Radiological characterization of Cay?rhan coal-fired power plant in Turkey

Natural radioactivity of Cay?rhan lignite coal treated at Cay?rhan (Ankara, Turkey) power plant, its ash and soil samples mixed with ash in the power plant field were investigated. For comparison, soil samples were collected from a distance of 4 km south of the plant. The analysis shows that the samples include natural radionuclides such as ²²⁶Ra, ²³²Th and ⁴⁰K. The mean activity concentrations of ²²⁶Ra, ²³²Th and ⁴⁰K were 57.82, 30.45 and 322.21 Bq · kg⁻¹, respectively. Obtained values shows that the average radium equivalent activity (Ra_eq), air-absorbed dose rate (D), annual effective dose (AED) and external hazard index (H_ex) for all samples are 123.9 Bq · kg⁻¹, 58.90 nGy · h⁻¹, 71.99 μSv · y⁻¹ and 0.34, respectively. The Ra_eq values of samples are lower than the limit of 370 Bq · kg⁻¹, equivalent to a γ-dose of 1.5 mSv · y⁻¹. The measured activity concentrations for these radionuclides were compared with the reported data of other countries.     

Ru oxide/carbon nanotube composites for supercapacitors prepared by spontaneous reduction of Ru(VI) and Ru(VII)

A novel method based on spontaneous reduction of Ru(VI) and Ru(VII) is reported for the deposition of Ru oxide on multi-walled carbon nanotubes (MWCNT). Both purified and acid functionalized nanotubes (p-MWCNT and a-MWCNT) have been used to produce composite materials for use in high power aqueous supercapacitors. Specific capacitances of 213 ± 16 F g⁻¹ and 184 ± 11 F g⁻¹ were obtained for Ru oxide/p-MWCNT and Ru oxide/a-MWCNT composites, respectively. Specific capacitances for the Ru oxide component were 704 ± 62 F g⁻¹ and 803 ± 72 F g⁻¹, respectively. Current vs. potential curves exhibited capacitance peaks at ca. +0.5 V vs. Ag/AgCl. The Ru oxide/p-MWCNT composite was shown to be stable over 20,000 charge/discharge cycles. An advantage of the method is that no pre-treatment of the MWCNT is required for optimum performance.     

Polyaniline nanofibers obtained by interfacial polymerization for high-rate supercapacitors

Polyaniline (PANI) nanofibers were fabricated by interfacial polymerization in the presence of para-phenylenediamine (PPD). The additives cannot only have a profound impact on the polymers morphology, but can also improve their specific energy and specific capacitances. It was found that PANI nanofibers prepared in the presence of PPD were longer and less entangled than those in the absence of PPD due to a much faster polymerization rate in initial stage. A specific capacitance value of 548 F g⁻¹, a specific power value of 127 W kg⁻¹ and a specific energy value of 36 Wh kg⁻¹ were obtained in polyaniline nanofibers prepared in the present of PPD at a constant discharge current density of 0.18 A g⁻¹.     

Biosorption properties of dried Neurospora crassa for the removal of Burazol Blue ED dye

Biosorption potential of dried Neurospora crassa for Burazol Blue ED was studied with respect to pH, equilibrium time, biomass concentration and temperature to determine equilibrium and kinetic model parameters. The most suitable pH, equilibrium time and biomass concentration were determined as 1 ± 0.2, 60 min and 1.6 g L^− 1, respectively, at 20 °C ± 1.0. The equilibrium data was best described by the Langmuir isotherm model. The maximum biosorption capacity (q_m) of biomass obtained from the Langmuir fit was 110.1 mg g^− 1 biomass at 30 °C. The overall biosorption process was best described by the pseudo-second-order kinetic model. The biosorption process was found to be favored at higher temperatures.     

Porous carbons prepared by using metal-organic framework as the precursor for supercapacitors

Several kinds of porous carbons were easily prepared by using metal-organic framework as both template and carbon precursor. Nanocasting is chosen to adjust the textures and structures with phenolic resin or carbon tetrachloride and ethylenediamine as the additional carbon sources. The carbon materials were further activated by potassium hydroxide (KOH). The electrochemical capacitance behaviors of these carbon materials were investigated in both aqueous and organic electrolytes. Energy densities of 9.4 W h kg⁻¹ in 6 M KOH and 31.2 W h kg⁻¹ in 1.5 M tetraethylammonium tetrafluoroborate acetonitrile solution can be obtained for one of the prepared porous carbon materials (MAC-A) with the surface area of 2222 m² g⁻¹ and the total pore volume of 1.14 cm³ g⁻¹. Due to its high packing density of 0.93 g cm⁻³, the related volumetric specific energy densities of 8.8 and 29.0 W h L⁻¹ can be got.     

Preparation of a graphene nanosheet/polyaniline composite with high specific capacitance

A graphene nanosheet (GNS)/polyaniline (PANI) composite was synthesized using in situ polymerization. The morphology and microstructure of samples were examined by scanning electron microscopy (SEM), transition electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy. Electrochemical properties were characterized by cyclic voltammetry (CV) and galvanostatic charge/discharge. GNS as a support material could provide more active sites for nucleation of PANI as well as excellent electron transfer path. The GNS was homogeneously coated on both surfaces with PANI nanoparticles (∼2 nm), and a high specific capacitance of 1046 F g⁻¹ (based on GNS/PANI composite) was obtained at a scan rate of 1 mV s⁻¹ compared to 115 F g⁻¹ for pure PANI. In addition, the energy density of GNS/PANI composite could reach 39 W h kg⁻¹ at a power density of 70 kW kg⁻¹.     

Varying carbon structures templated from KIT-6 for optimum electrochemical capacitance

Bicontinuous ordered mesoporous carbons (OMCs), fabricated from a KIT-6 template using aluminosilicate as catalyst and furfuryl alcohol as carbon source, were successfully prepared and studied as electrodes in supercapacitors. Their structures were characterized by transmission electron microscopy (TEM), small-angle X-ray diffraction (SAXD) and N₂ cryosorption methods. Using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), the capacitive performance of the OMCs was found to be strongly dependent on the mesostructure. Specific capacitance value greater than 130 F g⁻¹ at 20 mV s⁻¹ were obtained from an OMC that featured high surface area with the existence of additional large pores to enhance the specific capacitance at high discharge rate. For the OMC with the best performance, we found that a power density as high as 4.5 kW kg⁻¹ at an energy density of 6.1 Wh kg⁻¹ can be delivered when the discharge current density is 20 A g⁻¹ and can also be continuously charged and discharged with little variation in capacitance after 2500 cycles. These results indicate that this OMC with optimized structure has potential to be used as a power component in electric vehicles.     

Small capacity decay of lithium iron phosphate (LiFePO4) synthesized continuously in supercritical water: Comparison with solid-state method

Nanosize lithium iron phosphate (LiFePO₄) particles are synthesized using a continuous supercritical hydrothermal synthesis method at 25 MPa and 400 °C under various flow rates. The properties of LiFePO₄ synthesized in supercritical water including purity, crystallinity, atomic composition, particle size, surface area and thermal stability are compared with those of particles synthesized using a conventional solid-state method. Smaller size particles ranging 200-800 nm, higher BET surface area ranging 6.3-15.9 m² g⁻¹ and higher crystallinity are produced in supercritical water compared to those of the solid-state synthesized particles (3-15 μm; 2.4 m² g⁻¹). LiFePO₄ synthesized in supercritical water exhibit higher discharge capacity of 70-80 mAh g⁻¹ at 0.1 C after 30 cycles than that of the solid-state synthesized LiFePO₄ (60 mAh g⁻¹), which is attributed to the smaller size particles and the higher crystallinity. Smaller capacity decay at from 135 to 125 mAh g⁻¹ is observed during the 30 cycles in carbon-coated LiFePO₄ synthesized using supercritical water while rapid capacity decay from 158 to 140 mAh g⁻¹ is observed in the carbon-coated LiFePO₄ synthesized using the solid-state method.     

Charge/discharge characteristics of sulfur composite cathode materials in rechargeable lithium batteries

The charge and discharge characteristics of lithium batteries with sulfur composite cathodes have been investigated. The sulfur composites showed novel electrochemical characteristics. The analysis of the differential capacity indicated that the discharge process showed two voltage plateaus of 2.10 V and 1.88 V, and the charge process also presented two voltage plateaus of 2.22 V and 2.36 V. The overcharge test showed that the composite cannot be charged over 4.0 V, the voltage always stopped at about 3.9 V during charging, indicating that the composite presented the intrinsic safety for the overcharge of lithium batteries. The overcharge can cause serious safety problem for the conventional Li-ion batteries. The overcharge test also showed that the batteries with sulfur composite were destroyed when the upper cut-off voltage was over 3.6 V. However, the composite presented good reversible capacity after it was deep discharged even to 0 V. It showed stable cycleability and high cycling capacity of 1000 mAh g⁻¹ when cycling between 0.1 V and 3.0 V, indicative of the different characteristic from the conventional oxide cathode materials. The prototype polymer battery with the composite cathode material presented the energy density of 246 Wh kg⁻¹ and 401 Wh L⁻¹.     

Enhanced electrochemical properties of LiFePO4/C synthesized with two kinds of carbon sources,PEG-4000 (organic) and Super p (inorganic)

Olivine structured LiFePO₄/C cathode was synthesized via a freeze-drying route and followed by microwave heating with two kinds of carbon sources: PEG-4000 (organic) and Super p (inorganic). XRD patterns indicate that the as-prepared sample has an olivine structure and carbon modification does not affect the structure of the sample. Image of SEM shows a uniform and optimized particles size, which greatly improves the electrochemical properties. TEM result reveals the amorphous carbon around the surface of the particles. At a low rate of 0.1 C, the LiFePO₄/C sample presents a high discharge capacity of 157.8 mAh g⁻¹ which is near the theoretical capacity (170 mAh g⁻¹), and it still attains to 149.1 mAh g⁻¹ after 200 cycles. It also exhibits an excellent rate capacity with high discharge capacities of 143.2 mAh g⁻¹, 137.5 mAh g⁻¹, 123.7 mAh g⁻¹ and 101.6 mAh g⁻¹ at 0.5 C, 1.0 C, 2.0 C and 5.0 C, respectively. EIS results indicate that the charge transfer resistance of LiFePO₄ decreases greatly after carbon coating.     

Porous polythiophene as a cathode material for lithium batteries with high capacity and good cycling stability

Polythiophene (PTh) has been synthesized by chemical oxidative polymerization and used as an active cathode material in lithium batteries. The lithium batteries are characterized by cyclic voltammetry (CV), galvanostatic charge/discharge cycling and electrochemical impedance spectroscopic studies (EIS). The lithium battery with the PTh cathode exhibits a discharge voltage of 3.7 V compared to Li⁺/Li and excellent electrochemical performance. PTh can provide large discharge capacities above 50 mA h g⁻¹ and good cycle stability at a high current density 900 mA g⁻¹. After 500 cycles, the discharge capacity is maintained at 50.6 mA h g⁻¹. PTh is a promising candidate for high-voltage power sources with excellent electrochemical performance.     

Polyfurfuryl alcohol derived activated carbons for high power electrical double layer capacitors

Polyfurfuryl alcohol (PFA) derived activated carbons were prepared by the acid catalysed polymerization of furfuryl alcohol, followed by potassium hydroxide activation. Activated carbons with apparent BET surface areas ranging from 1070 to 2600 m² g⁻¹, and corresponding average micropore sizes between 0.6 and 1.6 nm were obtained. The porosity of these carbons can be carefully controlled during activation and their performance as electrode materials in electric double layer capacitors (EDLCs) in a non-aqueous electrolyte (1 M Et₄NBF₄/ACN) is investigated.Carbon materials with a low average pore size (<∼0.6 nm) exhibited electrolyte accessibility issues and an associated decrease in capacitance at high charging rates. PFA carbons with larger average pore sizes exhibited greatly improved performance, with specific electrode capacitances of 150 F g⁻¹ at an operating voltage window of 0-2.5 V; which corresponds to 32 Wh kg⁻¹ and 38 kW kg⁻¹ on an active material basis. These carbons also displayed an outstanding performance at high current densities delivering up to 100 F g⁻¹ at current densities as high as 250 A g⁻¹. The exceptionally high capacitance and power of this electrode material is attributed to its good electronic conductivity and a highly effective combination of micro- and fine mesoporosity.     

The preparation of nano-sulfur/MWCNTs and its electrochemical performance

In this work, a novel nano-sulfur/MWCNTs composite with modified multi-wall carbon nano-tubes (MWCNTs) as sulfur-fixed matrix for Li/S battery is reported. Based on different solubility of sulfur in different solvents, nano-sulfur/MWCNTs composite was prepared by solvents exchange method. The composite was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The modified MWCNTs are considered that not only acts as a conducting material, but also a matrix for sulfur. The electrochemical performance of the nano-sulfur/MWCNTs composite was tested. The results indicated that nano-sulfur/MWCNTs composite had the specific capacity of 1380 mAh g⁻¹, 1326 mAh g⁻¹ and 1210 mAh g⁻¹ in the initial cycle at 100 mA g⁻¹, 200 mA g⁻¹ and 300 mAh g⁻¹ discharge rates respectively, and remained a reversible capacity of 1020 mAh g⁻¹, 870 mAh g⁻¹ and 810 mAh g⁻¹ after 30 cycles. The electrochemical performances confirm that the modified MWCNTs as sulfur-fixed matrix show better ability than any other carbon in cathode of Li/S batteries that had been reported.     

Development of screen-printed carbon electrodes modified with functionalized mesoporous silica nanoparticles: Application to voltammetric stripping determination of Pb(II) in non-pretreated natural waters

A screen-printed carbon electrode modified with functionalized mesoporous silica nanoparticles (MTTZ-MSU-2) was developed and evaluated for reliable quantification of trace Pb(II) ions by anodic stripping square wave voltammetry in non-pretreated natural waters. The optimal operating conditions were 5 min preconcentration time and 120 s electrolysis time in HCl 0.2 M. The electrode displayed excellent linear behavior in the concentration range examined (1-30 μg L⁻¹) with a limit of detection of 0.1 μg L⁻¹. The screen-printed carbon modified electrode has long service time and good single and inter-electrode reproducibility. Applicability to spiked drinking water, river water and groundwater was demonstrated without any sample pre-treatment (recoveries between 97% and 106%, RSD 4-7%). On the basis of the present data, mercury-free screen-printed electrodes modified with functionalized mesoporous silicas have the potential to become the next-generation analyzers for decentralized heavy metal monitoring in environmental samples.     

Radiological characteristics of pulverized fly ashes produced in Turkish coal-burning thermal power plants

The objective of this study is to determine radiological characteristics of pulverized fly ash (PFA) collected from the 15 coal-burning thermal power plants (TPPs) in operation by means of gamma spectrometric technique and to assess the radiological impacts from the utilization of PFA samples examined as filling and cover material in earthwork applications. Also, the annual effective doses received by workers handling PFA and members of the public living in a house near the PFA pile/landfill were estimated using methods specified in the Radiation Protection 122. The activity concentrations of ²²⁶Ra, ²³²Th and ⁴⁰K measured in PFA samples were tabulated for each TPP. The activity results show that Turkish PFA may have relatively high natural radioactivity content, depending on its origin reaching in the case of Kangal PFA 2720 Bq kg⁻¹ of ²²⁶Ra. The values of external exposure indexes (radium equivalent activity index and gamma index) calculated for PFA samples are within the recommended safety limits. As well, the highest mean total annual effective doses estimated as 7.3 × 10⁻⁵ Sv y⁻¹ for workers and 1.5 × 10⁻⁴ Sv y⁻¹ for members of the public are significantly lower than the annual limit of 1.0 × 10⁻³ Sv y⁻¹.     

TiO2 nanotube arrays annealed in CO exhibiting high performance for lithium ion intercalation

Anatase titania nanotube arrays were fabricated by means of anodization of Ti foil and annealed at 400 °C in respective CO and N₂ gases for 3 h. Electrochemical impendence spectroscopy study showed that CO annealed arrays possessed a noticeably lower charge-transfer resistance as compared with arrays annealed in N₂ gas under otherwise the same conditions. TiO₂ nanotube arrays annealed in CO possessed much improved lithium ion intercalation capacity and rate capability than N₂ annealed samples. At a high charge/discharge current density of 320 mA g⁻¹, the initial discharge capacity in CO annealed arrays was found to be as high as 223 mAh g⁻¹, 30% higher than N₂ annealed arrays, ∼164 mAh g⁻¹. After 50 charge/discharge cycles, the discharge capacity in CO annealed arrays remained at ∼179 mAh g⁻¹. The improved intercalation capacity and rate capability could be attributed to the presence of surface defects like Ti-C species and Ti³⁺ groups with oxygen vacancies, which not only improved the charge-transfer conductivity of the arrays but also possibly promoted phase transition.     

Anodic stripping voltammetric measurement of trace heavy metals at antimony film carbon paste electrode

The antimony film carbon paste electrode (SbF-CPE) was prepared in situ on the carbon paste substrate electrode as a “mercury-free” electrochemical sensor. Its aptitude for measuring some selected trace heavy metals has been demonstrated in combination with square-wave anodic stripping voltammetry in non-deaerated model solutions of 0.01 M hydrochloric acid with pH 2. Some important operational parameters, such as deposition potential, deposition time, and concentration of antimony ions were optimized, and the electroanalytical performance of the SbF-CPE was critically compared with both bismuth film carbon paste electrode (BiF-CPE) and mercury film carbon paste electrode (MF-CPE) using Cd(II) and Pb(II) as test metal ions. In comparison with BiF-CPE and MF-CPE, the SbF-CPE exhibited superior electroanalytical performance in more acidic medium (pH 2) associated with favorably low hydrogen evolution, improved stripping response for Cd(II), and moreover, stripping signals corresponding to Cd(II) and Pb(II) at the SbF-CPE were slightly narrower than those observed at bismuth and mercury counterparts. In addition, the comparison with antimony film electrode prepared at the glassy carbon substrate electrode displayed higher stripping current response recorded at the SbF-CPE. The newly developed sensor revealed highly linear behavior in the examined concentration range from 5 to 50 μg L⁻¹, with limits of detection (3σ) of 0.8 μg L⁻¹ for Cd(II), and 0.2 μg L⁻¹ for Pb(II) in connection with 120 s deposition step, offering good reproducibility of ±3.8% for Cd(II), and ±1.2% for Pb(II) (30 μg L⁻¹, n = 10). Preliminary experiments disclosed that SbF-CPE and MF-CPE exhibit comparable performance for measuring trace concentration levels of Zn(II) in acidic medium with pH 2, whereas its detection with BiF-CPE was practically impossible. Finally, the practical applicability of SbF-CPE was demonstrated via measuring Cd(II) and Pb(II) in a real water sample.     

Subaquatic oxidation of coal by water-dissolved oxygen

Subaquatic oxidation of two bituminous coals by water-dissolved oxygen was investigated using batch reactor equipped with membrane oxygen sensor. Effects of time, temperature and coal grain size were studied as basic parameters influencing the oxidation process. Obtained results showed the subaquatic coal oxidation can be considered as interaction of the first reaction order with respect to oxygen. From temperature dependence of oxidation rate, activation energies E = 72 ± 4 kJ mol⁻¹ and/or 50 ± 4 kJ mol⁻¹ were calculated. For the samples, oxygen consumption R_O2 was found to be in the range of 2 × 10⁻⁷ mol O₂ kg⁻¹ s⁻¹ to 6 × 10⁻⁷ mol O₂ kg⁻¹ s⁻¹, such values being quite comparable with R_O2 for aerial oxidation of bituminous coals.     

Electrodeposited PbO2 thin film as positive electrode in PbO2/AC hybrid capacitor

Lead dioxide (PbO₂) thin films were prepared on Ti/SnO₂ substrates by means of electrodeposition method. Galvanostatic technique was applied in PbO₂ film formation process, and the effect of deposition current on morphology and crystalline form of the PbO₂ thin films was studied by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The energy storage capacity of the prepared PbO₂ electrode was investigated by means of cyclic voltammetry (CV) and charge/discharge cycles, and a rough surface structure PbO₂ film was selected as positive electrode in the construction of PbO₂/AC hybrid capacitor in a 1.28 g cm⁻³ H₂SO₄ solution. The electrochemical performance was determined by charge/discharge tests and electrochemical impedance spectroscopy (EIS). The results showed that the PbO₂/AC hybrid capacitor exhibited high capacitance, good cycling stability and long cycle life. In the voltage range of 1.8-0.8 V during discharge process, considering the weight of all components of the hybrid capacitor, including the two electrodes, current collectors, H₂SO₄ electrolyte and separator, the specific energy and power of the device were 11.7 Wh kg⁻¹ and 22 W kg⁻¹ at 0.75 mA cm⁻², and 7.8 Wh kg⁻¹ and 258 W kg⁻¹ at 10 mA cm⁻² discharge currents, respectively. The capacity retains 83% of its initial value after 3000 deep cycles at the 4 C rate of charge/discharge.     

Removal of Remazol Brilliant Blue R dye from aqueous solutions by adsorption onto immobilized Scenedesmus quadricauda: Equilibrium and kinetic modeling studies

The green algae Scenedesmus quadricauda was immobilized in alginate gel beads. The immobilized active (IASq) and heat inactivated S.quadricauda (IHISq) were used for the removal of Remazol Brilliant Blue R (CI 61200, Reactive Blue 19, RBBR) from aqueous solutions in the concentration range 25-200 mg L^− 1. At 150 mg L^− 1 initial dye concentration the IASq and IHISq exhibited the highest dye uptake capacity at 30 °C, at the initial pH value of 2.0. At the same initial dye concentration in the batch system the adsorption capacity was determined for IASq as 44.2; 44.9 and 45.7 mg g^− 1 in 30, 60 and 300 min, respectively. After 300 min the adsorption capacity hardly changed during the adsorption time. The IHISq of adsorption capacity was observed as 47.6; 47.8 and 48.3 mg g^− 1 in 30, 60 and 300 min, respectively. After 300 min the adsorption capacity was not changed for 24 h. The Langmuir, Freundlich, Temkin, Dubinin-Radushkevich and Flory-Huggins isotherm models were used to fit the equilibrium biosorption data. The Langmuir, Freundlich and Dubinin-Radushkevich equations have better coefficients than Temkin and Flory-Huggins equation describing the RBBR dye adsorption onto IASq and IHISq. The monomolecular biosorption capacity of the biomass was found to be 68 and 95.2 mg g^− 1 for IASq and IHISq, respectively. From the Dubinin-Radushkevich model, the mean free energy was calculated as 6.42-7.15 kJ mol^− 1 for IASq and IHISq, indicating that the biosorption of dye was taken place in physical adsorption reactions. The experimental data were also tested in terms of kinetic characteristics and it was determined that the biosorption process of dye was well explained with pseudo-second-order kinetics.