Preparation and Conducting Behavior of Amphibious Organic/Inorganic Hybrid Proton Exchange Membranes Based on Benzyltetrazole

A series of novel amphibious organic/inorganic hybrid proton exchange membranes with H3PO4 doped which could be used under both wet and dry conditions was prepared through a sol-gel process based on acrylated triethoxysilane（A-TES） and benzyltetrazole-modified triethoxysilane（BT-TES）.The dual-curing approach including UV-curing and thermal curing was used to obtain the crosslinked membranes.Polyethylene glycol（400） diacrylate（PEGDA） was used as an oligomer to form the polymeric matrix.The molecular structures of precursors were characterized by 1 H,13 C and 29 Si NMR spectra.The thermogravimetric analysis（TGA） results show that the membranes exhibit acceptable thermal stability for their application at above 200 oC.The differential scanning calorimeter（DSC） determination indicates that the crosslinked membranes with the mass ratios of below 1.6 of BT-TES to A-TES and the same mass of H3PO4 doped as that of A-TES possess the-T g s,and the lowest T g（-28.9 ℃） exists for the membrane with double mass of H3PO4 doped as well.The high proton conductivity in a range of 9.4―17.3 mS/cm with the corresponding water uptake of 19.1%―32.8% of the membranes was detected at 90 oC under wet conditions.Meanwhile,the proton conductivity in a dry environment for the membrane with a mass ratio of 2.4 of BT-TES to A-TES and double H3PO4 loading increases from 4.89×10-2 mS/cm at 30 ℃ to 25.7 mS/cm at 140 ℃.The excellent proton transport ability under both hydrous and anhydrous conditions demonstrates a potential application in the polymer electrolyte membrane fuel cells.

Preliminary investigation of phosphorus adsorption onto two types of iron oxide-organic matter complexes

Iron oxide（FeO）coated by natural organic matter（NOM）is ubiquitous.The associations of minerals with organic matter（OM）significantly changes their surface properties and reactivity,and thus affect the environmental fate of pollutants,including nutrients（e.g.,phosphorus（P））.In this study,ferrihydrite/goethite-humic acid（FH/GE–HA）complexes were prepared and their adsorption characteristics on P at various p H and ionic strength were investigated.The results indicated that the Fe O–OM complexes showed a decreased P adsorption capacity in comparison with bare Fe O.The maximum adsorption capacity（Q（max））decreased in the order of FH（22.17 mg/g）〉FH-HA（5.43 mg/g）〉GE（4.67 mg/g）〉GE-HA（3.27 mg/g）.After coating with HA,the amorphous FH–HA complex still showed higher P adsorption than the crystalline GE–HA complex.The decreased P adsorption observed might be attributed to changes of the Fe O surface charges caused by OM association.The dependence of P adsorption on the specific surface area of adsorbents suggests that the Fe O component in the complexes is still the main contributor for the adsorption surfaces.The P adsorptions on Fe O–HA complexes decreased with increasing initial p H or decreasing initial ionic strength.A strong dependence of P adsorption on ionic strength and p H may demonstrate that outer-sphere complexes between the OM component on the surface and P possibly coexist with inner-sphere surface complexes between the Fe O component and P.Therefore,previous over-emphasis on the contributions of original minerals to P immobilization possibly over-estimates the P loading capacity of soils,especially in humic-rich areas.

Phosphatase activity and culture conditions of the yeast Candida mycoderma sp. and analysis of organic phosphorus hydrolysis ability

Orthophosphate is an essential but limiting macronutrient for plant growth. About 67% cropland in China lacks sufficient phosphorus, especially that with red soil. Extensive soil phosphorus reserves exist in the form of organic phosphorus, which is unavailable for root uptake unless hydrolyzed by secretory acid phosphatases. Thus, many microorganisms with the ability to produce phosphatase have been exploited. In this work, the activity of an extracellular acid phosphatase and yeast biomass from Candida mycoderma was measured under different culture conditions, such as pH, temperature, and carbon source. A maximal phosphatase activity of 8.47 × 10^5±0.11× 10^5 U/g was achieved by C. Mycoderma in 36 hr under the optimal conditions. The extracellular acid phosphatase has high activity over a wide pH tolerance range from 2.5 to S.0 （optimum pH 3.5）. The effects of different phosphorus compounds on the acid phosphatase production were also studied. The presence of phytin, lecithin or calcium phosphate reduced the phosphatase activity and biomass yield significantly. In addition, the pH of the culture medium was reduced significantly by lecithin. The efficiency of the strain in releasing orthophosphate from organic phosphorus was studied in red soil （used in planting trees） and rice soil （originating as red soil）. The available phosphorus content was increased by 230% after inoculating 20 days in rice soil and decreased by 50% after inoculating 10 days in red soil. This work indicates that the yeast strain C. mycoderma has potential application for enhancing phosphorus utilization in plants that grow in rice soil.

Underestimation of phosphorus fraction change in the supernatant after phosphorus adsorption onto iron oxides and iron oxide–natural organic matter complexes

The phosphorus（P） fraction distribution and formation mechanism in the supernatant after P adsorption onto iron oxides and iron oxide-humic acid（HA） complexes were analyzed using the ultrafiltration method in this study.With an initial P concentration of 20 mg/L（I =0.01 mol/L and pH = 7）,it was shown that the colloid（1 kDa-0.45 μm） component of P accounted for 10.6%,11.6%,6.5%,and 4.0%of remaining total P concentration in the supernatant after P adsorption onto ferrihydrite（FH）,goethite（GE）,ferrihydrite-humic acid complex（FH-HA）,goethite-humic acid complex（GE-HA）,respectively.The 〈1 kDa component of P was still the predominant fraction in the supernatant,and underestimated colloidal P accounted for 2.2%,55.1%,45.5%,and 38.7%of P adsorption onto the solid surface of FH,FH-HA,GE and GE-HA,respectively.Thus,the colloid P could not be neglected.Notably,it could be interpreted that Fe3＋ hydrolysis from the adsorbents followed by the formation of colloidal hydrous ferric oxide aggregates was the main mechanism for the formation of the colloid P in the supernatant.And colloidal adsorbent particles co-existing in the supernatant were another important reason for it.Additionally,dissolve organic matter dissolved from iron oxide-HA complexes could occupy large adsorption sites of colloidal iron causing less colloid P in the supernatant.Ultimately,we believe that the findings can provide a new way to deeply interpret the geochemical cycling of P,even when considering other contaminants such as organic pollutants,heavy metal ions,and arsenate at the sediment/soil-water interface in the real environment.