Stabilizing and Improving Solar H2 Generation from Zn(0.5)Cd(0.5)S Nanorods@MoS2/RGO Hybrids via Dual Charge Transfer Pathway.

The incorporated Zn(0.5)Cd(0.5)S (ZCS) nanorods with MoS2/RGO cocatalysts by a simultaneous reduction reaction was reported. The preparation of RGO and formation of MoS2 with intimate interfacial contact with ZCS were achieved. Through the optimizing of each component proportion, the ZCS@MoS2/RGO hybrid with 1.5 wt % MoS2 and 3 wt % RGO showed the highest photocatalytic H2 production activity (2.31 mmol/h) with long time stability (50 h). The relative mechanism has been investigated. It is believed that the stabilizing and improving solar H2 generation is originating from dual charge transfer pathway from excited ZCS to RGO, then to MoS2 due to intimate interfacial structure.

Application of surface-enhanced infrared absorption spectroscopy to investigate pyridine adsorption on platinum-group electrodes.

In situ surface-enhanced infrared absorption spectroscopy (SEIRAS) was applied to investigate adsorption configurations of pyridine (Py) on platinum, palladium, ruthenium, and rhodium nanoparticle film electrodes. The results reveal that alpha-pyridyl species predominantly form on Pt electrodes by assuming an edge-on configuration with its ring N and alpha-C atoms bonding to the Pt surface, while on Ru and Rh electrodes pyridine molecules essentially remain intact by adopting a slightly edge-tilted configuration through bonding with its N lone pair electrons. Py adsorption on a Pd electrode may lie in between the above two cases; both alpha-pyridyl species and edge-tilted intact pyridine could be significantly present. Further comparison of the typical adsorption configurations on the above four electrodes with those on Ag, Au, Cu, Cd, and Ni film electrodes suggests that valence electrons and the periodic row of metals may play an important role in determining the adsorption configuration.

In situ surface-enhanced IR absorption spectroscopy on CO adducts of iron protoporphyrin IX self-assembled on a Au electrode.

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.

Extending in situ attenuated-total-reflection surface-enhanced infrared absorption spectroscopy to ni electrodes.

Surface-enhanced infrared absorption spectroscopy (SEIRAS) in the attenuated-total-reflection configuration (ATR-SEIRAS) has been applied for the first time to Ni electrodes. SEIRA-active Ni electrodes were obtained through initial chemical deposition of a 60-nm-thick Au underlayer on the reflecting plane of an ATR Si prism followed by potentiostatic electrodeposition of a 40-nm-thick Ni overlayer in a modified Watt's electrolyte. The Ni nanoparticle film thus obtained exhibited exceptionally enhanced IR absorption for the surface probe molecule CO while maintaining unipolar and normally directed bands. With the advantages of ATR-SEIRAS, free H2O molecules coadsorbed with CO at the Ni electrode were revealed, and their role in the electrooxidation of the CO adlayer at the Ni electrode is discussed. In addition, the conversion of bridge to linearly bonded CO at Ni electrode in a neutral solution was clearly identified upon electrooxidation of the CO adlayer. ATR-SEIRAS was also used to characterize the adsorption configuration of a pyridine adlayer at the Ni electrode. Both A1 and B1 modes of adsorbed pyridine were detected with comparably large intensities, essentially maintaining the spectral feature of pyridine molecules rather than that of "alpha-pyridyl species", which strongly suggests an "edge-tilted pyridine" configuration present at the Ni electrode, a configuration intermediate between the "end-on pyridine" and "edge-on alpha-pyridyl" adsorption modes reported in the literature.

Tunable surface-enhanced infrared absorption on au nanofilms on si fabricated by self-assembly and growth of colloidal particles.

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.