Variations of antibacterial activity and silver characteristic of silver‐containing activated carbon fibers undergoing cyclic antibacterial tests

Seven cycles of antibacterial tests were performed on silver‐containing activated carbon fibers derived from liquefied wood (WACF/Ag) to investigate the variations of their antibacterial activity and silver characteristics. The results showed that all the WACF/Ag had the excellent antibacterial durability. Less silver ions were released from WACF/Ag prepared at the soaking concentration of 0.2 mol/L. Both silver and silver ion content followed a decreasing trend with an increase in cycle number of antibacterial tests, and the significant drop occurred in the first cycle. The silver on the surface and in mesopores was almost removed in the first cycle of antibacterial tests, while that in micropores was released slowly with increasing cycle number of antibacterial tests. The schematic illustrations for WACF/Ag revealed that the number of silver nanoparticles in micropores had the determined effect on the antibacterial durability. POLYM. COMPOS., 38:1404–1411, 2017. © 2015 Society of Plastics Engineers     

Effect of precursor composition on the activation of pitchbased carbon fibers

Pure and silver-containing carbon fibers were prepared from isotropic pitch precursors supplied by Conoco, Inc., and a Korean research team and activated in carbon dioxide to varying degrees of burn-off. The specific activation rates for the carbon fibers were measured as well as the nitrogen adsorption characteristics of the activated carbon fibers. Scanning electron microscopy was used to investigate the surface morphology and the behavior of silver particles during the activation process. Molecular composition of the two pitch precursors was determined using a gas chromatograph mass spectrometer and a MALDI TOF mass spectrometer. Results showed that specific surface area increased with the burn-off, and the trends were similar for the pure and silver-containing fibers formed from both isotropic pitch precursors. However, the catalytic behavior of silver during activation, the activation rate, and even the pore characteristics of the activated fiber were found to be dependent on the molecular composition of the precursor pitch.     

Characterization of Silver Particles in Silver-Containing Activated Carbon Fibers Prepared from Liquefied Wood

Silver particles in silver-containing activated carbon fibers prepared from liquefied wood were characterized by X-ray diffraction, X-ray photoelectron spectrometer, scanning electron microscope, and nitrogen adsorption isotherms. Silver irons (Ag⁺) and metallic silver (Ag⁰) were detected in fibers, and the amount of Ag⁰ was much higher than that of Ag⁺. Ag⁰ were migrated and aggregated together to form silver particles with a wide size (0–5μm), which were distributed in micropores, mesopores, and surface of fibers. The mean size of silver particles on the surface was directly related to soaking concentration, while the larger silver particles were easier to peel off from the surface. Also, the increasing micropores and mesopores were blocked by silver particles at higher concentration, and some blocked mesopores were converted into micropores. When the washing treatment was carried out, the silver particles on the surface were removed significantly, resulting in an increase in mesopore quantity. However, most of the silver particles in micropores were firmly supported. The silver-containing activated carbon fibers showed the high and lasting antibacterial activity.     

Accelerated growth of carbon nanofibers using physical mixtures and alloys of Pd and Co in an ethylene–hydrogen environment

The rate of catalytic carbon nanofiber formation from a mixture of ethylene and hydrogen at 550 °C was found to be dramatically faster over physical mixtures of palladium and cobalt micron scale particles than over either metal independently. The rate correlated with the metal fraction nearly identically for either Pd or Co rich mixtures. The highest rate increase over either pure metal was observed for a 1:1 mass ratio (∼150 times faster), although significant increases were found even at metal ratios of 11:1 (∼45 times faster). There was no direct evidence of extensive alloy formation from the mixed powders which suggests that a synergistic mechanism driven by proximity only may be responsible for the observed rate increases. It is thought a species (e.g. hydrogen atoms) formed at one metal (e.g. palladium) diffuses to the other where it accelerates carbon deposition by affecting the other catalyst material directly, or by generating favorable radical species. Kinetic synergism was also observed for Pd–Co alloys, although it was clearly less dramatic than that found for mixtures. Still, the fundamental similarity in behavior suggests that on the alloy surface two site types exist: one primarily Pd and one primarily Co.     

The effect of processing conditions on microstructure of Pd-containing activated carbon fibers

Palladium-doped activated carbon fibers are being evaluated as candidate materials for enhanced hydrogen storage at near ambient conditions. Pd-doped fibers were spun using a Pd salt mixed with an isotropic pitch precursor. Experimental techniques such as in situ X-ray analysis, thermogravimetric studies, scanning transmission electron microscopy and gas adsorption were employed to understand how processing conditions for the production of Pd-doped activated carbon fibers affect the microstructure, pore development, and dispersion of metal particles throughout the fibers. The results showed that PdO phase is present in the stabilized fibers and that this oxide phase is stable up to about 250 °C. The oxide phase transforms into Pd metal with increasing heat treatment temperature, going through the formation of an intermediate carbide phase. Sintering of Pd particles was observed with heat treatment at temperatures over 750 °C. It was also found that pore development during physical activation with CO₂ was not significantly affected by the presence of Pd particles within the fibers.     

Preparation and characterization of trilobal activated carbon fibers

The objective of this research was to evaluate the effectiveness of several different methods for controlling the pore size and pore size distribution in activated carbon fibers. Variables studied included fiber shape, activation time, and the addition of small amounts of silver nitrate. Pure isotropic pitch and the same isotropic pitch containing 1 wt.% silver were melt spun to form fibers with round and trilobal cross sections. These fibers were then stabilized, carbonized, and activated in carbon dioxide. Field emission scanning electron microscopy (FE SEM), electron dispersive spectra (EDS), and wavelength dispersive spectra (WDS) were used to monitor the size and distribution of the silver particles in the fibers before and after activation. Each of these analyses showed that the distribution of silver particles was extremely uniform before and after activation. The fibers were also weighed before and after activation to determine the percent burn-off. The BET specific surface areas of the activated fibers were determined from N₂ adsorption isotherms measured at −196 °C. The results showed that round and trilobal fibers with equivalent cross-sectional areas yielded similar burn-off values and specific surface areas after activation. Also, activation rates were found to be independent of CO₂ flow rate. The porosity of the activated fibers depended on the total time of activation and the cross-sectional area of fibers. The N₂ adsorption measurements showed that the activated fibers had extremely high specific surface areas (greater than 3000 m²/g) and high degrees of meso- and macro-porosity. FE SEM was also used to investigate surface texture and size of pore openings on the surfaces of the activated fibers. The photos showed that silver particles generated surface macro- and mesopores, in agreement with the inferences from N₂ adsorption measurements.     

Preparation of Polymer-stabilized Palladium–silver Bimetallic Nanoparticles by γ-irradiation and their Catalytic Properties for Hydrogenation of cis,cis-1,3-Cyclooctadiene

Polyvinypyrrolidone (PVP)-stabilized Pd-Ag bimetallic colloids were successfully prepared in an acetone:2-propanol solution mixture of palladium acetate and silver perchlorate, and in an aqueous solution of palladium nitrate and silver nitrate by γ-irradiation. The prepared PVP-stabilized bimetallic nanoparticles were characterized by UV, TEM, XRD, and XPS. In Pd–Ag bimetallic nanoparticles, the XPS data indicated that the constituent elements were in the metallic state, and the palladium atoms were concentrated on the surface of the alloy cluster. These PVP-stabilized bimetallic nanoparticles were used as catalysts for hydrogenation of cis,cis-1,3-cyclooctadiene (COD).     

Synthesis of transition metal-doped carbon xerogels by solubilization of metal salts in resorcinol–formaldehyde aqueous solution

The pore texture of carbon materials obtained from evaporative drying and pyrolysis of resorcinol–formaldehyde aqueous gels is controlled by the initial pH of the precursors solution. In order to produce transition metal-containing carbons with tailored texture, various metallic salts were dissolved in the precursors solution. When necessary, a complexing agent (HEDTA or DTPA) was added to render the metal ions soluble. Ni, Fe and Pd loaded carbon xerogels were synthesized and their pore texture was studied after evaporative drying and after pyrolysis. The carbon texture was also studied with regard to the nature of the metal and the amount of complexing agent. The solubilization of transition metal salts in the resorcinol–formaldehyde aqueous solution does not prevent the texture regulation, even though this texture control is influenced: the limits of the pH interval leading to micro–mesoporous carbon materials can slightly differ when a metal salt and/or a complexing agent are added. The pH range shift depends mainly on the amount and nature of the complexing agent, but also slightly on the nature of the metal ion. Nevertheless, the metal particles obtained are rather big (diameter > 15 nm). For catalytic applications, the metal dispersion must be enhanced, especially in the case of expensive metals.     

The influence of the structural and electronic characteristics of palladium on the activity and selectivity of Pd/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Pd-Co/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for the hydrogenation of acetylene hydrocarbons

The influence of the structural and electronic characteristics of nonpromoted and cobalt-promoted Pd catalysts on their adsorption and catalytic properties is studied. It is shown that the conversion of vinylacetylene depends on the dispersion of palladium for both types of catalysts synthesized from acetate and acetylacetonate complexes. The palladium acetylacetonate catalysts have a higher palladium dispersion than the samples obtained from acetate complex solutions, thus leading to a higher conversion of vinylacetylene. It is established that the selectivity of vinylacetylene conversion into 1,3-butadiene on palladium acetate and acetylacetonate catalysts depends on the state of the 3d orbitals of surface Pd atoms. The palladium acetate catalysts are characterized by a higher electron density on the 3d orbital in comparison with the acetylacetonate samples, thus producing higher selectivities of vinylacetylene conversion into 1,3-butadiene. The introduction of cobalt into Pd/δ-Al₂O₃ catalyst synthesized from acetylacetonate complex leads to the formation of bimetallic Pd-Co particles, in which Pd atoms have higher electron density than those in the nonpromoted Pd/δ-Al₂O₃ catalyst, due probably to the donation of electron density from promoter atoms, with a resulting decline in the adsorption ability of bimetallic particles with regard to 1,3-butadiene and hydrogen. As a consequence, the selectivity of vinylacetylene conversion into 1,3-butadiene increases. Requirements for the size, dispersion, and electronic characteristics of the active component in the catalysts for the selective hydrogenation of vinylacetylene are formulated, and two techniques for their synthesis are proposed.     

Adsorption properties of polyacrylonitrile‐based activated carbon hollow fiber

In this work, polyacrylonitrile (PAN) hollow fibers are pretreated with ammonium dibasic phosphate and then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The adsorption properties of the resultant activated carbon hollow fibers (ACHF) prepared in different conditions were studied. The results show that the adsorption properties of ACHF change regularly with preparing conditions of ACHF. The different adsorption ratios to three adsorbates reflect the number of micropores and mesopores in PAN‐based ACHF. Pretreatment with phosphate can increase the number of mesopores. Proper oxidation temperature and time can increase the number of micropores and mesopores. When carbonization temperature is more than 900°C and carbonization time ranges from 50 to 90 min, the number of micropores and mesopores, especially mesopores, greatly increases. Compared with other treatments, activation treatment greatly increases the number of micropores and mesopores, and the dominant pore sizes of mesopores in PAN‐based ACHF are from 2 to 10 nm. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 602–607, 2004     

Flameless Combustion Synthesis of Ni and Ag Nanoparticles in Ballasted Systems: A Time‐Resolved X‐ray Diffraction Study

The combustion of cellulose nitrate in ballasted mixtures containing an organic binder and nickel hydroxycarbonate or silver carbonate as precursors resulted Ni or Ag nanoparticles. The formation of Ni and Ag nanoparticles from flameless combustion of cellulose nitrate was monitored by time‐resolved X‐ray diffraction. During the formation of the Ag nanoparticles, the diffraction patterns exhibited only signals from decreasing amounts of the precursor and newly simultaneously formed 20–30 nm silver particles. It was detected that in the systems with Ni precursor the formation of the Ni 5–10 nm crystals proceeded by some 2–3 s diffraction‐silent intermediate states of the whole system.     

Enhancement of the methylene blue adsorption rate for ultramicroporous carbon fiber by addition of mesopores

Predominant mesopores were added to pitch-based activated carbon fiber (0.7 nm of average pore width) by Ca(NO₃)₂-impregnated chemical activation. The influence of the concentration of calcium nitrate solution, reactivation temperature and reactivation time on the mesopore development of ACF were examined. The development of mesopores in the reactivated ACF was evidenced by an explicit hysteresis of N₂ adsorption isotherm at 77 K. The pore volume ratio of mesopores to micropores reached to 3-4. The addition of predominant mesopores to ACF enhanced the liquid phase adsorption rate of methylene blue by more than 10 times.     

Single‐stage Treatment in Selective Hydrogenation of Acetylene over CDS Type of Pd‐Ag/Al2O3 Catalyst

The (computer designed shape) CDS type of Pd‐Ag/Al₂O₃ catalyst in single‐stage reactor provides superior catalytic activity and selectivity of ethylene in comparison with those of existed two‐stage reactors packed with G‐58B catalyst under industrial operating conditions. In this research, the contents of palladium and silver of catalysts were analyzed by inductive coupling plasma (ICP). The X‐ray photoelectron spectroscopy (XPS) showed that Pd‐Ag alloy has been formed. Higher yield of ethylene may be interpreted by both geometric and electronic effect induced from silver metal. By means of Pyrolysis/GC/MS analysis of used catalysts, the components of carbonaceous deposits were found to be n‐alkenes, including n‐C8 ～ n‐C16 or n‐C18, which may result from oligomerization of acetylene.     

Activated carbon impregnation with ag and cu composed nanoparticles for escherichia coli contaminated water treatment

This study aimed to produce modified granular activated carbon (GAC) by low concentrations of silver (Ag) and/or copper (Cu) nanoparticles with antibacterial capacity for application in water purification. Modified porous materials were produced from the vacuum impregnation method, at the concentrations (mass of metal/mass of activated carbon) of Ag 8 x 10^?4 g/g (Ag 0.08 %), Cu 1 x 10^?2 g/g (Cu 1 %), and Ag 8 x 10^?4 g/g + Cu 1 x 10^?2 g/g (Ag 0.08 % Cu 1 %). The reduction of the metal salts in NPs of Ag and Cu in their metallic forms or oxides was carried out by the thermal decomposition method. The characterization of the produced porous material was performed by x‐ray diffraction, programmed temperature reduction, scanning electron microscopy, x‐ray dispersive energy spectroscopy, electron transmission microscopy, and specific surface area measurements: Brunauer, Emmet, and Teller; micropore area (t method); pore size distribution (DA method); and volume and diameter of micropores (HK method) and mesopores (BJH method). In the structure of the material produced, Ag and Cu metal compounds and AgO and CuO oxides were identified, with average crystallite sizes of < 60 nm. The efficiency of the inactivation of Escherichia coli was more significant in the GAC modified with the combination of NPs (GAC/NP‐AgCu) (6.4 log ₁₀ units), evidencing the synergistic effect of the metals when compared to GAC/NP‐Ag (0.56 log₁₀ units) and GAC/NP‐Cu (1.31 log₁₀ units) modified porous material. Thus, these antibacterial materials can be used for application in water purification, improving the bacteriological quality of water intended for human consumption, noting that the low concentration of metals used can provide exceptional process efficiency.     

含铁MCM-41的合成与表征

实验采用液相沉积方式,向MCM-41有序介孔微球的介孔中引入铁盐,通过加热使铁盐分解,铁以氧化物纳米颗粒或Fe-O纳米团簇的形式存在于有序介孔微球的介孔中,从而获得含铁MCM-41有序介孔微球.对不同铁含量的MCM-41进行了比较性表征,并研究了不同铁源对含铁MCM-41合成的影响.研究表明,以Fe(acac)₃的甲苯溶液和Fe(NO₃)₃的水溶液为铁源时,所得试样中铁的含量均随铁离子浓度的增大而增大.铁离子浓度相同时,由前者所得试样的载铁量是后者的3～4倍,最大铁负载量达1 mmol&#8226;g^-1.载铁后,有序介孔微球的比表面积、孔容和孔径均减小.以Fe(NO₃)₃的水溶液为铁源时,载铁前驱体试样煅烧后,MCM-41的硅氧骨架发生收缩,而以Fe(acac)₃的甲苯溶液为铁源时,MCM-41的硅氧骨架未见变化.因此,从载铁量及负载过程对有序介孔材料骨架结构的影响看,Fe(acac)₃的甲苯溶液作为铁源用于合成含铁MCM-41优于Fe(NO₃)₃的水溶液.     

Binding of metal cations by natural substances

The binding of mercuric chloride and other metal salts to bark, activated sludge (Milorganite), chitosan, poly(p-aminostyrene), and other natural and synthetic materials was investigated by specific atomic absorption and x-ray fluorescence spectroscopy. The synthetic poly(aminostyrene) was included for comparison with the natural polyamine chitosan. Our results show that a wide range of natural materials are potentially useful for the removal of toxic and precious metals that may be present in industrial effluents, mine waters, or other water supply. Such metal salts include those of mercury, lead, zinc, cadmium, copper, nickel, cobalt, iron, manganese, silver, platinum, palladium, and gold.     

Homogeneous catalytic hydrogenation of soybean oil: Palladium acetylacetonate

Soybean oil was hydrogenated with palladium acetylacetonate at 60–170 C, 150 psi hydrogen and 1–60 ppm palladium. The best linolenate selectivity (K_Le/K_Lo=3.5−3.7) was found at 80–120 C. At 120 C palladium acetylacetonate hydrogenated faster than the heterogeneous Pd-on-carbon catalyst.Trans isomerization with the homogeneous catalyst was much higher compared to Pd-on-carbon catalyst. The low activity of the palladium complex at low temperatures was improved with the addition of triethylaluminum. Among other metal acetylacetonates tested only nickel and chromium were mildly active, whereas cobalt and copper were devoid of catalyst activity.     

碳载体处理对Pd催化氧化甲酸的影响

采用饱和Co盐浸渍碳黑,然后高温热处理.发现处理后的碳黑微孔体积减少,介孔体积增加,更适于作为催化剂的载体.用处理后的碳黑制备的碳载Pd催化剂比未处理的碳黑做载体制备的催化剂对甲酸氧化具有更高的电催化活性.XRD结果可以看出,经Co盐浸渍处理过的碳黑中含有一定量的Co,有助于金属Pd在碳黑表面的分散,增加活性金属的电化...     

Molybdocobaltate cobalt salts: New starting materials for hydrotreating catalysts

This paper deals with the use of Anderson heteropolyanions as alternative starting materials to the ammonium heptamolybdate and cobalt nitrate for the preparation of hydrotreatment oxidic precursors. Ammonium and cobalt salts of molybdocobaltate anions were synthesized and impregnated on alumina. The evolution of these compounds along the different steps of preparation of the oxidic precursors has been followed using various physical techniques such as Raman, XAS and UV–vis spectroscopies. It has been shown that the nature of the surface oxomolybdenum phase strongly depends on the nature of the starting salt. After sulfidation under H₂/H₂S, the performances of these new catalysts have been evaluated in hydrodesulfuration of thiophene. It appears that the cobalt salt of the decamolybdocobaltate anion [Co₂Mo₁₀O₃₈H₄]⁶⁻, with a Co/Mo ratio equal to 0.5, allows us to improve the catalytic conversion by comparison to reference catalysts prepared with ammonium heptamolybdate and cobalt nitrate as starting materials. It has been shown that this improvement is due to the preservation of the heteropolyanionic structure up to the drying step.     

Deactivation and coke formation on palladium and platinum catalysts in vegetable oil hydrogenation

Deactivation of palladium and platinum catalysts due to coke formation was studied during hydrogenation of methyl esters of sunflower oil. The supported metal catalysts were prepared by impregnating γ-alumina with either palladium or platinum salts, and by impregnating α-alumina with palladium salt. The catalysts were reused for several batch experiments. The Pd/γ-Al₂O₃ catalyst lost more than 50% of its initial activity after four batch experiments, while the other catalysts did not deactivate. Samples of used catalysts were cleaned from remaining oil by repeated extractions with methanol, and the amount of coke formed on the catalysts was studied by temperature-programmed oxidation. The deactivation of the catalyst is a function of both the metal and the support. The amount of coke increased on the Pd/γ-Al₂O₃ catalyst with repeated use, but the amount of coke remained approximately constant for the Pt/γ-Al₂O₃ catalyst. Virtually no coke was detected on the Pd/α-Al₂O₃ catalyst. The formation of coke on Pd/α-Al₂O₃ may be slower than on the Pd/γ-Al₂O₃ owing to the carrier’s smaller surface area and less acidic character. The absence of deactivation for the Pt/γ-Al₂O₃ catalyst may be explained by slower formation of coke precursors on platinum compared to palladium.