Metal Organic Frameworks (MOFs) represent a promising class of metallic catalysts for reduction of nitrogen-containing contaminants (NCCs), such as 4-nitrophenol (4-NP). Nevertheless, most researches involving MOFs for 4-NP reduction employ noble metals in the form of fine powders, making these powdered noble metal-based MOFs impractical and inconvenient for realistic applications. Thus, it would be critical to develop non-noble-metal MOFs which can be incorporated into macroscale and porous supports for convenient applications. Herein, the present study proposes to develop a composite material which combines advantageous features of macroscale/porous supports, and nanoscale functionality of MOFs. In particular, copper foam (CF) is selected as a macroscale porous medium, which is covered by nanoflower-structured CoO to increase surfaces for growing a cobaltic MOF, ZIF-67. The resultant composite comprises of CF covered by CoO nanoflowers decorated with ZIF-67 to form a hierarchical 3D-structured catalyst, enabling this ZIF-67@Cu foam (ZIF@CF) a promising catalyst for reducing 4-NP, and other NCCs. Thus, ZIF@CF can readily reduce 4-NP to 4-AP with a significantly lower Ea of 20 kJ/mol than reported values. ZIF@CF could be reused over 10 cycles and remain highly effective for 4-NP reduction. ZIF@CF also efficiently reduces other NCCs, such as 2-nitrophenol, 3-nitrophenol, methylene blue, and methyl orange. ZIF@CF can be adopted as catalytic filters to enable filtration-type reduction of NCCs by passing NCC solutions through ZIF@CF to promptly and conveniently reduce NCCs. The versatile and advantageous catalytic activity of ZIF@CF validates that ZIF@CF is a promising and practical heterogeneous catalyst for reductive treatments of NCCs.
A flow-through optical fibre chemical sensor for the determination of Co(II) at trace level using immobilised 2-(4-pyridylazo)resorcinol (PAR) as the reagent phase is proposed. PAR is physically adsorbed onto XAD-7. This method provided a great sensitivity and simplicity with wide linear response range from 1x10(-2) to 1x10(3)ppm and detection limit of 20ppb. This method also showed a reproducible result with relative standard deviation (R.S.D.) of 1.78% and response time of approximately 5min. The response towards Co(II) was also reversible using acidified KCl as the regenerating solution. Interference studies showed that Cr(III) significantly interfered during the determination. Excellent agreement with reference to inductively coupled plasma optical emission spectroscopy (ICPOES) method was achieved when the developed sensor was applied for determination of Co(II) in aqueous samples.
Hyperaccumulation is generally highly specific for a single element, for example nickel (Ni). The recently-discovered hyperaccumulator Glochidion cf. sericeum (Phyllanthaceae) from Malaysia is unusual in that it simultaneously accumulates nickel and cobalt (Co) with up to 1500 μg g-1 foliar of both elements. We set out to determine whether distribution and associated ligands for Ni and Co complexation differ in this species. We postulated that Co hyperaccumulation coincides with Ni hyperaccumulation operating on similar physiological pathways. However, the ostensibly lower tolerance for Co at the cellular level results in the exudation of Co on the leaf surface in the form of lesions. The formation of such lesions is akin to phytotoxicity responses described for manganese (Mn). Hence, in contrast to Ni, which is stored principally inside the foliar epidermal cells, the accumulation response to Co consists of an extracellular mechanism. The chemical speciation of Ni and Co, in terms of the coordinating ligands involved and principal oxidation state, is similar and associated with carboxylic acids (citrate for Ni and tartrate or malate for Co) and the hydrated metal ion. Some oxidation to Co3+, presumably on the surface of leaves after exudation, was observed.
For x- and gamma- irradiations delivering entrance doses from 2- up to 1000 Gy to commercial 1.0 mm thick borosilicate glass microscope slides, study has been made of their thermoluminescence yield. With an effective atomic number of 10.6 (approximating bone equivalence), photon energy dependency is apparent in the low x-ray energy range, with interplay between the photoelectric effect and attenuation. As an example, over the examined dose range, at 120 kVp the photon sensitivity has been found to be some 5× that of 60Co gamma irradiations, also with repeatability to within ~1%. The glow-curves, taking the form of a single prominent broad peak, have been deconvolved yielding at best fit a total of five peaks, the associated activation energies and frequency factors also being obtained. The results indicate borosilicate glass slides to offer promising performance as a low-cost passive radiation dosimeter, with utility for both radiotherapy and industrial applications.
Since 5-sulfosalicylic acid (SFA) has been increasingly released to the environment, SO4--based oxidation processes using Oxone have been considered as useful methods to eliminate SFA. As Co3O4 has been a promising material for OX activation, the four 3D Co3O4 catalysts with distinct morphologies, including Co3O4-C (with cubes), Co3O4-P (with plates), Co3O4-N (with needles) and Co3O4-F (with floral structures), are fabricated for activating OX to degrade SFA. In particular, Co3O4-F not only exhibits the highest surface area but also possesses the abundant Co2+ and more reactive surface, making Co3O4-F the most advantageous 3D Co3O4 catalyst for OX activation to degrade SFA. The mechanism of SFA by this 3D Co3O4/OX is also investigated and the corresponding SFA degradation pathway has been elucidated. The catalytic activities of Co3O4 catalysts can be correlated to physical and chemical properties which were associated with particular morphologies to provide insights into design of 3D Co3O4-based catalysts for OX-based technology to degrade emerging contaminants, such as SFA.
The upgrade recycling of cast-iron scrap chips towards β-FeSi₂ thermoelectric materials is proposed as an eco-friendly and cost-effective production process. By using scrap waste from the machining process of cast-iron components, the material cost to fabricate β-FeSi₂ is reduced and the industrial waste is recycled. In this study, β-FeSi₂ specimens obtained from cast iron scrap chips were prepared both in the undoped form and doped with Al and Co elements. The maximum figure of merit (ZT) indicated a thermoelectric performance of approximately 70% in p-type samples and nearly 90% in n-type samples compared to β-FeSi₂ prepared from pure Fe and other published studies. The use of cast iron scrap chips to produce β-FeSi₂ shows promise as an eco-friendly and cost-effective production process for thermoelectric materials.
This study deals with the development of alumina-supported cobalt (Co/Al2O3) catalysts with remarkable performance in dry reforming of methane (DRM) and least carbon deposition. The influence of Co content, calcination, and reduction temperatures on the physicochemical attributes and catalyst activity of the developed catalysts was extensively studied. For this purpose, several characterization techniques including ICP-MS, H2 pulse chemisorption, HRTEM, H2-TPR, N2 adsorption desorption, and TGA were implemented, and the properties of the developed catalysts were carefully analyzed. The impact of reaction temperature, feed gas ratio, and gas hourly space velocity (GHSV) on the reactants conversion and products yield was investigated. Use of 10%Co/Al2O3 catalyst, calcined at 500°C and reduced under H2 at 900°C in DRM reaction at 850°C, CH4/CO2 ratio of 1:1, and GHSV of 6 L.g-1.h-1 resulted in a remarkable catalytic activity and sustainable performance in long-term operation where great CO2 (96%) and CH4 (98%) conversions and high H2 (83%) and CO (91%) yields with a negligible carbon deposition (3 wt%) were attained in 100-h on-stream reaction. The good performance of the developed catalyst in DRM reaction was attributed to the small Co particle size with well-dispersion on the alumina support which increased the catalytic activity and also the strong metal-support interaction which inhibited any serious metal sintering and enhanced the catalyst stability.
The present study examines the synthesis of Co3O4 ultra-nanosheets (Co3O4 UNSs) and Co3O4 ultra-nanosheet-Ni(OH)2 (Co3O4 UNS-Ni(OH)2) via solvothermal process and their application as non-enzymatic electrochemical sensors for glucose detection. X-ray diffraction and transmission electron microscopy results confirmed the Co3O4 UNS deposition on Ni(OH)2 surface. The presence of Co3O4 UNSs on Ni (OH) 2 surface improved the sensitivity of glucose detection, from the increase of glucose oxidation peak current at the Co3O4 UNS-Ni(OH)2/glassy carbon electrode (current density: 2000μA·cm(-2)), compared to the Co3O4 UNSs. These results confirmed that Ni(OH)2 on glassy carbon electrode is a sensitive material for glucose detection, moreover the Co3O4 UNSs can increase the interaction and detection of glucose due to their high surface area. The estimated limit of detection (S/N=3) and limit of quantification (S/N=10) of the linear segment (5-40μM) are 1.08μM and 3.60μM respectively. The reproducibility experiments confirmed the feasibility of Co3O4 UNS-Ni(OH)2 for the quantitative detection of certain concentration ranges of glucose.
The [Co(Me(2)Salen)(PBu(3))(OH(2))]BF4 and [Co(Me(2)Salen)(PPh(3))(Solv)]BF(4), complexes were synthesized and characterized by FT-IR, UV-Vis, (1)H NMR spectroscopy and elemental analysis techniques. The coordination geometry of [Co(Me(2)Salen)(PPh(3))(H(2)O)]BF(4) was determined by X-ray crystallography. It has been found that the complex is containing [Co(Me(2)Salen)(PPh(3))(H(2)O)]BF(4) and [Co(Me(2)Salen)(PPh(3))(EtOH)]BF(4) hexacoordinate species in the solid state. Cobalt atom exhibits a distorted octahedral geometry and the Me(2)Salen ligand has the N2O2 coordinated environment in the equatorial plane. The [Co(Me(2)Salen)(PPh(3))(H(2)O)]BF(4) complex shows a dimeric structure via hydrogen bonding between the phenolate oxygen and hydrogens of coordinated H2O molecule. These complexes were incorporated into Montmorillonite-K10 nanoclay. The modified clays were identified by FT-IR, XRD, EDX, TGA/DTA, SEM and TEM techniques. According to the XRD results of the new nanohybrid materials, the Schiff base complexes are intercalated in the interlayer spaces of the clay. SEM and TEM micrographs show that the resulting hybrid nanomaterials have layer structures. Also, TGA/DTG results show that the intercalation reaction was taken place successfully.
A series of experiments were carried out to determine the best medium for the recovery of cobalt by means of an electrogenerative system. Use of the electrogenerative system with a chloride medium had shown promising performance with the highest free energy of -389.8 kJ mol(-1) compared to that with sulphate and nitrate media. Subsequently, the influence of catholyte concentrations on cobalt recovery using the electrogenerative process was carried out by varying the initial cobalt concentration and sodium chloride concentration. The results showed that almost 100% recovery was attained within 1-4 h of the recovery process. Influence of pH was investigated where the electrogenerative system performed best between pH 5.0 and 7.0. Maximum cell performance of 83% with 99% cobalt removal was obtained at 90 min when 100 mg L(-1) of Co(2+) in 0.5 M NaCl was taken as catholyte solution. The values of ΔH(o) and ΔS(o) of the process were evaluated as 33.41 kJ mol(-1) and 0.13 kJ mol(-1), respectively.
The potential of Mg(x)Co(2-)(x)O(2) as heterogeneous reusable catalyst in transesterification of palm oil to methyl ester was investigated. The catalyst was prepared via co-precipitation of the metal hydroxides at different Mg-Co ratios. Mg(1.7)Co(0.3)O(2) catalyst was more active than Mg(0.3)Co(1.7)O(2) in the transesterification of palm oil with methanol. The catalysts calcined at temperature 300 °C for 4 h resulted in highly active oxides and the highest transesterification of 90% was achieved at methanol/oil molar ratio of 9:1, catalyst loading of 5.00 wt.%, reaction temperature of 150 °C and reaction time of 2 h. The catalyst could easily be removed from reaction mixture, but showed 50% decrease in activity when reused due to leaching of active sites.
Photopyroelectric (PPE) spectroscopy is a nondestructive tool that is used to study the optical properties of the ceramics (ZnO + 0.4MnO(2) + 0.4Co(3)O(4) + xV(2)O(5)), x = 0-1 mol%. Wavelength of incident light, modulated at 10 Hz, was in the range of 300-800 nm. PPE spectrum with reference to the doping level and sintering temperature is discussed. Optical energy band-gap (E(g)) was 2.11 eV for 0.3 mol% V(2)O(5) at a sintering temperature of 1025 °C as determined from the plot (ρhυ)(2)versushυ. With a further increase in V(2)O(5), the value of E(g) was found to be 2.59 eV. Steepness factor 'σ(A)' and 'σ(B)', which characterize the slope of exponential optical absorption, is discussed with reference to the variation of E(g). XRD, SEM and EDAX are also used for characterization of the ceramic. For this ceramic, the maximum relative density and grain size was observed to be 91.8% and 9.5 μm, respectively.
As cobalt (Co) represents an effective transition metal for activating Oxone to degrade contaminants, tricobalt tetraoxide (Co3O4) is extensively employed as a heterogeneous phase of Co for Oxone activation. Since Co3O4 can be manipulated to exhibit various shapes, 2-dimensional plate-like morphology of Co3O4 can offer large contact surfaces. If the large plate-like surfaces can be even porous, forming porous nanoplate Co3O4 (PNC), such a PNC should be a promising catalyst for Oxone activation. Therefore, a facile but straightforward method is proposed to prepare such a PNC for activating Oxone to degrade pollutants. In particular, a cobaltic coordination polymer with a morphology of hexagonal nanoplate, which is synthesized through coordination between Co2+ and thiocyanuric acid (TCA), is adopted as a precursor. Through calcination, CoTCA could be transformed into hexagonal nanoplate-like Co3O4 with pores to become PNC. This PNC also shows different characteristics from the commercial Co3O4 nanoparticle (NP) in terms of surficial reactivity and textural properties. Thus, PNC exhibits a much higher catalytic activity than the commercial Co3O4 NP towards activation of Oxone to degrade a model contaminant, salicylic acid (SA). Specifically, SA was 100% degraded by PNC activating Oxone within 120 min, and the Ea of SA degradation by PNC-activated Oxone is 70.2 kJ/mol. PNC can also remain stable and effective for SA degradation even in the presence of other anions, and PNC could be reused over multiple cycles without significant loss of catalytic activity. These features validate that PNC is a promising and useful Co-based catalyst for Oxone activation.
This study investigates the characteristics and application of the optically-stimulated luminescence dosimeter (OSLD) in cobalt-60 high dose rate (HDR) brachytherapy, and compares the results with the dosage produced by the treatment planning system (TPS). The OSLD characteristics comprised linearity, reproducibility, angular dependence, depth dependence, signal depletion, bleaching rate and cumulative dose measurement. A phantom verification exercise was also conducted using the Farmer ionisation chamber and in vivo diodes. The OSLD signal indicated a supralinear response (R2 = 0.9998). It exhibited a depth-independent trend after a steep dose gradient region. The signal depletion per readout was negligible (0.02%), with expected deviation for angular dependence due to off-axis sensitive volume, ranging from 1 to 16%. The residual signal of the OSLDs after 1 day bleached was within 1.5%. The accumulated and bleached OSLD signals had a standard deviation of ± 0.78 and ± 0.18 Gy, respectively. The TPS was found to underestimate the measured doses with deviations of 5% in OSLD, 17% in the Farmer ionisation chamber, and 7 and 8% for bladder and rectal diode probes. Discrepancies can be due to the positional uncertainty in the high-dose gradient. This demonstrates a slight displacement of the organ at risk near the steep dose gradient region will result in a large dose uncertainty. This justifies the importance of in vivo measurements in cobalt-60 HDR brachytherapy.
The aim of this study was to determine the suitability of tannin-added Rhizophora spp. particleboards as phantom materials in the application of low- and high-energy photons. The tannin-added Rhizophora spp. particleboards and density plug phantoms were created with a target density of 1.0 g/cm3. The elemental composition and effective atomic number of the particleboards were measured using energy dispersive X-ray analysis. The mass attenuation coefficient of the particleboards for low-energy photons were measured using the attenuation of X-ray fluorescence. The mass attenuation coefficients of high-energy photons were measured using the attenuation of 137Cs and 60Co gamma energies. The results were compared to the calculated value of water using XCOM calculations. The results showed that the effective atomic number and mass attenuation coefficients of tannin-added Rhizophora spp. particleboards were similar to those of water, indicating the suitability of tannin-added Rhizophora spp. particleboards as phantom materials for low- and high-energy photons.
In vivo dosimetry in high dose-rate (HDR) intracavitary brachytherapy (ICBT) is important for assessing the true dose received by surrounding organs at risk during treatment. It also serves as part of the treatment delivery quality assurance and verification program with the use of a suitable dosimeter. Such a dosimeter should be characterized under brachytherapy conditions before clinical application to ensure the accuracy of in vivo measurement. In this study, a MOSFET-based detector, MOSkin, was calibrated and characterized under HDR Cobalt-60 (Co-60) brachytherapy source. MOSkin possessed the major advantages of having small physical and dosimetric sizes of 4.8 × 10-6 mm3 with the ability to provide real-time measurements. Using solid water and polymethyl methacrylate (PMMA) phantom, the detectors' reproducibility, linearity, angular and distance dependency was tested for its suitability as an in vivo detector. Correction factors to account for differences in depth measurements were determined. The MOSkin detector showed a reliable response when tested under Co-60 brachytherapy range of doses with an excellent linearity of R2 = 0.9997 and acceptable reproducibility. A phantom verification study was also conducted to verify the differences between MOSkin responses and treatment planning (TPS) calculated doses. By taking into account several correction factors, deviations ranging between 0.01 and 0.4 Gy were found between MOSkin measured and TPS doses at measurement distance of 20-55 mm. The use of MOSkin as the dosimeter of choice for in vivo dosimetry under Co-60 brachytherapy condition is feasible.
This study aims to investigate the potential of porous Co3O4 nanorods as the cathode catalyst for oxygen reduction reaction (ORR) in aqueous air cathode microbial fuel cells (MFCs). The porous Co3O4 nanorods were synthesized by a facile and cost-effective hydrothermal method. Three different concentrations (0.5mg/cm(2), 1mg/cm(2), and 2mg/cm(2)) of Co3O4 nanorods coated on graphite electrodes were used to test its performance in MFCs. The results showed that the addition of porous Co3O4 nanorods enhanced the electrocatalytic activity and ORR kinetics significantly and the overall resistance of the system was greatly reduced. Moreover, the MFC with a higher concentration of the catalyst achieved a maximum power density of 503±16mW/m(2), which was approximately five times higher than the bare graphite electrode. The improved catalytic activity of the cathodes could be due to the porous properties of Co3O4 nanorods that provided the higher number of active sites for oxygen.
The emergence of unintentional poisoning and uncontrolled vector diseases have contributed to sensor technologies development, leading to the more effective detection of diseases. In this study, we present the combination of graphene-based material with surface plasmon resonance technique. Two different graphene-based material sensor chips were prepared for rapid and quantitative detection of dengue virus (DENV) and cobalt ion (Co2+) as an example of typical metal ions. As the fundamental concept of surface plasmon resonance (SPR) sensor that relies on the refractive index of the sensor chip surface, this research focused on the SPR signal when the DENV and Co2+ interact with the graphene-based material sensor chip. The results demonstrated that the proposed sensor-based graphene layer was able to detect DENV and Co2+ as low as 0.1 pM and 0.1 ppm respectively. Further details in the detection and quantification of analyte were also discussed in terms of sensitivity, affinity, and selectivity of the sensor.