The Effect of Sulfate Ion on the Isomerization of n-Butane to iso-Butane

The effect of sulfate ion (SO42-) loading on the properties of Pt/SO42- -ZrO2 and on the catalytic isomerization of n-butane to iso-butane was studied. The catalyst was prepared by impregnation of Zr(OH)4 with H2SO4 and platinum solution followed by calcination at 600℃. Ammonia TPD and FT-IR were used to confirm the distribution of acid sites and the structure of the sulfate species. Nitrogen physisorption and X-ray diffraction were used to confirm the physical structures of Pt/SO42--ZrO2. XRD pattern showed that the presence of sulfate ion stabilized the metastable tetragonal phase of zirconia and hindered the transition of amorphous phase to monoclinic phase of zirconia. Ammonia TPD profiles indicated the distributions of weak and medium acid sites observed on 0.1 N and 1.0 N sulfate in the loaded catalysts. The addition of 2.0 N and 4.0 N sulfate ion generated strong acid site and decreased the weak and medium acid sites. However, the XRD results and the specific surface area of the catalysts indicated that the excessive amount of sulfate ion collapsed the structure of the catalyst. The catalysts showed high activity and stability for isomerization of n-butane to iso-butane at 200℃under hydrogen atmosphere. The conversion of n-butane to iso-butane per specific surface area of the catalyst increased with the increasing amount of sulfate ion owing to the existence of the bidentate sulfate and/or polynucleic sulfate species ((ZrO)2SO2), which acts as an active site for the isomerization.     

ACTIVATION ENERGY OF DESORPTION OF DIBENZOFURAN ON ACTIVATED CARBONS

Three kinds of commercial activated carbons, such as Norit RBI, Monolith and Chemviron activated carbons, were used as adsorbents for adsorption of dibenzofiuran. The average pore size and specific surface area of these activated carbons were measured Temperature Programmed Desorption (‘TPD) experiments were conducted to measure the TPD curves of dibenzofuran on the activated carbons, and then the activation energy for desorption of dibenzofuran on the activated carbons was estimated. The results showed that the Chemviron and the Norit RB1 activated carbon maintained higher specific surface area and larger micropore pore volume in comparison with the Monolith activated carbon, and the activation energy for the desorption of dibencofuran on these two activated carbons was higher than that on the Monolith activated carbon. The smaller the pore of the activated carbon was, the higher the activated energy of dibenzofiuran desorption was.     

Sorption removal of cephalexin by HNO3 and H2O2 oxidized activated carbons

Cephalexin’s traces within pharmaceutical effluents have toxic impact toward ecological and human health.Low-cost activated carbon derived from Trapa natans husk was oxidized with hydrogen peroxide and nitric acid,and tested for their ability to remove cephalexin from aqueous solutions.Oxidization with H2O2 showed negative effect on the cephalexin sorption,whereas HNO3 oxidization improved the adsorption.The cephalexin adsorption isotherms on the native and HNO3 oxidized carbons correlated well with the Freundlich equation while their kinetics followed the pseudo-second order model.The removal of cephalexin by the native and HNO3 oxidized carbons was found to be most favored at low ionic strength and strong acidic conditions.Based on the thermal and FTIR analyses,the interaction mechanisms of the interaction between cephalexin and the carbons were proposed.Electrostatic attraction,hydrophobic interaction and chemical bonding with surface functional groups were demonstrated as primary mechanisms for cephalexin removal.The nitrogen functionalities on the carbon surface were considered to be an important factor affecting the adsorption process.     

Effect of bismuth species on propylene aromatization over BiHZSM-5 catalysts

The catalytic behavior of Bi-impregnated HZSM-5 zeolites in propylene aroma-tization and the surface properties of the zeoh'tes were determined by microreactor, XRD, XPS, NH3-TPD and IR-TPD. The mechanism of the reaction and the effect of surface properties of the zeolites on the reaction were also investigated. Experimental data showed that Bi-impregnation made the strength of B-acid sites decrease, the strength of L-acid sites and the concentration of both strong B-acid sites and strong L-acid sites increase. Bi-impregnation also induced sub-strong acid sites. These were the factors that made the aromatic products of the reaction increase. The strong interaction between the impregnant and zeolite surface reached maximum at Bi2O3 = 3.5 wt%. Above this value, covering effect of impregnant caused a decrease of aromatic products.     

Sorption Removal of Pb（Ⅱ） from Solution by Uncalcined and Calcined MgAl-Layered Double Hydroxides

Layered double hydroxide （LDH） with a Mg/Al molar ratio of 1 ： 1 was synthesized by using a co-precipitation method and its calcined product （CLDH） was obtained by calcination of the MgAl-LDH at 500 ℃. The sorption removal of Pb^2＋ from solution was investigated, finding that both LDH and CLDH show good sorption ability and they could be used as a new type of environmental sorbent for the removal of Pb^2＋ from water. The sorption kinetics and the sorption isotherms of Pb^2＋ on both LDH and CLDH can be described by the pseudo-second order kinetics and Freundlich isotherm, respectively, under the studied conditions. The sorption amounts of Pb^2＋ on LDH and CLDH are independent of pH in a pH range of about 3-10. The presence of NaNO3 may inhibit the sorption of Pb^2＋ on LDH while hardly affect that on CLDH. The sorption mechanism of Pb^2＋ on LDH and CLDH may be attributed to the surface precipitation and the surface complex adsorption. The surface complex adsorption may be further distinguished to the chemical binding adsorption forming the inner-sphere surface complexes and the electrostatic binding adsorption forming the outer-sphere surface complexes. The sorption mechanism of Pb^2＋ on LDH may be attributed to the surface precipitation and the electrostatic binding adsorption, while that on CLDH may be attributed to the surface precipitation and the chemical binding adsorption.     

Preparation of activated carbons and their adsorption properties for greenhouse gases: CH4 and CO2

Three kinds of activated carbons were prepared using coconut-shells as carbon precursors and characterized by XRD, FT-IR and texture property test. The results indicate that the prepared activated carbons were mainly amorphous and only a few impurity groups were adsorbed on their surfaces. The texture property test reveals that the activated carbons displayed different texture properties, especially the micropore size distribution. The adsorption capacities of the activated carbons were investigated by adsorbing CH4, CO2, N2 and O2 at 25 ?C in the pressure range of 0-200 kPa. The results reveal that all the activated carbons had high CO2 adsorption capacity, one of which had the highest CO2 adsorption value of 2.55 mmol/g at 200 kPa. And the highest adsorption capacity for CH4 of the activated carbons can reach 1.93 mmol/g at 200 kPa. In the pressure range of 0-200 kPa, the adsorption capacities for N2 and O2 were increased linearly with the change of pressure and K-AC is an excellent adsorbent towards the adsorption separation of greenhouse gases.     

Investigation of the interaction of DNA and neutral red by?uorescence spectroscopic analysis

The binding characteristics of neutral red (NR) with DNA were investigated by fluorescence spectrometry. Chemometrics approach as singular value decomposition (SVD) was used to evaluate the number of spectral species in the drug-DNA binding process, and then the intrinsic binding constant of 1.6 104 in base pairs and the binding site number of 0.97 were obtained from the Scatchard plot.     

Synthesis of Poly(isosorbide carbonate) via Melt Polycondensation Catalyzed by Ca/SBA-15 Solid Base

Ca/SBA-15 solid bases with different Ca/Si atomic ratios were prepared by a one-pot route and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a transesterification polymerization process.The relationship between physicochemical properties and catalytic performance for Ca/SBA-15 in this melt process was investigated by means of various characterization techniques.It was found that basic site amount and strength were responsible for this transesterification process;the weak and medium basic sites inclined to promote polycondensation reaction.It was worth noting that strong basic sites could favor the decomposition of the resultant PIC,resulting in the decrease of weight-average molecular weight(Mw)and yield,and the sample with Ca/Si atomic ratio of 0.4 exhibited the best catalytic performance,giving PIC with Mw of 4.88×104 g/mol and Tg of 169°C at the optimal conditions.This excellent activity can be ascribed to the presence of rich basic sites and specific basic strength on the surface of0.4Ca/SBA-15.     

Investigation of the interaction of DNA and neutral red by fluorescence spectroscopic analysis

The binding characteristics of neutral red (NR) with DNA were investigated by fluorescence spectrometry. Chemometrics approach as singular value decomposition (SVD) was used to evaluate the number of spectral species in the drug-DNA binding process, and then the intrinsic binding constant of 1.6 × 104 in base pairs and the binding site number of 0.97 were obtained from the Scatchard plot.     

Studies on the binding of vinpocetine to human serum albumin by molecular spectroscopy and modeling

The interaction between vinpocetine(VPC) and human serum albumin(HSA) in physiological buffer(pH 7.40) was investigated by fluorescence,FT-IR,UV-vis absorption and molecular modeling.VPC effectively quenched the intrinsic fluorescence of HSA via static quenching.The binding site number n and apparent binding constant K_a,corresponding thermodynamic parametersΔG,ΔH andΔS at different temperatures were calculated.The synchronous fluorescence and FT-IR spectra were used to investigate the structural change of HSA molecules with addition of VPC.Molecular modeling indicated that VPC could bind to the site I of HSA and hydrophobic interaction was the major acting force,which was in agreement with the binding mode study.     

Investigation of radionuclide 63Ni(II) sequestration mechanisms on mordenite by batch and EXAFS spectroscopy study

The sorption behavior and microscopic sequestration mechanisms of radionuclide 63Ni(II) on mordenite as a function of aging time,ionic strength,initial 63Ni(Ⅱ) concentrations,solid content and coexistent electrolyte ions were investigated by the com-bination of batch and EXAFS techniques.Macroscopic experiment results show that the sorption of 63Ni(Ⅱ) is dependent on ionic strength at pH<7,and independent of ionic strength at pH>7.The sorption percentage of 63Ni(Ⅱ) on mordenite increases with increasing solid content,while the sorption capacity decreases as solid content increases.The presence of different elec-trolyte ions can enhance or inhibit the sorption of Ni(II) on mordenite in various degrees.EXAFS analysis results of the sam-ples under three different ionic strengths suggest that the retained 63Ni(Ⅱ) in these samples exists in an octahedral environment with six water ligands.In the initial period of rapid uptake,the sorption of 63Ni(Ⅱ) is dominated by the formation of in-ner-sphere surface complexes.As aging time increases,63Ni(Ⅱ) sequestration behavior tends to be mainly controlled by the formation of Ni phyllosilicate co-precipitates and/or Ni(OH)2(s) precipitates.Results for the second shell fit of the sample pre-pared at an initial 63Ni(Ⅱ) concentration of 100 mg/L indicate the possible formation of Ni polynuclear surface complexes.Both the macroscopic sorption data and the molecular level evidence of 63Ni(Ⅱ) surface speciation at the mordenite/water in-terfaces should be factored into better predictions of the mobility and bioavailability of 63Ni(Ⅱ) in environment mediums.     

STUDY ON THE ADSORPTION BEHAVIOR OF Pb（Ⅱ） ON NANOMETER ATTAPULGITE BY FAAS

The adsorptive behavior of nanometer attapulgite modified by acid to Pb（Ⅱ） was investigated by flame atomic absorption spectrometry （FAAS） in this paper. The mainly effect parameters ott the adsorptive efficiency of Pb（Ⅱ）, such as the acidity of the solution, the amount of attapulgite, oscillation time and static time were studied. Also the influencing factors of the recovery efficiency of Pb（Ⅱ）, including the concentration of hydrochloric acid, the volume of hydrochloric acid, oscillation time and static time were investigated. The adsorptive capacity of Pb（Ⅱ） on nanometer attapulgite was 26.5mg/g and the adsorptive capacity of first cycle and second cycle regenerated nanometer attapulgite were 26.5mg/g and 26.3mg/g, respectively. The results obtained indicated that the regenerated effect was good.     

Preparation and Characterization of Nano-Structured SiO2 Thin Films on Carbon Steel

Nano-structured SiO2 thin films were prepared on the surface of carbon steel for the first time by LPD. The compositions of the films were analyzed by XPS, and the surface morphology of the thin films were observed by AFM. The thin films were constituted by compact particles of SiO2, and there was no Fe in the films. In the process of film forming, the SiO2 colloid particles were deposited or absorbed directly onto the surface of carbon steel substrates that were activated by acid solution containing inhibitor, and corrosion of the substrates was avoided. The nano-structured SiO2 thin films that were prepared had excellent protective efficiency to the carbon.     

TiO2和Mg-Fe型类水滑石特征电离/络合平衡常数研究

The intrinsic surface reaction constants, pKa1^int, pKa2^int, p^＊KC^int and p^＊KA^int , were evaluated by a modifieddouble extrapolation （MDE） for TiO2 without structural charge and Mg-Fe hydrotalcite-like compounds （HTlc） with structural charge, respectively. The results of intrinsic surface reaction constants for TiO2 were compared with those obtained by class double extrapolation （CDE） in literature. Furthermore, the values of intrinsic surface reaction constants obtained by MDE were used to simulate the charging behaviors of the materials. The following conclusions were obtained. For TiO2 without structural charge, the pKa1^int and pKa2^int evaluated by MDE are equal to those by CDE, however the p^＊KC^int and p^＊KA^int evaluated by MDE are much different from those by CDE. In principle, the results of the p^＊KC^int and p^＊KA^int evaluated by MDE are more accurate than those by CDE. The values of intrinsic surface reaction constants obtained by MDE can excellently simulate the charging curves for TiO2 with the triple layer model （TLM）. For HTlc with positive structural charge, the results of ^＊KC^int=0 and ^＊KA^int →∞ were obtained by MDE, which means the inert electrolyte chemical binding does not exist; the point of zero net charge （PZNC） of c-independence also exist as the same as solid without structural charge, and the PHPZNC obtained by the acid-base titration can excellently be simulated and the surface charging tendency can be simulated to a great extent using the pKa1^int and pKa2^int evaluated by MDE and the diffuse layer model （DLM）.     

ADSORPTION OF METHYLENE BLUE FROM AQUEOUS SOLUTION ON ATTAPULGITE

Batch adsorption experiments were carried out for the removal of methylene blue （MB） from aqueous solution using attapulgite as adsorbent. The effects of various parameters such as temperature, contact time, the pH value, and attapulgite dosage on the adsorption performance were investigated. The standard curve and regression equation were established by spectrophotometry. The adsorption experimental results showed that the adsorption equilibrium data were well in accord with Langmuir adsorptive model. The optimal result was acquired under the experimental condition of attapulgite dosage 0.18g, MB concentration 50.0mg/L, pH 10, and adsorption time 20min at room temperature.     

Preparation and photocatalytic activity of TiO_2-coated granular activated carbon composites by a molecular adsorption-deposition method

TiO2 nanoparticle-coated granular activated carbon (GAC) composite photocatalysts (CPs) were suc-cessfully prepared by a molecular adsorption-deposition (MAD) method. The CPs were detected by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), BET surface area and UV-Vis adsorption spectroscopy, and their photoactivity was evaluated by methyl orange (MO) photodegradation. The results show that small-sized TiO2 nanoparticles were dispersed well, deposited on the surface of GAC, and showed slight blue shift in comparison with pure TiO2. With the increase in TiO2 content, the CPs showed band gaps in lower energy, smaller surface areas and the higher content of Ti3 ions. Compared with pure TiO2 and others CPs samples, CPs-382 sample showed the highest photoactivity due to the optimum TiO2 content and surface area besides the synergic effect of photocatalytic degradation of TiO2 and adsorptive property of GAC. In addition, the CPs could be very easily reclaimed, recycled and reused for methyl orange removal while high photoactivity is pre-served.     

Understanding the adsorption mechanism of Ni(II) on graphene oxides by batch experiments and density functional theory studies

The graphene oxides(GOs) have attracted multidisciplinary study because of their special physicochemical properties. The high surface area and large amounts of oxygen-containing functional groups make GOs suitable materials for the efficient elimination of heavy metal ions from aqueous solutions. Herein the sorption of Ni(II) on GOs was studied using batch experiments, and the results showed that the sorption of Ni(II) is strongly dependent on p H and ionic strength at pH8, and independent of ionic strength at pH8. The sorption of Ni(II) is mainly dominated by outer-sphere surface complexation and ion exchange at low p H, and by inner-sphere surface complexation at high p H. The interaction of Ni(II) with GOs was also investigated by theoretical density functional theory(DFT) calculations, and the results show that the sorption of Ni(II) on GOs is mainly attributed to the –COH and –COC groups and the DFT calculations show that Ni(II) forms stable GO_Ni_triplet structure with the binding energy of -39.44 kcal/mol, which is in good agreement with the batch sorption experimental results. The results are important for the application of GOs as adsorbents in the efficient removal of Ni(II) from wastewater in environmental pollution cleanup.     

Hydrophobic surface modification of chitosan gels by stearyl for improving the activity of immobilized lipase

The hydrophobic surface modification of chitosan gels was carried out using the amidating reaction of amido groups on a gel surface with stearic acid activated by 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride(EDC) and N-hydroxysuccinimide (NHS).Lipases from Candida rugosa were adsorbed on the nascent chitosan gels(CS) and stearyl-modified gels(SCS) with different degrees of amidation.The increased surface hydrophobicity of chitosan gels improved the adsorption capacity and activity of the ...     

CO_2 capture over molecular basket sorbents: Effects of SiO_2 supports and PEG additive

The objective of this work is to study the influences of silica supports and PEG additive on the sorption performance of molecular basket sorbent(MBS) for CO_2 capture consisting of polyethylenimine and one of the following supports: SBA-15(2-D structure), TUD-1(3-D sponge-like structure) and fumed silica HS-5(3-D disordered structure). Effects of the supports regarding pore structures and pore properties, the PEI loading amount as well as the sorption temperature were examined. Furthermore, polyethylene glycol(PEG) was introduced as an additive into the sorbents and its effect was investigated at different PEI loadings and sorption temperatures. The results suggest that the pore properties of MBS(after PEI loading) play a more important role in the CO_2 sorption capacity, rather than those of the supports alone.MBS with 3D pore structure exhibits higher CO_2 sorption capacity and amine efficiency than those with 2D-structured support. Among the sorbents studied, fumed silica(HS-5) based MBS showed the highest CO_2 sorption capacity in the temperature range of 30-95 °C, probably due to its unique interstitial pores formed by the aggregation of polymer-loaded SiO_2 particles. It was found that the temperature dependence is directly related to the PEI surface coverage layers. The more PEI surface coverage layers, the higher diffusion barrier for CO_2 and the stronger temperature dependence of CO_2 capacity. 3D MBS exceeds 2D MBS at the same PEI coverage layers due to lower diffusion barrier. Adding PEG can significantly enhance the CO_2 sorption capacity and improve amine efficiency of all MBS, most likely by alleviating the diffusion barrier within PEI bulk layers through the inter-molecular interaction between PEI and PEG.     

The First-principles Study of Hydrogen Adsorption and Diffusion on the Biaxial Strained Fe(110) Surface

Hydrogen is known to play a negative role in mechanical properties of steel due to hydrogen embrittlement. Surface strain modifies the surface reactivity. In this paper, we employed spin-polarized periodic density functional to study the atomic H adsorption and diffusion on the biaxial strained Fe(110) surface. The result shows that the adsorption of H at the Tf site is the most stable on compressive surface and tensile surface. And H atom on the top site relaxes to Tf site on the strained surface. The adsorbed hydrogen atom at all calculated adsorption sites relaxes towards the surface due to the tensile strain. Lattice compression makes the bonding strength weaker between H atom and the surface. The analysis of the partial density of states shows that H 1 s orbital hybridizes with the Fe 4 s orbital. The result of charge density difference shows electrons are transferred from Fe to H atom. Compressive strain reduces the transferred electrons and decreases the Mulliken electrons of Fe 4 s orbital, which weaken the bonding interaction between H and Fe atoms. H atom diffuses into subsurface through a distorted tetrahedron. Surface strain does not change diffusion path but affects the diffusion barrier energy. Tetrahedron gap volume in the transition state of compressive system decreases to increase the diffusion barrier. This suggests compressive strain impedes H penetrating into the Fe subsurface. The present results indicate that it is a way to control adsorption and diffusion of hydrogen on the Fe surface by surface strain.