sigrist, E.S. Lins, T.A. Morhart, et al. “Optimization of a Commercial Variable Angle Accessory for Entry Level Users of Electrochemical Attenuated Total Reflection Surface-Enhanced Infrared Absorption Spectroscopy (ATR SEIRAS)”. Appl. Spectrosc. 2019; 73(12): 1394–1402.

T.A. Morhart, S.T. Read, G. Wells, M. Jacobs, et al. “Micromachined Multigroove Silicon ATR FT-IR Internal Reflection Elements for Chemical Imaging of Microfluidic Devices”. Anal. Methods. 2019; 11(45): 5776–5783.

2018 (4)

T.A. Morhart, S. Read, G. Wells, M. Jacobs, et al. “Attenuated Total Reflection Fourier Transform Infrared (ATR FT-IR) Spectromicroscopy Using Synchrotron Radiation and Micromachined Silicon Wafers for Microfluidic Applications”. Appl. Spectrosc. 2018; 72(12): 1781–1789.

R.A. Wong, Y. Yokota, M. Wakisaka, et al. “Discerning the Redox-Dependent Electronic and Interfacial Structures in Electroactive Self-Assembled Monolayers”. J. Am. Chem. Soc. 2018; 140(42): 13672–13679.

D. Bizzotto, I.J. Burgess, T. Doneux, et al. “Beyond Simple Cartoons: Challenges in Characterizing Electrochemical Biosensor Interfaces”. ACS Sens. 2018; 3(1): 5–12.

G.V. Fortunato, E. Pizzutilo, A.M. Mingers, O. Kasian, et al. “Impact of Palladium Loading and Interparticle Distance on the Selectivity for the Oxygen Reduction Reaction Toward Hydrogen Peroxide”. J. Phys. Chem. C. 2018; 122(28): 15878–15885.

2017 (2)

K. Jiang, J.-Y. Wang, T.-T. Zhao, W.-B. Cai. “Formic Acid Oxidation at Palladium Electrode in Acidic Media Containing Chloride Anions: An In Situ ATR SEIRAS Investigation”. J. Electroanal. Chem. 2017; 800: 77–81.

Y. Feng, E.R. Dionne, V. Toader, et al. “Odd–Even Effects in Electroactive Self-Assembled Monolayers Investigated by Electrochemical Surface Plasmon Resonance and Impedance Spectroscopy”. J. Phys. Chem. C. 2017; 121(44): 24626–24640.

2016 (2)

K. Tu, M.J. Lardner, T.A. Morhart, S.M. Rosendahl, et al. “Spatial Mapping of Methanol Oxidation Activity on a Monolithic Variable-Composition PtNi Alloy Using Synchrotron Infrared Microspectroscopy”. J. Phys. Chem. C. 2016; 120(41): 23640–23647.

H. Mistry, F. Behafarid, R. Reske, A.S. Varela, et al. “Tuning Catalytic Selectivity at the Mesoscale via Interparticle Interactions”. ACS Catal. 2016; 6(2): 1075–1080.

2015 (3)

M.J. Lardner, K. Tu, S.M. Rosendahl, et al. “Spatiotemporal Mapping of Diffusion Layers Using Synchrotron Infrared Radiation”. Electrochim. Acta. 2015; 162: 72–78.

R. Schlögl. “Heterogeneous Catalysis”. Angew. Chem. Int. Ed. 2015; 54(11): 3465–3520.

N. Nerngchamnong, D. Thompson, L. Cao, L. Yuan, et al. “Nonideal Electrochemical Behavior of Ferrocenyl–Alkanethiolate SAMs Maps the Microenvironment of the Redox Unit”. J. Phys. Chem. C. 2015; 119(38): 21978–21991.

2014 (1)

U.E. Zhumaev, A.S. Lai, I.V. Pobelov, A. Kuzume, et al. “Quantifying Perchlorate Adsorption on Au(111) Electrodes”. Electrochim. Acta. 2014; 146: 112–118.

2013 (2)

A.V. Rudnev, U. Zhumaev, T. Utsunomiya, C. Fan, et al. “Ferrocene-Terminated Alkanethiol Self-Assembled Monolayers: An Electrochemical and In Situ Surface-Enhanced Infra-Red Absorption Spectroscopy Study”. Electrochim. Acta. 2013; 107: 33–44.

H. Tian, Y. Dai, H. Shao, H.-Z. Yu. “Modulated Intermolecular Interactions in Ferrocenylalkanethiolate Self-Assembled Monolayers on Gold”. J. Phys. Chem. C. 2013; 117(2): 1006–1012.

2012 (1)

S.R. Smith, S. Han, A. McDonald, et al. “An Electrochemical Approach to Fabricate a Heterogeneous Mixed Monolayer on Planar Polycrystalline Au and its Characterization with Lateral Force Microscopy”. J. Electroanal. Chem. 2012; 666: 76–84.

2008 (1)

A. Schneider, L. Colmenares, Y.E. Seidel, Z. Jusys, et al. “Transport Effects in the Oxygen Reduction Reaction on Nanostructured, Planar Glassy Carbon Supported Pt/GC Model Electrodes”. Phys. Chem. Chem. Phys. 2008; 10(14): 1931–1943.

2006 (2)

S.-J. Huo, X.-K. Xue, Q.-X. Li, et al. “Extending in Situ Attenuated-Total-Reflection Surface-Enhanced Infrared Absorption Spectroscopy to Ni Electrodes”. J. Phys. Chem. B. 2006; 110(9): 4162–4169.

L.Y.S. Lee, T.C. Sutherland, S. Rucareanu, R.B. Lennox. “Ferrocenylalkylthiolates as a Probe of Heterogeneity in Binary Self-Assembled Monolayers on Gold”. Langmuir. 2006; 22(9): 4438–4444.

2005 (1)

R.C. Chambers, C.E. Inman, J.E. Hutchison. “Electrochemical Detection of Nanoscale Phase Separation in Binary Self-Assembled Monolayers”. Langmuir. 2005; 21(10): 4615–4621.

2004 (1)

M. Hiroto, O. Masatoshi. “Surface-Enhanced Infrared Spectrum of CO Adsorbed on Cu Electrodes in Solution”. Chem. Lett. 2004; 33(3): 278–279.

2002 (2)

T. Auletta, F.C.J.M. van Veggel, D.N. Reinhoudt. “Self-Assembled Monolayers on Gold of Ferrocene-Terminated Thiols and Hydroxyalkanethiols”. Langmuir. 2002; 18(4): 1288–1293.

C. Pecharromán, A. Cuesta, C. Gutiérrez. “Comments on the Paper by M.-S. Zheng, S.-G. Sun Entitled ‘In Situ FT-IR Spectroscopic Studies of CO Adsorption on Electrodes with Nanometer-scale Thin Films of Ruthenium in Sulfuric Acid Solutions’ [J. Electroanal. Chem. 500 (2001) 223]”. J. Electroanal. Chem. 2002; 529(2): 145–154.

2001 (2)

A.S. Viana, A.H. Jones, L.M. Abrantes, M. Kalaji. “Redox Induced Orientational Changes in a Series of Short Chain Ferrocenyl Alkyl Thiols Self-Assembled on Gold(111) Electrodes”. J. Electroanal. Chem. 2001; 500(1): 290–298.

J.J. Calvente, R. Andreu, M. Molero, et al. “Influence of Spatial Redox Distribution on the Electrochemical Behavior of Electroactive Self-Assembled Monolayers”. J. Phys. Chem. B. 2001; 105(39): 9557–9568.

1999 (1)

A.E. Bjerke, P.R. Griffiths, W. Theiss. “Surface-Enhanced Infrared Absorption of CO on Platinized Platinum”. Anal. Chem. 1999; 71(10): 1967–1974.

1998 (1)

F. Bensebaa, T.H. Ellis, A. Badia, R.B. Lennox. “Thermal Treatment of n-Alkanethiolate Monolayers on Gold, as Observed by Infrared Spectroscopy”. Langmuir. 1998; 14(9): 2361–2367.

1997 (1)

S. Ye, Y. Sato, K. Uosaki. “Redox-Induced Orientation Change of a Self-Assembled Monolayer of 11-Ferrocenyl-1-undecanethiol on a Gold Electrode Studied by In Situ FT-IRRAS”. Langmuir. 1997; 13(12): 3157–3161.

1993 (2)

M. Osawa, K.-I. Ataka, K. Yoshii, T. Yotsuyanagi. “Surface-Enhanced Infrared ATR Spectroscopy for In Situ Studies of Electrode/Electrolyte Interfaces”. J. Electron Spectrosc. Relat. Phenom. 1993; 64–65: 371–379.

L. Bertilsson, B. Liedberg. “Infrared Study of Thiol Monolayer Assemblies on Gold: Preparation, Characterization, and Functionalization of Mixed Monolayers”. Langmuir. 1993; 9(1): 141–149.

1992 (1)

D.D. Popenoe, R.S. Deinhammer, M.D. Porter. “Infrared Spectroelectrochemical Characterization of Ferrocene-Terminated Alkanethiolate Monolayers at Gold”. Langmuir. 1992; 8(10): 2521–2530.

1991 (2)

K. Uosaki, Y. Sato, H. Kita. “Electrochemical Characteristics of a Gold Electrode Modified with a Self-Assembled Monolayer of Ferrocenylalkanethiols”. Langmuir. 1991; 7(7): 1510–1514.

C.A. Widrig, C. Chung, M.D. Porter. “The Electrochemical Desorption of n-Alkanethiol Monolayers from Polycrystalline Au and Ag Electrodes”. J. Electroanal. Chem. Interfacial Electrochem. 1991; 310(1): 335–359.

1990 (1)

C.E.D. Chidsey, C.R. Bertozzi, T.M. Putvinski, A.M. Mujsce. “Coadsorption of Ferrocene-Terminated and Unsubstituted Alkanethiols on Gold: Electroactive Self-Assembled Monolayers”. J. Am. Chem. Soc. 1990; 112(11): 4301–4306.

1987 (1)

M.D. Porter, T.B. Bright, D.L. Allara, C.E.D. Chidsey. “Spontaneously Organized Molecular Assemblies. 4. Structural Characterization of n-Alkyl Thiol Monolayers on Gold by Optical Ellipsometry, Infrared Spectroscopy, and Electrochemistry”. J. Am. Chem. Soc. 1987; 109(12): 3559–3568.

1980 (1)

A.J. Steckl, G. Mohammed. “The Effect of Ambient Atmosphere in the Annealing of Indium Tin Oxide Films”. J. Appl. Phys. 1980; 51(7): 3890–3895.

Abrantes, L.M.

A.S. Viana, A.H. Jones, L.M. Abrantes, M. Kalaji. “Redox Induced Orientational Changes in a Series of Short Chain Ferrocenyl Alkyl Thiols Self-Assembled on Gold(111) Electrodes”. J. Electroanal. Chem. 2001; 500(1): 290–298.

Adiga, P.

O.Q. Carvalho, P. Adiga, S.K. Murthy, J.L. Fulton, et al. “Understanding the Role of Surface Heterogeneities in Electrosynthesis Reactions”. iScience. 2020; 23(12): 101814.

Allara, D.L.

M.D. Porter, T.B. Bright, D.L. Allara, C.E.D. Chidsey. “Spontaneously Organized Molecular Assemblies. 4. Structural Characterization of n-Alkyl Thiol Monolayers on Gold by Optical Ellipsometry, Infrared Spectroscopy, and Electrochemistry”. J. Am. Chem. Soc. 1987; 109(12): 3559–3568.

Andreu, R.

J.J. Calvente, R. Andreu, M. Molero, et al. “Influence of Spatial Redox Distribution on the Electrochemical Behavior of Electroactive Self-Assembled Monolayers”. J. Phys. Chem. B. 2001; 105(39): 9557–9568.

Andvaag, I.R.

I.R. Andvaag, T.A. Morhart, O.J.R. Clarke, I.J. Burgess. “Hybrid Gold–Conductive Metal Oxide Films for Attenuated Total Reflectance Surface Enhanced Infrared Absorption Spectroscopy”. ACS Appl. Nano Mater. 2019; 2(3): 1274–1284.

Arble, C.

E. Strelcov, C. Arble, H. Guo, B.D. Hoskins, et al. “Nanoscale Mapping of the Double Layer Potential at the Graphene–Electrolyte Interface”. Nano Lett. 2020; 20(2): 1336–1344.

Ataka, K.-I.

M. Osawa, K.-I. Ataka, K. Yoshii, T. Yotsuyanagi. “Surface-Enhanced Infrared ATR Spectroscopy for In Situ Studies of Electrode/Electrolyte Interfaces”. J. Electron Spectrosc. Relat. Phenom. 1993; 64–65: 371–379.

Auletta, T.

T. Auletta, F.C.J.M. van Veggel, D.N. Reinhoudt. “Self-Assembled Monolayers on Gold of Ferrocene-Terminated Thiols and Hydroxyalkanethiols”. Langmuir. 2002; 18(4): 1288–1293.

Badia, A.

F. Bensebaa, T.H. Ellis, A. Badia, R.B. Lennox. “Thermal Treatment of n-Alkanethiolate Monolayers on Gold, as Observed by Infrared Spectroscopy”. Langmuir. 1998; 14(9): 2361–2367.

Baskin, A.

Y.-H. Lu, J.M. Larson, A. Baskin, X. Zhao, et al. “Infrared Nanospectroscopy at the Graphene–Electrolyte Interface”. Nano Lett. 2019; 19(8): 5388–5393.

Behafarid, F.

H. Mistry, F. Behafarid, R. Reske, A.S. Varela, et al. “Tuning Catalytic Selectivity at the Mesoscale via Interparticle Interactions”. ACS Catal. 2016; 6(2): 1075–1080.

Bensebaa, F.

F. Bensebaa, T.H. Ellis, A. Badia, R.B. Lennox. “Thermal Treatment of n-Alkanethiolate Monolayers on Gold, as Observed by Infrared Spectroscopy”. Langmuir. 1998; 14(9): 2361–2367.

Bertilsson, L.

L. Bertilsson, B. Liedberg. “Infrared Study of Thiol Monolayer Assemblies on Gold: Preparation, Characterization, and Functionalization of Mixed Monolayers”. Langmuir. 1993; 9(1): 141–149.

Bertozzi, C.R.

C.E.D. Chidsey, C.R. Bertozzi, T.M. Putvinski, A.M. Mujsce. “Coadsorption of Ferrocene-Terminated and Unsubstituted Alkanethiols on Gold: Electroactive Self-Assembled Monolayers”. J. Am. Chem. Soc. 1990; 112(11): 4301–4306.

Bizzotto, D.

D. Bizzotto, I.J. Burgess, T. Doneux, et al. “Beyond Simple Cartoons: Challenges in Characterizing Electrochemical Biosensor Interfaces”. ACS Sens. 2018; 3(1): 5–12.

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A.E. Bjerke, P.R. Griffiths, W. Theiss. “Surface-Enhanced Infrared Absorption of CO on Platinized Platinum”. Anal. Chem. 1999; 71(10): 1967–1974.

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M.D. Porter, T.B. Bright, D.L. Allara, C.E.D. Chidsey. “Spontaneously Organized Molecular Assemblies. 4. Structural Characterization of n-Alkyl Thiol Monolayers on Gold by Optical Ellipsometry, Infrared Spectroscopy, and Electrochemistry”. J. Am. Chem. Soc. 1987; 109(12): 3559–3568.

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I.R. Andvaag, T.A. Morhart, O.J.R. Clarke, I.J. Burgess. “Hybrid Gold–Conductive Metal Oxide Films for Attenuated Total Reflectance Surface Enhanced Infrared Absorption Spectroscopy”. ACS Appl. Nano Mater. 2019; 2(3): 1274–1284.

D. Bizzotto, I.J. Burgess, T. Doneux, et al. “Beyond Simple Cartoons: Challenges in Characterizing Electrochemical Biosensor Interfaces”. ACS Sens. 2018; 3(1): 5–12.

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K. Jiang, J.-Y. Wang, T.-T. Zhao, W.-B. Cai. “Formic Acid Oxidation at Palladium Electrode in Acidic Media Containing Chloride Anions: An In Situ ATR SEIRAS Investigation”. J. Electroanal. Chem. 2017; 800: 77–81.

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J.J. Calvente, R. Andreu, M. Molero, et al. “Influence of Spatial Redox Distribution on the Electrochemical Behavior of Electroactive Self-Assembled Monolayers”. J. Phys. Chem. B. 2001; 105(39): 9557–9568.

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N. Nerngchamnong, D. Thompson, L. Cao, L. Yuan, et al. “Nonideal Electrochemical Behavior of Ferrocenyl–Alkanethiolate SAMs Maps the Microenvironment of the Redox Unit”. J. Phys. Chem. C. 2015; 119(38): 21978–21991.

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O.Q. Carvalho, P. Adiga, S.K. Murthy, J.L. Fulton, et al. “Understanding the Role of Surface Heterogeneities in Electrosynthesis Reactions”. iScience. 2020; 23(12): 101814.

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R.C. Chambers, C.E. Inman, J.E. Hutchison. “Electrochemical Detection of Nanoscale Phase Separation in Binary Self-Assembled Monolayers”. Langmuir. 2005; 21(10): 4615–4621.

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C.E.D. Chidsey, C.R. Bertozzi, T.M. Putvinski, A.M. Mujsce. “Coadsorption of Ferrocene-Terminated and Unsubstituted Alkanethiols on Gold: Electroactive Self-Assembled Monolayers”. J. Am. Chem. Soc. 1990; 112(11): 4301–4306.

M.D. Porter, T.B. Bright, D.L. Allara, C.E.D. Chidsey. “Spontaneously Organized Molecular Assemblies. 4. Structural Characterization of n-Alkyl Thiol Monolayers on Gold by Optical Ellipsometry, Infrared Spectroscopy, and Electrochemistry”. J. Am. Chem. Soc. 1987; 109(12): 3559–3568.

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C.A. Widrig, C. Chung, M.D. Porter. “The Electrochemical Desorption of n-Alkanethiol Monolayers from Polycrystalline Au and Ag Electrodes”. J. Electroanal. Chem. Interfacial Electrochem. 1991; 310(1): 335–359.

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I.R. Andvaag, T.A. Morhart, O.J.R. Clarke, I.J. Burgess. “Hybrid Gold–Conductive Metal Oxide Films for Attenuated Total Reflectance Surface Enhanced Infrared Absorption Spectroscopy”. ACS Appl. Nano Mater. 2019; 2(3): 1274–1284.

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A. Schneider, L. Colmenares, Y.E. Seidel, Z. Jusys, et al. “Transport Effects in the Oxygen Reduction Reaction on Nanostructured, Planar Glassy Carbon Supported Pt/GC Model Electrodes”. Phys. Chem. Chem. Phys. 2008; 10(14): 1931–1943.

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H. Tian, Y. Dai, H. Shao, H.-Z. Yu. “Modulated Intermolecular Interactions in Ferrocenylalkanethiolate Self-Assembled Monolayers on Gold”. J. Phys. Chem. C. 2013; 117(2): 1006–1012.

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D.D. Popenoe, R.S. Deinhammer, M.D. Porter. “Infrared Spectroelectrochemical Characterization of Ferrocene-Terminated Alkanethiolate Monolayers at Gold”. Langmuir. 1992; 8(10): 2521–2530.

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X.-Y. Ma, C. Ding, H. Li, K. Jiang, et al. “Revisiting the Acetaldehyde Oxidation Reaction on a Pt Electrode by High-Sensitivity and Wide-Frequency Infrared Spectroscopy”. J. Phys. Chem. Lett. 2020; 11(20): 8727–8734.

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D. Bizzotto, I.J. Burgess, T. Doneux, et al. “Beyond Simple Cartoons: Challenges in Characterizing Electrochemical Biosensor Interfaces”. ACS Sens. 2018; 3(1): 5–12.

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F. Bensebaa, T.H. Ellis, A. Badia, R.B. Lennox. “Thermal Treatment of n-Alkanethiolate Monolayers on Gold, as Observed by Infrared Spectroscopy”. Langmuir. 1998; 14(9): 2361–2367.

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A.V. Rudnev, U. Zhumaev, T. Utsunomiya, C. Fan, et al. “Ferrocene-Terminated Alkanethiol Self-Assembled Monolayers: An Electrochemical and In Situ Surface-Enhanced Infra-Red Absorption Spectroscopy Study”. Electrochim. Acta. 2013; 107: 33–44.

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Y. Feng, E.R. Dionne, V. Toader, et al. “Odd–Even Effects in Electroactive Self-Assembled Monolayers Investigated by Electrochemical Surface Plasmon Resonance and Impedance Spectroscopy”. J. Phys. Chem. C. 2017; 121(44): 24626–24640.

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G.V. Fortunato, E. Pizzutilo, A.M. Mingers, O. Kasian, et al. “Impact of Palladium Loading and Interparticle Distance on the Selectivity for the Oxygen Reduction Reaction Toward Hydrogen Peroxide”. J. Phys. Chem. C. 2018; 122(28): 15878–15885.

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O.Q. Carvalho, P. Adiga, S.K. Murthy, J.L. Fulton, et al. “Understanding the Role of Surface Heterogeneities in Electrosynthesis Reactions”. iScience. 2020; 23(12): 101814.

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A.E. Bjerke, P.R. Griffiths, W. Theiss. “Surface-Enhanced Infrared Absorption of CO on Platinized Platinum”. Anal. Chem. 1999; 71(10): 1967–1974.

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C. Pecharromán, A. Cuesta, C. Gutiérrez. “Comments on the Paper by M.-S. Zheng, S.-G. Sun Entitled ‘In Situ FT-IR Spectroscopic Studies of CO Adsorption on Electrodes with Nanometer-scale Thin Films of Ruthenium in Sulfuric Acid Solutions’ [J. Electroanal. Chem. 500 (2001) 223]”. J. Electroanal. Chem. 2002; 529(2): 145–154.

Han, S.

S.R. Smith, S. Han, A. McDonald, et al. “An Electrochemical Approach to Fabricate a Heterogeneous Mixed Monolayer on Planar Polycrystalline Au and its Characterization with Lateral Force Microscopy”. J. Electroanal. Chem. 2012; 666: 76–84.

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M. Hiroto, O. Masatoshi. “Surface-Enhanced Infrared Spectrum of CO Adsorbed on Cu Electrodes in Solution”. Chem. Lett. 2004; 33(3): 278–279.

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E. Strelcov, C. Arble, H. Guo, B.D. Hoskins, et al. “Nanoscale Mapping of the Double Layer Potential at the Graphene–Electrolyte Interface”. Nano Lett. 2020; 20(2): 1336–1344.

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S.-J. Huo, X.-K. Xue, Q.-X. Li, et al. “Extending in Situ Attenuated-Total-Reflection Surface-Enhanced Infrared Absorption Spectroscopy to Ni Electrodes”. J. Phys. Chem. B. 2006; 110(9): 4162–4169.

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R.C. Chambers, C.E. Inman, J.E. Hutchison. “Electrochemical Detection of Nanoscale Phase Separation in Binary Self-Assembled Monolayers”. Langmuir. 2005; 21(10): 4615–4621.

Inman, C.E.

R.C. Chambers, C.E. Inman, J.E. Hutchison. “Electrochemical Detection of Nanoscale Phase Separation in Binary Self-Assembled Monolayers”. Langmuir. 2005; 21(10): 4615–4621.

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T.A. Morhart, S.T. Read, G. Wells, M. Jacobs, et al. “Micromachined Multigroove Silicon ATR FT-IR Internal Reflection Elements for Chemical Imaging of Microfluidic Devices”. Anal. Methods. 2019; 11(45): 5776–5783.

T.A. Morhart, S. Read, G. Wells, M. Jacobs, et al. “Attenuated Total Reflection Fourier Transform Infrared (ATR FT-IR) Spectromicroscopy Using Synchrotron Radiation and Micromachined Silicon Wafers for Microfluidic Applications”. Appl. Spectrosc. 2018; 72(12): 1781–1789.

Jiang, K.

X.-Y. Ma, C. Ding, H. Li, K. Jiang, et al. “Revisiting the Acetaldehyde Oxidation Reaction on a Pt Electrode by High-Sensitivity and Wide-Frequency Infrared Spectroscopy”. J. Phys. Chem. Lett. 2020; 11(20): 8727–8734.

K. Jiang, J.-Y. Wang, T.-T. Zhao, W.-B. Cai. “Formic Acid Oxidation at Palladium Electrode in Acidic Media Containing Chloride Anions: An In Situ ATR SEIRAS Investigation”. J. Electroanal. Chem. 2017; 800: 77–81.

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A.S. Viana, A.H. Jones, L.M. Abrantes, M. Kalaji. “Redox Induced Orientational Changes in a Series of Short Chain Ferrocenyl Alkyl Thiols Self-Assembled on Gold(111) Electrodes”. J. Electroanal. Chem. 2001; 500(1): 290–298.

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G.V. Fortunato, E. Pizzutilo, A.M. Mingers, O. Kasian, et al. “Impact of Palladium Loading and Interparticle Distance on the Selectivity for the Oxygen Reduction Reaction Toward Hydrogen Peroxide”. J. Phys. Chem. C. 2018; 122(28): 15878–15885.

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K. Uosaki, Y. Sato, H. Kita. “Electrochemical Characteristics of a Gold Electrode Modified with a Self-Assembled Monolayer of Ferrocenylalkanethiols”. Langmuir. 1991; 7(7): 1510–1514.

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U.E. Zhumaev, A.S. Lai, I.V. Pobelov, A. Kuzume, et al. “Quantifying Perchlorate Adsorption on Au(111) Electrodes”. Electrochim. Acta. 2014; 146: 112–118.

Lai, A.S.

U.E. Zhumaev, A.S. Lai, I.V. Pobelov, A. Kuzume, et al. “Quantifying Perchlorate Adsorption on Au(111) Electrodes”. Electrochim. Acta. 2014; 146: 112–118.

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K. Tu, M.J. Lardner, T.A. Morhart, S.M. Rosendahl, et al. “Spatial Mapping of Methanol Oxidation Activity on a Monolithic Variable-Composition PtNi Alloy Using Synchrotron Infrared Microspectroscopy”. J. Phys. Chem. C. 2016; 120(41): 23640–23647.

M.J. Lardner, K. Tu, S.M. Rosendahl, et al. “Spatiotemporal Mapping of Diffusion Layers Using Synchrotron Infrared Radiation”. Electrochim. Acta. 2015; 162: 72–78.

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Y.-H. Lu, J.M. Larson, A. Baskin, X. Zhao, et al. “Infrared Nanospectroscopy at the Graphene–Electrolyte Interface”. Nano Lett. 2019; 19(8): 5388–5393.

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L.Y.S. Lee, T.C. Sutherland, S. Rucareanu, R.B. Lennox. “Ferrocenylalkylthiolates as a Probe of Heterogeneity in Binary Self-Assembled Monolayers on Gold”. Langmuir. 2006; 22(9): 4438–4444.

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L.Y.S. Lee, T.C. Sutherland, S. Rucareanu, R.B. Lennox. “Ferrocenylalkylthiolates as a Probe of Heterogeneity in Binary Self-Assembled Monolayers on Gold”. Langmuir. 2006; 22(9): 4438–4444.

F. Bensebaa, T.H. Ellis, A. Badia, R.B. Lennox. “Thermal Treatment of n-Alkanethiolate Monolayers on Gold, as Observed by Infrared Spectroscopy”. Langmuir. 1998; 14(9): 2361–2367.

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X.-Y. Ma, C. Ding, H. Li, K. Jiang, et al. “Revisiting the Acetaldehyde Oxidation Reaction on a Pt Electrode by High-Sensitivity and Wide-Frequency Infrared Spectroscopy”. J. Phys. Chem. Lett. 2020; 11(20): 8727–8734.

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S.-J. Huo, X.-K. Xue, Q.-X. Li, et al. “Extending in Situ Attenuated-Total-Reflection Surface-Enhanced Infrared Absorption Spectroscopy to Ni Electrodes”. J. Phys. Chem. B. 2006; 110(9): 4162–4169.

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J.A. Sigrist, E.S. Lins, T.A. Morhart, et al. “Optimization of a Commercial Variable Angle Accessory for Entry Level Users of Electrochemical Attenuated Total Reflection Surface-Enhanced Infrared Absorption Spectroscopy (ATR SEIRAS)”. Appl. Spectrosc. 2019; 73(12): 1394–1402.

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Y.-H. Lu, J.M. Larson, A. Baskin, X. Zhao, et al. “Infrared Nanospectroscopy at the Graphene–Electrolyte Interface”. Nano Lett. 2019; 19(8): 5388–5393.

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X.-Y. Ma, C. Ding, H. Li, K. Jiang, et al. “Revisiting the Acetaldehyde Oxidation Reaction on a Pt Electrode by High-Sensitivity and Wide-Frequency Infrared Spectroscopy”. J. Phys. Chem. Lett. 2020; 11(20): 8727–8734.

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M. Hiroto, O. Masatoshi. “Surface-Enhanced Infrared Spectrum of CO Adsorbed on Cu Electrodes in Solution”. Chem. Lett. 2004; 33(3): 278–279.

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S.R. Smith, S. Han, A. McDonald, et al. “An Electrochemical Approach to Fabricate a Heterogeneous Mixed Monolayer on Planar Polycrystalline Au and its Characterization with Lateral Force Microscopy”. J. Electroanal. Chem. 2012; 666: 76–84.

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G.V. Fortunato, E. Pizzutilo, A.M. Mingers, O. Kasian, et al. “Impact of Palladium Loading and Interparticle Distance on the Selectivity for the Oxygen Reduction Reaction Toward Hydrogen Peroxide”. J. Phys. Chem. C. 2018; 122(28): 15878–15885.

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H. Mistry, F. Behafarid, R. Reske, A.S. Varela, et al. “Tuning Catalytic Selectivity at the Mesoscale via Interparticle Interactions”. ACS Catal. 2016; 6(2): 1075–1080.

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J.J. Calvente, R. Andreu, M. Molero, et al. “Influence of Spatial Redox Distribution on the Electrochemical Behavior of Electroactive Self-Assembled Monolayers”. J. Phys. Chem. B. 2001; 105(39): 9557–9568.

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J.A. Sigrist, E.S. Lins, T.A. Morhart, et al. “Optimization of a Commercial Variable Angle Accessory for Entry Level Users of Electrochemical Attenuated Total Reflection Surface-Enhanced Infrared Absorption Spectroscopy (ATR SEIRAS)”. Appl. Spectrosc. 2019; 73(12): 1394–1402.

T.A. Morhart, S.T. Read, G. Wells, M. Jacobs, et al. “Micromachined Multigroove Silicon ATR FT-IR Internal Reflection Elements for Chemical Imaging of Microfluidic Devices”. Anal. Methods. 2019; 11(45): 5776–5783.

I.R. Andvaag, T.A. Morhart, O.J.R. Clarke, I.J. Burgess. “Hybrid Gold–Conductive Metal Oxide Films for Attenuated Total Reflectance Surface Enhanced Infrared Absorption Spectroscopy”. ACS Appl. Nano Mater. 2019; 2(3): 1274–1284.

T.A. Morhart, S. Read, G. Wells, M. Jacobs, et al. “Attenuated Total Reflection Fourier Transform Infrared (ATR FT-IR) Spectromicroscopy Using Synchrotron Radiation and Micromachined Silicon Wafers for Microfluidic Applications”. Appl. Spectrosc. 2018; 72(12): 1781–1789.

K. Tu, M.J. Lardner, T.A. Morhart, S.M. Rosendahl, et al. “Spatial Mapping of Methanol Oxidation Activity on a Monolithic Variable-Composition PtNi Alloy Using Synchrotron Infrared Microspectroscopy”. J. Phys. Chem. C. 2016; 120(41): 23640–23647.

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C.E.D. Chidsey, C.R. Bertozzi, T.M. Putvinski, A.M. Mujsce. “Coadsorption of Ferrocene-Terminated and Unsubstituted Alkanethiols on Gold: Electroactive Self-Assembled Monolayers”. J. Am. Chem. Soc. 1990; 112(11): 4301–4306.

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O.Q. Carvalho, P. Adiga, S.K. Murthy, J.L. Fulton, et al. “Understanding the Role of Surface Heterogeneities in Electrosynthesis Reactions”. iScience. 2020; 23(12): 101814.

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N. Nerngchamnong, D. Thompson, L. Cao, L. Yuan, et al. “Nonideal Electrochemical Behavior of Ferrocenyl–Alkanethiolate SAMs Maps the Microenvironment of the Redox Unit”. J. Phys. Chem. C. 2015; 119(38): 21978–21991.

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Pizzutilo, E.

G.V. Fortunato, E. Pizzutilo, A.M. Mingers, O. Kasian, et al. “Impact of Palladium Loading and Interparticle Distance on the Selectivity for the Oxygen Reduction Reaction Toward Hydrogen Peroxide”. J. Phys. Chem. C. 2018; 122(28): 15878–15885.

Pobelov, I.V.

U.E. Zhumaev, A.S. Lai, I.V. Pobelov, A. Kuzume, et al. “Quantifying Perchlorate Adsorption on Au(111) Electrodes”. Electrochim. Acta. 2014; 146: 112–118.

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D.D. Popenoe, R.S. Deinhammer, M.D. Porter. “Infrared Spectroelectrochemical Characterization of Ferrocene-Terminated Alkanethiolate Monolayers at Gold”. Langmuir. 1992; 8(10): 2521–2530.

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M.D. Porter, T.B. Bright, D.L. Allara, C.E.D. Chidsey. “Spontaneously Organized Molecular Assemblies. 4. Structural Characterization of n-Alkyl Thiol Monolayers on Gold by Optical Ellipsometry, Infrared Spectroscopy, and Electrochemistry”. J. Am. Chem. Soc. 1987; 109(12): 3559–3568.

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C.E.D. Chidsey, C.R. Bertozzi, T.M. Putvinski, A.M. Mujsce. “Coadsorption of Ferrocene-Terminated and Unsubstituted Alkanethiols on Gold: Electroactive Self-Assembled Monolayers”. J. Am. Chem. Soc. 1990; 112(11): 4301–4306.

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T.A. Morhart, S. Read, G. Wells, M. Jacobs, et al. “Attenuated Total Reflection Fourier Transform Infrared (ATR FT-IR) Spectromicroscopy Using Synchrotron Radiation and Micromachined Silicon Wafers for Microfluidic Applications”. Appl. Spectrosc. 2018; 72(12): 1781–1789.

Read, S.T.

T.A. Morhart, S.T. Read, G. Wells, M. Jacobs, et al. “Micromachined Multigroove Silicon ATR FT-IR Internal Reflection Elements for Chemical Imaging of Microfluidic Devices”. Anal. Methods. 2019; 11(45): 5776–5783.

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K. Tu, M.J. Lardner, T.A. Morhart, S.M. Rosendahl, et al. “Spatial Mapping of Methanol Oxidation Activity on a Monolithic Variable-Composition PtNi Alloy Using Synchrotron Infrared Microspectroscopy”. J. Phys. Chem. C. 2016; 120(41): 23640–23647.

M.J. Lardner, K. Tu, S.M. Rosendahl, et al. “Spatiotemporal Mapping of Diffusion Layers Using Synchrotron Infrared Radiation”. Electrochim. Acta. 2015; 162: 72–78.

Rucareanu, S.

L.Y.S. Lee, T.C. Sutherland, S. Rucareanu, R.B. Lennox. “Ferrocenylalkylthiolates as a Probe of Heterogeneity in Binary Self-Assembled Monolayers on Gold”. Langmuir. 2006; 22(9): 4438–4444.

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A.V. Rudnev, U. Zhumaev, T. Utsunomiya, C. Fan, et al. “Ferrocene-Terminated Alkanethiol Self-Assembled Monolayers: An Electrochemical and In Situ Surface-Enhanced Infra-Red Absorption Spectroscopy Study”. Electrochim. Acta. 2013; 107: 33–44.

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A. Schneider, L. Colmenares, Y.E. Seidel, Z. Jusys, et al. “Transport Effects in the Oxygen Reduction Reaction on Nanostructured, Planar Glassy Carbon Supported Pt/GC Model Electrodes”. Phys. Chem. Chem. Phys. 2008; 10(14): 1931–1943.

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H. Tian, Y. Dai, H. Shao, H.-Z. Yu. “Modulated Intermolecular Interactions in Ferrocenylalkanethiolate Self-Assembled Monolayers on Gold”. J. Phys. Chem. C. 2013; 117(2): 1006–1012.

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J.A. Sigrist, E.S. Lins, T.A. Morhart, et al. “Optimization of a Commercial Variable Angle Accessory for Entry Level Users of Electrochemical Attenuated Total Reflection Surface-Enhanced Infrared Absorption Spectroscopy (ATR SEIRAS)”. Appl. Spectrosc. 2019; 73(12): 1394–1402.

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