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In situ scanning tunneling microscopy (STM) was used to examine the spatial structures of n-alkane thiols (1-hexanethiol, 1-nonanethiol, and 1-octahexanethiol) and arylthiols (benzenethiol and 4-hydroxybenzenethiol) adsorbed on well-ordered Pt111 electrodes in 0.1 M HClO4. The electrochemical potential and molecular flux were found to be the dominant factors in determining the growth mechanisms, final coverages, and spatial structures of these organic adlayers. Depending on the concentrations of the thiols, deposition of self-assembled monolayers (SAMs) followed either the nucleation-and-growth mechanism or the random fill-in mechanism. Low and high thiol concentrations respectively produced two ordered structures, (2 x 2) and (square root of 3 x square root of 3)R30 degrees , between 0.05 and 0.3 V. On average, an ordered domain spanned 500 A when the SAMs were made at 0.15 V, but this dimension shrank substantially once the potential was raised above 0.3 V. This potential-induced order-to-disorder phase transition resulted from a continuous deposition of thiols, preferentially at domain boundaries of (square root of 3 x square root of 3 x )R30 degrees arrays. All molecular adlayers were completely disordered by 0.6 V, and this restructuring event was irreversible with potential modulation. Since all thiols were arranged in a manner similar to that adopted by sulfur adatoms (Sung et al. J. Am. Chem. Soc. 1997, 119, 194), it is likely that they were adsorbed mainly through their sulfur headgroups in a tilted configuration, irrespective of the coverage. Both the sulfur and phenyl groups of benzenethiol admolecules gave rise to features with different corrugation heights in the molecular-resolution STM images. All thiols were adsorbed strongly enough that they remained intact at a potential as negative as -1.0 V in 0.1 M KOH.

Mixed monolayers of stearic acid (SA) and octadecylamine (ODA) at the air/water interface were investigated in this article. The miscibility of the two compounds was evaluated by the measurement of surface pressure-area per molecule (pi-A) isothems and the direct observation of Brewster angle microscopy (BAM) on the water surface. The two compounds were spread individually on the subphase (method 1) or premixed first in the spreading solvent and then cospread (method 2). The effect of spreading method on the miscibility of the two compounds was also studied. The results show that the mixed monolayers prepared by method 1 cannot get a well-mixed state. The isotherms of mixed monolayers preserve both characteristics of SA and ODA and exhibit two collapse points. The calculated excess surface area is very small. Besides, distinguished domains corresponding to those of pure SA and ODA can be inspected from the BAM images. Such results indicate that SA and ODA cannot get a well-mixed phase via 2-dimensional mixing. On the contrary, in the mixed monolayer prepared by cospreading, the two compounds exhibit high miscibility. In the pi-A isotherms, the individual characteristics of SA and ODA disappear. The calculated excess area exhibits a highly positive deviation which indicates the existence of special interaction between the two compounds. The low compressibility of isotherm implies the highly rigid characteristic of the mixed monolayer. which was also sustained by the striplike collapse morphology observed from the BAM. The rigid characteristic of SA/ODA mixed monolayer was attributed to the formation of "catanionic surfactant" by electrostatic adsorption of headgroups of SA and ODA or to the formation of salt by acid-base reaction.

3-Mercapto-1-propanesulfonic acid (MPS) and bis(3-sulfopropyl) disulfide (SPS) adsorbed on a Au(111) electrode were studied by using in situ scanning tunneling microscopy (STM). Although the adsorptions of MPS and SPS are known to be oxidative and reductive, respectively, on an Au(111) electrode, these two admolecules behave similarly in terms of phase evolution, surface coverage, potential for stripping, and characteristics of cyclic voltammetry. However, different adsorption mechanisms of these molecules result in different structures. Raising electrode potential causes more MPS and SPS molecules to adsorb, yielding ordered adlattices between 0.67 and 0.8 V (vs reversible hydrogen electrode). The ordered adlattices of MPS and SPS appear as striped and netlike structures with molecules adsorbed parallel to the Au(111) surface. Switching potential to 0.9 V or more positive still does not result in upright molecular orientation, possibly inhibited by electrostatic interaction between the end group of -SO(3)(-) and the Au(111) electrode. Lowering the potential to 0.4 V disrupted the ordered adlayer. Stripping voltammetric experiments show that MPS and SPS admolecules are desorbed from Au(111) at the same potential, suggesting that these molecules are both adsorbed via their sulfur headgroups. The S-S bond in SPS is likely broken upon its adsorption on Au(111).

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In-situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV) were used to study the phase evolution of 11-mercapto-1-undecanol (MUO) adlayer on an Au(111) electrode. The effect of various electrolytes, including HClO 4 and H 2 SO 4 , on the adsorption behavior was studied. The MUO adsorption was found to initiate mainly at the intersectional corner of herringbone rows of an Au(111) reconstruction structure in both of the electrolytes. The following growth of an adsorbed cluster develops first along the face-centeredcubic (fcc) position of the herringbone structure. In the HClO 4 solution, the MUO molecule is first adsorbed in a flat-lying orientation when the dose concentration of MUO is low, growing to an ordered domain of striped structure (β phase) with a molecular arrangement of (12 × 3). When the surface coverage becomes high, the hydrocarbon chains of MUO lift off from the Au(111) plane, forming a more condensed and saturated phase, the φ phase, identified as ( 3 × 3)R30°. At a high dose concentration of MUO, however, the striped phase does not appear. Due to the fast adsorption of thiol groups at high dose concentrations, the hydrocarbon chains-gold interaction is inhibited, and therefore, a flat-lying orientation of MUO molecules cannot be obtained. In the H 2 SO 4 solution, the striped phase does not form even at a low dose concentration and, instead, the φ phase appears directly in the low-coverage stage. The distinct phenomena observed for the two electrolytes are attributed to the different interactions of anionic ions with the gold surface. It has been shown that sulfate ions adsorb more strongly than perchlorate ions on a gold surface. The strongly adsorbed sulfate ions in the electrical double layer are supposed to resist the direct contact of hydrocarbon chain with the gold surface which also prevents the formation of a flat-lying orientation.

Self-assembled monolayers (SAMs) of 6-mercapto-1-hexanol (MHO) on an Au(111) electrode were prepared in an electrochemical system. The adsorption behavior of MHO and the time-dependent organization of the SAM were investigated by in situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV). The results show that a potential higher than 0.28 V (relative to RHE) is required to induce the adsorption of MHO. At 0.28 V, the MHO molecules adsorb in a flat-lying orientation, forming an ordered striped phase with a molecular arrangement of ([Formula: see text]). However, the adlayer is not stable at this potential. The adsorbed striped phase may recover to the herringbone feature of the gold substrate due to the desorption of adsorbed MHO. At a higher potential (0.35 V), the adlayer becomes stable and can undergo a phase evolution from the striped phase to a condensed structure, identified as c([Formula: see text]). This structure can also be described as a c(4 × 2) superlattice of a [Formula: see text] hexagonal adlattice. The surface coverage of the MHO SAM is identical to the saturated structure of an 11-mercapto-1-undecanol (MUO) SAM reported in a previous work, [Formula: see text]. However, the STM image of MHO adlayer shows a modulation in intensity, reflecting the presence of various conformations of adsorbed molecules. This result is attributed to the shorter chain length of MHO, which gives a weaker van der Waals interaction between adsorbed molecules. This effect also results in a higher charge permeability across the adlayer and a lower striping potential to an MHO SAM.

Cyclic voltammetry (CV) and in situ scanning tunneling microscopy (STM) were used to examine four dithiol molecules, including 1,6-hexanedithiol, 1,9-nonanedithiol, 1,2-benzenedithiol, and 1,3-benzenedithiol, adsorbed on well-ordered Pt(111) electrodes in 0.1 M HClO(4). The open-circuit potential (OCP) of Pt(111) electrodes decreased substantially from 0.95 to 0.3 V (versus reversible hydrogen electrode) upon the adsorption of dithol molecules, which indicates that these adsorbates injected electrons into the Pt electrode. For all dithiol molecules, ordered adlattices of p(2 x 2) and (square root 3 x square root 3)R30 degrees were formed when the dosing concentration was lower than 150 microM and the potential of Pt(111) was more negative than 0.5 V. Raising the potential of Pt(111) from 0.1 to 0.4 V or more positive values could transform p(2 x 2) to (square root 3 x square root 3)R30 degrees before it turned disarray. The insensitivity of the structure of dithiol adlayers with their chemical structures was explained by upright molecular orientation with the formation of one Pt-S bond per dithiol molecule. This molecular orientation was independent of the coverage of dithiol molecules, as nucleation seeds produced at the beginning of adsorption were also constructed with p(2 x 2). The triangular-shaped STM molecular resolution suggested 3-fold binding of sulfur headgroup on Pt(111). All dithiols were adsorbed so strongly on Pt(111) electrodes that switching the potential negatively to the onset of hydrogen evolution in 0.1 M HClO(4) or water reduction in 1 M KOH could not displace dithiol admolecules.