Dechlorination of chlorinated methanes by Pd/Fe bimetallic nanoparticles

This paper examined the potential of using Pd/Fe bimetallic nanoparticles to dechlorinate chlorinated methanes including dichloromethane (DCM), chloroform (CF) and carbon tetrachloride (CT). Pd/Fe bimetallic nanoparticles were prepared by chemical precipitation method in liquid phase and characterized in terms of specific surface area (BET), size (TEM), morphology (SEM), and structural feature (XRD). With diameters on the order of 30-50 nm, the Pd/Fe bimetallic nanoparticles presented obvious activity, and were suited to efficient catalytic dechlorination of chlorinated methanes. The effects of some important reaction parameters, such as Pd loading (weight ratio of Pd to Fe), Pd/Fe addition (Pd/Fe bimetallic nanoparticles to solution ratio) and initial pH value, on dechlorination efficiency were sequentially studied. It was found that the maximum dechlorination efficiency was obtained for 0.2 wt% Pd loading. The dechlorination efficiency was observed to increase with increasing Pd/Fe addition. The optimal pH value for dechlorination reaction of chlorinated methanes was about 7. Kinetics of chlorinated methane dechlorination in the catalytic reductive system of Pd/Fe bimetallic particles were investigated. The dechlorination reaction complied with pseudo-first-order kinetics.     

纳米钯/铁双金属颗粒对一氯乙酸的脱氯

为了提高零价铁对氯代有机物还原脱氯的性能,采用还原沉淀法制备了纳米钯/铁双金属颗粒.利用X射线衍射(XRD)、X射线荧光光谱(XRF)、扫描电子显微镜(SEM)、透射电镜(TEM)、以及BET-N2比表面积法对纳米钯/铁双金属颗粒进行了表征.结果表明,制备的纳米钯/铁双金属颗粒中Fe主要以α-Fe0形式存在.纳米钯/铁双金属颗粒的直径约为30～50nm,比表面积约51m2/g.纳米钯/铁双金属颗粒对一氯乙酸还原脱氯的脱氯率是还原铁粉和纳米铁粉对一氯乙酸还原脱氯的脱氯率的7.9倍和1.7倍.     

Retention indexes for temperature-programmed gas chromatography of polychlorinated biphenyls

A noninteger retention index was defined based on a series of PCB internal standards, namely congeners 8 (2,4'-dichlorobiphenyl), 31 (2,4',5-trichlorobiphenyl), 44 (2,2',3,5'-tetrachlorobiphenyl), 101 (2,2',4,5,5'-pentachlorobiphenyl), 138 (2,2',3,4,4',5'-hexachlorobiphenyl), 180 (2,2',3,4,4',5,5'-heptachlorobiphenyl), and 194 (2,2',3,3',4,4',5,5'-octachlorobiphenyl). These retention index markers are common congeners present in technical mixtures and most environmental samples, and they show a linear dependence of retention time on the number of chlorine atoms, in the temperature-programmed analysis. The index values are calculated with a single regression equation instead of the Van den Dool and Kratz equation. The retention indexes of all 209 PCBs on two commonly used columns (DB-XLB and DB-5), as well as on a supplementary column of DB-17 in capillary gas chromatography, were determined using this system. The reliability of the retention index is quite good, with the average 95% confidence limits for three measurements on each PCB being +/-0.1 index unit under the same chromatographic conditions and +/-0.4 index unit under different column head pressures. The effect of heating rate of the programmed runs on the retention index was also investigated. The inversion of the elution order of some congener pairs on the DB-XLB column for different temperature heating rates was observed. Our index values were compared with those of Castello and Testini.     

Optical study of the reduction of hexavalent chromium by iron-based nanoparticles

In this paper, a simple method was presented to measure the concentration change in the Cr(VI)-contained waste water during treatment by nanoparticles, based on its optical absorption spectral evolution which exhibits a good linear relationship between the absorbance of the peak at 348 nm and Cr6+ ion concentration. The iron and Fe/Pd bimetal nanoparticles were prepared and used for removal of Cr6+ in waste water. It has been found that presented method for concentration determination based on optical spectral evolution is effective and flexible. The nanoparticles have higher efficiency than normal iron powders and Fe/Pd bimetallic nanoparticles show faster removal of the Cr6+ than iron nanoparticles. The study is of importance in environmental remediation or pollution treatment of heavy metal ions in water and even soil.     

Debromination of polybrominated diphenyl ethers by Ni/Fe bimetallic nanoparticles: influencing factors, kinetics, and mechanism

Polybrominated diphenyl ethers have been identified as a new class of organic pollutants with ecological risk due to their toxicity, bioaccumulation, and global distribution. Proper remediation technologies are needed to remove them from the environment. In this paper, Ni/Fe bimetallic nanoparticles were synthesized by chemical deposition and used to degrade decabromodiphenyl ether (BDE209). The characteristics of Ni/Fe nanoparticles were analyzed by transmission electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, and Brunnaer-Emmett-Teller surface area analysis. Ni/Fe bimetallic nanoparticles with diameters in the order of 20-50 nm could effectively degrade BDE209 in the solvent (tetrahydrofuran/water). Influence factors, such as Ni/Fe nanoparticle dosage, initial BDE209 concentration, and Ni loading, on the removal of BDE209 were studied. The results indicated that the degradation of BDE209 followed pseudo-first-order kinetics, and the degradation rate of BDE209 increased with increasing the amount of nano Ni/Fe particles, Ni/Fe ratio, and decreasing the initial concentration of BDE209. Through analyzed the mass balance of the BDE209 removal, degradation was the main process of BDE209 removal. The mechanism of debromination was deduced by analyzing the reaction products using gas chromatography-mass spectrometry, the bromide ion in the solution and varying the solvent conditions. Stepwise hydrogen reduction is the main process of debromination, and the hydrion play an important role in the reaction. Moreover, the experiment of long term performance and leaching of Ni were also carried out to test the stability and durability of Ni/Fe nanoparticles in BDE209 degradation.     

Microbial synthesis of core/shell gold/palladium nanoparticles for applications in green chemistry

We report a novel biochemical method based on the sacrificial hydrogen strategy to synthesize bimetallic gold (Au)–palladium (Pd) nanoparticles (NPs) with a core/shell configuration. The ability of Escherichia coli cells supplied with H₂ as electron donor to rapidly precipitate Pd(II) ions from solution is used to promote the reduction of soluble Au(III). Pre-coating cells with Pd(0) (bioPd) dramatically accelerated Au(III) reduction, with the Au(III) reduction rate being dependent upon the initial Pd loading by mass on the cells. Following Au(III) addition, the bioPd–Au(III) mixture rapidly turned purple, indicating the formation of colloidal gold. Mapping of bio-NPs by energy dispersive X-ray microanalysis suggested Au-dense core regions and peripheral Pd but only Au was detected by X-ray diffraction (XRD) analysis. However, surface analysis of cleaned NPs by cyclic voltammetry revealed large Pd surface sites, suggesting, since XRD shows no crystalline Pd component, that layers of Pd atoms surround Au NPs. Characterization of the bimetallic particles using X-ray absorption spectroscopy confirmed the existence of Au-rich core and Pd-rich shell type bimetallic biogenic NPs. These showed comparable catalytic activity to chemical counterparts with respect to the oxidation of benzyl alcohol, in air, and at a low temperature (90°C).     

Thermal diffusivity of nanofluids containing Au/Pd bimetallic nanoparticles of different compositions

Colloidal suspensions of bimetallic Au/Pd nanoparticles were prepared by simultaneous reduction of the metal ions from their corresponding chloride salts with polymer (PVP) stabilizer. Thermal properties of water containing bimetallic nanoparticles with different nominal compositions (Au/Pd = 12/1, 5/1, 1/1, 1/5) were measured using the mode mismatched dual-beam thermal lens technique to determine the effect of particle composition on the thermal diffusivity of the nanofluids. The characteristic time constant of the transient thermal lens was estimated by fitting the experimental data to the theoretical expression for transient thermal lens. The thermal diffusivity of the nanofluids (water, containing Au/Pd bimetallic nanoparticles) is seen to be strongly dependent on the composition of the particles. The maximum diffusivity was achieved for the nanoparticles with highest Au/Pd molar ratio. A possible mechanism for such high thermal diffusivity of the nanofluids with bimetallic particles is given. UV-Vis spectroscopy, TEM and high-resolution electron microscopy (HREM) techniques were used to characterize the Au/Pd bimetallic nanoparticles.     

Bimetallic Pd/Al particles for highly efficient hydrodechlorination of 2-chlorobiphenyl in acidic aqueous solution

Pd-based bimetallic materials have been widely studied for the effective hydrodechlorination (HDC) of aqueous chloroorganic compounds. However, the reaction functions of metal substrates and mechanism responsible for changes in reactivity have not been fully elucidated. Here, we synthesized Pd-based bimetals with Mg, Al, Mn, Zn, Fe, Sn, and Cu to explore the influence of metal substrates on HDC reactivity of 2-chlorobiphenyl (2-PCB). Bimetals exhibited disparate reactivity toward 2-PCB in acidic solution. Among these bimetals, Pd/Al particles presented the highest stability and relatively high reactivity to remove 2-PCB. The maintenance and regeneration of Al substrate are attributed to its particular corrosion properties which provide an efficient recycling between Al element and its oxide layer. The fresh and reacted Pd/Al samples were characterized by ICP-OES, SEM, XRD, and BET. The investigation of the pH effect on 2-PCB HDC further revealed the particular behaviour of Al surface. The effect of Pd loading amount on the HDC indicated that the optimal Pd content in terms of catalytic activity was related to the Pd dispersion degree. Finally, a mechanism for 2-PCB HDC on the Pd/Al surface was proposed.     

Studies on dechlorination of DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) using magnesium/palladium bimetallic system

The aim of our investigation was to compare the rates of dechlorination of DDT using Mg0/Pd4+ system in two different reaction phases, namely, water-acetone and 0.05% biosurfactant in water. Since palladium is expensive and its toxicity effects are not well known we also examined the reuse efficiency of Pd0 immobilized on alumina for dechlorinating DDT. Studies on the dechlorination of DDT in water-acetone (1:1, v/v) and 0.05% biosurfactant phases revealed that the reaction followed second order kinetics and rate of reaction is dependent upon both initial concentrations of the target compound and Mg0/Pd4+. The presence of acid enhanced the rate of reaction by providing protons and preventing passivation of metal that occurs due to deposition of magnesium hydroxide. GC-MS analyses revealed the formation of completely dechlorinated hydrocarbon skeleton of DDT namely, diphenylethane (DPE), as the end product in both reaction phases (water-acetone and 0.05% biosurfactant in water) thereby implying the removal of all five chlorine atoms (three alkyl and two aryl) of DDT. The optimum ratio of water and acetone to facilitate successful dechlorination reaction was found to be 9:1. Results suggested that salt form (K2PdCl6) of palladium had higher potential to dechlorinate DDT as compared to pellet (Pd0-alumina) form (efficiencies of 95 and 36%, respectively, for 100 ppm initial concentration of DDT). We noted that Pd0-alumina pellets could be reused at least four times for successful dechlorination of DDT provided Mg0 granules are present in sufficient quantity. Technical grade DDT (50 ppm) containing significant amounts of DDD was dechlorinated almost completely by the Mg0/Pd4+ (10mg/0.2mg/ml) within 1h in water-biosurfactant phase. Our studies reveal that Mg/Pd system is a promising option due to its high reactivity and its ability to achieve complete dechlorination of DDT. This bimetallic system may be useful for designing indigenous permeable barriers or reactors for the treatment of DDT contaminated water.     

Carbon nanotube formation over laser ablated M and M/Pd (M = Fe,Co, Ni) catalysts: The effect of Pd addition

Monometallic and bimetallic M and M/Pd (M = Fe, Co, Ni) nanoparticles were prepared by pulsed Nd:YAG laser ablation of bulk M and Pd targets in acetone and transferred onto Si wafers to catalyze carbon nanotubes from decomposition of liquid petroleum gas via thermal chemical vapor deposition at 750°C. Transmission electron microscopy and optical extinction study revealed that the prepared M and M/Pd nanoparticles have rather spherical shape and their aspect ratios are nearly one. In comparison to monometallic M catalysts by addition of Pd, the average sizes of produced bimetallic M/Pd catalysts increased. Carbon nanotubes' characterization revealed that by addition of Pd to laser ablated M catalysts the average diameter, the yield, and quality of end product carbon nanotubes were increased. The average diameter of grown carbon nanotubes increases as: Ni < Ni/Pd < Co < Co/Pd < Fe < Fe/Pd and the quality of them increases as: Ni < Co < Fe < Ni/Pd < Fe/Pd < Co/Pd.     

Hydrodechlorination of chlorobenzene over polymer-stabilized palladium-platinum bimetallic colloidal nanocatalysts

Poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized Pd, Pt, Pd-Pt nanocatalysts were prepared and characterized by transmission electron microscopy (TEM). Hydrogenation of chlorobenzene was carried out over these colloidal nanocatalysts under ambient conditions. The catalytic properties for the hydrogenation of chlorobenzene depended on the composition of the bimetallic nanocatalysts. The conversion of chlorobenzene over PVP-Pd (83.64%) was higher than that of PVP-Pt (66.67%), which indicated that the activity of Pd was higher than that of Pt. In 10 hrs. the conversions of all the bimetallic nanocatalysts were higher than that of PVP-Pt (66.67%) monometallic nanocatalysts, and the maximum conversion of chlorobenzene (95.34%) was achieved using PVP-Pd/Pt = 1/1 catalytic system, which was much higher than that of the physical mixture of monometallic nanocatalysts (PVP-Pd and PVP-Pt) at the same Pd/Pt ratio as the PVP-Pd/Pt bimetallic nanocatalysts used. The selectivity to benzene and cyclohexane of the bimetallic nanocatalysts (with < or = 40 mol% Pt) was similar to that of PVP-Pd monometallic nanocatalysts, and nearly approximately 100% selectivity to benzene could be obtained, the selectivity to cyclohexane increased slowly with increasing of platinum content in bimetallic nanocatalysts.     

Complete dechlorination of DDT and its metabolites in an alcohol mixture using NaOH and Pd/C catalyst

DDT (1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane) was dechlorinated in 2-propanol/methanol (99:1v/v) by means of stoichiometric reaction with NaOH and subsequent catalytic dechlorination over Pd/C catalyst. When DDT was treated with a molar excess of NaOH ([NaOH]/[DDT]=9) in the alcohol mixture at room temperature, DDT disappeared within 15min. The reaction of DDT produced an equimolar amount of HCl to yield DDE (1,1-bis(4-chlorophenyl)-2,2-dichloroethylene). The produced DDE was successfully dechlorinated to a chlorine-free product (1,1-diphenylethane, 97% yield) by addition of Pd/C to the alkaline solution and heating at 40 degrees C for 4h. DDD (1,1-bis(4-chlorophenyl)-2,2-dichloroethane) was also dechlorinated to 1,1-diphenylethane in a similar manner. Possible dechlorination pathways for DDT, DDE, and DDD were investigated by observation of the partially dechlorinated intermediates by means of gas chromatography/mass spectrometry (GC/MS).     

Catalytic stepwise nitrate hydrogenation in batch-recycle fixed-bed reactors

Pd (1.0 wt.%)-Cu (0.3 wt.%) bimetallic and Pd (1.0 wt.%) monometallic catalysts were synthesized by means of incipient-wetness impregnation technique and deposited on alumina spheres (dp=1.7 mm). The prepared catalysts were tested at T=298 K and p(H2)=1.0 bar in the integrated process of catalytic liquid-phase hydrogenation of aqueous nitrate solutions, in which the denitration step was carried out consecutively in separate, single-flow fixed-bed reactor units operating in a batch-recycle mode. In the first reactor packed with a Pd-Cu bimetallic catalyst, nitrate ions were transformed to nitrites at pH 12.5 with a selectivity as high as 93%; the rest was found in the form of ammonium ions. Liquid-phase nitrite hydrogenation to nitrogen in the second reactor unit packed with a Pd monometallic catalyst was conducted at low pH values of 3.7 and 4.5, respectively. Although these values are well below the pHpzc of examined catalyst (6.1), which assured that the nitrite reduction was carried out over a positively charged catalyst surface, up to 15% (23% in the presence of 5.0 g/l NaCl in the solution) of initial nitrite content was converted to undesired ammonium ions. Since a negligible amount of these species (below 0.5mg/l) was produced at identical operating conditions over a powdered Pd/gamma-Al2O3 catalyst, it is believed that the enhanced production of ammonium ions observed in the second fixed-bed reactor is due to the build-up of pH gradients in liquid-filled pores of spherical catalyst particles. Both Pd-Cu bimetallic and Pd monometallic catalysts were chemically resistant in the investigated range of pH values.     

Structure determination of chitosan-stabilized Pt and Pd based bimetallic nanoparticles by X-ray photoelectron spectroscopy and transmission electron microscopy

Chitosan (CTS)-stabilized bimetallic nanoparticles were prepared at room temperature (rt.) in aqueous solution. Palladium (Pd) and platinum (Pt) were selected as the first metals while iron (Fe) and nickel (Ni) functioned as the second metals. In order to obtain the noble metal core-transition metal shell structures, bimetallic nanoparticles were prepared in a two-step process: the preparation of mono noble metallic (Pd or Pt) nanoparticles and the deposition of transition metals (Fe or Ni) on the surface of the monometallic nanoparticles. The structures of the nanoparticles were studied using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The XPS results show that Pd and Pt exist mainly in zero valences. The presence of Fe and Ni in the bimetallic nanoparticles affects the binding energy of Pd and Pt. Moreover, the studies of O 1s spectra indicate the presence of Fe or Ni shells. The analyses of TEM micrographs give the particle size and size distributions while the high-resolution TEM (HRTEM) micrographs show the existence of noble metal core lattices. The results confirm the formation of noble metal core-transition metal shell structures.     

Characterization and activity of Pd-modified TiO2 catalysts for photocatalytic oxidation of NO in gas phase

Pd-modified TiO(2) prepared by thermal impregnation method was used in this study for photocatalytic oxidation of NO in gas phase. The physico-chemical properties of Pd/TiO(2) catalysts were characterized by X-ray diffraction analysis (XRD), Brunauer-Emmett-Teller measurements (BET), X-ray photoelectron spectrum analysis (XPS), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), UV-vis diffuse reflectance spectra (UV-vis DRS) and photoluminescence spectra (PL). It was found that Pd dopant existed as PdO particles in as-prepared photocatalysts. The results of PL spectra indicated that the photogenerated electrons and holes were efficiently separated after Pd doping. During in situ XPS study, it was found that the content of hydroxyl groups on the surface of Pd/TiO(2) increased when the catalyst was irradiated by UV light, which could result in the improvement of photocatalytic activity. The activity test showed that the optimum Pd dopant content was 0.05 wt.%. And the maximum conversion of NO was about 72% higher than that of P25 when the initial concentration of NO was 200 ppm, which showed that Pd/TiO(2) photocatalysts could be potentially applied to oxidize higher concentration of NO.     

Synthesis and characterization of Co–Fe nanoparticles supported on mesoporous silicas

Co–Fe bimetallic samples containing 25 wt% total of metal content were prepared by incipient wetness impregnation of cobalt nitrate and iron nitrate salts over hexagonal mesoporous silica (HMS) and SBA-15 supports. Changes in the textural properties and reduction behavior were compared with monometallic cobalt/iron-based samples. The samples were characterized by N₂ physisorption, X-ray diffraction (XRD), H₂-temperature programmed reduction (TPR), transmission electron microscopy (TEM) and H₂ chemisorption. The amount of incorporated metal was estimated by atomic absorption spectroscopy (AAS). Morphological properties revealed that after introduction of the metal to the SBA-15 support, the specific area, pore volume and pore diameter decreased to a lesser extent for bimetallic samples. XRD measurements detected the formation of Co₃O₄ and CoFe₂O₄ phases for both bimetallic samples. TPR profiles indicated similar behavior for both the bimetallic and monometallic samples. Higher temperatures were observed for the reducibility of Co–Fe/HMS as compared to Co–Fe/SBA-15. Dispersion values of the bimetallic samples were higher than Fe monometallic samples and lower than Co monometallic samples according to hydrogen chemisorption. The particle size distribution of the bimetallic samples estimated by TEM microphotographs showed a smaller fraction of larger size particles for Co–Fe/SBA-15.     

Catalytic reduction of chlorinated and recalcitrant compounds in contaminated water

Catalysis dechlorination of chlorinated organic matter by palladium/iron bimetallic particles represents one of the latest innovative technologies for contaminated soil and groundwater remediation. The reaction of dechlorination is believed to take place on the surface site of the catalyst in a pseudo-first-order mode. The dechlorination rate increases with an increase of the bulk loading of palladium due to the increase of both the surface loading of palladium and the total surface area exposed. The results show that no other intermediates were generated besides Cl-, benzene and chlorobenzene during dechlorination of o-dichlorobenzene.     

Immobilization of 2,2'-dipyridyl onto bentonite and its adsorption behavior of copper(II) ions

In this study, the immobilization of 2,2'-dipyridyl onto bentonite was firstly carried out and it was then used for the adsorption of copper(II) ions from aqueous solutions. The variation of the parameters of pH, contact time, initial copper(II) concentration and temperature were investigated in the adsorption experiments. The XRD, FTIR, elemental and thermal analyses were performed to observe the immobilization of 2,2'-dipyridyl onto natural bentonite. The adsorption data obtained were well described by the Langmuir adsorption isotherm model at all studied temperatures. The results indicated that the maximum adsorption capacity was 54.07 mg g(-1) from the Langmuir isotherm model at 50 degrees C. The thermodynamic parameters indicated that the adsorption process is spontaneous, endothermic and chemical in nature. The kinetic parameters of the adsorption were calculated from the experimental data. According to these parameters, the best-fit was obtained by the pseudo-second-order kinetic model. The results showed that 2,2'-dipyridyl-immobilized bentonite can be used as the effective adsorbent for the removal of heavy metal contaminants.     

掺杂Fe元素对Pd/C催化剂性能的影响

用Fe作为掺杂元素, 以活性炭为载体, 通过浸渍还原方法制备了Pd:Fe原子比分别为1:1、2:1、1:2的Pd-Fe/C催化剂.采用TEM和XRD技术对合金催化剂的物理性质进行了测试. 结果表明, 获得的Pd-Fe/C催化剂合金粒子在载体上分布均匀, 粒径<5nm,Fe的掺杂量对Pd/C催化剂晶体结构有很大影响, 通过电化学性能测试比较, 分析了三个不同比例的Pd-Fe/C催化剂和Pd/C催化剂对氢和甲酸的电催化氧化性能. 结果得出:在相同的峰值电位下, 几种催化剂的电流密度大小顺序为: Pd-Fe/C(1:1)>Pd-Fe/C(2:1)>Pd/C>Pd-Fe/C(1:2). 结果表明, 适量掺杂Fe提高了Pd/C催化剂的催化性能, 且Pd:Fe原子比为1:1时催化性能最好.     

等离子体射流辅助双催化剂原位催化法合成碳纳米管

以甲烷为碳源，Fe2O3／Ni为固定相催化剂，在常压条件下利用等离子体射流的高温将甲烷裂解生成碳自由基和氢气。同时联合原位催化法将碳自由基在Fe2O3／Ni双催化剂的共同作用下生长出碳纳米管。运用TEM和元素分析等测试手段对所得碳纳米管进行形貌、含量、结构的表征分析。结果表明，在一定反应条件下，可获得外径为10nm-30nm，管长约数百纳米、产率为75％左右的碳纳米管。与单催化剂相比，双催化剂的联合催化作用更有利于碳管的生长。