Search results for: hydrothermal carbonization

Authors: Melanie Francois, Gilles Caboche, Frederic Demoisson, Francois Maeght, Maria Paola Carpanese, Lionel Combemale, Pascal Briois

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Finding new clean, and efficient way for energy production is one of the actual global challenges. Advances in fuel cell technology have shown that, for few years, Protonic Ceramic Fuel Cell (PCFC) has attracted much attention in the field of new hydrogen energy thanks to their lower working temperature, possible higher efficiency, and better durability than classical SOFC. On the contrary of SOFC, where O²⁻ oxygen ion is the charge carrier, PCFC works with H⁺ proton as a charge carrier. Consequently, the lower activation energy of proton diffusion compared to the one of oxygen ion explains those benefits and allows PCFC to work in the 400-600°C temperature range. Doped-BaCeO₃ is currently the most chosen material for this application because of its high protonic conductivity; for example, BaCe₀.₉Y₀.₁O₃ δ exhibits a total conductivity of 1.5×10⁻² S.cm⁻¹ at 600°C in wet H₂. However, BaCeO₃ based perovskite has low stability in H₂O and/or CO₂ containing atmosphere, which limits their practical application. On the contrary, BaZrO₃ based perovskite exhibits good chemical stability but lower total conductivity than BaCeO₃ due to its larger grain boundary resistance. By substituting zirconium with 20% of yttrium, it is possible to achieve a total conductivity of 2.5×10⁻² S.cm⁻¹ at 600°C in wet H₂. However, the high refractory property of BaZr₀.₈Y₀.₂O₃-δ (noted BZY20) causes problems to obtain a dense membrane with large grains. Thereby, using a synthesis process that gives fine particles could allow better sinterability and thus decrease the number of grain boundaries leading to a higher total conductivity. In this work, BaZr₀.₈Y₀.₂O₃-δ have been synthesized by classical batch hydrothermal device and by a continuous hydrothermal device developed at ICB laboratory. The two variants of this process are able to work in supercritical conditions, leading to the formation of nanoparticles, which could be sintered at a lower temperature. The as-synthesized powder exhibits the right composition for the perovskite phase, impurities such as BaCO₃ and YO-OH were detected at very low concentration. Microstructural investigation and densification rate measurement showed that the addition of 1 wt% of ZnO as sintering aid and a sintering at 1550°C for 5 hours give high densified electrolyte material. Furthermore, it is necessary to heat the synthesized powder prior to the sintering to prevent the formation of secondary phases. It is assumed that this thermal treatment homogenizes the crystal structure of the powder and reduces the number of defects into the bulk grains. Electrochemical impedance spectroscopy investigations in various atmospheres and a large range of temperature (200-700°C) were then performed on sintered samples, and the protonic conductivity of BZY20 has been highlighted. Further experiments on half-cell, NiO-BZY20 as anode and BZY20 as electrolyte, are in progress.

Keywords: hydrothermal synthesis, impedance measurement, Y-doped BaZrO₃, proton conductor

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Authors: Zehui Du, Chaiwat Prapainainar, Paisan Kongkachuichay, Paweena Prapainainar

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The aim of this work was to obtain small crystalline size and high crystallinity of mordenites and analcimes, by modifying the aging time, agitation, water content, crystallization temperature and crystallization time. Two different hydrothermal methods were studied. Both methods used Na2SiO3 as the silica source, NaAlO2 as the aluminum source, and NaOH as the alkali source. The first method used HMI as the template while the second method did not use the template. Mordenite crystals with spherical shape and bimodal in size of about 1 and 5 µm were obtained from the first method using conditions of 24 hr aging time, 170°C and 24 hr crystallization. Modernites with high crystallinity were formed using agitation system in the crystallization process. It was also found that the aging time of 2 hr and 24 hr did not much affect the formation of mordenite crystals. Analcime crystals were formed in spherical shape and facet on surface with the size between 13-15 µm by the second method using the conditions of 30 minutes aging time, 170°C and 24 hr crystallization without calcination. By increasing water content, the crystallization process was slowed down and resulted in smaller analcime crystals. Larger size of analcime crystals were observed when the samples were calcined at 300°C and 580°C. Higher calcination temperature led to higher crystal growth and resulted in larger crystal size. Finally, mordenite and analcime was used as fillers in zeolite/Nafion composite membrane to solve the fuel cross over problem in direct alcohol fuel cell.

Keywords: analcime, hydrothermal synthesis, mordenite, zeolite

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Authors: Manish Saha, Manish Kumar Niranjan, Saket Asthana

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The K₀.₅Na₀.₅NbO₃ (KNN) system has emerged as one of the most promising lead-free piezoelectric over the years. In this work, we perform a comprehensive investigation of electronic structure, lattice dynamics and dielectric/ferroelectric properties of the room temperature phase of KNN by combining ab-initio DFT-based theoretical analysis and experimental characterization. We assign the symmetry labels to KNN vibrational modes and obtain ab-initio polarized Raman spectra, Infrared (IR) reflectivity, Born-effective charge tensors, oscillator strengths etc. The computed Raman spectrum is found to agree well with the experimental spectrum. In particular, the results suggest that the mode in the range ~840-870 cm-¹ reported in the experimental studies is longitudinal optical (LO) with A_1 symmetry. The Raman mode intensities are calculated for different light polarization set-ups, which suggests the observation of different symmetry modes in different polarization set-ups. The electronic structure of KNN is investigated, and an optical absorption spectrum is obtained. Further, the performances of DFT semi-local, metal-GGA and hybrid exchange-correlations (XC) functionals, in the estimation of KNN band gaps are investigated. The KNN bandgap computed using GGA-1/2 and HSE06 hybrid functional schemes are found to be in excellant agreement with the experimental value. The COHP, electron localization function and Bader charge analysis is also performed to deduce the nature of chemical bonding in the KNN. The solid-state reaction and hydrothermal methods are used to prepare the KNN ceramics, and the effects of grain size on the physical characteristics these ceramics are examined. A comprehensive study on the impact of different synthesis techniques on the structural, electrical, and photocatalytic properties of ferroelectric ceramics KNN. The KNN-S prepared by solid-state method have significantly larger grain size as compared to that for KNN-H prepared by hydrothermal method. Furthermore, the KNN-S is found to exhibit higher dielectric, piezoelectric and ferroelectric properties as compared to KNN-H. On the other hand, the increased photocatalytic activity is observed in KNN-H as compared to KNN-S. As compared to the hydrothermal synthesis, the solid-state synthesis causes an increase in the relative dielectric permittivity (ε^') from 2394 to 3286, remnant polarization (P_r) from 15.38 to 20.41 μC/cm^², planer electromechanical coupling factor (k_p) from 0.19 to 0.28 and piezoelectric coefficient (d_33) from 88 to 125 pC/N. The KNN-S ceramics are also found to have a lower leakage current density, and higher grain resistance than KNN-H ceramic. The enhanced photocatalytic activity of KNN-H is attributed to relatively smaller particle sizes. The KNN-S and KNN-H samples are found to have degradation efficiencies of RhB solution of 20% and 65%, respectively. The experimental study highlights the importance of synthesis methods and how these can be exploited to tailor the dielectric, piezoelectric and photocatalytic properties of KNN. Overall, our study provides several bench-mark important results on KNN that have not been reported so far.

Keywords: lead-free piezoelectric, Raman intensity spectrum, electronic structure, first-principles calculations, solid state synthesis, photocatalysis, hydrothermal synthesis

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Authors: Nabat Gojaeva, Mikayil Naghiyev, Sultan Jafarov, Gular Mikayilova

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Chovdar ore area is located in the contact of Dashkesan caldera and Shamkir horst-graben uplift, which comprises the central part of Lok-Karabakh Island arcs of South Caucasus metallogenic province in terms of regional tectonics. One of the main structural features of formation of the Mereh and Aghyokhush group of low sulfidation epithermal gold deposits, locating in the north peripheric part of the ore area, is involving the crossing areas of ore-hosting and ore-forming Pan-Caucasian-direction structurally-compound faults with the meridional, rhombically shaped faults. In addition, another significant feature is the temporally two- or three-stage ore formation. In the first stage -an early phase of Upper Bathonian age, sulfides are the dominant minerals, in the second stage- late ‘productive’ phase of Upper Bathonian age, mainly gold mineralization is formed. Also, in the Upper Jurassic – Lower Cretaceous ages, rarely-encountered Cu-polymetallic ore formations are documented. Finally, in the last stage, the re-dislocation of ore-formation is foreseen in the previously-formed mineralization areas. The faults in the strike and dip directions formed shearing, brecciation, sulfide mineralization aureoles, and hydrothermal alteration zones in the wall rocks along with the local depression blocks. The geological-structural analysis of the area shows that multiple and various morphogenetic volcano-tectonically fault systems have developed in the area. These fault systems have played a trap role for ore-formation in the intersected parts of faults mentioned above. Thus, in the referred parts, mostly predominance of felsic volcanism and metasomatic alteration (silicification, argillitic, etc.) of wall rocks, as well as the products of this volcanism, account for the inclusion of hydrothermal ore-forming fluids along these faults. It is possible to determine temporally and lithological-structural connection between the ore-formation along with local depression blocks and faults as borders for products of felsic volcanism of Upper Cretaceous-Lesser Jurassic ages, in the results of the replacement of hydrothermal alteration zones with relatively low-temperature metasomatic alterations while moving from the felsic parts to the margins, and due to being non-ore bearing intermediate and intermediate-felsic magmatic facies.

Keywords: Aghyokhush, fault, gold deposit, Mereh

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Authors: Getenet Aseged Zeleke

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The aim of this project was to study the synthesis of activated carbon from low-cost animal beef and the characterization of the product obtained. The bone was carbonized in an inert atmosphere at three different temperatures (500°C, 700oC and 900°C) in an electric furnace, followed by activation with hydrochloric acid. The activated animal bone charcoals obtained were characterized by using scanning electron microscopy (SEM)to observe the effect of activation compared to the unactivated bone charcoal. The following parameters were also determined: ash content, moisture content, volatile content, fixed carbon, pH, pore volume and bulk (apparent) density. The characterization result showed that the activated bone charcoal has good properties and is compared favorably with other reference activated carbons.

Keywords: bones, carbonization, activation, characterization, activated carbon

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Authors: Jae-Yong Sim, Jung-Hun Kwon, Ji-Sung Park, Kee-Joe Lim

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One of the latest trends for insulation systems to improve the insulation performance is the use of eco-friendly hybrid insulation using compressed dry-air. Despite the excellent insulation performance of sulphurhexafluoride (SF6) gas, its use has been restricted due to the problems with significant global warming potential (GWP). Accordingly, lightning impulse performance of the hybrid insulation system covered with an aluminum trihydrate/silicone rubber (ATH/SIR) nanocomposite was examined in air at atmospheric pressure and in compressed air at pressures between 0.2 and 0.6 MPa. In the experiments, the most common breakdown path took place along the surface of the covered rod. The insulation reliability after several discharges should be guaranteed in hybrid insulation. On the other hand, the surface of the covered rod was carbonized after several discharges. Therefore, nanoscale ATH can be used as a reinforcement of covered dielectrics to inhibit carbonization on the surface of a covered rod. The results were analyzed in terms of the surface resistivity of the cover dielectrics.

Keywords: nanocomposite, hybrid insulation, ATH, dry-air

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Authors: Viney Dixit, Rohit R. Shahi, Ashish Bhatnagar, P. Jain, T. P. Yadav, O. N. Srivastava

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Carbons are being widely investigated as hydrogen storage material owing to their light weight, fast hydrogen absorption kinetics and low cost. However, these materials suffer from low hydrogen storage capacity at room temperature. The aim of the present study is to synthesize carbon based material which shows moderate hydrogen storage at room temperature. For this purpose, hydrogenation characteristics of natural precursor coconut kernel is studied in this work. The hydrogen storage measurement reveals that the as-synthesized materials have good hydrogen adsorption and desorption capacity with fast kinetics. The synthesized material absorbs 8 wt.% of hydrogen at liquid nitrogen temperature and 2.3 wt.% at room temperature. This could be due to the presence of certain elements (KCl, Mg, Ca) which are confirmed by TEM.

Keywords: coconut kernel, carbonization, hydrogenation, KCl, Mg, Ca

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Authors: Atef Y. Shenouda, Anton A. Momchilov

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Graphene and CdO with different stoichiometric ratios of Cd(CH₃COO)₂ and graphene samples were prepared by hydrothermal reaction. The crystalline phases of pure CdO and 3CdO:1graphene were identified by X-ray diffraction (XRD). The particle morphology was studied with SEM. Furthermore, impedance measurements were applied. Galvanostatic measurements for the cells were carried out using potential limits between 0.01 and 3 V vs. Li/Li⁺. The current cycling intensity was 10⁻⁴ A. The specific discharge capacity of 3CdO-1G cell was about 450 Ah.Kg⁻¹ up to more than 100 cycles.

Keywords: CdO, graphene, negative electrode, lithium battery

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Authors: Muhammad A. Nadeem, Shaheed Ullah

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The article reports the synthesis of Cr2O3/C nanocomposites obtained by the direct carbonization of PFA/MIL-101(Cr) bulk composite. The nanocomposites were characterized by various instrumental techniques like powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and the surface characterized were investigated via N2 adsorption/desorption analysis. TEM and SAED analysis shows that turbostatic graphitic carbon was obtained with high crystallinity. The nanocomposites were tested for electrochemical supercapacitor and the faradic and non-Faradic processes were checked through cyclic voltammetry (CV). The maximum specific capacitance calculated for Cr2O3/C 900 sample from CV measurement is 301 F g-1 at 2 mV s-1 due to its maximum charge storing capacity as confirm by frequency response analysis.

Keywords: nanocomposites, transmission electron microscopy, non-faradic process

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Authors: Muhammed Ertugrul Celoglu, Beyza Furtana, Mehmet Yilmaz, Baha Vural Kok

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Biomass, which is considered to be one of the largest renewable energy sources in the world, has a potential to be utilized as a bitumen additive after it is processed by a wide variety of thermochemical methods. Furthermore, biomasses are renewable in short amounts of time, and they possess a hydrocarbon structure. These characteristics of biomass promote their usability as additives. One of the most common ways to create materials with significant economic values from biomasses is the processes of pyrolysis. Pyrolysis is defined as the process of an organic matter’s thermochemical degradation (carbonization) at a high temperature and in an anaerobic environment. The resultant liquid substance at the end of the pyrolysis is defined as bio-oil, whereas the resultant solid substance is defined as biochar. Olive pomace is the resultant mildly oily pulp with seeds after olive is pressed and its oil is extracted. It is a significant source of biomass as the waste of olive oil factories. Because olive pomace is waste material, it could create problems just as other waste unless there are appropriate and acceptable areas of utilization. The waste material, which is generated in large amounts, is generally used as fuel and fertilizer. Generally, additive materials are used in order to improve the properties of bituminous binders, and these are usually expensive materials, which are produced chemically. The aim of this study is to investigate the usability of biochars obtained after subjecting olive pomace and smashed olive seeds, which are considered as waste materials, to pyrolysis as additives in bitumen modification. In this way, various ways of use will be provided for waste material, providing both economic and environmental benefits. In this study, olive pomace and smashed olive seeds were used as sources of biomass. Initially, both materials were ground and processed through a No.50 sieve. Both of the sieved materials were subjected to pyrolysis (carbonization) at 400 ℃. Following the process of pyrolysis, bio-oil and biochar were obtained. The obtained biochars were added to B160/220 grade pure bitumen at 10% and 15% rates and modified bitumens were obtained by mixing them in high shear mixtures at 180 ℃ for 1 hour at 2000 rpm. Pure bitumen and four different types of bitumen obtained as a result of the modifications were tested with penetration, softening point, rotational viscometer, and dynamic shear rheometer, evaluating the effects of additives and the ratios of additives. According to the test results obtained, both biochar modifications at both ratios provided improvements in the performance of pure bitumen. In the comparison of the test results of the binders modified with the biochars of olive pomace and smashed olive seed, it was revealed that there was no notable difference in their performances.

Keywords: bituminous binders, biochar, biomass, olive pomace, pomace, pyrolysis

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Authors: Marcin Zielinski, Marcin Debowski, Paulina Rusanowska, Magda Dudek

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As a result of sonification, the destruction of complex biomass structures results in an increase in the biogas yield from the conditioned material. First, the amount of organic matter released into the solution due to disintegration was determined. This parameter was determined by changes in the carbon content in liquid phase of the conditioned substrate. The amount of carbon in the liquid phase increased with the prolongation of the sonication time to 16 min. Further increase in the duration of sonication did not cause a statistically significant increase in the amount of organic carbon in the liquid phase. The disintegrated material was then used for respirometric measurements for determination of the impact of the conditioning process used on methane fermentation effectiveness. The relationship between the amount of energy introduced into the lignocellulosic substrate and the amount of biogas produced has been demonstrated. Statistically significant increase in the amount of biogas was observed until sonication of 16 min. Further increase in energy in the conditioning process did not significantly increase the production of biogas from the treated substrate. The biogas production from the conditioned substrate was 17% higher than from the reference biomass at that time. The ultrasonic disintegration method did not significantly affect the observed biogas composition. In all series, the methane content in the produced biogas from the conditioned substrate was similar to that obtained with the raw substrate sample (51.1%). Another method of substrate conditioning was hydrothermal depolymerization. This method consists in application of increased temperature and pressure to substrate. These phenomena destroy the structure of the processed material, the release of organic compounds to the solution, which should lead to increase the amount of produced biogas from such treated biomass. The hydrothermal depolymerization was conducted using an innovative microwave heating method. Control measurements were performed using conventional heating. The obtained results indicate the relationship between depolymerization temperature and the amount of biogas. Statistically significant value of the biogas production coefficients increased as the depolymerization temperature increased to 150°C. Further raising the depolymerization temperature to 180°C did not significantly increase the amount of produced biogas in the respirometric tests. As a result of the hydrothermal depolymerization obtained using microwave at 150°C for 20 min, the rate of biogas production from the Sida silage was 780 L/kg VS, which accounted for nearly 50% increase compared to 370 L/kg VS obtained from the same silage but not depolymerised. The study showed that by microwave heating it is possible to effectively depolymerized substrate. Significant differences occurred especially in the temperature range of 130-150ºC. The pre-treatment of Sida hermaphrodita silage (biogas substrate) did not significantly affect the quality of the biogas produced. The methane concentration was about 51.5% on average. The study was carried out in the framework of the project under program BIOSTRATEG funded by the National Centre for Research and Development No. 1/270745/2/NCBR/2015 'Dietary, power, and economic potential of Sida hermaphrodita cultivation on fallow land'.

Keywords: disintegration, biogas, methane fermentation, Virginia fanpetals, biomass

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Authors: A. Kamarchoua, A. A. Bebaa, A. Douadi

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The current work has a goal of the preparation of activated carbon from the stones of dates from southern Algeria (El-Oued province) using a simple pyrolysis proceeded by chemical impregnation in sulphuric acid. For the preparation of the carbon, we choose the diameter of the pellets (0.5-1)mm, activation by acid and water (1:1), carbonization at 450˚C. The prepared carbon has the following characteristics: specific surface 125.86 m2/g, methylene blue number 40, CCE = 0.3meq.g/l, IR and micrographics SEM. The activated carbon thus obtained is used at the water purification in wastewater treatment plant (WWTP) at Kouinine, El- Oued province, to totally eliminate phosphorus. We analyzed the water at the WWTP before the purification procedure. In this study, we have looked at the effect of the following parameters on the adsorption of carbon: the pH, the contact time (Tc) and the agitation speed (Va). The best conditions for phosphorus adsorption are: pH=4 or pH >5, Tc = 60 min and Va = 900 rotations per minute.

Keywords: activated carbon, date stones, pyrolysis, phosphate pollutants

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Authors: Atef Y. Shenouda, Fei Xu

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Cu₃SbS₃ (CAS) was synthesized by direct solid-state reaction from elementary Cu, Sb, & S and hydrothermal reaction using thioacetamide (TAM). Crystal structure and morphology for the prepared phases of Cu₃SbS₃ were studied via X-ray diffraction (XRD) and field emission scanning electron microscope (FESEM). The band gap energies are 2 and 2.2 eV for the prepared samples. The two samples are as anode for Na ion storage. They show high initial capacity to 490 mAh/g. Na cell prepared from TAM sample shows 280 mAh/g after 25 cycles vs. 60 mAh/g for elemental sample.

Keywords: Cu3SbS3, sodium batteries, thioacetamide, sulphur sources

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Authors: P. Kaewchanthuek, R. Rawonghad, B. Marungsri

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This paper presents the experimental results of high-density polyethylene cable spacers for 22 kV distribution systems under salt water dip wheel test based on IEC 62217. The strength of anti-tracking and anti-erosion of cable spacer surface was studied in this study. During the test, dry band arc and corona discharge were observed on cable spacer surface. After 30,000 cycles of salt water dip wheel test, obviously surface erosion and tracking were observed especially on the ground end. Chemical analysis results by fourier transforms infrared spectroscopy showed chemical changed from oxidation and carbonization reaction on tested cable spacer. Increasing of C=O and C=C bonds confirmed occurrence of these reactions.

Keywords: cable spacer, HDPE, ageing of cable spacer, salt water dip wheel test

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Authors: Doaa Hamdi, Ahmed Hashem

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The present study aims at integrating the ASTER data and Landsat 8 data to discriminate and map alteration and/or mineralization zones in addition to delineating different lithological units of Humr Akarim Granites area. The study area is located at 24º9' to 24º13' N and 34º1' to 34º2'45"E., covering a total exposed surface area of about 17 km². The area is characterized by rugged topography with low to moderate relief. Geologic fieldwork and petrographic investigations revealed that the basement complex of the study area is composed of metasediments, mafic dikes, older granitoids, and alkali-feldspar granites. Petrographic investigations revealed that the secondary minerals in the study area are mainly represented by chlorite, epidote, clay minerals and iron oxides. These minerals have specific spectral signatures in the region of visible near-infrared and short-wave infrared (0.4 to 2.5 µm). So that the ASTER imagery processing was concentrated on VNIR-SWIR spectrometric data in order to achieve the purposes of this study (geologic mapping of hydrothermal alteration zones and delineate possible radioactive potentialities). Mapping of hydrothermal alterations zones in addition to discriminating the lithological units in the study area are achieved through the utilization of some different image processing, including color band composites (CBC) and data transformation techniques such as band ratios (BR), band ratio codes (BRCs), principal component analysis(PCA), Crosta Technique and minimum noise fraction (MNF). The field verification and petrographic investigation confirm the results of ASTER imagery and Landsat 8 data, proposing a geological map (scale 1:50000).

Keywords: remote sensing, petrography, mineralization, alteration detection

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Authors: Daniel F. Sava, Anton Ficai, Bogdan S. Vasile, Georgeta Voicu, Ecaterina Andronescu

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The energy crisis and environmental contamination are very serious problems, therefore searching for better and sustainable renewable energy is a must. It is predicted that the global energy demand will double until 2050. Solar water splitting and photocatalysis are considered as one of the solutions to these issues. The use of oxide semiconductors for solar water splitting and photocatalysis started in 1972 with the experiments of Fujishima and Honda on TiO2 electrodes. Since then, the evolution of nanoscience and characterization methods leads to a better control of size, shape and properties of materials. Although the past decade advancements are astonishing, for these applications the properties have to be controlled at a much finer level, allowing the control of charge-carrier lives, energy level positions, charge trapping centers, etc. Graphene has attracted a lot of attention, since its discovery in 2004, due to the excellent electrical, optical, mechanical and thermal properties that it possesses. These properties make it an ideal support for photocatalysts, thus graphene composites with oxide semiconductors are of great interest. We present in this work the synthesis and characterization of graphene-related materials and oxide semiconductors and their different composites. These materials can be used in constructing devices for different applications (batteries, water splitting devices, solar cells, etc), thus showing their application flexibility. The synthesized materials are different morphologies and sizes of TiO2, ZnO and Fe2O3 that are obtained through hydrothermal, sol-gel methods and graphene oxide which is synthesized through a modified Hummer method and reduced with different agents. Graphene oxide and the reduced form could also be used as a single material for transparent conductive films. The obtained single materials and composites were characterized through several methods: XRD, SEM, TEM, IR spectroscopy, RAMAN, XPS and BET adsorption/desorption isotherms. From the results, we see the variation of the properties with the variation of synthesis parameters, size and morphology of the particles.

Keywords: composites, graphene, hydrothermal, renewable energy

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Authors: Iris Vural Gursel, Andrea Ramirez

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Effective utilization of lignin is an important mean for developing economically profitable biorefineries. Current literature suggests that large amounts of lignin will become available in second generation biorefineries. New conversion technologies will, therefore, be needed to carry lignin transformation well beyond combustion to produce energy, but towards high-value products such as chemicals and transportation fuels. In recent years, significant progress on catalysis has been made to improve transformation of lignin, and new catalytic processes are emerging. In this work, a techno-economic assessment of two of these novel conversion routes and comparison with more established lignin pyrolysis route were made. The aim is to provide insights into the potential performance and potential hotspots in order to guide the experimental research and ease the commercialization by early identifying cost drivers, strengths, and challenges. The lignin conversion routes selected for detailed assessment were: (non-catalytic) lignin pyrolysis as the benchmark, direct hydrodeoxygenation (HDO) of lignin and hydrothermal lignin depolymerisation. Products generated were mixed oxygenated aromatic monomers (MOAMON), light organics, heavy organics, and char. For the technical assessment, a basis design followed by process modelling in Aspen was done using experimental yields. A design capacity of 200 kt/year lignin feed was chosen that is equivalent to a 1 Mt/y scale lignocellulosic biorefinery. The downstream equipment was modelled to achieve the separation of the product streams defined. For determining external utility requirement, heat integration was considered and when possible gasses were combusted to cover heating demand. The models made were used in generating necessary data on material and energy flows. Next, an economic assessment was carried out by estimating operating and capital costs. Return on investment (ROI) and payback period (PBP) were used as indicators. The results of the process modelling indicate that series of separation steps are required. The downstream processing was found especially demanding in the hydrothermal upgrading process due to the presence of significant amount of unconverted lignin (34%) and water. Also, external utility requirements were found to be high. Due to the complex separations, hydrothermal upgrading process showed the highest capital cost (50 M€ more than benchmark). Whereas operating costs were found the highest for the direct HDO process (20 M€/year more than benchmark) due to the use of hydrogen. Because of high yields to valuable heavy organics (32%) and MOAMON (24%), direct HDO process showed the highest ROI (12%) and the shortest PBP (5 years). This process is found feasible with a positive net present value. However, it is very sensitive to the prices used in the calculation. The assessments at this stage are associated with large uncertainties. Nevertheless, they are useful for comparing alternatives and identifying whether a certain process should be given further consideration. Among the three processes investigated here, the direct HDO process was seen to be the most promising.

Keywords: biorefinery, economic assessment, lignin conversion, process design

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Authors: Aura Alejandra Burbano Patino, Mariela Agotegaray, Veronica Lassalle, Fernanda Horst

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Water pollution is of worldwide concern due to its importance as an essential resource for life. Industrial and urbanistic growth are anthropogenic activities that have caused an increase of undesirable compounds in water. In the last decade, emerging pollutants have become of great interest since, at very low concentrations (µg/L and ng/L), they exhibit a hazardous effect on wildlife, aquatic ecosystems, and human organisms. One group of emerging pollutants that are a matter of study are pharmaceuticals. Their high consumption rate and their inappropriate disposal have led to their detection in wastewater treatment plant influent, effluent, surface water, and drinking water. In consequence, numerous technologies have been developed to efficiently treat these pollutants. Adsorption appears like an easy and cost-effective technology. One of the most used adsorbents of emerging pollutants removal is carbon-based materials such as hydrochars. This study aims to use a magnetic hydrochar nanocomposite to be employed as an adsorbent for diclofenac removal. Kinetics models and the adsorption efficiency in real water samples were analyzed. For this purpose, a magnetic hydrochar nanocomposite was synthesized through the hydrothermal carbonization (HTC) technique hybridized to co-precipitation to add the magnetic component into the hydrochar, based on iron oxide nanoparticles. The hydrochar was obtained from sunflower husk residue as the precursor. TEM, TGA, FTIR, Zeta potential as a function of pH, DLS, BET technique, and elemental analysis were employed to characterize the material in terms of composition and chemical structure. Adsorption kinetics were carried out in distilled water and real water at room temperature, pH of 5.5 for distilled water and natural pH for real water samples, 1:1 adsorbent: adsorbate dosage ratio, contact times from 10-120 minutes, and 50% dosage concentration of DCF. Results have demonstrated that magnetic hydrochar presents superparamagnetic properties with a saturation magnetization value of 55.28 emu/g. Besides, it is mesoporous with a surface area of 55.52 m²/g. It is composed of magnetite nanoparticles incorporated into the hydrochar matrix, as can be proven by TEM micrographs, FTIR spectra, and zeta potential. On the other hand, kinetic studies were carried out using DCF models, finding percent removal efficiencies up to 85.34% after 80 minutes of contact time. In addition, after 120 minutes of contact time, desorption of emerging pollutants from active sites took place, which indicated that the material got saturated after that t time. In real water samples, percent removal efficiencies decrease up to 57.39%, ascribable to a possible mechanism of competitive adsorption of organic or inorganic compounds, ions for active sites of the magnetic hydrochar. The main suggested adsorption mechanism between the magnetic hydrochar and diclofenac include hydrophobic and electrostatic interactions as well as hydrogen bonds. It can be concluded that the magnetic hydrochar nanocomposite could be valorized into a by-product which appears as an efficient adsorbent for DCF removal as a model emerging pollutant. These results are being complemented by modifying experimental variables such as pollutant’s initial concentration, adsorbent: adsorbate dosage ratio, and temperature. Currently, adsorption assays of other emerging pollutants are being been carried out.

Keywords: environmental remediation, emerging pollutants, hydrochar, magnetite nanoparticles

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Authors: Andrea Alfaro Barajas, Arturo I. Martinez

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3D photothermal structure of carbon was synthesized using PET bottles waste and sodium chloride through controlled carbonization. Characterization techniques such as X-ray photoelectron spectroscopy, X-ray diffraction, BET, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, spectrophotometry, and mechanical compression were carried out. The carbon showed physical integrity > 90%, an absorbance > 90% between 300-1000nm of the solar spectrum, and a high specific surface area from 450 to 620 m2/g. The X-ray was employed to examine the phase structure; the obtained pattern shows an amorphous material. A higher intensity of band D with respect to band G was confirmed by Raman Spectroscopy. C-OH, COOH, C-O, and C-C bonds were obtained from the deconvolution of the high-resolution C1s orbital. Macropores of 160 to 180µm and micropores of 0.5 to 2nm were observed by SEM and TEM images, respectively. Such combined characteristics of carbon confer efficient evaporation of water under 1 sun irradiation > 60%.

Keywords: solar-absorber, carbon, water-evaporation, interfacial

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Authors: F. G Okibe, C. E Gimba, V. O Ajibola, I. G Ndukwe, E. D. Paul

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A full factorial experimental design technique at two levels and four factors (24) was used to optimize the adsorption at 615 nm of Xylene Cyanol ff in aqueous solutions onto activated carbon prepared from brachystegia eurycoma seed hulls by chemical carbonization method. The effect of pH (3 and 5), initial dye concentration (20 and 60 mg/l), adsorbent dosage (0.01 and 0.05 g), and contact time (30 and 60 min) on removal efficiency of the adsorbent for the dye were investigated at 298K. From the analysis of variance, response surface and cube plot, adsorbent dosage was observed to be the most significant factor affecting the adsorption process. However, from the interaction between the variables studied, the optimum removal efficiency was 96.80 % achieved with adsorbent dosage of 0.05 g, contact time 45 minutes, pH 3, and initial dye concentration 60 mg/l.

Keywords: factorial experimental design, adsorption, optimization, brachystegia eurycoma, xylene cyanol ff

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Authors: Somen Mondal, Subrata Kumar Majumder

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Removal of metal pollutants by efficient activated carbon is challenging research in the present-day scenario. In the present study, the characteristic features of an efficient activated carbon (AC) synthesized from Indian gooseberry seed shells for the copper (II) adsorption are reported. A three-step chemical activation method consisting of the impregnation, carbonization and subsequent activation is used to produce the activated carbon. The copper adsorption kinetics and isotherms onto the activated carbon were analyzed. As per present investigation, Indian gooseberry seed shells showed the BET surface area of 1359 m²/g. The maximum adsorptivity of the activated carbon at a pH value of 9.52 was found to be 44.84 mg/g at 30°C. The adsorption process followed the pseudo-second-order kinetic model along with the Langmuir adsorption isotherm. This AC could be used as a favorable and cost-effective copper (II) adsorbent in wastewater treatment to remove the metal contaminants.

Keywords: activated carbon, adsorption isotherm, kinetic model, characterization

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Authors: Karen Fuchs, Michael Prokein, Nils Mölders, Manfred Renner, Eckhard Weidner

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Due to the high CO₂ emissions, the energy consumption for the production of sand-lime bricks is of great concern. Especially the production of quicklime from limestone and the energy consumption for hydrothermal curing contribute to high CO₂ emissions. Hydrothermal curing is carried out under a saturated steam atmosphere at about 15 bar and 200°C for 12 hours. Therefore, we are investigating the opportunity to replace quicklime and sand in the production of building materials with different types of slag as calcium-rich waste from steel production. We are also investigating the possibility of substituting conventional hydrothermal curing with CO₂ curing. Six different slags (Linz-Donawitz (LD), ferrochrome (FeCr), ladle (LS), stainless steel (SS), ladle furnace (LF), electric arc furnace (EAF)) provided by "thyssenkrupp MillServices & Systems GmbH" were ground at "Loesche GmbH". Cylindrical blocks with a diameter of 100 mm were pressed at 12 MPa. The composition of the blocks varied between pure slag and mixtures of slag and sand. The effects of pressure, temperature, and time on the CO₂ curing process were studied in a 2-liter high-pressure autoclave. Pressures between 0.1 and 5 MPa, temperatures between 25 and 140°C, and curing times between 1 and 100 hours were considered. The quality of the CO₂-cured blocks was determined by measuring the compressive strength by "Ruhrbaustoffwerke GmbH & Co. KG." The degree of carbonation was determined by total inorganic carbon (TIC) and X-ray diffraction (XRD) measurements. The pH trends in the cross-section of the blocks were monitored using phenolphthalein as a liquid pH indicator. The parameter set that yielded the best performing material was tested on all slag types. In addition, the method was scaled to steel slag-based building blocks (240 mm x 115 mm x 60 mm) provided by "Ruhrbaustoffwerke GmbH & Co. KG" and CO₂-cured in a 20-liter high-pressure autoclave. The results show that CO₂ curing of building blocks consisting of pure wetted LD slag leads to severe cracking of the cylindrical specimens. The high CO₂ uptake leads to an expansion of the specimens. However, if LD slag is used only proportionally to replace quicklime completely and sand proportionally, dimensionally stable bricks with high compressive strength are produced. The tests to determine the optimum pressure and temperature show 2 MPa and 50°C as promising parameters for the CO₂ curing process. At these parameters and after 3 h, the compressive strength of LD slag blocks reaches the highest average value of almost 50 N/mm². This is more than double that of conventional sand-lime bricks. Longer CO₂ curing times do not result in higher compressive strengths. XRD and TIC measurements confirmed the formation of carbonates. All tested slag-based bricks show higher compressive strengths compared to conventional sand-lime bricks. However, the type of slag has a significant influence on the compressive strength values. The results of the tests in the 20-liter plant agreed well with the results of the 2-liter tests. With its comparatively moderate operating conditions, the CO₂ curing process has a high potential for saving CO₂ emissions.

Keywords: CO₂ curing, carbonation, CCU, steel slag

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Authors: Seyed Mohsen Mousavi, Ali Reza Mahjoub, Bahjat Afshari Razani

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In this work, Fe/ZnO hollow spherical structures with high surface area using the template glucose was prepared by the hydrothermal method using an ultrasonic bath at room temperature was produced and were identified by FT-IR, XRD, FE-SEM and BET. The photocatalytic activity of synthesized spherical Fe/ZnO hollow sphere were studied in the destruction of Congo Red and Methylene Blue as Azo dyes. The results showed that the photocatalytic activity of Fe/ZnO hollow spherical structures is improved compared with ZnO hollow sphere and other morphologys.

Keywords: azo dyes, Fe/ZnO hollow sphere, hollow sphere nanostructures, photocatalyst

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Authors: Usman D. Hamza, Noor S. Nasri, Mohammed Jibril, Husna M. Zain

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Activated carbons (M4P0, M4P2, and M5P2) used in this research were produced from palm shell and polyetherether ketone (PEEK) via carbonization, impregnation, and microwave activation. The adsorption/desorption process was carried out using static volumetric adsorption. Regeneration is important in the overall economy of the process and waste minimization. This work focuses on the thermal regeneration of the CO2 exhausted microwave activated carbons. The regeneration strategy adopted was thermal with nitrogen purge desorption with N2 feed flow rate of 20 ml/min for 1 h at atmospheric pressure followed by drying at 1500C. Seven successive adsorption/regeneration processes were carried out on the material. It was found that after seven adsorption regeneration cycles; the regeneration efficiency (RE) for CO2 activated carbon from palm shell only (M4P0) was more than 90% while that of hybrid palm shell-PEEK (M4P2, M5P2) was above 95%. The cyclic adsorption and regeneration shows the stability of the adsorbent materials.

Keywords: activated carbon, palm shell-PEEK, regeneration, thermal

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Authors: Mutiara Effendi

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Nunukan Island is located on North Kalimantan of Indonesia. The region is one of Indonesia’s cross-border with Malaysia. In conjunction with its strategic geographic location, its potential as the new oil and gas resources has brought many researchers to do their studies here. The research area consists of claystone which criss-crossed with quarts sandstone. There are also rocks claystone-grained which are the weathering product of basaltic volcanic rocks. In some places, there are argillic clays which are the hydrothermal-altered product of Sei Apok ancient volcano. Geochemical study was established to learn the origin of the claystones, whether it came from weathering, hydrothermal alteration, or both. The samples used in this research are fresh rock, weathering rocks, hydrothermally-altered rock, and claystones. Chemical compositions of each sample were determined and their relations was studied. The studies encompass major and minor elements analysis using X-Ray Fluoresence (XRF) method and trace elements analysis, specifically rare earth elements, using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) method. The results were plotted on certain graphics to learn about the trend and the relations of each sample and element. Any changes in chemical compositions, like increase and decrease of elements or species, was analysed to learn about geological phenomenon that happens during the formation of claystones. The result of this study shows that claystones of Nunukan Island have relation with volcanic rocks of its surrounding area. Its chemical composition profile corresponds to weathering product of volcanic rocks rather than hydrothermally-altered product. The general profile also resembles claystone minerals of illite or montmorillonite, especially in the existence of aluminum, iron, potassium, and magnesium. Both minerals are formed in basic condition and commonly happen to shales. It is consistent with the fact that claystone was found mixing with shales and silt to clay grained mudstones in field exploration. Even though the general profile is much alike, the amount of each elements is not precisely the same as theoretically claystone mineral compositions because the mineral have not formed completely yet.

Keywords: claystone, geochemistry, ICP-MS, XRF

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Authors: Chi Man Luk, Ming Kiu Tsang, Chi Fan Chan, Shu Ping Lau

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Nitrogen-doped graphene quantum dots (N-GQDs) were fabricated by microwave-assisted hydrothermal technique. The optical properties of the N-GQDs were studied. The luminescence of the N-GQDs can be tuned by varying the excitation wavelength. Furthermore, two-photon luminescence of the N-GQDs excited by near-infrared laser can be obtained. It is shown that N-doping play a key role on two-photon luminescence. The N-GQDs are expected to find application in biological applications including bioimaging and sensing.

Keywords: graphene quantum dots, nitrogen doping, photoluminescence, two-photon fluorescence

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Authors: Adhitya Mangala, Yobel

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Bittuang geothermal prospect area located at Tana Toraja district, South Sulawesi. The geothermal system of the area related to Karua Volcano eruption product. This area has surface manifestation such as fumarole, hot springs, sinter silica and mineral alteration. Those prove that there are hydrothermal activities in the subsurface. However, the project and development of the area have not implemented yet. One of the important elements in geothermal exploration is to determine upflow and outflow zone. This information very useful to identify the target for geothermal wells and development which it is a risky task. The methods used in this research were Mercury (Hg) anomalies in soil, soil and manifestation temperature distribution and fault fracture density from 93 km² research area. Hg anomalies performed to determine the distribution of hydrothermal alteration. Soil and manifestation temperature distribution were conducted to estimate heat distribution. Fault fracture density (FFD) useful to determine fracture intensity and trend from surface observation. Those deliver Hg anomaly map, soil and manifestation temperature map that combined overlayed to fault fracture density map and geological map. Then, the conceptual model made from north – south, and east – west cross section to delineate upflow and outflow zone in this area. The result shows that upflow zone located in northern – northeastern of the research area with the increase of elevation and decrease of Hg anomalies and soil temperature. The outflow zone located in southern - southeastern of the research area which characterized by chloride, chloride - bicarbonate geothermal fluid type, higher soil temperature, and Hg anomalies. The range of soil temperature distribution from 16 – 19 °C in upflow and 19 – 26.5 °C in the outflow. The range of Hg from 0 – 200 ppb in upflow and 200 – 520 ppb in the outflow. Structural control of the area show northwest – southeast trend. The boundary between upflow and outflow zone in 1550 – 1650 m elevation. This research delivers the conceptual model with innovative methods that useful to identify a target for geothermal wells, project, and development in Bittuang geothermal prospect area.

Keywords: Bittuang geothermal prospect area, Hg anomalies, soil temperature, upflow and outflow zone

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Authors: Bita Bayatsarmadi, Shi-Zhang Qiao

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The development of ordered mesoporous carbon materials with controllable structures and improved physicochemical properties by doping heteroatoms such as nitrogen into the carbon framework has attracted a lot of attention, especially in relation to energy storage and conversion. Herein, a series of Nitrogen-doped mesoporous carbon spheres (NMC) was synthesized via a facile dual soft-templating procedure by tuning the nitrogen content and carbonization temperature. Various physical and (electro) chemical properties of the NMCs have been comprehensively investigated to pave the way for feasible design of nitrogen-containing porous carbon materials. The optimized sample showed a favorable electrocatalytic activity as evidenced by high kinetic current and positive onset potential for oxygen reduction reaction (ORR) due to its large surface area, high pore volume, good conductivity and high nitrogen content, which make it as a highly efficient ORR metal-free catalyst in alkaline solutions.

Keywords: porous carbon, N-doping, oxygen reduction reaction, soft-template

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Authors: Ratchadaporn Kaewmuang, Hussaya Maneesuwan, Thanyalak Chaisuwan, Sujitra Wongkasemjit

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Mesoporous materials have been used in many applications, such as adsorbent and catalyst. SBA-15, a 2D hexagonal ordered mesoporous silica material, has not only high specific surface area, but also thicker wall, larger pore size, better hydrothermal stability, and mechanical properties than M41s. However, pure SBA-15 still lacks of redox properties. Therefore, bimetallic incorporation into framework is of interest since it can create new active sites. In this work, Ti-Fe-SBA-15 is studied and successfully synthesized via sol-gel process, using silatrane, FeCl3, and titanium (VI) isopropoxide as silica, iron, and titanium sources, respectively. The products are characterized by SAXD, FE-SEM, and N2 adsorption/desorption, DR-UV, and XRF.

Keywords: SBA-15, mesoporous silica, bimetallic, titanium, iron, silatrane

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Authors: Anasheh Maridiroosi, Ali Reza Mahjoub, Hanieh Fakhri

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Heteropoly acid nanoparticles anchored on graphene oxide based on UiO-66 were synthesized via in-situ growth hydrothermal method and tested for photodegradation of a tetracycline as critical pollutant. Results showed that presence of graphene oxide and UiO-66 with high specific surface area, great electron mobility and various functional groups make an excellent support for heteropoly acid and improve photocatalytic efficiency up to 95% for tetracycline. Furthermore, total organic carbon (TOC) analysis verified 79% mineralization of this pollutant under optimum condition.

Keywords: heteropoly acid, graphene oxide, MOF, tetracycline

Procedia PDF Downloads 90