Role of Bridge-bonded Formate in Formic Acid Dehydration to CO at Pt Electrode： Electrochemial in-situ Infrared Spectroscopic Study

Formic acid （HCOOH） decomposition at Pt film electrode has been studied by electrochem- ical in situ FTIR spectroscopy under attenuated-total-reflection configuration, in order to clarify whether bridge-bonded formate （HCOOD） is the reactive intermediate for COad for-mation from HCOOH molecules. When switching from HCOOH-free solution to HCOOH- containing solution at constant potential （E=0.4 V vs. RHE）, we found that immediately upon solution switch COad formation rate is the highest, while surface coverage of formate is zero, then after COad formation rate decreases, while formate coverage reaches a steady state coverage quickly within ca. 1 s. Potential step experiment from E=0.75 V to 0.35 V, reveals that formate band intensity drops immediately right after the potential step, while the COad signal develops slowly with time. Both facts indicate that formate is not the reactive intermediate for formic acid dehydration to CO.

Restructuring of well-defined Pt-based electrode surfaces under mild electrochemical conditions

Since the 1980s,single-crystal Pt electrodes with well-defined surface structures have been deemed stable under mild electrochemical conditions(e.g.,in the potential region of electric double layers,underpotential deposition of hydrogen,or mild hydrogen evolution/OH adsorption)and have served as model electrodes for unraveling the structure-performance relation in electrocatalysis.With the advancement of in situ electrochemical microscopy/spectroscopy techniques,subtle surface restructuring under mild electrochemical conditions has been achieved in the last decade.Surface restructuring can considerably modify electrocatalytic properties by generating/destroying highly active sites,thereby interfering with the deduction of the structure-performance relation.In this review,we summarize recent progress in the restructuring of well-defined Pt(-based)electrode surfaces under mild electrochemical conditions.The importance of the meticulous structural characterization of Pt electrodes before,during,and after electrochemical measurements is demonstrated using CO adsorption/oxidation,hydrogen adsorption/evolution,and oxygen reduction as examples.The implications of present findings for correctly identifying the reaction mechanisms and kinetics of other electrocatalytic systems are also briefly discussed.

AC IMPEDANCE OF PHENYL ISO-THIOCYANATE ADSORBED ON PT ELECTRODE

The paper presents ac impedance behaviours of phenyl iso-thiocyanate adsorbed on Pt electrode.Nyquist plots are analysed and simulated,and parameters of relative equivalent circuits are obtained.

Ion-Conductive-Polymer-Film Actuators with Pt Electrodes Selectively Grown using Non-Electrolyzed Plating

Organic soft actuators are of special interest in many fields including intravascular neurosurgery. Ion conductive polymer film （ICPF） actuators have been one of the strong candidates. The ICPF investigated here was a cation-exchange membrane （Nation 117, Du Pont）. When a voltage is given between the metal eIectrodes of an ICPF actuator, the ICPF actuator bends in the water due to the motion of Li＋ cations with associated water. In order to increase the freedom of the deformation of the ICPF actuator, structures of independent electrode pairs were proposed. The electrodes were selectively deposited by non-electrokvzed plating including the Pt [（NH3）6]^4＋ deposition process in a [Pt（NH3）6]Cl4 solution and the reduction process in a NaBH4 solution. Here, an elastomer adhesive tape with a fine electrode patterns was used performances were reported in detail. as a mask. The actuators processing conditions and their actuator

Electrically enhanced photodegradation of an azodye(Acid Orange II) using a Pt/TiO_2 film electrode irradiating with an UV lamp

A photoelectrochemical process in the degradation of an azodye (Acid Orange II) on a Pt/TiO 2 film electrode was investigated. By using the glass device and the voltage stabilized source of direct current, decolorization ratios higher than 78% were observed during a period of 5h. Comparing this value with the sum of the decolorization ratios obtained by a sole application of electrochemical(lower than 3%) and photochemical(about 23%) procedures, a significant synergic effect between both processes was observed. The effects of adscititious voltage and pH value on the decolorization ratios were obvious while the effect of the amount of aeration was minor.

Kinetics Study on O2 Adsorption and OHad Desorption at Pt（111）, Its Implication to Oxygen Reduction Reaction Kinetics

Kinetics of dissociative O2 adsorption, OHad desorption, and oxygen reduction reaction （ORR） at Pt（111） electrode in 0.1 mol/L HClO4 has been investigated. Reversible OHad adsorption/desorption occurs at potentials from 0.6 V to 1.0 V （vs. RHE） with the exchange current density of ca. 50 mA/cm^2 at 0.8 V, the fast kinetics of OHad desorption indicates that it should not be the rate determining step for ORR. In the kineticor kinetic-mass transport mix controlled potential region, ORR current at constant potential displays slight decrease with reaction time. ORR current in the positive-going potential scan is slightly larger than that in the subsequent negative-going scan with electrode rotation speed （〉800 r/min） and slow potential scan rate （〈100 mV/s）. The open circuit potential of Pt/0.1 mol/L HClO4 interface increases promptly from 0.9 V to 1.0 V after switch from O2 free- to O2-saturated solution. The increase of open circuit potential as well as ORR current decays under potential control due to the accumulation of OHad from dissociative adsorption of O2. It indicates that at Pt（111） the net rate for O2 decomposition to OHad is slightly faster than that for OHad removal, one cannot simply use the assumption of rate determining step to discuss ORR kinetics. Instead, the ORR kinetics is determined by both the kinetics for O2 decomposition to OHad as well as the thermo-equilibrium of OHad＋H^＋＋e→←H2O.

Spillover on a Platinum Electrode Modified by MWNTs

The spillover phenomenon is observed on the platinum (Pt) disk electrode modified bymulti-wall carbon nanotubes (MWNTs). The rate of the spillover of oxygen-containing speciesproduced on Pt surface to and from MWNTs is fast. However for hydrogen-adatoms, thespillover is very weak. The selective spillover on the Pt/MWNTs electrode may provide a novelway to design catalysts.

Preliminary study on electrochemical reduction of carbon dioxide on nickel and platinum electrodes

The electrochemical reduction of carbon dioxide was investigated on nickel and platinum electrodes in 0.5 mol dm^-3 KHCO3 solutions. The main products were formic acid and carbon monoxide during the electroreduction of CO2, and the Faradaic efficiency for this process depended on the characteristics of the electrode. At ambient temperature and pressure, the Faradaic efficiency was measured to be 8.6% and 2.5 % respectively for the production of formic acid and CO with Pt electrode at - 1.3V vs Ag/AgCl （saturated KCl）. At this same potential, the Faradaic efficiency was measured to be 8.9% and 1.7% respectively with Ni electrode. Tafel plots showed that the electrochemical reduction of CO2 was not limited by the mass transfer process in the range of -0.8 to - 1.2V vs Ag/AgCl （saturated KCl）.

An Application of Real-time Error Compensation to a NC Twin-spindle Lathe

The processes of adsorption and oxidation of glycerol on Pt, Pt/Sbad and Pt/Sad electrodes were studied by using Cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM). The results demonstrated that the oxidation of glycerol depended strongly on oxidation states of electrode surface. Sb adatoms on Pt surface can adsorb oxygen at relatively low potentials, and exhibit catalytic effects for glycerol oxidation. In contrast to Pt electrodes, the oxidation peak potential of glycerol on Pt surface modified with Sb in saturation was negatively shifted by about 140 mV. In a contrary, the oxidation of S adatoms consumes oxygen species of Pt electrode surface. As a consequence, the oxidation of glycerol was inhibited on Pt surface modified with Sb in saturation. The EQCM studies provided quantitative results of surface mass variation during glycerol oxidation, and have thrown new light in elucidating different effects of adatoms Sbad and Sad on Pt electrode surface towards glycerol oxidation.

A New Amperometric Detector Cell for Capillary Zone Electrophoresis

A simple and convenient electrochemical detection cell for capillary electrophoresis is described in this paper. In this cell, alignment of the capillary working electrode with the separation capillary outlet can be achieved precisely and easily without the aid of the micropositioner or microscope. With end-column detection, the applicability of the cell as an amperometric detector for capillary electrophoresis is demonstrated by running several phenolic compounds in 50 mu m i.d, capillary with a capillary Pt electrode as the working electrode. Results obtained are satisfactory.

Studies of surface processes of electrocatalytic reduction of CO_(2) on Pt(210), Pt(310) and Pt(510)

Surface processes of CO_(2)reduction on Pt(210),Pt(310),and Pt(510)electrodes were studied by cyclic voltammetry.Different surface structures of these platinum single crystal electrodes were obtained by various treatment conditions.The experimental results illustrated that the electrocatalytic activity of Pt single crystal electrodes towards CO_(2)reduction is decreased in an order of Pt(210)>Pt(310)>Pt(510),i.e.,with the decrease of(110)step density on well-defined surfaces.When the surfaces were reconstructed due to oxygen adsorption,the catalytic activity of all the three electrodes has been enhanced to a cer-tain extent.Although the activity order remains unchanged,the electrocatalytic activity has been en-hanced more significantly as the density of(110)step sites is more intensive on the Pt single crystal surface.It has revealed that the more open the surface structure is,the more active the Pt single crystal electrode will be,and the easier for the electrode to be transformed into a surface structure that exhib-its higher activity under external inductions.However,the relatively ordered surfaces of Pt single crystal electrode are comparatively stable under the same external inductions.The present study has gained knowledge on the interaction between CO_(2)and Pt single crystal electrode surfaces at a micro-scopic level,and thrown new insight into understanding the surface processes of electrocatalytic re-duction of CO_(2).