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1.
A novel zinc-based metal–organic framework, {[Zn3(atz)2(pda)2]·2(H2O)}n (Zn-MOF; Hatz is 5-aminote-1H-terazole; H2pda is malonic acid), was prepared using the solvothermal method. Carbonization of the prepared Zn-MOF was conducted under elevated temperatures to investigate its phosphate adsorption performance. Through pre-adsorption experiments, the optimal carbonization temperature of 500 °C was determined, yielding Zn-MOF-500. Besides, multiple characterization methods were used to analyze the properties of Zn-MOF and Zn-MOF-500 materials before and after the adsorption of phosphate ions. The results showed that the BET surface area of Zn-MOF-500 was 18.57 m2/g, which was 16.37 times larger than that of the BET surface area of Zn-MOF. At 25 °C, Zn-MOF and Zn-MOF-500 exhibited an adsorption capacity of 123.44 and 226.07 mg/g, respectively. Based on the adsorption isotherms and the adsorption kinetics, the adsorption of PO43- occurs via monolayer. X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy (XPS) analysis showed that P was adsorbed on Zn-MOF and Zn-MOF-500 as the zinc hydrogen phosphate and zinc phosphate ions, respectively.  相似文献   

2.
Layered material of zinc hydroxychlorides (Zn5(OH)8Cl2·nH2O: ZHC), which is one of the basic zinc salts (BZS), was synthesized from ZnO nano-particles aged with aqueous ZnCl2 solutions at different temperatures ranging from 6 to 140 °C for 48 h. X-ray diffraction (XRD) results indicated that the diffraction peaks of ZnO completely disappeared by aging at 6 °C and the ZHC peaks were developed. By increasing the aging temperature, crystallinity of the layered structure was improved. At 6 °C, the ZHC particles were thin hexagonal plate particles with sizes ranging from 1 to 3 μm. The particle size of ZHC was independent of aging temperature. The atomic Cl/Zn ratios of all the ZHC materials were almost 0.2 less than 0.4 of the theoretical ratio, indicating that the synthetic ZHC is Cl-deficient. It seemed that half of Cl atoms in the layer were replaced with HCO3 and/or OH. The specific surface areas of ZHC estimated from N2 adsorption isotherms were ca. 10 m2 g−1 and were independent of the aging temperature. However, the H2O monolayer adsorption capacity per unit surface area (nw) for all the samples was higher than that of ZnO particles, revealing the high affinity of ZHC to H2O molecules. The nw values were increased by reducing the crystallinity of ZHC. This enhancement of H2O adsorption selectivity was thought to be related with less-crystallized parts of the particles.  相似文献   

3.
The application of newly synthesized Fe3O4/TiO2–SiO2 that is modified with zinc (FTSZ) as a sorbent, for the removal of arsenic from contaminated water has been investigated in the present study. SEM, FTIR, XRD, BET, Zeta potential sizer (ξ) analyses are used to determine the sorbent characterization. The effect of the operational parameters such as initial pH, initial concentration, and the contact time were studied. In addition, the equilibrium behavior of FTSZ in As(III) removal was investigated in the temperature range of 20–40 °C. The results showed that the equilibrium data were fitted well with Langmuir than Freundlich isotherm model. The maximum monolayer adsorption capacity estimated by Langmuir isotherm was 24.010 mg g?1. Thermodynamic parameters, ?H°, ?S° and ?G° were also calculated from graphical interpretation of the experimental data. Standard heats of sorption (?H°) were found to be endothermic and ?S° values were calculated to be positive for the sorption of As(III) onto the adsorbent.  相似文献   

4.
Nitrogen adsorption isotherm measured at ?196 °C for a macroporous α-alumina (α-Al2O3) is reported. This isotherm is compared with the previously reported adsorption data measured on LiChrospher 1000 silica and with available reference isotherms measured at moderate and high relative pressures on macroporous aluminas. The isotherm reported in this work for α-Al2O3 and that recorded previously on LiChrospher 1000 silica were used as reference data for adsorption characterization of ordered and disordered mesoporous aluminas by α s -plot analysis and pore size analysis. It is shown that both reference isotherms provide almost identical adsorption characteristics of the aforementioned mesoporous aluminas, indicating that the available reference data for the silica surface are also suitable for adsorption analysis of alumina-based materials.  相似文献   

5.
The thermal behavior of zinc carbodiimide Zn(NCN) was examined in the temperature range between 200 and 1100 °C in Ar atmosphere. The material starts to partially decompose at about 800 °C. Heat treatment at temperatures beyond 800 °C results in the formation of the byproducts nitrogen-containing bamboo-like multiwall carbon-nanotubes of 20–50 nm in diameter due to a partial decomposition of Zn(NCN) into dicyan (CN)2, zinc and nitrogen gas followed by the polymerization of the former product to paracyanogen (CN)n. At 1100 °C, the yield of the residual carbodiimide depends on the dwelling time and the initial amount of powder used for pyrolysis. One hour dwelling at 1100 °C yields ∼50% of the Zn(NCN) separated as pure material. Temperature-induced change in the band structure, namely indirect-to-direct band gap transition, is registered when compared the Zn(NCN) at room temperature with the residual material annealed at 1100 °C. The transition from indirect (Eg = 4.32 eV) to direct band gap (Eg = 4.93 eV) is due to the thermal annealing process which results in healing of crystal defects.  相似文献   

6.
Titanate nanotubes (TNTs) have been synthesized by a hydrothermal method using rutile TiO2 powder as titanium source. The determination of the structure and morphology was characterized by XRD, FTIR, SEM and TEM. The results indicate that the TNTs successfully synthesized under hydrothermal conditions of 150 °C. The adsorption of Th(IV) on TNTs was studied as a function of contact time, pH values, ionic strength, initial Th(IV) concentration and temperature under ambient conditions by using batch technique. The results indicate that adsorption of Th(IV) on TNTs is strongly dependent on pH values, but weakly dependent on ionic strength; Adsorption kinetics was better described by the pseudo-second-order model. The adsorption isotherms are simulated by Langmuir and Freundlich models well. ΔG°, ΔH° and ΔS° free energy were calculated from experimental data, The results indicate that the adsorption of Th(IV) on TNTs is an endothermic and a spontaneous process, and increases with increasing temperature. The adsorption of Th(IV) on TNTs is mainly dominated by chemical sorption or surface complexation.  相似文献   

7.
The adsorption of SO2 on alumina used in the aluminium industry, the so-called smelter-grade alumina, was studied in the temperature range 15–120°C. It was found that at temperatures lower than 40°C, sulphur dioxide was bonded to alumina reversibly by physical forces, and the adsorption could be described satisfactorily by the Langmuir adsorption isotherm. The heat of adsorption was estimated to be −33 kJ mol−1. At temperatures ranging from 80°C to 120°C, which prevail in dry scrubbers in the aluminium industry, the heat of adsorption was determined to be −56 kJ mol−1. When SO2 was adsorbed at temperatures higher than 80°C, about 30 % of the SO2 could not be desorbed even if the samples were heated up to 250°C. In the presence of SO2 and oxygen, the formation of sulphate was observed at temperatures above 90°C.  相似文献   

8.
The main objective of this work is to control the structural, textural and electrical properties of the system prepared by mixing molybdenum oxide with different amounts of germanium. The system is expected to be suitable as a catalyst for the photodegradation of methyl red (one of the dyes group) and the results of this study can throw some light on the relationship between the properties of this system and the extent of the dye degradation as indicated by the measurements of the photocatalytic activity. The composite materials (GexMoO3) were prepared by solid-state reaction between germanium and molybdenum oxide. The mixtures were made in Ge/MoO3 molar ratios of 0.01, 0.05, 0.1, 0.2, 0.5, and 1.0. The reaction was conducted in air at 700°C. The prepared samples were characterized by X-ray powder diffraction, micro-Raman spectroscopy, nitrogen adsorption measurements, diffuse reflectance spectrometry and UV-Vis absorption spectrophotometry. The addition of germanium has affected the photocatalytic activity of MoO3 as evidenced by an increase in the degradation extent of methyl red from about 14% (for pure oxide) to about 97% for GexMoO3 (x = 1). An enhancement in the photocatalytic activity was attributed to the change in the band gap and modification of the textural properties associated with the formation of GexMoO3 composites.  相似文献   

9.
Spectroelectrochemical and electrochemical methods were used to investigate the characteristics of heterogeneous electron transfer between cytochrome c and indium oxide electrodes. A linear temperature dependence of the formal potential of cytochrome c was observed from 5 to 75 °C in acidic media. This behavior is attributed to a linear variation in the conformation of ferricytochrome c that results in an increase in solvent exposure of the solvent-exposed heme edge. A break in the linear temperature dependence of the formal potential occurred at 40 °C in alkaline media. This reflects a distinct conformational change that accompanies the onset of thermal denaturation of ferricytochrome c. The small change in reaction center entropy, ΔS°rc, of ca. −54 J K−1 mol−1 in neutral and acidic media (5 to ⩾ 55 °C) and in alkaline media (below 40 °C) is consistent with a small shift to a more stable conformation of cytochrome c that occurs upon reduction.Adsorption of reactant and product was detected. The strength and type of adsorption were found to be temperature- and pH-dependent. The characteristics of electron transfer between cytochrome c and an electrode depend on bulk solvent properties and electrode surface characteristics.  相似文献   

10.
The paper concerns aluminium hydroxides precipitated during hydrolysis of aluminium acetate in ammonia medium, as well as aluminium oxides obtained through their calcination at 550, 900 or 1200°C for 2 h. The following techniques were used for analysing of obtained materials: thermal analysis, IR spectroscopy, X-ray diffraction, low-temperature nitrogen adsorption, adsorption-desorption of benzene vapours and scanning electron microscopy. Freshly precipitated boehmite/pseudoboehmite had high value of S BET, very good sorption capacity for benzene vapours, developed mesoporous structure and hydrophilic character. After prolonged refluxing at elevated temperature its crystallinity increased which was accompanied by a decrease of specific surface determined from nitrogen adsorption, decrease of sorption capacity for benzene vapours and weakening of the hydrophilic character. Calcination of all hydroxides at the temperature up to 1200°C resulted in the formation of α-Al2O3 via transition forms of γ-, δ-and θ-Al2O3. The samples of aluminium oxides obtained after calcination at 550 and 900°C were characterised with high values of specific surface area and displayed quite high heat resistance, probably due to a specific morphology of starting hydroxides. The process of ageing at elevated temperature developed thermal stability of aluminium oxides.  相似文献   

11.
Two different hybrid materials composed of gold nanoparticles (AuNPs) supported on either commercial niobium oxide HY 340 or mesoporous niobium oxide catalyzed the Friedel-Crafts alkylation of anisole by benzyl chloride. Excitation of the surface plasmon of the supported AuNPs allowed the reaction to occur at lower temperatures by acting as an alternative heat source. The localized heating produced via plasmon excitation permitted the acid catalyzed reaction to occur - at the Lewis acid sites on the Nb2O5 support - at 80 °C while thermal-dark reactions using a conventional heat source, required temperatures of 120 °C or higher. The catalytic activity of the tested hybrid materials decreased with storage time. However, the deactivation showed to be reversible upon lyophilisation indicating that the nature of the deactivation could be due to water adsorption.  相似文献   

12.
(Mn1 ? x M x )O2 (M = Co, Pd) materials synthesized under hydrothermal conditions and dried at 80°C have been characterized by X-ray diffraction, diffuse reflectance spectroscopy, electron microscopy, X-ray photoelectron spectroscopy, and adsorption and have been tested in CO oxidation under CO + O2 TPR conditions and under isothermal conditions at room temperature in the absence and presence of water vapor. The synthesized materials have the tunnel structure of cryptomelane irrespective of the promoter nature and content. Their specific surface area is 110–120 m2/g. MnO2 is morphologically uniform, and the introduction of cobalt or palladium into this oxide disrupts its uniformity and causes the formation of more or less crystallized aggregates varying in size. The (Mn,Pd)O2 composition contains Pd metal, which is in contact with the MnO2-based oxide phase. The average size of the palladium particles is no larger than 12 nm. The initial activity of the materials in CO oxidation, which was estimated in terms of the 10% CO conversion temperature, increases in the following order: MnO2 (100°C) < (Mn,Co)O2 (98°C) < (Mn,Co,Pd)O2 (23°C) < (Mn,Pd)O2 (?12°C). The high activity of (Mn,Pd)O2 is due to its surface containing palladium in two states, namely, oxidized palladium (interaction phase) palladium metal (clusters). The latter are mainly dispersed in the MnO2 matrix. This catalyst is effective in CO oxidation even at room temperature when there is no water vapor in the reaction mixture, but it is inactive in the presence of water vapor. Water vapor causes partial reduction of Mn4+ ions and an increase in the proportion of palladium metal clusters.  相似文献   

13.
A novel polyacrylonitrile (PAN)–titanium oxide (TiO2) nanofiber adsorbent functionalized with aminopropyltriethoxysilane (APTES) was fabricated by electrospinning. The adsorbent was characterized by SEM, FTIR, TEG and BET analyses. The pore diameter and surface area of the adsorbent were 3.1 nm and 10.8 m2 g?1, respectively. The effects of several variables, such as TiO2 and amine contents, pH, interaction time, initial concentration of metal ions, ionic strength and temperature, were studied in batch experiments. The kinetic data were analyzed by pseudo-first-order, pseudo-second-order and double-exponential models. Two isotherm models, namely Freundlich and Langmuir, were used for analysis of equilibrium data. The maximum adsorption capacities of Th(IV), Ni(II) and Fe(II) by Langmuir isotherm were found to be 250, 147 and 80 mg g?1 at 45 °C with pH of 5, 6 and 5, respectively, and greater adsorption of Th(IV) could be justified with the concept of covalent index and free energy of hydration. Calculation of ΔG°, ΔH° and ΔS° demonstrated that the nature of the Th(IV), Ni(II) and Fe(II) metal ions adsorption onto the PAN–TiO2–APTES nanofiber was endothermic and favorable at a higher temperature. The negative values of ΔG° for Th(IV) showed that the adsorption process was spontaneous, but these values for Ni(II)and Fe(II) were positive and so the adsorption process was unspontaneous. Increasing of ionic strength improved the adsorption of Ni(II) and Fe(II) on nanofiber adsorbent but decreased the adsorption capacity of Th(IV). The adsorption capacity was reduced slightly after six cycles of adsorption–desorption, so the nanofiber adsorbent could be used on an industrial scale. The inhibitory effect of Ni(II) and Fe(II) on the adsorption of Th(IV) was increased with an increase in the concentration of inhibitor metal ions.  相似文献   

14.

This work evaluates the effects of the sintering temperature (800 °C, 900 °C, 1000 °C) of SrTi1-xFexO3-δ (x = 0.35, 0.5, 0.7) porous electrodes on their electrochemical performance as potential oxygen electrode materials of solid oxide cells. The materials were prepared by a solid-state reaction method and revealed the expected cubic perovskite structure. After milling, the powders were characterised by a sub-micrometre particle size with high sinter-activity. It was shown that the lowest area specific resistance was achieved after sintering SrTi0.65Fe0.35O3 electrodes at 1000 °C, and SrTi0.5Fe0.5O3 and SrTi0.30Fe0.70O3 electrodes at 800 °C, which can be considered to be a relatively low temperature. In general, EIS measurements showed that increasing the Fe content results in lowered electrode polarisation and a decrease of the series resistance. Even though the studied materials have much lower total conductivities than state-of-the-art electrode materials (e.g. (La,Sr)(Co,Fe)O3), the polarisation resistances obtained in this work can be considered low.

  相似文献   

15.
Anatase TiO2 nanosheets (TiO2 NS) with dominant (001) facets and TiO2 nanoparticles (TiO2 NP) with dominant (101) facets are fabricated by hydrothermal hydrolysis of Ti(OC4H9)4 in the presence and absence of hydrogen fluoride (HF), respectively. Adsorption of N719 onto the as‐prepared samples from ethanol solutions is investigated and discussed. The adsorption kinetic data are modeled using the pseudo‐first‐order, pseudo‐second‐order, and intraparticle diffusion kinetics equations, and indicate that the pseudo‐second‐order kinetic equation and intraparticle diffusion model can better describe the adsorption kinetics. Furthermore, adsorption equilibrium data of N719 on the as‐prepared samples are analyzed by Langmuir and Freundlich models; this suggests that the Langmuir model provides a better correlation of the experimental data. The adsorption capacities (qmax) of N719 on TiO2 NS at various temperatures, determined using the Langmuir equation, are 65.2 (30 °C), 68.2 (40 °C), and 76.6 (50 °C) mg g−1, which are smaller than those on TiO2 NP, 92.4 (30 °C), 100.0 (40 °C), and 108.2 (50 °C) mg g−1, respectively. The larger adsorption capacities of N719 for TiO2 NP versus NS are attributed to its higher specific surface areas. However, the specific adsorption capacities (qmax/SBET) at various temperatures are 1.5 (30 °C), 1.6 (40 °C), and 1.7 (50 °C) mg m−2 for TiO2 NS, which are otherwise higher than those for NP, 0.9 (30 °C), 1.0 (40 °C), and 1.1 (50 °C) mg m−2, respectively. The larger specific adsorption capacities of N719 for TiO2 NS versus NP are because the (001) surface is more reactive for dissociative adsorption of reactant molecules compared with (101) facets. Notably, the qmax and qmax/SBET for both TiO2 samples increase with increasing temperature, suggesting that adsorption of N719 on the TiO2 surface is an endothermic process, which is further confirmed by the calculated thermodynamic parameters including free energy, enthalpy, and entropy of adsorption process. The present work will provide a new understanding on the adsorption process and mechanism of N719 molecules onto TiO2 NS and NP, and this should be of great importance for enhancing the performance of dye‐sensitized solar cells.  相似文献   

16.
A very intense study class of complex porous materials, metal–organic frameworks (MOFs), composed of diverse central metallic ions attached to organic linkers, was used in this study as adsorbant materials from wastewaters. Phosphonate MOFs were prepared by the reaction of divalent inorganic salts (CoSO4 · 7H2O, NiSO4 · 6H2O, CuSO4 · 5H2O,) with vinyl phosphonic acid in hydrothermal conditions, obtaining cobalt, nickel, and copper vinylphosphonate (CoVP, NiVP, and CuVP). During synthesis the experimental conditions were varied in terms of time, temperature, and pH. The synthesized materials were characterized by Fourier transform infrared, thermogravimetric analysis, scanning electron microscopy, and X-ray crystallography. The efficiency of MOFs as adsorbents was investigated for diverse initial dye concentrations at different pH values and at three temperatures (25, 40, and 55°C). The synthesized materials presented good efficiency in the elimination of anionic as well as cationic type of dyes from aqueous solutions. The highest adsorption capacities were obtained working at optimum solution pH 4.2 for Acid Orange 7 and 10 for Basic Fuchsine, using 1 g/L of MOFs at room temperature (25°C). The adsorption capacities increase in the following order: CuVP < NiVP < CoVP.  相似文献   

17.
The adsorption of U(VI) onto dried and pyrolyzed tea and coffee wastes was investigated. The adsorption properties of the materials were characterized by measuring uranium uptake as a function of solution pH, kinetics and adsorption isotherms. pH profile of uranium adsorption where UO2 2+ is expected to be the predominant species was measured between pH 0 and 4. Both Langmuir and Freundlich adsorption models were used to describe adsorption equilibria, and corresponding constants evaluated. Using the Langmuir model, the maximum adsorption capacity of uranium by dried tea and coffee wastes was 59.5 and 34.8 mg/g, respectively at 291 K. Adsorption thermodynamic constants, ΔH° ΔS° and ΔG° were also calculated from adsorption data obtained at three different temperatures. Adsorption thermodynamics of uranyl ions on dried tea and coffee systems indicated spontaneous and endothermic processes. Additionally, a Lagergren pseudo-second-order kinetic model was used to fit the kinetic experimental data for both adsorbents and the constants evaluated. Dried tea and coffee wastes proved to be effective adsorbents with high capacities and significant advantage of a very low cost.  相似文献   

18.
The effect of autoclaving a zinc oxide preparation containing SO2?4 under 5 and 10 atmospheres is studied by combining X-ray diffraction, differential thermal analysis, thermogravimetry and IR spectroscopy. Textural measurements are also carried out on the parent samples and those produced in the temperature range 200–1000°C.A new phase of a basic carbonates?ulphate, including ammonia in its coordination shell, is observed in the original preparation and having its d distances at 11.060, 8.954 and 2.714 Å. This is transformed to another phase at ~180°C which is also the main phase characterizing the autoclaved samples, and belongs to a basic zinc oxide—sulphate possessing d distances at 7.055, 2.468 and 2.805 Å. Autoclaving the oxide preparation under 10 atm gives hexagonal zinc oxide of high purity and crystallinity at 1000°C. An empirical formula is given for the oxide preparation which describes the different decomposition stages observed. At ~390°C, a reversible reduction process comprising oxygen evolution is observed.Autoclaving increases the area of the parent oxide and at temperatures below 600°C is a function of the structural changes. The autoclaving pressure is insignificant ?600°C.Pore structure analysis showed all the samples to be predominantly mesoporous, coexisting with some micropores except that autoclaved under 5 atm and heated at 250°C which is predominantly microporous. Autoclaving under 5 atm causes narrowing of the pores for products below 600°C. Autoclaving has little effect on the average pore radius ?600°C.Evaluation of the average pore radius from the constructed t-curves for parallel-plate pore idealization is discussed.  相似文献   

19.
By adjusting the local effective surfactant packing parameter through synthesis temperature, highly ordered SBA-16-type mesoporous silica materials have been synthesized by templating with a nonionic triblock copolymer Pluronic F68 in strongly acidic conditions at temperature 30~40°C with the addition of K2SO4. The prepared SBA-16-type mesoporous silica materials having Im3m cubic mesostructure were proved by the well-defined x-ray diffraction patterns combined with transmission electron microscopy. Scanning electron microscopy indicated that a transformation from faced-sphere to faced-polyhedron shape morphologies could be induced with increasing of the synthesis temperature. The nitrogen adsorption–desorption analysis revealed that the mean pore size (5.50~6.13 nm) of the prepared materials increased with increasing synthesis temperature. However, when the synthesis temperature exceeded 46°C, only disordered mesoporous silca was obtained. Our synthesis strategies by adjusting the local effective surfactant packing parameter through synthesis condition, even in a narrow range, would be used not only to optimize the synthesis conditions of reported mesoporous silca, but also to fabricate new mesoporous silica materials with well-ordered channel and anticipated morphologies.  相似文献   

20.
The oxidation of CO with oxygen over (0.25–6.4)% CuO/CeO2 catalysts in excess H2 is studied. CO conversion increases and the temperature range of the reaction decreases by 100 K as the CuO content is raised. The maximal CO conversion, 98.5%, is achieved on 6.4% CuO/CeO2 at 150°C. At T > 150°C, the CO conversion decreases as a result of the deactivation of part of the active sites because of the dissociative adsorption of hydrogen. CO is efficiently adsorbed on the oxidized catalyst to form CO-Cu+ carbonyls on Cu2O clusters and is oxidized by the oxygen of these clusters, whereas it is neither adsorbed nor oxidized on Cu0 of the reduced catalysts. The activity of the catalysts is recovered after the dissociative adsorption of O2 on Cu0 at T ~ 150°C. The activation energies of CO, CO2, and H2O desorption are estimated, and the activation energy of CO adsorption yielding CO-Cu+ carbonyls is calculated in the framework of the Langmuir-Hinshelwood model.  相似文献   

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