Fan Liu

Huazhong Agricultural University, Wu-han-shih, Hubei, China

Are you Fan Liu?

Claim your profile

Publications (98)226.76 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: Nanostructured birnessite, promising candidate for supercapacitor electrode materials, shows greatly improved discharge capacity and cyclic stability with vanadium doping. The influence of vanadium doping on the physicochemical properties and supercapacitance performance of birnessite-type manganese oxides is investigated. Crystal structures, micromorphologies, bond lengths and chemical compositions of vanadium doped birnessites are characterized by XRD, SEM, XPS, TGA, and titration. The electrochemical properties are analyzed using galvanostatic charge-discharge test, cyclic voltammetry, and electrochemical impedance spectroscopy. The results exhibit that V/Mn molar ratio can reach 0.16:1 when Mn(IV) and K+ are partially substituted by V(V) in birnessite. The thickness of disk-shaped crystal, bond length of Mn-O1 and manganese average oxidation state decreases first and then increases with an increase in V/Mn molar ratio in synthesis system. Charge-transfer resistance decreases after doping vanadium, and increases with an increase in the content of vanadium in birnessite. Diffusion resistance increases first and then decreases due to the change of particle size and pore size distribution. The highest specific capacitance of 245 F g-1 is obtained with excellent cyclic stability for doped birnessite with V/Mn molar ratio of 0.14:1. Our study indicates that vanadium remarkably affects micromorphology, substructure, and electrochemical properties of manganese dioxides.
    Journal of Power Sources 02/2015; 277. · 5.21 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Graphene-modified nanosized Ag3PO4 photocatalyst, fabricated by in situ growth strategy in an organic solvent, exhibits enhanced visible-light photocatalytic activity and stability compared with bare nanosized Ag3PO4 particles and conventional large-sized Ag3PO4 particles–graphene composite.
    Applied Catalysis B Environmental 01/2015; 162:196–203. · 6.01 Impact Factor
  • Annals of Microbiology 12/2014; · 1.04 Impact Factor
  • Materials Chemistry and Physics 12/2014; 148(3):783-789. · 2.13 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Although most reported biogenic Mn oxides are hexagonal birnessites, other types of biogenic Mn oxides also commonly occur in the environment. Compared to hexagonal birnessites, the sorption characteristics and the underlying mechanism of adsorption of heavy-metal ions to those of the other biogenic Mn oxides are still rarely addressed. A strain of Mn-oxidizing bacteria isolated from Claypani-Udic Argosols was identified as Bacillus with 16S rRNA sequencing analysis. The bacterial Mn(II) oxidation product is a poorly crystallized bixbyite-like Mn2O3 (α-Mn2O3). The maximum adsorption capacities of Zn(II) onto the biogenic Mn oxide at pH 6.00 and pH 4.00 were 663 mmol/kg and 629 mmol/kg, respectively. The complex structure of adsorbed Zn2 + was constrained using Zn EXAFS analysis, combined with structural parameters of the biogenic Mn oxide with alternately arranged regular and distorted MnO6 octahedra obtained through multiple-FEFF fitting of Mn EXAFS data. At a relatively low Zn2 + loading (100 mmol/kg, pH 6.00), Zn2 + adsorbed onto the biogenic Mn oxide with two types of tetrahedrally coordinated complexes, i.e. (1) coordinated with one regular/distorted MnO6 octahedron as a monodentate–mononuclear complex and (2) with two MnO6 octahedra (two regular, two distorted or a regular and a distorted) as a bidentate–binuclear complex. While, at a relatively high Zn2 + loading (556 mmol/kg, pH 4.00; 635 mmol/kg, pH 6.00), two types of octahedrally coordinated complexes are constrained, i.e. (1) coordinated with one regular/distorted MnO6 octahedron as a monodentate–mononuclear complex and (2) with one regular MnO6 octahedron as a bidentate mononuclear complex. This research extends further understanding on the formation of biogenic Mn oxides in the environment and the adsorption mechanism of heavy metals onto low-valence Mn oxides with distorted structures. The application of low valence biogenic Mn oxides to efficiently remove heavy metals from water is also shown to be promising.
    Chemical Geology 12/2014; 389:82–90. · 3.48 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Cadmium sulfide and oxide hexagonal nanoplates were prepared by a facile ion-exchange strategy and crystal transformation process by using morphology-analogous cadmium oxyhydroxide as a precursor. The precursors of uniform Cd(OH)2 hexagonal nanoplates was first synthesized by a simple ethylenediaminetetraacetic acid disodium salt assisted hydrothermal method. Then, through ion-exchange reactions of the as-prepared Cd(OH)2 precursors with S2− anions, cubic-phase CdS was formed immediately on the surface of Cd(OH)2 nanoplates. The above intermediates could be further completely converted into CdS and CdO nanoplates without morphology changes through thermal treatment at 280 °C for 4 h under a sulfur atmosphere and under air, respectively. The photocatalytic activity of all samples was evaluated by the photocatalytic decolorization of an aqueous solution of methylene blue and photocatalytic hydrogen production under visible-light irradiation. The results show that the CdS hexagonal nanoplates exhibit high visible-light photocatalytic degradation properties and photocatalytic hydrogen production activity. The enhanced visible-light photocatalytic activity can be related to several factors, including a suitable band gap, phase structure, and morphology of the hexagonal nanoplates.
    ChemPlusChem 09/2014; · 3.24 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Natural hexagonal birnessites are enriched in various transition metals (TMs). Many studies have examined the effects of single metal doping on the structures and properties of birnessites, but none focused on the simultaneous interaction mechanism of coprecipitation of two different TMs with birnessite. In this work Co and Ni co-doped hexagonal birnessites were synthesized and characterized by powder X-ray diffraction (XRD), elemental analysis, field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy to investigate the effects of co-doping on the structure and reactivity of birnessite and the crystal chemistry of Co and Ni. These co-doped birnessites have lower crystallinity, i.e., fewer manganese layers stacking in the c* direction, larger specific surface areas (SSAs) and increased Mn average oxidation states (AOSs) than the undoped birnessite, and Co exists in a valence of + 3. Co, Ni and Mn K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) spectra demonstrate an increase in edge-sharing Ni-Me (Me = Ni, Co and Mn) distances in birnessite layers with the increase of the contents of dopants while Mn-Me distances first decrease and then increase while those of Co-Me pairs are nearly constant, coupled with first a decrease and then increase of the in-plane unit-cell parameter b. The effect of co-doping on the amounts of structural Mn and K+, numbers of [MnO6] layers stacked in c* axis, and SSAs, are larger than the effects of doping with Co alone, but less than singly Ni doping. In birnessites doped with both Co and Ni, ~ 74-79% of the total Co and ~ 23-39% of the total Ni are present within the manganese layers. Compared with the spatial distribution of TM in singly doped birnessites, the coexistence of Ni hinders incorporation of Co into the layers during birnessite crystallization; however, coprecipitation with Co has little effects, neither hindrance nor promotion, on the insertion of Ni into the layers. These results provide insight into the interaction mechanism between coexisting Co, Ni within layered Mn oxides. It further helps us to interpret the geochemical characteristics of multi metals incorporation into natural Mn oxides and their effects on the structures and physicochemical properties of these minerals.
    Chemical Geology 08/2014; · 3.48 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: The bacterial abundance and community composition in four types of soils and their associated Fe-Mn nodules from Queyu (QY) in Shandong Province, Zaoyang (ZY), Wuhan (WH) in Hubei Province and Guiyang (GY) in Hunan Province, China were investigated using real-time PCR, cloning and sequencing approaches. It was found that the bacterial 16S rRNA gene copy numbers in the soils were almost 3 magnitudes greater than those in their corresponding nodules and positively correlated with OM. The bacterial diversity as indicated by Simpson and Shannon indices, were significantly lower in the nodules than in the soils. Remarkable divergence in bacterial community structure was observed between the soils and the nodules, and the difference was the mainly explained by OM. In contrast, the differences within the soils and within the nodules were minor, suggesting significant habitat filtering for the bacterial community composition in the nodules. Acidobacteria was the most abundant group (accounting for 28.6%–51.6%) in soil bacterial community while nodule bacterial community was predominated by Proteobacteria (accounting for 62.8%– 90.5%). A number of clones closely related to well-known Mn-oxidizing, Fe-oxidizing and Fe-reducing bacteria within Proteobacteria were retrieved mainly from nodules.
    Geomicrobiology 08/2014; 31(7). · 1.80 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: LiMn2O4 cathode materials with high discharge capacity and good cyclic stability were prepared by a simple one-step hydrothermal treatment of KMnO4, aniline and LiOH solutions at 120-180 °C for 24 h. The aniline/KMnO4 molar ratio (R) and hydrothermal temperature exhibited an obvious influence on the component and phase structures of the resulting product. The precursor KMnO4 was firstly reduced to birnessite when R was less than 0.2:1 at 120-150 °C. Pure-phased LiMn2O4 was formed when R was 0.2:1, and the LiMn2O4 was further reduced to Mn3O4 when R was kept in the range of 0.2-0.3 at 120-150 °C. Moreover, LiMn2O4 was fabricated when R was 0.15:1 at 180 °C. Octahedron-like LiMn2O4 about 300 nm was prepared at 120 °C, and particle size decreased with an increase in hydrothermal temperature. Especially, LiMn2O4 synthesized at 150 °C exhibited the best electrochemical performance with the highest initial discharge capacity of 127.4 mAh g-1 and cycling capacity of 106.1 mAh g-1 after 100 cycles. The high discharge capacity and cycling stability of the as-prepared LiMn2O4 cathode for rechargeable lithium batteries were ascribed to the appropriate particle size and larger cell volume.
    ChemInform 07/2014;
  • [Show abstract] [Hide abstract]
    ABSTRACT: Inositol hexakisphosphates are the most abundant organic phosphates (OPs) in most soils and sediments. Adsorption, desorption, and precipitation reactions at environmental interfaces govern the reactivity, speciation, mobility, and bioavailability of inositol hexakisphosphates in terrestrial and aquatic environments. However, surface complexation and precipitation reactions of inositol hexakisphosphates on soil minerals have not been well understood. Here we investigate the surface complexation-precipitation process and mechanism of myo-inositol hexakisphosphate (IHP, phytate) on amorphous aluminum hydroxide (AAH) using macroscopic sorption experiments and multiple spectroscopic tools. The AAH (16.01 μmol m(-2)) exhibits much higher sorption density than boehmite (0.73 μmol m(-2)) and α-Al2O3 (1.13 μmol m(-2)). Kinetics of IHP sorption and accompanying OH(-) release, as well as zeta potential measurements, indicate that IHP is initially adsorbed on AAH through inner-sphere complexation via ligand exchange, followed by AAH dissolution and ternary complex formation; last, the ternary complexes rapidly transform to surface precipitates and bulk phase analogous to aluminum phytate (Al-IHP). The pH level, reaction time, and initial IHP loading evidently affect the interaction of IHP on AAH. In situ ATR-FTIR and solid-state NMR spectra further demonstrate that IHP sorbs on AAH and transforms to surface precipitates analogous to Al-IHP, consistent with the results of XRD analysis. This study indicates that active metal oxides such as AAH strongly mediate the speciation and behavior of IHP via rapid surface complexation-precipitation reactions, thus controlling the mobility and bioavailability of inositol phosphates in the environment.
    Environmental Science and Technology 05/2014; · 5.48 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Visible light photocatalytic H2-production from aqueous solutions is of great importance for its potential application in converting solar energy into chemical energy. In this study, a series of CdS nanostructures with different contents of wurtzite (WZ) and zinc blende (ZB) phases were successfully synthesized by a simple solvothermal route in an ethylenediamine and ethylene glycol mixed solution. The solvent volume ratio of ethylenediamine in the mixed solution (R) exhibited an obvious influence on the crystalline phase and morphology of the resulting CdS products. With increasing R, the percentage of wurtzite first increased and then decreased, whilst the morphology changed from nanoparticles to multi-armed nanorods, and finally to long rods and sheets. The prepared multi-armed CdS nanorod samples showed especially high and stable photocatalytic H2-production activity with Pt (0.25 wt%) as a co-catalyst and lactic acid aqueous solution as a sacrificial reagent under visible light irradiation. The optimized CdS nanorods with the highest percentage (64%) of the WZ phase exhibited a high H2-production rate of 231.4 μmol h(-1) (about 16.6 times higher than that of CdS nanoparticles with a low percentage (38.4%) of WZ CdS) and with a quantum efficiency (QE) of 28% at 420 nm. This high photocatalytic H2-production activity could be attributed to the results of the positive synergistic effects of the hexagonal WZ phase and morphology of multi-armed nanorods.
    Dalton Transactions 03/2014; · 4.10 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Manganese(II) contamination is naturally occurring in many groundwater and surface water sources. Moreover, industrial wastewater is also responsible for much of the Mn(II) contamination. Nowadays, Mn(II) contamination has become a serious environmental problem in some regions of the world. To explore a biological approach for removing excessive amounts of aqueous Mn(II) from water, we found a new biocatalyst multicopper oxidase CueO, which was firstly proved to catalyze the oxidation of Mn(II) both in vitro and in vivo. Subsequently, we established a CueO-mediated catalysis system to prepare biogenic Mn oxide (BioMnOx), which was confirmed to be γ-Mn3O4 by X-ray diffraction. This newly prepared BioMnOx consisted of 53.6% Mn(II), 18.4% Mn(III) and 28.0% Mn(IV) characterized by X-ray photoelectron spectroscopy. It exhibited distinct polyhedral structure with nanoparticles of 150-350 nm diameters observed by transmission electron microscopy. Importantly, CueO could remove 35.7% of Mn(II) after a seven-day reaction, and on the other hand, the cueO-overexpressing Escherichia coli strain (ECueO) could also oxidize 58.1% dissolved Mn(II), and simultaneously remove 97.7% Mn(II). Based on these results, we suggest that ECueO strain and CueO enzyme have potential applications on Mn(II) decontamination in water treatment.
    Water Research 03/2014; 56C:304-313. · 5.32 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: In this work, two novel crown ether functionalized ionic liquid (FIL)-based solid phase microextraction (SPME) fibers were prepared by sol-gel technology using the synthesized 1-(trimethoxysily)propyl 3-(6'-oxo-benzo-15-crown-5 hexyl) imidazolium bis(trifluoromethanesulphonyl)imide ([TMSP(Benzo15C5)HIM][N(SO2CF3)2]) and 1-allyl-3-(6'-oxo-benzo-15-crown-5 hexyl) imidazolium bis(trifluoromethanesulphonyl)imide ([A(Benzo15C5)HIM][N(SO2CF3)2]) as selective stationary phases. Owing to the introduction of trimethoxysilypropyl to the imidazole cation, the [TMSP(Benzo15C5)HIM][N(SO2CF3)2] could be chemically bonded to the formed sol-gel silica substrate through the hydrolysis and polycondensation reaction. Similarly, the [A(Benzo15C5)HIM][N(SO2CF3)2] was able to participate in the formation of the organic-inorganic copolymer coatings through the free radical crosslinking reaction. These two fibers were determined to have "bubble-like" surface characteristics analogous to a previously prepared [A(Benzo15C5)HIM][PF6]-based fiber. Their thermal stabilities were much higher than that of the [A(Benzo15C5)HIM][PF6]-based coating. They were capable of withstanding temperatures as high as 400°C without evident loss of the crown ether FILs. They also had strong solvent, acid and alkali resistance, good coating preparation reproducibility and high selectivity for medium polar to polar compounds. The high selectivity of these two fibers could be attributed to the strong ion-dipole, hydrogen bonding and π-π interactions provided by the synergetic effect of ILs and benzo-15-crown-5 functionalities. Moreover, the selectivity of these two fibers was rather different although the structures of these two crown ether FILs were very similar. This is maybe because the relative contents of the crown ether FILs chemically bonded to the organic-inorganic copolymer coatings were quite different when prepared by different sol-gel reaction approaches.
    Analytica chimica acta 01/2014; 806C:152-164. · 4.31 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Spherical, ellipsoidal, and elongated hematite particles have been obtained via a simple chemical precipitation reaction of FeCl3 and NaOH in the presence of ascorbic acid (AA). The effects of pH, molar ratio of AA/Fe(III), and time on the formation and shape of the hematite particles were investigated. The optimal conditions to well obtain crystalline hematite are 0.1 mol/L FeCl3, 6 mol/L NaOH, pH 7, and AA/Fe(III) ratios of 0.5–2.0%. The presence of AA catalyzed the formation of hematite by reductive dissolution of ferrihydrite and the molar ratio of AA/Fe(III) determined the crystal structure and morphology of hematite. As the ratio of AA increased from 0.5 to 2%, the morphology changed from spherical to ellipsoidal particles and then to elongated particles. The dissolution of Fe(II) from the ferrihydrite precursor is enhanced by AA, and this leads to the formation of hematite by precipitation and crystallization. The effect of AA on the particle shape can be explained by the difference in AA adsorption on the various crystal planes. The hematite samples with different morphologies enhanced the photodegradation of methylene blue in an acid solution with peroxide; the elongated particles that had the highest specific surface area were most effective with the methylene blue degradation.
    Crystal Growth & Design 12/2013; 14(1):157–164. · 4.56 Impact Factor
  • Source
  • [Show abstract] [Hide abstract]
    ABSTRACT: The sorption and desorption characteristics of four kinds of organic phosphorus with different molecular structures (glycerophosphate (GP), glucose-6-phosphate (G6P), adenosine triphosphate (ATP), and myo-inositol hexakisphosphate (IHP)) on three kinds of aluminum (oxyhydr)oxides (amorphous Al(OH)3, boehmite, and alpha-Al2O3) were studied. The underlying mechanisms were also illustrated. Results showed that the maximum sorption amounts of OP onto Al (oxyhydr)oxides, on a per gram dry weight basis, decreased as following: amorphous Al(OH)3 > boehmite > alpha-Al2O3. This mainly related to the mineral crystallinity and surface heterogeneity. With the exception of sorption of IHP on amorphous Al (OH)3, the maximum sorption density decreased with increasing molecular weight (MW) of OP, following the order: GP > G6P > ATP > IHP. However, the sorption amount of IHP on amorphous Al (OH)3 was much higher than those of other OP, due to the transformation of surface complexes of IHP to surface precipitation and thus enhancing the sorption. The sorption kinetics results showed that sorption of OP underwent the first onset rapid sorption, i. e. a certain amount of sorption occurred within an onset extremely short period, and a following long and slow sorption process. Amorphous Al (OH)3 had the greatest onset rapid sorption density, and the onset rapid sorption density of OP on Al (oxyhydr) oxides decreased with increasing MW. Desorption capacities of OP by KCl and citrate solutions related to the surface affinity between OP and boehmite. Initial desorption percentages by KCl decreased in the order: G6P (10.53%) > GP(6.91%) > ATP (3.06%) > IHP (0.8%). The maximum desorption percentages of OP by citrate were 4-5 times greater than those by KCl. During resorption process of P by KCl, the maximum desorption rate achieved after a fast desorption in a few hours, followed by diffusion-resorption during which the desorption percentage gradually decreased. Specially, both diffusion-resorption and surface precipitation promoted the resorption of IHP on mineral surface. Conclusively, the strong specific sorption of OP occurs on the surface of Al (oxyhydr) oxides, and molecular structure and size of OP as well as the crystallinity and crystal structure of minerals are the key factors affecting the interfacial reactions and environmental behaviors of OP.
    Huan jing ke xue= Huanjing kexue / [bian ji, Zhongguo ke xue yuan huan jing ke xue wei yuan hui "Huan jing ke xue" bian ji wei yuan hui.] 11/2013; 34(11):4482-9.
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Binding of lead (Pb) to soil fulvic acid (JGFA), soil humic acids (JGHA, JLHA) and lignite-based humic acid (PAHA) was investigated through binding isotherms and XAFS. Pb binding to humic substances (HS) increased with increasing pH and decreasing ionic strength. The NICA-Donnan model could describe Pb binding to the HS satisfactorily. The comparison of the model parameters showed substantial differences in median Pb affinity constants between JGFA, PAHA and the soil HAs. Milne's 'generic' parameters didn't provide an adequate prediction for the soil samples.. The Pb binding prediction with 'generic' parameters for the soil HAs could be improved significantly by using the value nPb1=0.92 instead of the 'generic' value nPb1=0.60. The nPb1/nH1 ratios obtained were relatively high, indicating monodentate Pb binding to the carboxylic-type groups. The nPb2/nH2 ratios depended somewhat on the method of optimization, but the values were distinctly lower than the nPb1/nH1 ratios, especially when the optimization was based on Pb bound vs. log [Pb]. These low values indicate bidentate binding to the phenolic-type groups at high Pb concentration. The NICA-Donnan model does not consider bidentate binding of Pb to a carboxylic- and a phenolic-type group. The EXAFS results at high Pb loading testified that Pb was bound in bidentate complexes of one carboxylic and one phenolic group (salicylate-type) or two phenolic groups (catechol-type) in ortho position.
    Environmental Science & Technology 09/2013; · 5.48 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Manganese-oxidizing bacteria in the aquatic environment have been comprehensively investigated. However, little information is available about the distribution and biogeochemical significance of these bacteria in terrestrial soil environments. In this study, stratified soils were initially examined to investigate the community structure and diversity of manganese-oxidizing bacteria. Total 344 culturable bacterial isolates from all substrata exhibited Mn(II)-oxidizing activities at the range of 1 µM to 240 µM of the equivalent MnO2. The high Mn(II)-oxidizing isolates (>50 mM MnO2) were identified as the species of phyla Actinobacteria, Firmicutes and Proteobacteria. Seven novel Mn(II)-oxidizing bacterial genera (species), namely, Escherichia, Agromyces, Cellulomonas, Cupriavidus, Microbacterium, Ralstonia, and Variovorax, were revealed via comparative phylogenetic analysis. Moreover, an increase in the diversity of soil bacterial community was observed after the combined enrichment of Mn(II) and carbon-rich complex. The phylogenetic classification of the enriched bacteria represented by predominant denaturing gradient gel electrophoresis bands, was apparently similar to culturable Mn(II)-oxidizing bacteria. The experiments were further undertaken to investigate the properties of the Mn oxide aggregates formed by the bacterial isolates with high Mn(II)-oxidizing activity. Results showed that these bacteria were closely encrusted with their Mn oxides and formed regular microspherical aggregates under prolonged Mn(II) and carbon-rich medium enrichment for three weeks. The biotic oxidation of Mn(II) to Mn(III/IV) by these isolates was confirmed by kinetic examinations. X-ray diffraction assays showed the characteristic peaks of several Mn oxides and rhodochrosite from these aggregates. Leucoberbelin blue tests also verified the Mn(II)-oxidizing activity of these aggregates. These results demonstrated that Mn oxides were formed at certain amounts under the enrichment conditions, along with the formation of rhodochrosite in such aggregates. Therefore, this study provides insights into the structure and diversity of soil-borne bacterial communities in Mn(II)-oxidizing habitats and supports the contribution of soil-borne Mn(II)-oxidizing bacteria to Mn oxide mineralization in soils.
    PLoS ONE 09/2013; 8(9):e73778. · 3.53 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Fe-doped hexagonal birnessite was synthesized by adding Fe3+ to the initial reactants, and the effects of Fe doping on the structures and properties of birnessite were investigated and compared with the effects of Co and Ni doping. The underlying mechanisms controlling the incorporation of transition metals (TMs) into the birnessite structure were proposed. Compared to the un-doped control, Fe-doped birnessite has weaker crystallinity, i.e., less stacking of the phyllomanganate sheets in the c direction, and larger surface area. Combination of X-ray photoelectron spectroscopy (XPS) and Mn K-edge XANES and EXAFS spectra demonstrates that Fe doping decreases the Mn average oxidation state (AOS) but has little effect on the basic layer structure and local Mn environments. Fe(III) located in the birnessite layers exhibits high-spin (HS) configuration whereas layer Mn(III) and Co(III) plausibly adopt low-spin (LS) state. The TMs decrease the thickness of birnessite plate crystals along the c axis and affect the unit cell parameter b in the order Fe > Ni > Co. Co and Fe incorporate into the birnessite layers by substitution for Mn(IV) while Ni substitutes for Mn(III). The substitution of TMs into the birnessite layers is governed by the coordination radius (CR), crystal field stabilization energy (CFSE) and oxidation state of the TMs. The variations in potassium contents in doped birnessites together with TM K-edge EXAFS data indicate that most of the Fe (∼81–82%) or Ni (∼66–76%) incorporated into the birnessite structure exists in the interlayer regions, while most of the Co (∼71–80%) occurs in the manganese layers. The compatibility of these TM ions in the birnessite layers is in the order Co > Ni > Fe. The smaller the difference between the CR of Fe, Co or Ni and Mn(IV) or Mn(III), the more dopants are compatible within the Mn layers.
    Geochimica et Cosmochimica Acta 09/2013; 117:1–15. · 4.25 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: The influence of crystallite size on the adsorption reactivity of phosphate on 2-line to 6-line ferrihydrites was investigated by combining adsorption experiments, structure and surface analysis, and spectroscopic analysis. X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that the ferrihydrite samples possessed a similar fundamental structure with a crystallite size varying from 1.6 to 4.4 nm. N2 adsorption on freeze-dried samples revealed that the specific surface area (SSABET) decreased from 427 to 234 m(2) g(-1) with increasing crystallite size and micropore volume (Vmicro) from 0.137 to 0.079 cm(3) g(-1). Proton adsorption (QH) at pH 4.5 and 0.01 M KCl ranged from 0.73 to 0.55 mmol g(-1). Phosphate adsorption capacity at pH 4.5 and 0.01 M KCl for the ferrihydrites decreased from 1690 to 980 μmol g(-1) as crystallite size increased, while the adsorption density normalized to SSABET was similar. Phosphate adsorption on the ferrihydrites exhibited similar behavior with respect to both kinetics and the adsorption mechanism. The kinetics could be divided into three successive first-order stages: relatively fast adsorption, slow adsorption, and a very slow stage. With decreasing crystallite size, ferrihydrites exhibited increasing rate constants per mass for all stages. Analysis of OH(-) release and attenuated total reflectance infrared spectroscopy (ATR-IR) and differential pair distribution function (d-PDF) results indicated that initially phosphate preferentially bound to two Fe-OH2(1/2+) groups to form a binuclear bidentate surface complex without OH(-) release, with smaller size ferrihydrites exchanging more Fe-OH2(1/2+) per mass. Subsequently, phosphate exchanged with both Fe-OH2(1/2+) and Fe-OH(1/2-) with a constant amount of OH(-) released per phosphate adsorbed. Also in this stage binuclear bidentate surface complexes were formed with a P-Fe atomic pair distance of ∼3.25 Å.
    Environmental Science & Technology 08/2013; · 5.48 Impact Factor

Publication Stats

381 Citations
226.76 Total Impact Points

Institutions

  • 2003–2015
    • Huazhong Agricultural University
      • • College of Resources and Environment
      • • College of Life Science and Technology
      Wu-han-shih, Hubei, China
    • Zhejiang University
      • College of Environmental and Resource Sciences
      Hangzhou, Zhejiang Sheng, China
  • 2012
    • Wuhan Institute of Technology
      Wu-han-shih, Hubei, China
  • 2010
    • Wageningen University
      • Laboratory of Physical Chemistry and Colloid Science
      Wageningen, Provincie Gelderland, Netherlands
    • Northeast Institute of Geography and Agroecology
      • Institute of Urban Environment
      Beijing, Beijing Shi, China