ELECTROCHEMICAL STUDY OF ISOPOLY-OXOMETALLATE AND HETEROPOLY-OXOMETALLATE FILM MODIFIED MICROELECTRODES .2. ELECTROCHEMICAL-BEHAVIOR OF ISOPOLYMOLYBDIC ACID MONOLAYER MODIFIED CARBON-FIBER MICROELECTRODES

In this paper the electrochemical properties of isopolymolybdic anion thin film modified carbon fibre (CF) microelectrode prepared by simple dip coating have been described. The modified electrode shows three couples of surface redox waves between + 0.70 and - 0.1 V vs. sce in 2 M H2SO4 solution with good stability and reversibility. The pH of solution has a marked effect on the electrochemical behaviour and stability of the film, the stronger the acidity of electrolyte solution is, the better the stability and reversibility of isopolymolybdic anion film CF microelectrode will be. The scanning potential range strongly influences on the electrochemical behaviour of the film. The isopolymolybdic anion film prepared by the dip coating resulting a monolayer with estimated surface concentration (F) 2.8 x 10(-11) mol cm-2. From the half-peak widths and peak areas of the surface redox waves of the film electrode, the first three surface waves are corresponding to two-electron processes. The electron energy spectra show the products by six electrons reduction are a mixture of Mo(VI) and Mo(V) species. The electrochemical reaction of the isopolymolybdic anion monolayer can be expressed as Mo8O264- + mH+ + 2ne half arrow right over half arrow left [HmMo8-2n(VI)Mo2n(V)O26](4,2n-m)-n = 1, 2, 3; m = 2, 5, 7.

ELECTROCHEMICAL STUDY OF ISOPOLYOXOMETALLATES AND HETEROPOLYOXOMETALLATES FILM MODIFIED MICROELECTRODES .1. PRETREATMENT AND MODIFICATION OF THE MO80-26(4-) MODIFIED CARBON-FIBER MICROELECTRODE

In this paper the preparation of isopoly- and heteropolyoxometallates (IPA and HPA) thin film modified carbon fiber (CF) microelectrodes and the factor that influences the modification of IPA and HPA films are described. IPA and HPA film modified CF microelectrodes can all be prepared by cyclic potential scan and simple dip coating. The modified electrodes prepared are very stable and reversible in acidic solution with monolayer characteristics. The electrochemical pretreatment of CF microelectrodes plays an important role in the modification of IPA and HPA film. The absorption of IPA and HPA film on electrode surfaces has been discussed on the basis of surface conditions of the CF microelectrode and the structure of IPA and HPA.

东南极格罗夫山地区的土壤特征及其环境研究

The Grove Mountains, including 64 nunataks, is situated on an area about 3200km2 in the inland ice cap of east Antarctica in Princess Elizabeth land (72o20'-73°101S, 73°50'-75o40'E), between Zhongshan station and Dome A, about 450km away from Zhongshan station (69°22'S, 76°22'E). Many workers thought there was no pedogenesis in the areas because of the less precipitation and extreme lower temperature. However, during the austral summer in 1999-2000, the Chinaer 16 Antarctic expedition teams entered the inland East Antarctica and found three soil spots in the Southern Mount Harding, Grove Mountains, East Antarctica. It is the first case that soils are discovered in the inland in East Antarctica. Interestingly, the soils in this area show clay fraction migration, which is different from other cold desert soils. In addition, several moraine banks are discovered around the Mount Harding. The soil properties are discussed as below. Desert pavement commonly occurs on the three soil site surfaces, which is composed of pebbles and fragments formed slowly in typical desert zone. Many pebbles are subround and variegated. These pebbles are formed by abrasion caused by not only wind and wind selective transportation, but also salt weathering and thaw-freezing action on rocks. The wind blows the boulders and bedrocks with snow grains and small sands. This results in rock disintegration, paved on the soil surface, forming desert pavement, which protects the underground soil from wind-blow. The desert pavement is the typical feature in ice free zone in Antarctica. There developed desert varnish and ventifacts in this area. Rubification is a dominant process in cold desert Antarctic soils. In cold desert soils, rubification results in relatively high concentrations of Fed in soil profile. Stained depth increases progressively with time. The content of Fed is increasing up to surface in each profile. The reddish thin film is observed around the margin of mafic minerals such as biotite, hornblende, and magnetite in parent materials with the microscope analyzing on some soil profiles. So the Fed originates from the weathering of mafic minerals in soils. Accumulations of water-soluble salts, either as discrete horizons or dispersed within the soil, occur in the soil profiles, and the salt encrustations accumulate just beneath surface stones in this area. The results of X-ray diffraction analyses show that the crystalline salts consist of pentahydrite (MgSO4-5H2O), hexahydrite (MgSO4-6H2O), hurlbutite (CaBe2(PO4)2), bloedite (Na2Mg(S04)2-4H2O), et al., being mainly sulfate. The dominant cations in 1:5 soil-water extracts are Mg2+ and Na+, as well as Ca2+ and K+, while the dominant anion is SO42-, then NO3-, Cl- and HCO3-. There are white and yellowish sponge materials covered the stone underside surface, of which the main compounds are quartz (SiO2, 40.75%), rozenite (FeSOKkO, 37.39%), guyanaite (Cr2O3-1.5H2O, 9.30%), and starkeyite (MgSO4-4H2O, 12.56%). 4) The distribution of the clay fraction is related to the maximum content of moisture and salts. Clay fraction migration occurs in the soils, which is different from that of other cold desert soils. X-ray diffraction analyses show that the main clay minerals are illite, smectite, then illite-smectite, little kaolinite and veirniculite. Mica was changed to illite, even to vermiculite by hydration. Illite formed in the initial stage of weathering. The appearance of smectite suggests that it enriched in magnesium, but no strong eluviation, which belongs to cold and arid acid environment. 5) Three soil sites have different moisture. The effect moisture is in the form of little ice in site 1. There is no ice in site 2, and ice-cement horizon is 12 cm below the soil surface in site 3. Salt horizon is 5-10 cm up to the surface in Site 1 and Site 2, while about 26cm in site 3. The differentiation of the active layer and the permafrost are not distinct because of arid climate. The depth of active layer is about 10 cm in this area. Soils and Environment: On the basis of the characteristics of surface rocks, soil colors, horizon differentiation, salt in soils and soil depth, the soils age of the Grove Mountains is 0.5-3.5Ma. No remnants of glaciations are found on the soil sites of Mount Harding, which suggests that the Antarctic glaciations have not reached the soil sites since at least 0.5Ma, and the ice cap was not much higher than present, even during the Last Glacial Maximum. The average altitude of the contact line of level of blue ice and outcrop is 2050m, and the altitude of soil area is 2160m. The relative height deviation is about 110m, so the soils have developed and preserved until today. The parental material of the soils originated from alluvial sedimentary of baserocks nearby. Sporepollen were extracted from the soils, arbor pollen grains are dominant by Pinus and Betula, as well as a small amount Quercus, Juglans, Tilia and Artemisia etc. Judging from the shape and colour, the sporepollen group is likely attributed to Neogene or Pliocene in age. This indicates that there had been a warm period during the Neogene in the Grove Mountains, East Antarctica.