Formic acid fractionation towards highly efficient cellulose-derived PdAg bimetallic catalyst for H_(2) evolution

The present work,in which cellulose isolated from formic acid fractionation(FAC)is decorated with polyetherimide(PEI)to attain highly efficient cellulose-derived PdAgbimetallic catalyst(PdAg-PEI-FAC),has been investigated,and the catalyst properties are characterized by XRD,XPS,BET,ICP-AES and HAADF-STEM.The as-obtained Pd_(3.75)Ag_(3.75)-PEI-FAC exhibits excellent catalytic performance for H_(2)evolution from a sodium formate-free formic acid(FA)aqueous medium at ambient temperature and the turnover frequency(TOF)reaches a high value of 2875 h^(-1)which is superior to most of the previously reported Pd-based heterogeneous catalysts supported on a carbon matrix in the literature.The remarkable catalytic activities of PdAg-PEI-FAC result from high dispersion Pd and synergistic effects between the PdAg bimetallic system.Furthermore,the amide(-NH)group in PEI coated on cellulose acting as a proton scavenger efficiently improves the catalytic property of catalyst.In addition,the critical factors affecting H;release,such as FA concentration,reaction temperature,PdAg compositions and support matrix type,are also evaluated.Based on the experimental results,the probable three-step mechanism of H_(2)evolution from FA over Pd_(3.75)Ag_(3.75)-PEI-FAC is proposed.In the end,the activation energy(Ea)of Pd_(3.75)Ag_(3.75)-PEI-FAC catalyst is calculated to 53.97 kJ mol^(-1),and this catalyst shows unique robustness and satisfactory re-usability with no loss of catalytic activity after five recycles.The findings in this work provide a novel routine from lignocellulose fractionation towards cellulose-derived catalyst for H_(2)evolution.

Adsorption characterizations of fulvic acid fractions onto kaolinite

Fulvic acids extracted from a typical rice-production region near Taihu Lake of China were fractionated into three fractions including F4.8, F7.0 and F11.0 （eluted by pH 4.8 buffer, pH 7.0 buffer and pH 11.0 buffer, respectively）. Sorption of fulvic acid （FA） fractions onto kaolinite was studied by batch adsorption experiments, and characterizations of kaolinite before and after adsorption were investigated using scanning electron microscopy （SEM）. Adsorption isotherms of kaolinite for three FA fractions fit well with the Langrnuir adsorption model. The adsorption density of the three fractions was positively correlated with the ratio of the amount of the alkyl carbon to that of carboxyl and carbonyl carbon in FA fractions and followed an order of F11.0 〉 F7.0 〉 F4.8. Hydrophobic interaction was one of the control mechanisms for the sorption of FA fraction onto kaolinite. SEM images confirmed that compared to blank kaolinite samples, kaolinite samples coated by a FA fraction displayed an opener and more dispersed conformation resulting from the disruption of the floc structure in complex. Dispersion of kaolinite after adsorption was due to the repulsion between negatively charged FA-coated particles, which is closely related to the amount of FA fractions absorbed on kaolinite.

Isotherm and kinetic studies on the adsorption of humic acid molecular size fractions onto clay minerals

Humic acid(HA)can adsorb onto mineral surfaces,modifying the physicochemical properties of the mineral.Therefore,understanding the sorption behavior of HA onto mineral surfaces is of particular interest,since the fate and transport of many organic and inorganic contaminants are highly correlated to HA adsorbed onto clay surfaces.Due to the extreme heterogeneity of HA,the extracted IHSS Leonardite humic acid(LHA)used in this work was fractionated using an ultrafiltration technique(UF)into different molecular size fractions(Fr1,>0.2μm;Fr2,0.2 pm-300,000 daltons;Fr3,300,000-50,000 daltons;Fr4,50,000-10,000 daltons;Fr5,10,000-1000 daltons).Equilibrium and the kinetics of LHA and fraction adsorption onto kaolinite and montmorillonite were investigated.The results demonstrated that the maximum adsorption capacity of LHA,Frl,Fr2,Fr3,Fr4,and Fr5 was 5.99,13.69,10.29,7.02,5.9&and 5.09 on kaolinite while it was 8.29,22.62,13.17,8.91,8.62,and 5.69 on montmorillonite,respectively.The adsorption equilibrium data showed that the adsorption behavior of LHA and its fractions could be described more practically by the Langmuir model than the Freundlich model.The rate of humic acid fraction adsorption onto clays increased with decreasing molecular size fraction and increasing carboxylic group content.Pseudo-first-and second-order models were used to assess the kinetic data and the rate constants.The results explained that LHA and its fractions adsorption on clay minerals conformed more to pseudosecondo rder.

A Comparative Study on the Effect of BCG-PSN and Thymopeptides on T-lymphocyte Subsets of Normal and Immunosuppressed Mice

To compare the effects of polysaccharide nucleic acid fraction of bacillus calmette guerin (BCG PSN) and thymopeptides on T lymphocytes of normal and immunosuppressed mice, CD4 + and CD8 + T lymphocyte subsets of single nucleic cell in thymus, spleen and peripheral blood were detected successively by flow cytometry after application of BCG PSN and thymopeptides. Meanwhile, CD4 +/CD8 + ratio was also calculated. The results showed that both BCG PSN and thymopeptides could decrease the proportion of CD4 + CD8 + T lymphocyte subsets in the thymus, at the same time increase CD4 + T lymphocyte, CD8 +T lymphocyte proportion in the three tissues. The fluctuation in amplitude was greater in thymopeptides group than that in BCG PSN group. It is concluded that acting location of thymopeptides is in thymus, its stimulating action is stronger than that of BCG PSN, while BCG PSN not only accelerates the differentiation in thymus, but also has some direct stimulation to peripheral CD4 +T lymphocytes, and can maintain CD4 +/CD8 + ratio within normal range. So, BCG PSN is safer.

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.

Clumped Isotope Analysis of Calcite and Dolomite Mixtures Using Selective Acid Extraction

Acid extraction methods have been used in the last half century to selectively extract the CO_(2)produced from different carbonate minerals in mixed samples.However,these methods are often time-consuming and labor intensive.Their application to clumped isotope(Δ47)analysis has not been demonstrated.We propose here an acid extraction method with phosphoric acid for bulk stable and clumped isotope analysis that treats mixtures of calcite and dolomite the same regardless of the proportional composition.CO_(2)evolved from calcite is extracted by allowing a reaction with phosphoric acid to proceed for 10 min at 50℃.We then extract CO_(2)evolved from dolomite by rapid ramping the acid temperature from 50 to 90℃and allowing the reaction to complete.The experimental results show that our method yields accurate calcite and dolomiteΔ_(47)values from mixed samples under different proportional compositions.Our method also displays equal or higher accuracy for calciteδ^(13)C and dolomiteδ^(13)C andδ^(18)O values from mixtures when compared to previous studies.Our approach exhibits higher sample throughput than previous methods,is adequate for clumped isotopic analysis and simplifies the reaction progression from over 24 h to less than 2 h,while maintaining relatively high isotopic obtaining accuracy.It yet poorly resolves calciteδ18O values,as found with previous methods.

Association of serum uric acid with different levels of glucose and related factors

Background Previous studies have demonstrated that serum uric acid （UA） is an independent predictor of incident type 2 diabetes mellitus （T2DM） in general populations. This study aimed to investigate specific characteristics of UA and its relationship between UA and blood glucose and other risk factors in the Chinese population.Methods A total of 946 subjects were included in this study. UA, glucose, insulin, fractional excretion of UA （FEua）,creatinine clearance rate （Ccr）, hemoglobin A1c （HbA1c）, fructosamine （FA）, blood pressure and lipids were studied and also reexamined after the patients underwent two weeks of combined therapeutics.Results UA levels were the highest in subjects with impaired glucose regulation （IGR）, followed by subjects with normoglycemia （NGT） and finally by subjects with T2DM. The level of the 2-hour postprandial insulin and the area under the curve for insulin （AUCins） showed a similar tendency. The UA levels initially increased with increasing fasting blood glucose （FBG） and postprandial blood glucose （PPBG） levels, up to 7 mmol/L and 10 mmol/L, respectively, and thereafter decreased at higher FBG and PPBG levels. Compared with subjects in the lower serum UA quartile, subjects in the upper quartile of serum UA levels had higher weights, triglyceride levels, and creatinine levels as well as lower Ccr and FEua levels. Compared with women＇s group, UA levels were higher, and FEua levels were lower in men＇s group. Sex,body mass index （BMI）, mean arterial blood pressure （MAP）, serum triglycerides （TG）, FA and Ccr were independent correlation factors of UA. UA decreased and FEua increased after the patients underwent a combined treatment.Conclusions UA increased initially and then decreased as glucose levels increased from NGT to IGR and T2DM.Compared with NGT and T2DM, IGR subjects had higher SUA levels, which related to its high levels of insulin. Under T2DM, male gender, BMI, MAP, Ccr, TG and FA are independent correlation factors of UA. Glucose-lowering,antihypertensive, lipemia-regulating combined treatments were of advantage to decline of SUA of T2DM.

Cr(Ⅵ) reduction capability of humic acid extracted from the organic component of municipal solid waste

The capacity of humic acid extracted from organic waste （HAw） to reduce Cr（Ⅵ） was tested at pH 2.5,4 and 6 and compared with coal-derived humic acid （HAc）.HAw was more effective than HAc in reducing Cr（Ⅵ）.The kinetics of Cr（Ⅵ） reductions depended strongly on pH.The calculation of the apparent rate coefficients indicated that HAw was more efficient at reducing Cr（Ⅵ） than HAc,but was also more efficient than HAs from soil and peat.The reduction capability of HAs depends on the type of functional groups （i.e.,thiols and phenols） present,rather than the free radicals.HAw was more efficient at reducing Cr（Ⅵ） than HAc because more reactive phenols were present,i.e.,methoxy-and methyl-phenols.

Assessment of Potential Nutrient Release from Phosphate Rock and Dolostone for Application in Acid Soils

Finding alternative local sources of plant nutrients is a practical, low-cost, and long-term strategy. In this study, laboratory column experiments were conducted in a completely randomized design to evaluate the feasibility of using phosphate rock and dolostone as fertilizers or acid-neutralizing agents for application in tropical acid soils. The dissolution rates of different particle-size fractions(0.063–0.25, 0.25–0.5, and 0.5–2 mm) of both rocks were studied by citric acid solution at p H 4 and 2 and water, with extraction times of 1, 3, 5, 7, 12, 24, 72, 144, 240, and 360 h. The results showed that the dissolution of both rocks depended on the particle size,leaching solution, and extraction time. The dissolution rate of rock-forming minerals increased as the specific surface area increased,corresponding to a decrease in particle size. In all cases, the release kinetics was characterized by two phases: 1) a first stage of rapid release that lasted 24 h and would ensure short-term nutrient release, and 2) a second stage of slow release after 24 h, representing the long-term nutrient release efficiency. Both rocks were suitable as slow-release fertilizers in strongly acid soils and would ensure the replenishment of P, Ca, and Mg. A combination of fine and medium particle-size fractions should be used to ensure high nutrient-release efficiency. Much work could remain to determine the overall impact of considerable amounts of fresh rocks in soils.