It is well known that mineral surfaces play an important role as catalysts for abiotic polymerization of amino acids to form peptides, which are the main components of the first self-replicating system. Understanding ...It is well known that mineral surfaces play an important role as catalysts for abiotic polymerization of amino acids to form peptides, which are the main components of the first self-replicating system. Understanding the mechanism behind the adsorption of simple amino acids on mineral surfaces is a topic of great interest not only in field of prebiotic evolution and but also in many other branches of material sciences. Various clay minerals have been suggested for studying how organic molecules were first synthesized in a prebiotic “inorganic” environment. Among them, pyrite (FeS<sub>2</sub>) is one of the most potential minerals as it possesses a highly reactive surface to drive molecular adsorption in prebiotic chemistry reactions. Recent theoretical experiments suggest that amino acids are adsorbed on the pyrite surface depending on its surface structures. However, these results have not been tested experimentally, and the exact mechanism of the specific interactions on this mineral has not been fully resolved yet at the molecular level. In this work, through quantitative force analysis with atomic force microscope (AFM) in which a single amino acid residue was mounted on the tip apex of AFM probe, we were able to find the reaction sites and study the interaction forces between the amino acid and the pyrite surface. Our results of Raman spectroscopic studies and force measurements with a well-designed AFM probe demonstrated for the first time that pyrite provided higher adsorption probabilities of amino acid residues for the chemical reactions at surfaces.展开更多
A batch experiment was conducted to investigate the adsorption of an acid dye(Acid Orange 51) and a basic dye(Safranine) from aqueous solutions by the sludge-based activated carbon(SBAC). The results show that the ads...A batch experiment was conducted to investigate the adsorption of an acid dye(Acid Orange 51) and a basic dye(Safranine) from aqueous solutions by the sludge-based activated carbon(SBAC). The results show that the adsorption of Acid Orange 51 decreases at high p H values, whereas the uptake of Safranine is higher in neutral and alkaline solutions than that in acidic conditions. The adsorption time needed for Safranine to reach equilibrium is shorter than that for Acid Orange 51. The uptakes of the dyes both increase with temperature increasing, indicating that the adsorption process of the dyes onto SBAC is endothermic. The equilibrium data of the dyes are both best represented by the Redlich-Peterson model. At 25 °C, the maximum adsorption capacities of SBAC for Acid Orange 51 and Safranine are 248.70 mg/g and 525.84 mg/g, respectively. The Elovich model is found to best describe the adsorption process of both dyes, indicating that the rate-limiting step involves the chemisorption. It can be concluded that SBAC is a promising material for the removal of Acid Orange 51 and Safranine from aqueous solutions.展开更多
The adsorption behaviors and mechanism of a novel chelate resin, macroporous phosphonic acid resin(PAR)for Gd(Ⅲ)were investigated. The statically and dynamically saturated adsorption capacity is respectively 308 mg&#...The adsorption behaviors and mechanism of a novel chelate resin, macroporous phosphonic acid resin(PAR)for Gd(Ⅲ)were investigated. The statically and dynamically saturated adsorption capacity is respectively 308 mg·g^(-1)resin and 296 mg·g^(-1)resin at 298 K in HAc-NaAc medium at pH 5.6. Gd(Ⅲ)adsorbed on PAR can be reductively eluted by 0.5～5.0 mol·L^(-1) HCl used as eluant and the elution percentage is up to 94.7% in 1.0 mol·L^(-1) HCl. The resin can be regenerated and reused without apparent decrease in adsorption capacity. The apparent adsorption rate constant is k_(298)=3.96×10^(-5) s^(-1). The adsorption behavior of PAR for Gd(Ⅲ) conforms to the Freundlich isotherm. The thermodynamic adsorption parameter, enthalpy change △H of PAR for Gd(Ⅲ)is 22.6kJ·mol^(-1). The apparent adsorption activation energy(Ea)of PAR for Gd(Ⅲ)is 5.0 kJ·mol^(-1). The molar coordination ratio of the functional group of PAR to Gd(Ⅲ)is about 3∶1. The adsorption mechanism of PAR for Gd(Ⅲ)was examined by using chemical method and IR spectrometry.展开更多
Two novel weakly basic anion exchange resins（SZ-1 and SZ-2） were prepared via the reaction of macroporous chloromethylated polystyrene-divinylbenzene（Cl-PS-DVB） beads with dicyclohexylamine and piperidine, respect...Two novel weakly basic anion exchange resins（SZ-1 and SZ-2） were prepared via the reaction of macroporous chloromethylated polystyrene-divinylbenzene（Cl-PS-DVB） beads with dicyclohexylamine and piperidine, respectively. The physicochemical structures of the resulting resins were characterized using Fourier Transform Infrared Spectroscopy and pore size distribution analysis. The adsorption behavior of SZ-1 and SZ-2 for benzenesulfonic acid（BA） was evaluated, and the common commercial weakly basic anion exchanger D301 was also employed for comparison purpose. Adsorption isotherms and influence of solution p H, temperature and coexisting competitive inorganic salts（Na2SO4and Na Cl） on adsorption behavior were investigated and the optimum desorption agent was obtained.Adsorption isotherms of BA were found to be well represented by the Langmuir model.Thermodynamic parameters involving ΔH, ΔG and ΔS were also calculated and the results indicate that adsorption is an exothermic and spontaneous process. Enhanced selectivity of BA sorption over sulfate on the two novel resins was observed by comparison with the commercial anion exchanger D301. The fact that the tested resins loaded with BA can be efficiently regenerated by Na Cl solution indicates the reversible sorption process. From a mechanistic viewpoint, this observation clearly suggests that electrostatic interaction is the predominant adsorption mechanism. Furthermore, results of column tests show that SZ-1possesses a better adsorption property than D301, which reinforces the feasibility of SZ-1for potential industrial application.展开更多
In the present work, the behavior of folic acid （FA） molecule adsorbed onto single-walled carbon nanotube （SWCNT） was examined using the DFT-B3LYP/6-31G＊ level. In order to obtain information about the binding fe...In the present work, the behavior of folic acid （FA） molecule adsorbed onto single-walled carbon nanotube （SWCNT） was examined using the DFT-B3LYP/6-31G＊ level. In order to obtain information about the binding features of SWCNT as adsorbent with FA molecule, several studies, including the structural and electronic parameters and also the Atoms in Molecules （AIM） analysis, were performed. It was observed that the FA molecule via hydrogen bond prefers to adsorb on SWCNT with adsorption energy of about -18.70 kcal/mol. The molecular orbitals （HOMO and LUMO）, natural bond orbital （NBO）,analysis, and density of states （DOS） plot indicated that a charge about 0.032 [ e [ is transferred from the FA molecule to the nanotube. After solvation energy calculations, it was found that the presence of a polar solvent causes an increase in FA adsorption on the single-walled carbon nanotube. Topological features such as electron energy density （Hc） and Laplacian of the electron density （V2p~） demonstrate partial covalent nature for H（ll6）...O（10） interaction in the FA/SWCNT complex. According to the calculated results, the single-walled carbon nanotubes are expected to be a potential efficient adsorbent for the adsorption of folic acid drug and also can be used as a suitable drug delivery vehicle within biological systems.展开更多
The adsorption behavior of folic acid onto（5,0） zigzag and（5,5） armchair carbon nanotube（SWCNT） has been investigated using B3 LYP density functional at the 6-31G＊ level. The adsorption energies,molecular orbit...The adsorption behavior of folic acid onto（5,0） zigzag and（5,5） armchair carbon nanotube（SWCNT） has been investigated using B3 LYP density functional at the 6-31G＊ level. The adsorption energies,molecular orbital analysis and structural changes at the adsorption site are indicative of covalent adsorption on the zigzag SWCNT surface,while the adsorption is physical on the armchair SWCNT surface. The density of states（DOS） Plot and the quantum molecular descriptors（QMD） are witness to the significant changes in the electronic properties of SWCNT systems after the attachment of adsorbed species to the tube surface. According to the calculated results,the single-walled carbon nanotubes are expected to be a potential efficient adsorbent for the adsorption of folic acid drug and also can be used as a suitable drug delivery vehicle within biological systems.展开更多
Commercial grade weakly basic resin D301 was impregnated with iron through a simple method using ferric chloride. Experiments for single, bisolute and trinary competitive adsorption were carried out to investigate the...Commercial grade weakly basic resin D301 was impregnated with iron through a simple method using ferric chloride. Experiments for single, bisolute and trinary competitive adsorption were carried out to investigate the adsorption behavior of 2-naphthalenesulfonic acid(NSA), sulfuric acid and sulfurous acid from their solution at 298 K onto the novel hybrid iron impregnated D301(Fe-D301). Adsorption affinity of NSA on Fe-D301 was found to be much higher than that of sulfuric acid, while adsorption affinity of sulfuric acid was slightly higher than that of sulfurous acid. The data of single-solute adsorption were fitted to the Langmuir model and the Freundlich adsorption model. The non-ideal competitive adsorbed model coupled with the single-solute adsorption models were used to predict the bisolute and trinary-solute competitive adsorption equilibria. The NICM coupled with the Langmuir model yields the favorable representation of the bisolute and trinary-solute competitive adsorption behavior.展开更多
A comparison of the adsorption of benzoic acid and p-nitrobenzoic acid on the new hypercrosslinked polymeric adsorbent AM-1, with that by macroporous Amberlite XAD-4, including the equilibrium adsorption isotherms, th...A comparison of the adsorption of benzoic acid and p-nitrobenzoic acid on the new hypercrosslinked polymeric adsorbent AM-1, with that by macroporous Amberlite XAD-4, including the equilibrium adsorption isotherms, the dynamic adsorption behaviors through column and the adsorption thermodynamics were studied. Results show that Freundlich equation gives a fitting adsorption isotherm. The specific surface of AM-1 is only 67% of that of Amberlite XAD-4, but the adsorption capacities on AM-1 are much higher about 125%~166% than that on Amberlite XAD-4, which is contributed to the micropore mechanism and polarity. The negative values of the adsorption enthalpy are indicative of an exothermic process. Enthalpy and free energy changes of adsorption both manifest a physic-sorption process. The negative values of the adsorption entropy indicate that the adsorption is well consistent with the restricted mobilities and the configurations of the adsorbed benzoic acid molecules on the surface of studied adsorbents with superficial heterogeneity. Both adsorbents were used in mini-column experiments for adsorbing benzoic acid expecting to elucidate the higher breakthrough adsorption capacity of the new hypercrosslinked polymeric adsorbent AM-1 as compared with that of Amberlite XAD-4.展开更多
Insights from the adverse effect of humic acid （HA） on arsenate removal with hydrous ferric oxide （HFO） coprecipitation can further our understanding of the fate of As（V） in water treatment process. The motivati...Insights from the adverse effect of humic acid （HA） on arsenate removal with hydrous ferric oxide （HFO） coprecipitation can further our understanding of the fate of As（V） in water treatment process. The motivation of our study is to explore the competitive adsorption mechanisms of humic acid and As（V） on HFO on the molecular scale. Multiple complementary techniques were used including macroscopic adsorption experiments, surface enhanced Raman scattering （SERS）, extended X-ray absorption fine structure （EXAFS） spectroscopy, flow-cell attenuated total reflectance Fourier transform infrared （ATR-FTIR） measurement, and charge distribution multisite complexation （CD- MUSIC） modeling. The As（V） removal efficiency was reduced from over 95% to about 10% with the increasing HA concentration to 25 times of As（V） mass concentration. The SERS analysis excluded the HA-As（V） complex formation. The EXAFS results indicate that As（V） formed bidentate binuclear surface complexes in the presence of HA as evidenced by an As-Fe distance of 3.26--3.31 ,~. The in situ ATR-FTIR measurements show that As（V） replaces surface hydroxyl groups and forms inner- sphere complex. High concentrations of HA may physically block the surface sites and inhibit the As（V） access. The adsorption of As（V） and HA decreased the point of zero charge of HFO from 7.8 to 5.8 and 6.3, respectively. The CD-MUSIC model described the zeta potential curves and adsorption edges of As（V） and HA reasonably well.展开更多
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 environment...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.展开更多
（2,3-Dimethylbutyl）（2,4,40-trimethylpentyl）phosphinic acid（INET-3） was impregnated onto dry macroporous resins XAD-16 and pretreated XAD-16 with ethyl alcohol and HCl（Pre-XAD-16） to prepare the solvent impregn...（2,3-Dimethylbutyl）（2,4,40-trimethylpentyl）phosphinic acid（INET-3） was impregnated onto dry macroporous resins XAD-16 and pretreated XAD-16 with ethyl alcohol and HCl（Pre-XAD-16） to prepare the solvent impregnated resins SIRs-INET-3/XAD-16 and SIRs-INET-3/Pre-XAD-16. The molecular weight distribution of the low molecular weight（LMW） polymers washed off by ethyl alcohol during XAD-16 pretreatment was determined by gel permeation chromatography（GPC）. The macroporous resins（XAD-16 ＆ Pre-XAD-16）, the corresponding solvent impregnated resins（SIRs-INET-3/XAD-16 ＆SIRs-INET-3/Pre-XAD-16） and the PVA coated SIRs-INET-3/Pre-XAD-16 with boric acid as cross-linking agent were characterized by FT-IR, SEM-EDS and TGA. The effects of XAD-16 pretreatment and PVA coating technology on RE（III） adsorption equilibrium time, INET-3 losses during extraction and adsorption capacity were investigated. The adsorption kinetics, selectivity and stripping behaviors of SIRs-INET-3/XAD-16 were further studied. The washed off LMW polymers had the Mn of 36,656, Mw of 40,310 and polydispersity coefficient of 1.10. The SIRs-INET-3/XAD-16 had shorter equilibrium time,less INET-3 loss and more Tm（III） adsorption capacity than the SIRs-INET-3/Pre-XAD-16. The PVA coated SIRs-INET-3/Pre-XAD-16 had less INET-3 loss and more Tm（III） adsorption capacity but longer equilibrium time than the uncoated SIRs-INET-3/Pre-XAD-16. The adsorption of RE（III） on the SIRsINET-3/XAD-16 followed the pseudo-second-order kinetic model. The Tm（III） accumulative adsorption amounts onto SIRs-INET-3/XAD-16 after eight extraction stages was 23.6 mg/g. The separation factors of adjacent heavy RE（III） β（Er/Ho）, β（Tm/Er）, β（Yb/Tm） and β（Lu/Yb） values were 1.76, 2.59, 2.56 and 1.19,respectively. The adsorbed Lu（III） onto the SIRs-INET-3/XAD-16 can be stripped completely by 1.0 mol/L H2SO4.展开更多
Soil and sediment play a crucial role in the fate and transport of perfiuorooctane sulfonate （PFOS） in the environment. However, the molecular mechanisms of major soil/sediment components on PFOS adsorption remain u...Soil and sediment play a crucial role in the fate and transport of perfiuorooctane sulfonate （PFOS） in the environment. However, the molecular mechanisms of major soil/sediment components on PFOS adsorption remain unclear. This study experimentally isolated three major components in soil/sediment： humin/kerogen, humic/fulvic acid （HA/FA）, and inorganic component after removing organics, and explored their contributions to PFOS adsorption using batch adsorption experiments and molecular dynamic simulations. The results suggest that the humin/kerogen component dominated the PFOS adsorption due to its aliphatic features where hydrophobic effect and phase transfer are the primary adsorption mechanism. Compared with the humin/kerogen, the HA/FA component contributed less to the PFOS adsorption because of its hydrophilic and polar characteristics. The electrostatic repulsion between the polar groups of HA/FA and PFOS anions was attributable to the reduced PFOS adsorption. When the soil organic matter was extracted, the inorganic component also plays a non-negligible role because PFOS molecules might form surface complexes on SiO2 surface. The findings obtained in this study illustrate the contribution of organic matters in soils and sediments to PFOS adsorption and provided new perspective to understanding the adsorption process of PFOS on micro-interface in the environment.展开更多
A novel chelating resin OABA,capable of removing Cu（Ⅱ） from aqueous solution,was synthesized via the reaction of macroporous chloromethylated PS-DVB copolymer beads with orotic acid.The elemental analysis（EA）,Fou...A novel chelating resin OABA,capable of removing Cu（Ⅱ） from aqueous solution,was synthesized via the reaction of macroporous chloromethylated PS-DVB copolymer beads with orotic acid.The elemental analysis（EA）,Fourier transform infrared spectroscopy（FT-IR）,and scanning electron microscopy microscope-energy dispersive X-ray spectroscopy（SEM-EDS） were used in the characterization of the synthesized chelating resin.Multiple,static batch adsorption experiments were conducted at different initial concentrations and temperatures.OABA showed good adsorption capacity for Cu（Ⅱ） and the equilibrium data could be well matched with the Freundlich isotherm model.Coexisting sodium chloride and calcium chloride in solutions favored the Cu（Ⅱ） adsorption.Moreover,the desorption process of Cu（Ⅱ） was tested and over 90%regeneration efficiency for the spent OABA was achieved at ammonia concentrations ranging from 1.0%to 2.0%.The results suggested that OABA would be a potential alternative adsorbent for Cu（Ⅱ）,even with other heavy metal ion treatments of wastewater.展开更多
Low-cost activated carbons（ACs） were prepared from four kinds of solid wastes：petroleum coke,Enteromorpha prolifera,lignin from papermaking black liquid and hair,by pyrophosphoric acid（H_4P_2O_7） activation.Therm...Low-cost activated carbons（ACs） were prepared from four kinds of solid wastes：petroleum coke,Enteromorpha prolifera,lignin from papermaking black liquid and hair,by pyrophosphoric acid（H_4P_2O_7） activation.Thermo-gravimetric analysis of the pyrolysis of H_4P_2O_7-precursor mixtures implied that H_4P_2O_7 had different influences on the pyrolysis behavior of the four raw materials.N_2 adsorption/desorption isotherms,scanning electron microscopy,Fourier transform infrared spectroscopy and adsorption capacities for dyes were used to characterize the prepared activated carbons.AC derived from E.prolifera exhibited the highest surface area（1094 m^2/g） and maximum monolayer adsorption capacity for malachite green（1250 mg/g）.Kinetic studies showed that the experimental data were in agreement with the pseudo-second-order model.The adsorption isotherms were well described by the Langmuir isotherm model,indicating the adsorption of dye onto the ACs proceeded by monolayers.展开更多
Homogeneous columnar Cu film with fully embedded nanotwins was successfully fabricated on Ti/Cu seed layer on silicon wafer. The nanotwins with thickness of tens of nanometers are generally parallel to the silicon sur...Homogeneous columnar Cu film with fully embedded nanotwins was successfully fabricated on Ti/Cu seed layer on silicon wafer. The nanotwins with thickness of tens of nanometers are generally parallel to the silicon surface, showing a strong （111 ） preferred orientation. The acid concentration was found to be important in influencing the formation of nanoscale twins. By adjusting the acid concentration, the nanotwins can be induced from the top columnar grain to middle columnar grain and reach the bottom equiaxed grain, and a microstructural transformation model was given. A theory focusing on the cathode overpotential was proposed to reveal the effect of acid concentration on the growth mechanism of nanoscale twins. An appropriate adsorption proportion of hydrogen on cathode （acid concentration 17 ml L^-1） could increase the overpotential which supplies adequate nucleation energy for nanoscale twins formation.展开更多
An investigation has been made on the adsorption and decomposition of formic acid on slightly oxidized Nb(110)surface(0/Nb atom ratio=0.2)using high resolution electron energy loss spectroscopy(HREELS),and a correspon...An investigation has been made on the adsorption and decomposition of formic acid on slightly oxidized Nb(110)surface(0/Nb atom ratio=0.2)using high resolution electron energy loss spectroscopy(HREELS),and a corresponding surface reaction mode is given.At 140 K,formic acid of low exposure on such an Nb(110)surface decomposed to formate,which bonded on Nb in monodentate configuration,simultaneously some formate decomposed to CO,which adsorbed on the surface.Formic acid multilayers formed when the exposure was high.While the temperature was increased to above 190 K,multilayer formic acid desorbed,and the surface was covered with mon-odentate-bonded formate and CO.In the temperature range of 250-300 K,chemisorbed formate changed from monodentate configuration into bridging configuration and CO molecules disappeared.The decomposition of formate at higher temperatures led to the oxidation of Nb.The formate formed in the high exposure case was so stable that it did not decompose even the temperature was as high as 540 K.展开更多
文摘It is well known that mineral surfaces play an important role as catalysts for abiotic polymerization of amino acids to form peptides, which are the main components of the first self-replicating system. Understanding the mechanism behind the adsorption of simple amino acids on mineral surfaces is a topic of great interest not only in field of prebiotic evolution and but also in many other branches of material sciences. Various clay minerals have been suggested for studying how organic molecules were first synthesized in a prebiotic “inorganic” environment. Among them, pyrite (FeS<sub>2</sub>) is one of the most potential minerals as it possesses a highly reactive surface to drive molecular adsorption in prebiotic chemistry reactions. Recent theoretical experiments suggest that amino acids are adsorbed on the pyrite surface depending on its surface structures. However, these results have not been tested experimentally, and the exact mechanism of the specific interactions on this mineral has not been fully resolved yet at the molecular level. In this work, through quantitative force analysis with atomic force microscope (AFM) in which a single amino acid residue was mounted on the tip apex of AFM probe, we were able to find the reaction sites and study the interaction forces between the amino acid and the pyrite surface. Our results of Raman spectroscopic studies and force measurements with a well-designed AFM probe demonstrated for the first time that pyrite provided higher adsorption probabilities of amino acid residues for the chemical reactions at surfaces.
基金Project(51008106)supported by the National Natural Science Foundation of China
文摘A batch experiment was conducted to investigate the adsorption of an acid dye(Acid Orange 51) and a basic dye(Safranine) from aqueous solutions by the sludge-based activated carbon(SBAC). The results show that the adsorption of Acid Orange 51 decreases at high p H values, whereas the uptake of Safranine is higher in neutral and alkaline solutions than that in acidic conditions. The adsorption time needed for Safranine to reach equilibrium is shorter than that for Acid Orange 51. The uptakes of the dyes both increase with temperature increasing, indicating that the adsorption process of the dyes onto SBAC is endothermic. The equilibrium data of the dyes are both best represented by the Redlich-Peterson model. At 25 °C, the maximum adsorption capacities of SBAC for Acid Orange 51 and Safranine are 248.70 mg/g and 525.84 mg/g, respectively. The Elovich model is found to best describe the adsorption process of both dyes, indicating that the rate-limiting step involves the chemisorption. It can be concluded that SBAC is a promising material for the removal of Acid Orange 51 and Safranine from aqueous solutions.
文摘The adsorption behaviors and mechanism of a novel chelate resin, macroporous phosphonic acid resin(PAR)for Gd(Ⅲ)were investigated. The statically and dynamically saturated adsorption capacity is respectively 308 mg·g^(-1)resin and 296 mg·g^(-1)resin at 298 K in HAc-NaAc medium at pH 5.6. Gd(Ⅲ)adsorbed on PAR can be reductively eluted by 0.5～5.0 mol·L^(-1) HCl used as eluant and the elution percentage is up to 94.7% in 1.0 mol·L^(-1) HCl. The resin can be regenerated and reused without apparent decrease in adsorption capacity. The apparent adsorption rate constant is k_(298)=3.96×10^(-5) s^(-1). The adsorption behavior of PAR for Gd(Ⅲ) conforms to the Freundlich isotherm. The thermodynamic adsorption parameter, enthalpy change △H of PAR for Gd(Ⅲ)is 22.6kJ·mol^(-1). The apparent adsorption activation energy(Ea)of PAR for Gd(Ⅲ)is 5.0 kJ·mol^(-1). The molar coordination ratio of the functional group of PAR to Gd(Ⅲ)is about 3∶1. The adsorption mechanism of PAR for Gd(Ⅲ)was examined by using chemical method and IR spectrometry.
基金supported by the National Natural Science Foundation of China(No.51578131)the Natural Science Foundation of Jiangsu Province,China(No.BK20131287)the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Two novel weakly basic anion exchange resins（SZ-1 and SZ-2） were prepared via the reaction of macroporous chloromethylated polystyrene-divinylbenzene（Cl-PS-DVB） beads with dicyclohexylamine and piperidine, respectively. The physicochemical structures of the resulting resins were characterized using Fourier Transform Infrared Spectroscopy and pore size distribution analysis. The adsorption behavior of SZ-1 and SZ-2 for benzenesulfonic acid（BA） was evaluated, and the common commercial weakly basic anion exchanger D301 was also employed for comparison purpose. Adsorption isotherms and influence of solution p H, temperature and coexisting competitive inorganic salts（Na2SO4and Na Cl） on adsorption behavior were investigated and the optimum desorption agent was obtained.Adsorption isotherms of BA were found to be well represented by the Langmuir model.Thermodynamic parameters involving ΔH, ΔG and ΔS were also calculated and the results indicate that adsorption is an exothermic and spontaneous process. Enhanced selectivity of BA sorption over sulfate on the two novel resins was observed by comparison with the commercial anion exchanger D301. The fact that the tested resins loaded with BA can be efficiently regenerated by Na Cl solution indicates the reversible sorption process. From a mechanistic viewpoint, this observation clearly suggests that electrostatic interaction is the predominant adsorption mechanism. Furthermore, results of column tests show that SZ-1possesses a better adsorption property than D301, which reinforces the feasibility of SZ-1for potential industrial application.
文摘In the present work, the behavior of folic acid （FA） molecule adsorbed onto single-walled carbon nanotube （SWCNT） was examined using the DFT-B3LYP/6-31G＊ level. In order to obtain information about the binding features of SWCNT as adsorbent with FA molecule, several studies, including the structural and electronic parameters and also the Atoms in Molecules （AIM） analysis, were performed. It was observed that the FA molecule via hydrogen bond prefers to adsorb on SWCNT with adsorption energy of about -18.70 kcal/mol. The molecular orbitals （HOMO and LUMO）, natural bond orbital （NBO）,analysis, and density of states （DOS） plot indicated that a charge about 0.032 [ e [ is transferred from the FA molecule to the nanotube. After solvation energy calculations, it was found that the presence of a polar solvent causes an increase in FA adsorption on the single-walled carbon nanotube. Topological features such as electron energy density （Hc） and Laplacian of the electron density （V2p~） demonstrate partial covalent nature for H（ll6）...O（10） interaction in the FA/SWCNT complex. According to the calculated results, the single-walled carbon nanotubes are expected to be a potential efficient adsorbent for the adsorption of folic acid drug and also can be used as a suitable drug delivery vehicle within biological systems.
文摘The adsorption behavior of folic acid onto（5,0） zigzag and（5,5） armchair carbon nanotube（SWCNT） has been investigated using B3 LYP density functional at the 6-31G＊ level. The adsorption energies,molecular orbital analysis and structural changes at the adsorption site are indicative of covalent adsorption on the zigzag SWCNT surface,while the adsorption is physical on the armchair SWCNT surface. The density of states（DOS） Plot and the quantum molecular descriptors（QMD） are witness to the significant changes in the electronic properties of SWCNT systems after the attachment of adsorbed species to the tube surface. According to the calculated results,the single-walled carbon nanotubes are expected to be a potential efficient adsorbent for the adsorption of folic acid drug and also can be used as a suitable drug delivery vehicle within biological systems.
基金Supported by the National Natural Science Foundation of China(No.21276027)the Higher Educational Science and Technology Program of Shandong Province,China(No.J14LC05)
文摘Commercial grade weakly basic resin D301 was impregnated with iron through a simple method using ferric chloride. Experiments for single, bisolute and trinary competitive adsorption were carried out to investigate the adsorption behavior of 2-naphthalenesulfonic acid(NSA), sulfuric acid and sulfurous acid from their solution at 298 K onto the novel hybrid iron impregnated D301(Fe-D301). Adsorption affinity of NSA on Fe-D301 was found to be much higher than that of sulfuric acid, while adsorption affinity of sulfuric acid was slightly higher than that of sulfurous acid. The data of single-solute adsorption were fitted to the Langmuir model and the Freundlich adsorption model. The non-ideal competitive adsorbed model coupled with the single-solute adsorption models were used to predict the bisolute and trinary-solute competitive adsorption equilibria. The NICM coupled with the Langmuir model yields the favorable representation of the bisolute and trinary-solute competitive adsorption behavior.
基金Educational Committee of Jiangsu Province. (01KJD150004)
文摘A comparison of the adsorption of benzoic acid and p-nitrobenzoic acid on the new hypercrosslinked polymeric adsorbent AM-1, with that by macroporous Amberlite XAD-4, including the equilibrium adsorption isotherms, the dynamic adsorption behaviors through column and the adsorption thermodynamics were studied. Results show that Freundlich equation gives a fitting adsorption isotherm. The specific surface of AM-1 is only 67% of that of Amberlite XAD-4, but the adsorption capacities on AM-1 are much higher about 125%~166% than that on Amberlite XAD-4, which is contributed to the micropore mechanism and polarity. The negative values of the adsorption enthalpy are indicative of an exothermic process. Enthalpy and free energy changes of adsorption both manifest a physic-sorption process. The negative values of the adsorption entropy indicate that the adsorption is well consistent with the restricted mobilities and the configurations of the adsorbed benzoic acid molecules on the surface of studied adsorbents with superficial heterogeneity. Both adsorbents were used in mini-column experiments for adsorbing benzoic acid expecting to elucidate the higher breakthrough adsorption capacity of the new hypercrosslinked polymeric adsorbent AM-1 as compared with that of Amberlite XAD-4.
基金supported by the National Natural Science Foundation of China (No. 41373123, 41023005, 21321004)Research Center for EcoEnvironmental Sciences, Chinese Academy of Sciences (No. YSW2013A01)
文摘Insights from the adverse effect of humic acid （HA） on arsenate removal with hydrous ferric oxide （HFO） coprecipitation can further our understanding of the fate of As（V） in water treatment process. The motivation of our study is to explore the competitive adsorption mechanisms of humic acid and As（V） on HFO on the molecular scale. Multiple complementary techniques were used including macroscopic adsorption experiments, surface enhanced Raman scattering （SERS）, extended X-ray absorption fine structure （EXAFS） spectroscopy, flow-cell attenuated total reflectance Fourier transform infrared （ATR-FTIR） measurement, and charge distribution multisite complexation （CD- MUSIC） modeling. The As（V） removal efficiency was reduced from over 95% to about 10% with the increasing HA concentration to 25 times of As（V） mass concentration. The SERS analysis excluded the HA-As（V） complex formation. The EXAFS results indicate that As（V） formed bidentate binuclear surface complexes in the presence of HA as evidenced by an As-Fe distance of 3.26--3.31 ,~. The in situ ATR-FTIR measurements show that As（V） replaces surface hydroxyl groups and forms inner- sphere complex. High concentrations of HA may physically block the surface sites and inhibit the As（V） access. The adsorption of As（V） and HA decreased the point of zero charge of HFO from 7.8 to 5.8 and 6.3, respectively. The CD-MUSIC model described the zeta potential curves and adsorption edges of As（V） and HA reasonably well.
基金supported by the National Natural Science Foundation of China(Nos.41171198,41403079)the China Postdoctoral Science Foundation(No.2013M542238)+1 种基金the Chongqing Special Postdoctoral Science Foundation(No.Xm2014023)the Fundamental Research Funds for the Central Universities(No.XDJK2015B035)
文摘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.
基金Project supported by the National Natural Science Foundation of China(21301104)the State Key Laboratory of Chemical Engineering(SKLCh E-14A04)the Fundamental Research Funds for the Central Universities(FRFTP-16-019A3)
文摘（2,3-Dimethylbutyl）（2,4,40-trimethylpentyl）phosphinic acid（INET-3） was impregnated onto dry macroporous resins XAD-16 and pretreated XAD-16 with ethyl alcohol and HCl（Pre-XAD-16） to prepare the solvent impregnated resins SIRs-INET-3/XAD-16 and SIRs-INET-3/Pre-XAD-16. The molecular weight distribution of the low molecular weight（LMW） polymers washed off by ethyl alcohol during XAD-16 pretreatment was determined by gel permeation chromatography（GPC）. The macroporous resins（XAD-16 ＆ Pre-XAD-16）, the corresponding solvent impregnated resins（SIRs-INET-3/XAD-16 ＆SIRs-INET-3/Pre-XAD-16） and the PVA coated SIRs-INET-3/Pre-XAD-16 with boric acid as cross-linking agent were characterized by FT-IR, SEM-EDS and TGA. The effects of XAD-16 pretreatment and PVA coating technology on RE（III） adsorption equilibrium time, INET-3 losses during extraction and adsorption capacity were investigated. The adsorption kinetics, selectivity and stripping behaviors of SIRs-INET-3/XAD-16 were further studied. The washed off LMW polymers had the Mn of 36,656, Mw of 40,310 and polydispersity coefficient of 1.10. The SIRs-INET-3/XAD-16 had shorter equilibrium time,less INET-3 loss and more Tm（III） adsorption capacity than the SIRs-INET-3/Pre-XAD-16. The PVA coated SIRs-INET-3/Pre-XAD-16 had less INET-3 loss and more Tm（III） adsorption capacity but longer equilibrium time than the uncoated SIRs-INET-3/Pre-XAD-16. The adsorption of RE（III） on the SIRsINET-3/XAD-16 followed the pseudo-second-order kinetic model. The Tm（III） accumulative adsorption amounts onto SIRs-INET-3/XAD-16 after eight extraction stages was 23.6 mg/g. The separation factors of adjacent heavy RE（III） β（Er/Ho）, β（Tm/Er）, β（Yb/Tm） and β（Lu/Yb） values were 1.76, 2.59, 2.56 and 1.19,respectively. The adsorbed Lu（III） onto the SIRs-INET-3/XAD-16 can be stripped completely by 1.0 mol/L H2SO4.
基金supported by the National Basic Research Program (973) of China (No. 2014CB441102)the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB14020201)Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences (No. YSW2013A01)
文摘Soil and sediment play a crucial role in the fate and transport of perfiuorooctane sulfonate （PFOS） in the environment. However, the molecular mechanisms of major soil/sediment components on PFOS adsorption remain unclear. This study experimentally isolated three major components in soil/sediment： humin/kerogen, humic/fulvic acid （HA/FA）, and inorganic component after removing organics, and explored their contributions to PFOS adsorption using batch adsorption experiments and molecular dynamic simulations. The results suggest that the humin/kerogen component dominated the PFOS adsorption due to its aliphatic features where hydrophobic effect and phase transfer are the primary adsorption mechanism. Compared with the humin/kerogen, the HA/FA component contributed less to the PFOS adsorption because of its hydrophilic and polar characteristics. The electrostatic repulsion between the polar groups of HA/FA and PFOS anions was attributable to the reduced PFOS adsorption. When the soil organic matter was extracted, the inorganic component also plays a non-negligible role because PFOS molecules might form surface complexes on SiO2 surface. The findings obtained in this study illustrate the contribution of organic matters in soils and sediments to PFOS adsorption and provided new perspective to understanding the adsorption process of PFOS on micro-interface in the environment.
基金the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘A novel chelating resin OABA,capable of removing Cu（Ⅱ） from aqueous solution,was synthesized via the reaction of macroporous chloromethylated PS-DVB copolymer beads with orotic acid.The elemental analysis（EA）,Fourier transform infrared spectroscopy（FT-IR）,and scanning electron microscopy microscope-energy dispersive X-ray spectroscopy（SEM-EDS） were used in the characterization of the synthesized chelating resin.Multiple,static batch adsorption experiments were conducted at different initial concentrations and temperatures.OABA showed good adsorption capacity for Cu（Ⅱ） and the equilibrium data could be well matched with the Freundlich isotherm model.Coexisting sodium chloride and calcium chloride in solutions favored the Cu（Ⅱ） adsorption.Moreover,the desorption process of Cu（Ⅱ） was tested and over 90%regeneration efficiency for the spent OABA was achieved at ammonia concentrations ranging from 1.0%to 2.0%.The results suggested that OABA would be a potential alternative adsorbent for Cu（Ⅱ）,even with other heavy metal ion treatments of wastewater.
文摘Low-cost activated carbons（ACs） were prepared from four kinds of solid wastes：petroleum coke,Enteromorpha prolifera,lignin from papermaking black liquid and hair,by pyrophosphoric acid（H_4P_2O_7） activation.Thermo-gravimetric analysis of the pyrolysis of H_4P_2O_7-precursor mixtures implied that H_4P_2O_7 had different influences on the pyrolysis behavior of the four raw materials.N_2 adsorption/desorption isotherms,scanning electron microscopy,Fourier transform infrared spectroscopy and adsorption capacities for dyes were used to characterize the prepared activated carbons.AC derived from E.prolifera exhibited the highest surface area（1094 m^2/g） and maximum monolayer adsorption capacity for malachite green（1250 mg/g）.Kinetic studies showed that the experimental data were in agreement with the pseudo-second-order model.The adsorption isotherms were well described by the Langmuir isotherm model,indicating the adsorption of dye onto the ACs proceeded by monolayers.
基金financially supported by the National Natural Science Foundation of China(No.51401218)the Osaka University Visiting Scholar Program(No.J135104902)
文摘Homogeneous columnar Cu film with fully embedded nanotwins was successfully fabricated on Ti/Cu seed layer on silicon wafer. The nanotwins with thickness of tens of nanometers are generally parallel to the silicon surface, showing a strong （111 ） preferred orientation. The acid concentration was found to be important in influencing the formation of nanoscale twins. By adjusting the acid concentration, the nanotwins can be induced from the top columnar grain to middle columnar grain and reach the bottom equiaxed grain, and a microstructural transformation model was given. A theory focusing on the cathode overpotential was proposed to reveal the effect of acid concentration on the growth mechanism of nanoscale twins. An appropriate adsorption proportion of hydrogen on cathode （acid concentration 17 ml L^-1） could increase the overpotential which supplies adequate nucleation energy for nanoscale twins formation.
基金supported by the National Natural Science Foundation of China
文摘An investigation has been made on the adsorption and decomposition of formic acid on slightly oxidized Nb(110)surface(0/Nb atom ratio=0.2)using high resolution electron energy loss spectroscopy(HREELS),and a corresponding surface reaction mode is given.At 140 K,formic acid of low exposure on such an Nb(110)surface decomposed to formate,which bonded on Nb in monodentate configuration,simultaneously some formate decomposed to CO,which adsorbed on the surface.Formic acid multilayers formed when the exposure was high.While the temperature was increased to above 190 K,multilayer formic acid desorbed,and the surface was covered with mon-odentate-bonded formate and CO.In the temperature range of 250-300 K,chemisorbed formate changed from monodentate configuration into bridging configuration and CO molecules disappeared.The decomposition of formate at higher temperatures led to the oxidation of Nb.The formate formed in the high exposure case was so stable that it did not decompose even the temperature was as high as 540 K.
