A versatile two-step wet process to fabricate Pt, Pd, Rh, and Ru nanoparticle films (simplified as nanofilms hereafter) for in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) study of electrochemical interfaces is presented, which incorporates an initial chemical deposition of a gold nanofilm on the basal plane of a silicon prism with the subsequent electrodepostion of desired platinum group metal overlayers. Galvanostatic electrodeposition of Pt, Rh, and Pd from phosphate or perchloric acid electrolytes, or potentiostatic electrodeposition of Ru from a sulfuric acid electrolyte, yields sufficiently "pinhole-free" overlayers as evidenced by electrochemical and spectroscopic characterizations. The Pt group metal nanofilms thus obtained exhibit strongly enhanced IR absorption. In contrast to the corresponding metal films electrochemically deposited directly on glassy carbon and bulk metal electrodes, the observed enhanced absorption for the probe molecule CO exhibits normal unipolar band shapes. Scanning tunneling microscopic (STM) images reveal that fine nanoparticles of Pt group metals are deposited around wavy and stepped bunches of Au nanoparticles of relatively large sizes. This ubiquitous strategy is expected to open a wide avenue for extending ATR surface-enhanced IR absorption spectroscopy to explore molecular adsorption and reactions on technologically important transition metals, as exemplified by successful real-time spectroscopic and electrochemical monitoring of the oxidation of CO at Pd and that of methanol at Pt nanofilm electrodes. The spectral features of free water molecules coadsorbed with CO on Pt, Pd, Rh, and Ru are also discussed.

Adsorption and electro-oxidation of CO on a polycrystalline Pt electrode in acidic solutions were systematically revisited by in situ attenuated-total-reflection surfaceenhanced infrared absorption spectroscopy (ATR-SEIRAS) in conjunction with related GramÀSchmidt response analysis. CO was either adsorbed in the double-layer region, i.e., 0.45 V (RHE) (denoted as CO @DL ) or in the hydrogen underpotential deposition region, i.e., 0.1 V (RHE) (denoted as CO @UPD ). The results indicate that the CO @UPD and H 2 O free coexisted structure (or simply costructure) forms only at a sufficiently high global CO coverage (H 2 O free denotes hydrogen-bonding-broken water); In contrast, the CO @DL and H 2 O free costructure forms in an earlier adsorption phase, less dependent on the global CO coverage. The partial oxidation of CO from solution and weakly adsorbed CO L at the active sites is suggested to yield a prepeak that occurs with the relaxation of the CO ad -H 2 O free costructure and the disorganization of the outer water net layers. In the main oxidation process, the oxidation of CO @UPD tends to proceed via the "mean-field approximation" kinetics due to the high CO ad mobility resulting from the oxidation prepeak. The oxidation process of CO @DL is, however, likely via the "nucleation and growth" kinetics due to the good stability of the local CO @DL and H 2 O free costructured islands. The H 2 O free can be better assigned to the "probe" of the local CO ad coverage rather than the main oxygenated species for CO ad oxidation according to the spectral results for both CO @UPD and CO @DL .

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Au colloids were used to fabricate nanoscale-tunable Au nanofilms on silicon for surface-enhanced IR absorption bases in both ambient and electrochemical environments. This wet process incorporates the self-assembly of colloidal Au monolayer using 3-aminopropyl trimethoxysilane as the organic coupler with subsequent chemical plating in an Au(III)/hydroxylamine solution. FTIR spectroscopy in transmission mode of the probe species SCN- was used to evaluate the apparent surface enhancement in IR absorption of 2D Au colloid arrays and chemically plated Au particles. The nanostructure of Au films was examined by atomic force microscopy. The IR and AFM results show that the apparent surface enhancement factor (1-2 orders of magnitude) increases with increasing sizes and/or contact, and the severe aggregation of Au nanoparticles may cause the bipolar band shape. Cyclic voltammetry on the Au nanofilm obtained by the above nucleation and growth strategy exhibits a feasible electrochemical stability and behavior. In situ ATR-FTIR measurement of p-nitrobenzoic acid adsorption demonstrates that the as-grown Au film yields rather promising surface enhancement as well.

A practically modified ATR configuration has been proposed for in situ electrochemical surface-enhanced IR absorption spectroscopy (SEIRAS) by sandwiching an ultrathin water interlayer between a hemicylindrical ZnSe prism and a Si wafer as an integrated window. This new ATR optics significantly enhances the throughput of an effective IR beam across the ZnSe/gap/Si/metal film, enabling high-quality spectral fingerprints down to 700 cm(-1) to be readily detected at larger incidence angles without compromising the electrochemical feasibility and stability of metallic films deposited on Si. The advantages of this modified ATR-SEIRAS have been initially applied to explore two selected systems: wide-ranged in situ ATR-SEIRA spectra provided strong evidence in support of the formate intermediate pathway for methanol electrooxidation at the Pt electrode in an acid solution; in addition, new spectral fingerprints revealed comprehensive orientational information about of the p-nitrobenzoate species at Pt electrode as a result of the dissociative adsorption of p-nitrobenzoic acid molecules from an acid solution.

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The surface coordination chemistry of carbon monoxide with the reduced form (Fe(II)PP) of iron(III) protoporphyrin IX (Fe(III)PP) monolayer self-assembled on a Au electrode in 0.1 M HClO4 was studied for the first time by using in situ ATR-surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS). Both mono- and biscarbonyl adducts [simplified as Fe(II)(CO)PP and Fe(II)(CO)2PP, respectively] were detected, depending on the history of potential control. Initially, the Fe(II)(CO)PP predominates, and the intermediate transition potential for the conversion of Fe(II)(CO)PP to Fe(III)PP and CO was spectrally determined to be ca. 0.09 V (vs SCE). The ratio of Fe(II)(CO)2PP and Fe(II)(CO)PP increases after a potential excursion to a sufficiently positive value. Fe(II)(CO)2PP is much more stable against its electro-oxidation to Fe(III)PP than its counterpart Fe(II)(CO)PP with increasing potential. The observed change of coordination properties may be ascribed to an irreversible structural reorganization of the FePP adlayer caused by the potential excursion.

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