Effect of Electrolytic Medium on the Electrochemical Reduction of Graphene Oxide on Si(111) as Probed by XPS.

The wafer-scale integration of graphene is of great importance in view of its numerous applications proposed or underway. A good graphene-silicon interface requires the fine control of several parameters and may turn into a high-cost material, suitable for the most advanced applications. Procedures that can be of great use for a wide range of applications are already available, but others are to be found, in order to modulate the offer of different types of materials, at different levels of sophistication and use. We have been exploring different electrochemical approaches over the last 5 years, starting from graphene oxide and resulting in graphene deposited on silicon-oriented surfaces, with the aim of understanding the reactions leading to the re-establishment of the graphene network. Here, we report how a proper choice of both the chemical environment and electrochemical conditions can lead to a more controlled and tunable graphene-Si(111) interface. This can also lead to a deeper understanding of the electrochemical reactions involved in the evolution of graphene oxide to graphene under electrochemical reduction. Results from XPS, the most suitable tool to follow the presence and fate of functional groups at the graphene surface, are reported, together with electrochemical and Raman findings.

Adsorption Dynamics of Redox Active Species onto Polarized Surfaces of Sensitized NiO.

Mesoporous NiO films were deposited by means of a screen printing technique onto fluorine-doped tin oxide transparent electrodes and consequently sensitized with Erythrosin B (EryB) dye. The obtained colored NiO material was used as a working electrode in a three-electrode cell to study the evolution of the triple semiconductor/dye/electrolyte interface upon electrochemical polarization in dark conditions. The electrolyte was a solution of I3 -/I- in acetonitrile, with the redox couple representing the typical redox shuttle of dye-sensitized solar cells (DSCs). The adopted electrochemical conditions were devised in order to simulate the actual electrical environment of the NiO/dye photocathode in a light-soaked DSC. The use of a benchmark sensitizer EryB and of the most widely used redox mediator I3 -/I- is particularly meaningful for the study of the adsorption dynamics and the determination of possible degradative phenomena on the basis of the behavior of numerous analogue systems. Therefore, for the first time, the evolution of the NiO/EryB/I3 -/I- multiple interface was investigated combining the electrochemical characterization with ex situ spectroscopic analysis by means of X-ray photoelectron spectroscopy. The resulting picture shows that EryB in the immobilized state promotes the redox processes based on the I3 -/I- couple. Moreover, the EryB sensitizer inhibits the phenomena of recombination between the metal oxide semiconductor and the redox couple.

Noticeable Role of TFSI- Anion in the Carbon Cathode Degradation of Li-O2 Cells.

In this work we address the phenomena at the basis of the performance loss in a Li-O2 cell operating in the presence of a lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/tetraethylene glycol dimethyl ether (TEGDME) salt/solvent couple and a porous carbonaceous cathode. The cell was discharged/charged applying both voltage and capacity limits, and the effects of repeated galvanostatic cycling were addressed. The ex situ characterization of carbonaceous cathodes corresponding to different cutoff voltages was based on vibrational spectroscopies, transmission electron microscopy, and X-ray photoelectron spectroscopy. The reversible precipitation/decomposition of undesired products deriving from degradation of both carbon cathode and ethereal solvent is pointed out within a single voltage limited (2.0-4.6 V) discharge/charge cycle, whereas their irreversible accumulation on the surface of the electrode results after 100 capacity limited cycles. At the same time, the presence of polar degradation products (carbonates and carboxylates) at the cathode surface is accompanied by the buildup of a surface electric potential gradient, as revealed by differential binding energy shifts resulting from C 1s photoelectron spectra. This effect, seldom reported for Li-ion batteries, is for the first time put in evidence for a Li-O2 cell. Furthermore, the use of TFSI- anion is shown to lead to carbonate-based degradation products not involving the formation of Li2CO3. The peculiar occurrence of such degradation phenomena are attributed to the intrinsic low-donor number characteristic of the TFSI- anion.

Adsorption Behavior of I3- and I- Ions at a Nanoporous NiO/Acetonitrile Interface Studied by X-ray Photoelectron Spectroscopy.

The adsorption of I- and I3- anions, i.e., the two species constituting the most common redox couple of dye-sensitized solar cells (DSCs), onto the surface of screen-printed nanoporous NiO was studied by means of X-ray photoelectron spectroscopy (XPS). Nanoporous NiO films were deposited on transparent metallic fluorine-doped tin oxide (FTO) and polarized as working electrodes in a three-electrode cell with differently concentrated I-/I3- electrolytes to simulate the different conditions experienced by the NiO cathodes during the lifecycle of a p-type DSC (p-DSC) at those atomic sites not passivated by the dye. Bare NiO films were tested also as photocathodes of nonsensitized p-DSCs. The ex situ XPS analysis of I 4d ionization region of both reference and electrochemically treated NiO films showed that the presence of native and electrochemically generated Ni3+ and Ni4+ centers induces fast adsorption/desorption of I- ions and catalyzes their oxidation to I3- ions. The adsorption phenomena generated by I- and I3- species on nanoporous NiO electrodes can also induce an effect of electrochemical passivation toward a fraction of charged Ni sites. Such an effect would render these sites inactive for the further realization of those photoelectrochemical processes at the basis of the operation of a p-DSC.

Calix[4]arene-Functionalised Silver Nanoparticles as Hosts for Pyridinium-Loaded Gold Nanoparticles as Guests.

A series of lipophilic gold nanoparticles (AuNPs) circa 5 nm in diameter and having a mixed organic layer consisting of 1-dodecanethiol and 1-(11-mercaptoundecyl) pyridinium bromide was synthesised by reacting tetraoctylammonium bromide stabilised AuNPs in toluene with different mixtures of the two thiolate ligands. A bidentate ω-alkylthiolate calix[4]arene derivative was instead used as a functional protecting layer on AgNPs of approximately 3 nm. The functionalised nanoparticles were characterised by transmission electron microscopy (TEM), and by UV/Vis and X-ray photoelectron spectroscopy (XPS). Recognition of the pyridinium moieties loaded on the AuNPs by the calix[4]arene units immobilised on the AgNPs was demonstrated in solution of weakly polar solvents by UV/Vis titrations and DLS measurements. The extent of Au-AgNPs aggregation, shown through the low-energy shift of their surface plasmon bands (SPB), was strongly dependent on the loading of the pyridinium moieties present in the organic layer of the AuNPs. Extensive aggregation between dodecanethiol-capped AuNPs and the Ag calix[4]arene-functionalised NPs was also promoted by the action of a simple N-octyl pyridinium difunctional supramolecular linker. This linker can interdigitate through its long fatty tail in the organic layer of the dodecanethiol-capped AuNPs, and simultaneously interact through its pyridinium moiety with the calix[4]arene units at the surface of the modified AgNPs.

Surface Reactivity of a Carbonaceous Cathode in a Lithium Triflate/Ether Electrolyte-Based Li-O2 Cell.

Li-O2 batteries are currently one of the most advanced and challenging electrochemical systems with the potential to largely overcome the performances of any existing technology for energy storage and conversion. However, these optimistic expectations are frustrated by the still inadequate understanding of the fundamentals of the electrochemical/chemical reactions occurring at the cathode side, as well as within the electrolyte and at the three-phase interface. In this work, we illustrate the evolution of the morphology and composition of a carbonaceous cathode in the first discharge/charge in a Li-O2 cell with an ether-based electrolyte by X-ray photoemission spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy. Experiments have been carried out ex situ on electrodes recuperated from electrochemical cells stopped at various stages of galvanostatic discharge and charge. Apparently, a reversible accumulation and decomposition of organic and inorganic precipitates occurs upon discharge and charge, respectively. These precipitations and decompositions are likely driven by electrochemical and chemical parasitic processes due to the reactivity of the cathode carbonaceous matrix.

Probing the redox states at the surface of electroactive nanoporous NiO thin films.

Nanoporous NiO thin film electrodes were obtained via plasma-assisted microwave sintering and characterized by means of a combination of electrochemical techniques and X-ray photoelectron spectroscopy (XPS). The aim of this study is the elucidation of the nature of the surface changes introduced by the redox processes of this nanostructured material. NiO undergoes two distinct electrochemical processes of oxidation in aqueous electrolyte with the progress of NiO anodic polarization. These findings are consistent with the sequential formation of oxyhydroxide species at the surface, the chemical nature of which was assessed by XPS. Electronic relaxation effects in the Ni 2p spectra clearly indicated that the superficial oxyhydroxide species resulted to be ß-NiOOH and γ-NiOOH. We also show for the first time spectral evidence of an electrochemically generated Ni(IV) species. This study has direct relevance for those applications in which NiO electrodes are utilized in aqueous electrolyte, namely catalytic water splitting or electrochromism, and may constitute a starting point for the comprehension of electronic phenomena at the NiO/organic electrolyte interface of cathodic dye-sensitized solar cells (p-DSCs).

Assembly of gold nanoparticles on functionalized Si(100) surfaces through pseudorotaxane formation.

The assembly of gold nanoparticles (AuNPs) on a hydrogenated Si(100) surface, mediated by a series of hierarchical and reversible complexation processes, is reported. The proposed multi-step sequence involves a redox-active ditopic guest and suitable calix[n]arene-based hosts, used as functional organic monolayers of the two inorganic components. Surface reactions and controlled release of AuNPs have been monitored by application of XPS, atomic force microscopy (AFM), field-emission scanning electron microscopy (FESEM) and electrochemistry.

Electron-transfer processes in metal-free tetraferrocenylporphyrin. Understanding internal interactions to access mixed-valence States potentially useful for quantum cellular automata.

Redox properties of H(2)TFcP [TFcP(2-) = 5,10,15,20-tetraferrocenylporphyrin(2-)] were investigated using cyclic voltammetry, differential pulse voltammetry, and square-wave voltammetry methods in a large variety of solvents and electrolytes. When DMF, THF, and MeCN were used with TBAP as the supporting electrolyte, the first oxidation wave was assigned to a single four-electron oxidation process reflecting simultaneous oxidation of all iron(II) centers into iron(III) centers in H(2)TFcP. When an o-DCB (1,2-dichlorobenzene)/TBAP combination was used in electrochemical experiments, four ferrocene substituents underwent two very diffuse, "two-electron" stepwise oxidations. The use of a weakly coordinating TFAB ([NBu(4)][B(C(6)F(5))(4)]) electrolyte in o-DCB or DCM results in four single-electron oxidation processes for ferrocene substituents in which the first and second single-electron waves have a relatively large separation, while the second, third, and fourth oxidation processes are more closely spaced; similar results were observed when a DCM/TBAP system and an imidazolium cation-based ionic liquid ((bmim)Tf(2)N = N-butyl-N'-methylimidazolium bis(trifluoromethanesulfonyl)imide) were used. Spectroelectrochemical oxidation of H(2)TFcP in o-DCB or DCM with TFAB as the supporting electrolyte allowed for characterization of the mixed-valence [H(2)TFcP](+), [H(2)TFcP](2+), and [H(2)TFcP](3+) compounds by UV-vis spectroscopy in addition to the "all-Fe(III)" [H(2)TFcP](4+). The chemical oxidation of H(2)TFcP was tested using a variety of oxidants which resulted in formation of mixed-valence [H(2)TFcP](+) and [H(2)TFcP](2+) as well as [H(2)TFcP](4+), which were characterized by UV-vis-NIR, MCD, IR, Mossbauer, and XPS spectroscopy. The intervalence-charge-transfer bands observed in the near-IR region in [H(2)TFcP](+) and [H(2)TFcP](2+) complexes were analyzed using Hush formalism and found to be of class II (in Robin-Day classification) character with localized ferrous and ferric centers. Class II behavior of [H(2)TFcP](+) and [H(2)TFcP](2+) complexes was further confirmed by Mossbauer, IR, and XPS data.

Metal-free and transition-metal tetraferrocenylporphyrins part 1: synthesis, characterization, electronic structure, and conformational flexibility of neutral compounds.

H(2)TFcP [TFcP = 5,10,15,20-tetraferrocenyl porphyrin(2-)] was prepared by a direct tetramerization reaction between pyrrole and ferrocene carbaldehyde in the presence of a BF(3) catalyst, while the series of MTFcP (M = Zn, Ni, Co and Cu) were prepared by a metallation reaction between H(2)TFcP and respective metal acetates. All compounds were characterized by UV-vis and MCD spectroscopy, APCI MS and MS/MS methods, high-resolution ESI MS and XPS spectroscopy. Diamagnetic compounds were additionally characterized using (1)H and (13)C NMR methods, while the presence of low-spin iron(ii) centers in the neutral compounds was confirmed by Mössbauer spectroscopy and by analysis of the XPS Fe 2p peaks, revealing equivalent Fe sites. XPS additionally showed the influence on Fe 2p binding energies exerted by the distinct central metal ions. The conformational flexibility of ferrocene substituents in H(2)TFcP and MTFcP, was confirmed using variable-temperature NMR and computational methods. Density functional theory predicts that alpha,beta,alpha,beta atropisomers with ruffled porphyrin cores represent minima on the potential energy surfaces of both H(2)TFcP and MTFcP. The degree of non-planarity is central-metal dependent and follows the trend: ZnTFcP < H(2)TFcP approximately CuTFcP < CoTFcP < NiTFcP. In all cases, a set of occupied, predominantly ferrocene-based molecular orbitals were found between the highest occupied and the lowest unoccupied, predominantly porphyrin-based molecular orbitals. The vertical excitation energies of H(2)TFcP were calculated at the TDDFT level and confirm the presence of numerous predominantly metal-to-ligand charge-transfer bands coupled via configurational interaction with expected intra-ligand pi-pi* transitions.