THE ADSORPTION OF SULFATE ON GOLD(111) IN ACIDIC AQUEOUS-MEDIA - ADLAYER STRUCTURAL INFERENCES FROM INFRARED-SPECTROSCOPY AND SCANNING-TUNNELING-MICROSCOPY

The potential-dependent adsorption of sulfate on ordered Au(111) from acidic aqueous electrolytes has been examined in situ by means of IR r eflection-absorption spectroscopy (IRAS) and by atomic-resolution scan ning tunneling microscopy (STM) in order to explore further the nature of the adsorbate bonding and the structural changes attending the for mation of the ordered adlayer at high potentials, as observed recently using STM. Solution conditions that encompassed aqueous sulfuric acid , sulfuric acid/sulfate electrolytes of varying pH and dilute sulfate in excess perchloric acid were selected in order to facilitate compari sons with recent adsorbate compositional data extracted from chronocou lometric and radiotracer measurements which utilized the last mentione d type of electrolyte. Essentially the same ordered adlayer structures were deduced by STM to form at suitably high potentials (greater-than -or-equal-to 0.8 V/SCE) in both sulfuric acid and the mixed sulfate/ex cess perchloric acid media. The adlayer, which exhibits a (square-root 3 x square-root7) symmetry, involves a fractional sulfate coverage of 0.2, in accordance with chronocoulometic and radiotracer data. The pos sibility that the ordered sulfate adlayer incorporates coadsorbed hydr onium cations is discussed; such coadsorption is suggested by the pres ence of additional tunneling maxima in the STM images. The IRAS data d isplay a prominent S-O stretching band v(SO) at 1155-1220 cm-1, the po tential-dependent intensity of which correlates with sulfate surface c oncentrations reported earlier. The appearance of this v(SO) feature i s also insensitive to the electrolyte conditions, including pH, consis tent with its assignment to adsorbed sulfate rather than bisulfate. Th e v(SO) frequency exhibits only a slight (ca. 5 cm-1) downshift upon f orming the ordered adlayer, indicating that adsorbate ordering incurs no marked changes in sulfate speciation or surface bonding.