The oscillatory electro-oxidation of 2-propanol on platinum: the effect of temperature and addition of methanol.

The oscillatory electro-oxidation of 2-propanol on platinum and platinum-based catalysts has attracted growing attention in recent years due to its importance in the interconversion between chemical and electrical energies. This reaction might proceed with a very high selectivity to acetone, nearly without the formation of carbon dioxide, and the reversibility of the 2-propanol/acetone pair is very appropriate for hydrogen transfer. An important aspect of this system is the ubiquitous emergence of potential oscillations under current control, and it has been pointed out as a problem to be avoided and a primary cause of limitations to the use of 2-propanol in practical devices. Herein, we present an experimental study of the electrochemical instabilities in the electro-oxidation of 2-propanol on platinum. The system was studied using polycrystalline platinum, in acidic media and at different temperatures. Besides the extensive characterization of the potential oscillations, we have also discussed possible venues for engineering the dynamics to benefit from the potential oscillations. In this sense, we have also characterized the instabilities in the system containing a mixture of 2-propanol and methanol. The efficiency of a hypothetical fuel cell operated under different conditions is also presented.

Kinetics, Assembling, and Conformation Control of L-Cysteine Adsorption on Pt Investigated by in situ FTIR Spectroscopy and QCM-D.

A quartz crystal microbalance method with dissipation (QCM-D) and attenuated total reflection Fourier-transform infrared (ATR-FTIRS) spectroscopy were used to study the adsorption of L-cysteine (L-Cys) on Pt. Through QCM-D, it was possible to verify that the viscoelastic properties of the adsorbed species play an important role in the adsorption, rendering Sauerbrey's equation inapplicable. The modelling of QCM-D data exposed two different processes for the adsorption reaction. The first one had an activation time and is fast, whereas the second is slow. These processes were also resolved by ATR-FTIRS and identified to be water and anion adsorption preceded by L-Cys adsorption. Both techniques reveal that the degree of surface coverage is pH dependent. Spectroscopic data indicate that the conformation of L-Cys(ads) changes with pH and that the structures do not fully agree with those proposed in literature for other metallic surfaces. The assembling of the adsorbed monolayer appeared to be very fast, and it was not possible to determine or quantify this kinetics. The conformation is also controlled by applied potential, and the anion adsorption and interfacial water depends on the conformation of the adsorbed molecules.

The long and successful journey of electrochemically active amino acids. From fundamental adsorption studies to potential surface engineering tools.

Proteins have been the subject of electrochemical studies. It is possible to apply electrochemical techniques to obtain information about their structure due to the presence of five electroactive amino acids that can be oriented to the outside of the peptidic chain. These amino acids are L-Tryptophan (L-Trp), L-Tyrosine (L-Tyr), L-Histidine (L-His), L-Methionine (L-Met) and L-Cysteine (L-Cys); their electrochemical behavior being subject of extensive research, but it is still controversial. No spectroscopic investigations have been reported on L-Trp, and due to the short life time of the intermediates, ex situ techniques cannot be employed, leading to a never-ending discussion about possible intermediates. In the L-Tyr and L-His cases, spectroelectrochemical studies were performed and different intermediates were observed, suggesting that some intermediates may be observed under specific conditions, as proposed for L-Cys. This amino acid is the most interesting among the electroactive ones because of the presence of a thiol moiety at its side chain, leading to a wide range of oxidation states. It can adsorb onto surfaces of different crystallographic orientation in stereoselective conformation, modifying the surface for different applications.as a surface engineering tool since it plays the role of as an anchor for the growing of nanocrystals inside proteic templates.

Zn-doped MnOx nanowires displaying plentiful crystalline defects and tunable small cross-sections for an optimized volcano-type performance towards supercapacitors.

MnOx-based nanomaterials are promising large-scale electrochemical energy storage devices due to their high specific capacity, low toxicity, and low cost. However, their slow diffusion kinetics is still challenging, restricting practical applications. Here, a one-pot and straightforward method was reported to produce Zn-doped MnOx nanowires with abundant defects and tunable small cross-sections, exhibiting an outstanding specific capacitance. More specifically, based on a facile hydrothermal strategy, zinc sites could be uniformly dispersed in the α-MnOx nanowires structure as a function of composition (0.3, 2.1, 4.3, and 7.6 wt.% Zn). Such a process avoided the formation of different crystalline phases during the synthesis. The reproducible method afforded uniform nanowires, in which the size of cross-sections decreased with the increase of Zn composition. Surprisingly, we found a volcano-type relationship between the storage performance and the Zn loading. In this case, we demonstrated that the highest performance material could be achieved by incorporating 2.1 wt.% Zn, exhibiting a remarkable specific capacitance of 1082.2 F.g-1 at a charge/discharge current density of 1.0 A g-1 in a 2.0 mol L-1 KOH electrolyte. The optimized material also afforded improved results for hybrid supercapacitors. Thus, the results presented herein shed new insights into preparing defective and controlled nanomaterials by a simple one-step method for energy storage applications.

Novel Conducting and Biodegradable Copolymers with Noncytotoxic Properties toward Embryonic Stem Cells.

Electroactive biomaterials that are easily processed as scaffolds with good biocompatibility for tissue regeneration are difficult to design. Herein, the synthesis and characterization of a variety of novel electroactive, biodegradable biomaterials based on poly(3,4-ethylenedioxythiphene) copolymerized with poly(d,l lactic acid) (PEDOT-co-PDLLA) are presented. These copolymers were obtained using (2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol (EDOT-OH) as an initiator in a lactide ring-opening polymerization reaction, resulting in EDOT-PDLLA macromonomer. Conducting PEDOT-co-PDLLA copolymers (in three different proportions) were achieved by chemical copolymerization with 3,4-ethylenedioxythiophene (EDOT) monomers and persulfate oxidant. The PEDOT-co-PDLLA copolymers were structurally characterized by 1H NMR and Fourier transform infrared spectroscopy. Cyclic voltammetry confirmed the electroactive character of the materials, and conductivity measurements were performed via electrochemical impedance spectroscopy. In vitro biodegradability was evaluated using proteinase K over 35 days, showing 29-46% (w/w) biodegradation. Noncytotoxicity was assessed by adhesion, migration, and proliferation assays using embryonic stem cells (E14.tg2a); excellent neuronal differentiation was observed. These novel electroactive and biodegradable PEDOT-co-PDLLA copolymers present surface chemistry and charge density properties that make them potentially useful as scaffold materials in different fields of applications, especially for neuronal tissue engineering.

The long and successful journey of electrochemically active amino acids. From fundamental adsorption studies to potential surface engineering tools

ABSTRACT Proteins have been the subject of electrochemical studies. It is possible to apply electrochemical techniques to obtain information about their structure due to the presence of five electroactive amino acids that can be oriented to the outside of the peptidic chain. These amino acids are L-Tryptophan (L-Trp), L-Tyrosine (L-Tyr), L-Histidine (L-His), L-Methionine (L-Met) and L-Cysteine (L-Cys); their electrochemical behavior being subject of extensive research, but it is still controversial. No spectroscopic investigations have been reported on L-Trp, and due to the short life time of the intermediates, ex situ techniques cannot be employed, leading to a never-ending discussion about possible intermediates. In the L-Tyr and L-His cases, spectroelectrochemical studies were performed and different intermediates were observed, suggesting that some intermediates may be observed under specific conditions, as proposed for L-Cys. This amino acid is the most interesting among the electroactive ones because of the presence of a thiol moiety at its side chain, leading to a wide range of oxidation states. It can adsorb onto surfaces of different crystallographic orientation in stereoselective conformation, modifying the surface for different applications.as a surface engineering tool since it plays the role of as an anchor for the growing of nanocrystals inside proteic templates.