a b s t r a c tThe oscillatory electro-oxidation of methanol was studied by means of in situ infrared (IR) spectroscopy in the attenuated total reflection (ATR) configuration using a platinum film on a Si prism as working electrode. The surface-enhanced infrared absorption (SEIRA) effect considerably improves the spectroscopic resolution, allowing at following the coverage of some adsorbing species during the galvanostatic oscillations. Carbon monoxide was the main adsorbed specie observed in the induction period and within the oscillatory regime. The system was investigated at two distinct time-scales and its dynamics characterized accordingly. During the induction period the main transformation observed as the system move through the phase space towards the oscillatory region was the decrease of the coverage of adsorbed carbon, coupled to the increase of the electrode potential. Similar transition characterizes the evolution within the oscillatory region, but at a considerably slower rate. Experiments with higher time resolution revealed that the electrode potential oscillates in-phase with the frequency of the linearly adsorbed CO vibration and that the amount of adsorbed CO oscillates with small amplitude. Adsorbed formate was found to play, if any, a very small role. Results are discussed and compared with other systems.

The hollow precipitate tubes in chemical gardens conserve the nonequilibrium conditions present during their formation and are an important example of molecular processes causing complex macroscopic self-organization. We report a greatly simplified experimental model of these structures that is based on the formation of an inorganic membrane in a microfluidic device. Within this device, we induce the precipitation of Mn­(OH)2 and other metal hydroxides at the reactive interface of steadily injected NaOH and MnCl2 solutions. The resulting precipitate wall extends along the entire length of the reactor channel and can be positioned at will, and its width increases strictly in the direction of the metal solution. These thickening dynamics obey a square root law. The corresponding effective diffusion coefficient is proportional to [OH–], shows a sigmoidal dependence on [Mn2+], and also depends on the precipitating metal ion. The precipitate wall is permeable to methylene blue and strongly adsorbs methyl orange. Electron and optical microscopy reveals decaying micrometer-sized perturbations and a 40 μm thick gel-like layer on the surface exposed to the Mn2+ solution. The wall growth is also followed by in situ Raman spectroscopy. Potential applications toward materials and origins-of-life research are discussed.

To model ion transport across protocell membranes in Hadean hydrothermal vents, we consider both theoretically and experimentally the planar growth of a precipitate membrane formed at the interface between two parallel fluid streams in a 2D microfluidic reactor. The growth rate of the precipitate is found to be proportional to the square root of time, which is characteristic of diffusive transport. However, the dependence of the growth rate on the concentrations of hydroxide and metal ions is approximately linear and quadratic, respectively. We show that such a difference in ionic transport dynamics arises from the enhanced transport of metal ions across a thin gel layer present at the surface of the precipitate. The fluctuations in transverse velocity in this wavy porous gel layer allow an enhanced transport of the cation, so that the effective diffusivity is about one order of magnitude higher than that expected from molecular diffusion alone. Our theoretical predictions are in excellent agreement with our laboratory measurements of the growth of a manganese hydroxide membrane in a microfluidic channel, and this enhanced transport is thought to have been needed to account for the bioenergetics of the first single-celled organisms.

By means of in situ IR spectroscopy we investigate the effect of dissolved alkali cations on the electro-oxidation of ethylene glycol on platinum in alkaline media. The results revealed that the increase in the oxidation currents (Li(+) < Na(+) < K(+)) is reflected in the increase in the ratio between carbonate and oxalate produced.

Descreve-se neste artigo a observação experimental de dinâmica oscilatória durante a oxidação eletrocatalítica de metanol sobre platina. Além das, previamente relatadas, oscilações de potencial, oscilações de corrente obtidas sob controle potenciostático também são apresentadas. A região de existência de oscilações de corrente é mapeada no plano de bifurcação voltagem aplicada x resistência. Conjuntamente com investigações eletroquímicas, espectroscopia FTIR in situ também foi aplicada nestes estudos. Apesar de não ter sido possível acompanhar eventuais variações de intermediários reacionais durante as oscilações, tais experimentos revelaram que a cobertura média de monóxido de carbono permanece consideravelmente alta durante as oscilações. Os resultados são discutidos e comparados com as oscilações observadas na eletrooxidação de ácido fórmico, um sistema cujo comportamento é mais entendido e amplamente fundamentado por dados espectroscópicos obtidos in situ.It is described in this paper the experimental observation of oscillatory dynamics during the electrocatalytic oxidation of methanol on platinum. Besides the previously reported potential oscillations, current oscillations obtained under potentiostatic control are also presented. The existence region of current oscillations is mapped in an applied voltage x resistance bifurcation diagram. Conjointly with electrochemical investigations, in situ FTIR spectroscopy was also employed in the present studies. Although we were not able to follow eventual intermediate coverage changes during the oscillations, those experiments revealled that the mean coverage of adsorbed carbon monoxide remains appreciably high along the oscillations. Results are discussed and compared with the oscillations observed in the electrooxidation of formic acid, a system whose behavior is more understood and widely supported by in situ spectroscopic data. Keywords: current and potential oscillations, methanol, electrocatalysis, in situ FTIR IntroductionMethanol has been pointed as one of the most promising organic molecules to be used in large scale energy conversion systems, as in the so-called direct methanol fuel cells (DMFC). [1][2][3] Limitations associated to the high overpotential and the existence of parallel reaction pathways makes its understanding a rather challenging task. Studies have been carried out mainly on platinum surfaces, both polycrystalline and single crystals, by means of different electrochemical approaches sometimes coupled to other in situ and on line techniques. [4][5][6][7][8][9][10][11][12][13][14][15][16] In most of these reports, the focus stands on the electrocatalytic aspects of the methanol oxidation and encompasses questions such as the relationship between reaction rate and applied potential, the impact of the interfacial structure on reaction rate and selectivity, and the nature and geometry of adsorbates, to list a few. By far less studied however are the issues related to the complex kinetic aspects associated to the electrooxidation of methanol.In o...

Contrary to common belief, hollow precipitation tubes form in the absence of silicate if sodium hydroxide solution is injected into solutions of various metal ions. In many cases, the growth speed has a power law dependence on the flow rate. For vanadyl, we observe damped oscillations in the tube height.

Even when in contact with virtually infinite reservoirs, natural and manmade oscillators typically drift in phase space on a time-scale considerably slower than that of the intrinsic oscillator. A ubiquitous example is the inexorable aging process experienced by all living systems. Typical electrocatalytic reactions under oscillatory conditions oscillate for only a few dozen stable cycles due to slow surface poisoning that ultimately results in destruction of the limit cycle. We report the observation of unprecedented long-lasting temporal oscillations in the electro-oxidation of formic acid on an ordered intermetallic PtSn phase. The introduction of Sn substantially increases the catalytic activity and retards the irreversible surface oxidation, which results in the stabilization of more than 2200 oscillatory cycles in about 40 h; a 30-40-fold stabilization with respect to the behavior of pure Pt surfaces. The dynamics were modeled and numerical simulations point to the surface processes underlying the high stability.

Many inorganic precipitation reactions self-organize macroscopic tubes known as chemical gardens. We study the nonequilibrium formation of these structures by injecting aqueous sodium sulfide solution into a reservoir of iron(II) chloride solution. Our experiments reveal a distinct, concentration-dependent transition from convective plumes of reaction-induced, colloidal particles to mechanically connected, hollow tubes. The transition concentration (0.1 mol/L) is widely independent of the injection rate and causes a discontinuous change from the radius of the plume stalk to the radius of the tube. In addition, tubes have lower growth speeds than plumes. At the transition concentration, one observes the initial formation of a plume followed by the growth of a mechanically weak tube around a jet of upward-moving precipitation particles. We find that the plumes' morphology and geometric scaling are similar to that of laminar starting plumes in nonreactive systems. The characterization of dried tubes by X-ray diffraction indicates the presence of greigite and lepidocrocite.