Electrochemical and photoelectrochemical properties of nickel oxide (NiO) with nanostructured morphology for photoconversion applications

The cost-effective production of chemicals in electrolytic cells and the conversion of the radiation energy into electrical energy in photoelectrochemical cells (PECs) require the use of electrodes with large surface area, which possess either electrocatalytic or photoelectrocatalytic properties. In this context nanostructured semiconductors are electrodic materials of great relevance because of the possibility of varying their photoelectrocatalytic properties in a controlled fashion via doping, dye-sensitization or modification of the conditions of deposition. Among semiconductors for electrolysers and PECs the class of the transition metal oxides (TMOs) with a particular focus on NiO interests for the chemical-physical inertness in ambient conditions and the intrinsic electroactivity in the solid state. The latter aspect implies the existence of capacitive properties in TMO and NiO electrodes which thus act as charge storage systems. After a comparative analysis of the (photo)electrochemical properties of nanostructured TMO electrodes in the configuration of thin film the use of NiO and analogs for the specific applications of water photoelectrolysis and, secondly, photoelectrochemical conversion of carbon dioxide will be discussed. © 2018 Bonomo, Dini and Decker

Effect of sensitization on the electrochemical properties of nanostructured NiO

Screen-printed NiO electrodes were sensitized with 11 different dyes and the respective electrochemical properties were analyzed in a three-electrode cell with the techniques of cyclic voltammetry and electrochemical impedance spectroscopy. The dye sensitizers of NiO were organic molecules of different types (e.g., squaraines, coumarins, and derivatives of triphenyl-amines and erythrosine B), which were previously employed as sensitizers of the same oxide in dye-sensitized solar cells of p-type (p-DSCs). Depending on the nature of the sensitizer, diverse types of interactions occurred between the immobilized sensitizer and the screen-printed NiO electrode at rest and under polarization. The impedance data recorded at open circuit potential were interpreted in terms of two different equivalent circuits, depending on the eventual presence of the dye sensitizer on the mesoporous electrode. The fitting parameter of the charge transfer resistance through the electrode/electrolyte interface varied in accordance to the differences of the passivation action exerted by the various dyes against the electrochemical oxidation of NiO. Moreover, it has been observed that the resistive term RCT associated with the process of dark electron transfer between the dye and NiO substrate is strictly correlated to the overall efficiency of the photoconversion () of the corresponding p-DSC, which employs the same dye-sensitized electrode as photocathode

X-ray photoelectron spectroscopy investigation of nanoporous NiO electrodes sensitized with Erythrosine B

Nanoporous NiO thin films were prepared onto FTO glass substrates by means of screen-printing and were sensitized with Erythrosine B (EryB) dye. The obtained material was electrochemically treated and characterized with ex-situ X-ray photoelectron spectroscopy in order to gain information beneficial to the application of sensitized NiO as photocathodes of p-type dye-sensitized solar cells (p-DSCs). In particular, EryB-sensitized NiO films underwent a series of electrochemical treatments in LiClO4/Acetonitrile (ACN) electrolyte devised so as to simulate possible conditions the electrode might encounter during operation in the photoelectrochemical cell. Upon potential-cycling in a range where the two NiO faradic events Ni(II)→Ni(III) and Ni(III)→Ni(IV) occur, X-ray photoelectron spectroscopy revealed that Erythrosine B dye experiences a partial detachment from the NiO surface. This detachment seems to be paralleled by the formation of stable (Ni)+(ClO4)- couples. Overall, the EryB dye displayed an acceptable electrochemical stability onto the surface of NiO electrode up to 50 cyclic voltammetries in the range -0.27÷+1.13V vs. Ag/AgCl. These results are useful for the evaluation of electrochemical stability of the dye when this is immobilized onto an electrode surface and are beneficial for a better comprehension of the degradation phenomena operating in real photoconversion device. © 2017 Elsevier B.V

Nanostructured semiconductor materials for dye-sensitized solar cells

Since O'Regan and Grätzel's first report in 1991, dye-sensitized solar cells (DSSCs) appeared immediately as a promising low-cost photovoltaic technology. In fact, though being far less efficient than conventional silicon-based photovoltaics (being the maximum, lab scale prototype reported efficiency around 13%), the simple design of the device and the absence of the strict and expensive manufacturing processes needed for conventional photovoltaics make them attractive in small-power applications especially in low-light conditions, where they outperform their silicon counterparts. Nanomaterials are at the very heart of DSSC, as the success of its design is due to the use of nanostructures at both the anode and the cathode. In this review, we present the state of the art for both n-type and p-type semiconductors used in the photoelectrodes of DSSCs, showing the evolution of the materials during the 25 years of history of this kind of devices. In the case of p-type semiconductors, also some other energy conversion applications are touched upon. © 2017 Carmen Cavallo et al

First examples of pyran based colorants as sensitizing agents of p-Type Dye-Sensitized solar cells

Three different pyran based dyes were synthesized and tested for the first time as photosensitizers of NiO based p-type dye-sensitized solar cells (p-DSSC). The molecules feature a similar molecular structure and are based on a pyran core that is functionalized with electron acceptor groups of different strength and is symmetrically coupled to phenothiazine donor branches. Optical properties of the dyes are deeply influenced by the nature of the electron-acceptor group, so that the overall absorption of the three dyes covers the most of the visible spectrum. The properties of devices based on the NiO electrodes sensitized with the investigated dyes were evaluated under simulated solar radiation: the larger short circuit current density exceeded 1mA/cm2 and power conversion efficiency as high as 0.04% could be recorded. The performances of the fabricated p-DSSC have been compared to a reference cell sensitized with P1, a high level benchmark, which afforded a photoelectrochemical activity similar to the best example of our pyran sensitized devices (1.19 mA/cm2 and 0.049%)

Effect of sodium hydroxide pretreatment of NiOx cathodes on the performance of squaraine-sensitized p-type dye-sensitized solar cells

Squaraines are full-organic dyes employed as sensitizers in ptype dye-sensitized solar cells (p-DSSC). Their absorption spectrum shows a wide tunability that ranges from visible to NIR. Sensitization in the NIR region is crucial for exploiting a particularly intense portion of the solar spectrum. In this work three squaraines will be presented and tested as sensitizers in NiO-based p-type DSSC O4_C2, O4_C4 and O4_C12). The structures of the dyes differ for the length of the alkyl side chain (C2, C4 and C12). Alkyl side chains improve the solubility of the dye, influence the extent of dye loading on the electrode and affect the overall efficiency of devices. The generally low stability of squaraines represents a critical issue in view of their employment as sensitizers of p-DSSC. Such a problem becomes even more evident when this class of molecules is bound onto an acidic surface like the one of the photocathode here employed: non-stoichiometric nickel oxide (NiOx). NiOx possesses a quite acidic character because of the high surface concentration of Ni(III) sites. To buffer the surface acidity of NiOx due to the presence of high-valence states of nickel, we considered the electrode pretreatment with sodium hydroxide (NaOH) prior to sensitization. This assures a major stability of the solar cell. At the same time the chemisorbed hydroxyl moieties act as passivating agents of the Ni(III) sites thus diminishing the surface concentration of sites for dye anchoring. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Assessing the Structure of Protic Ionic Liquids Based on Triethylammonium and Organic Acid Anions

We present a computational analysis of the short-range structure of three protic ionic liquids based on strong organic acids: trifluoracetate, methanesulfonate, and triflate of triethylammonium. Accurate ab initio computations carried out on the gas-phase dimers show that the protonation of triethylamine is spontaneous. We have identified the anion-cation binding motif that is due to the presence of a strong hydrogen bond and to electrostatic interactions. The strength of the hydrogen bond and the magnitude of the binding energy decrease in the order trifluoroacetate ≳ methanesulfonate > triflate. The corresponding simulations of the bulk phases, obtained using a semiempirical evaluation of the interatomic forces, reveal that on short timescales, the state of the three liquids remains highly ionized and that the gas-phase cation-/anion-binding motif is preserved while no other peculiar structural features seem to emerge