Activation Energy Of Degradation Research Articles

Operationally stable perovskite solar modules enabled by vapor-phase fluoride treatment.

The ever-increasing power conversion efficiency of perovskite solar cells has illuminated the future of the photovoltaic industry, but the development of commercial devices is hampered by their poor stability. In this study, we report a scalable stabilization method using vapor-phase fluoride treatment, which achieves 18.1%-efficient solar modules (228 square centimeters) with accelerated aging-projected T80 lifetimes (time to 80% of efficiency remaining) of 43,000 ± 9000 hours under 1-sun illumination at 30°C. The high stability results from vapor-enabled homogeneous fluorine passivation over large-area perovskite surfaces, suppressing defect formation energy and ion diffusion. The extracted degradation activation energy of 0.61 electron volts for solar modules is comparable to that of most reported stable cells, which indicates that modules are not inherently less stable than cells and closes the cell-to-module stability gap.

An eco-friendly first and second derivative synchronous spectrofluorimetry for quantification of florfenicol in presence of its different degradation products. Application to kinetic stability study.

Two rapid, simple, sensitive and selective derivative spectrofluorimetric methods (first and second derivative synchronous spectrofluorimetric (FDSFS and SDSFS) procedures) have been developed for the analysis of florfenicol in the presence of its various degradation products. FDSFS was applied to assay the drug in the presence of its alkaline, oxidative and photolytic degradation products while SDSFS was used to quantify it in the presence of its acidic degradation product. These methods permitted quantification of florfenicol at corresponding λ Em of 288, 287, 279 and 284 nm without interferences from any of its degradation products. Full validation procedures were applied to the suggested method according to International Conference of Harmonization guidelines. Moreover, different degradation kinetic parameters were calculated such as half-life (t 1/2), degradation rate constant (K) and activation energy (E a). Using the analytical eco-scale, green analytical procedure index and analytical greenness metric approach AGREE as greenness assessment tools, the proposed method was found to be environmentally friendly.

Effect of metals and brominated flame retardants on thermal degradation kinetics of waste printed circuit board

Waste printed circuit board (WPCB) is an indispensable component in any waste electrical and electronic equipment (WEEE). A promising method for recycling WPCB is pyrolysis. To understand the effect of metals and brominated flame retardants (BFR) on WPCB pyrolysis, four samples were prepared, namely (a) raw WPCB (RW), (b) non-metallic WPCB (NM), (c) bromine extracted WPCB (RWBFR_ext) and (d) bromine and metal extracted WPCB (NMBFR_ext). The degradation kinetics study using the isoconversional methods: Friedman, Ozawa-Flynn-Wall (OFW), Kissinger–Akahira–Sunose (KAS), and Starink showed that the extraction of metals exhibited an increase in final degradation temperature and activation energy (Eα), and altered the reaction mechanism (f(a)) whereas, the reduction of BFR reduced initial degradation temperature. The identified kinetic triplets were verified using the reconstruction profiles. The parameters can be used in designing applications and developing an energy-efficient pyrolysis process.

Catalytic pyrolysis of pine needles using metal functionalized spent adsorbent derived catalysts: Kinetics, thermodynamics and prediction modelling using artificial neural network (ANN) approach

The current study was indented towards the evaluation of synergism of spent aluminum hydroxide nanoparticle (AHNP) adsorbent derived catalysts in the degradation of pine (Pinus roxburghii) needles through kinetics and thermodynamics analysis. Distinct kinetic (such as activation energy and pre-exponential factors) and thermodynamic (such as entropy, enthalpy, and Gibbs free energy) parameters were estimated through isoconversional (OFA and KAS) models. The study also aimed to envisage the reaction mechanism for all the distinct processes via Criado z master plots. Results illustrated the significant impact of all the different AHNP-derived catalysts in easing up the biomass degradation process. The KAS method evaluated the average activation energy for non-catalytic degradation as 130.01 kJ/mol, while the values changed to 120.95, 121.69, 125.99, 148.47 and 127.37 kJ/mol for Ni/AO, Fe/AO, Cu/AO, Zn/AO and Mo/AO catalyzed degradation, respectively. Amongst all, nickel (Ni/AO) and iron-doped (Fe/AO) catalysts brought the highest reduction in activation energy owing to the provision of strong acidic sites, high specific surface area, and better metal dispersion; subsequently leading to the increased rate of molecular scission and cracking reactions. Values of pre-exponential factor and thermodynamic parameter also displayed the positive impact of catalysts in terms of lowering down the molecular collisions, enthalpy, and disorderness of the system. Furthermore, artificial neural network (ANN) was also employed for the prediction of the biomass degradation where high regression (∼0.99) as well as low mean squared error (<10−5) illustrated the accurate prediction of complex biomass degradation by the ANN technique. Thus, the waste AHNP-derived catalysts have significant potential to be employed for the catalytic pyrolysis of pine needles together with aiding the cost-competitiveness, environmental sustainability, and renewability of the process.

An assessment of the role of nanosilica in thermal/thermo‐oxidative degradation mechanism of poly(lactic acid)/polybutylene adipate terephthalate blend nanocomposites

AbstractAs a packaging materials candidate, based on a polylactic acid/ polybutylene adipate terephthalate (PLA/PBAT) blends (90/10 and 75/25 wt/wt) containing 1, 3, and 5 phr hydrophilic (HPL) and hydrophobic (HPB) nanosilica (NS) particles in the presence of a multifunctional epoxide compatibilizer were prepared by melt mixing, in a twin‐screw extruder. Scanning electron microscopic studies confirmed a matrix‐droplet morphology with finer dispersed domains at higher NS content. Energy dispersive spectroscopy mapping also indicated uniform dispersion of NS in blends, with some agglomerates at higher content of nanoparticles. Moreover, transmission electron microscope was applied to study the impact of nanofillers' localization on the systems' morphology. It was observed that NS particles localized at the PLA‐PBAT interface. In addition, thermogravimetric analysis (TGA) was used to investigate thermal stability and thermal degradation kinetics. Data indicates that hydrophobic NS improved thermal stability. The activation energy of degradation was calculated using several techniques of data modeling, including Friedman, Flynn‐Ozawa‐Wall, and Kissinger‐Akahira‐Sunose models. Among blend nanocomposites, 75/25 blend containing 5 phr HPB NS had the maximum degradation activation energy, suggesting that this sample had the most resistance to heat degradation. The intensity of the TGA/FTIR peaks of the evolved products was found to be correlated with the activation energy. The Criado's technique was also used to investigate the changes in the thermal degradation mechanism.

Degradation kinetics of vitamins in different enteral feeding formulas during storage at different temperatures

Vitamin degradation may be affected differently by various food matrices. In this study, the kinetics of vitamin A, B1, and C degradation were directly compared in two types of enteral feeding formulas (EFFs) with different energy densities over a nine-month storage period at 4, 25, and 30 °C. The content of vitamins A, B1, and C was measured in the initial and stored formulas. The results justified the finding that the content of these vitamins was gradually decreased with storage time or temperature increases during the period. At each temperature during storage, the degradation of vitamins A, B1, and C followed first-order kinetics, and the rate constants calculated indicated the degradation of vitamins was temperature-dependent. The EFF-B exhibited a higher activation energy for vitamin degradation than that in the EFF-A, and the activation energy indicated an inverse relationship with the fat content of EFFs. The outcomes might provide a reference for the development and application of EEFs.

Curing and degradation kinetics of crosslinked epoxidized soybean oil with isosorbide-based curing agent

This work explores the synthesis of the isosorbide-based curing agent with methyltetrahydrophthalic anhydride (MTHPA). Synthesized for the first time, the isosorbide methylphthalate acid (IMPA) and its effects on the crosslinking of epoxidized soybean oil (ESO) are investigated. The curing and degradation kinetics of the synthesized compounds were investigated for molar ratios 1:1, 1:0.50 and 1:0.25 for ESO/IMPA and 1:1 ESO/MTHPA. ESO/IMPA 1:0.50 had the lowest cure activation energies during the highest cure conversion range, between 10% and 55%, and the highest degradation activation energies during the 30 and 60% conversion. The Friedman and Vyazovkin isoconversional models provided R2 > 0.99 for cure, except for the ESO/MTHPA composition, presenting a lower R2. In degradation kinetics, the Kissinger-Akahira-Sunose (KAS) and Ozawa-Flynn-Wall (OFW) kinetic models presented R2 > 0.99, while the degradation mechanisms were adequately adjusted with Avrami-Erofeev (An) and autocatalytic (n,m)th order (Cnm) during the first and second degradation step. Microstructural analyzes and deeper investigations into the degradation mechanisms in the solid state indicated that in the ESO/IMPA and ESO/MTHPA compounds the processes are controlled by diffusion.

Thermal degradation behavior and kinetics of porous polymer based on high functionality components

AbstractTwo kinds of porous polymer were prepared based on high functionality components. Thermogravimetric analysis (TGA) is used to compare the thermal degradation behavior and kinetics of these two materials. The thermogravimetric tests of rigid polyurethane foam (H‐RPUF) and polyurea aerogel (H‐PUA) were carried out in nitrogen atmosphere at different heating rates. The thermal degradation characteristics of the porous polymer were obtained. The apparent activation energy (Ea) of thermal degradation of the porous polymer was investigated by model‐free methods. The results showed that the thermal degradation temperature and ash content of H‐RPUF were higher than those of H‐PUA, and the volatile content was lower. With the rise of heating rate, thermal hysteresis effect of the two porous polymer was relatively high, while the release amount of volatiles was unchanged. For the Kissinger method, Ea of H‐PUA and H‐RPUF was 212.8 kJ mol−1 and 157.4 kJ mol−1, respectively. According to Starink method, the average activation energy of H‐PUA and H‐RPUF was 220.2 kJ mol−1 and 107.2 kJ mol−1, respectively. Obtained by Flynn‐Wall‐Ozawa model, the average activation energy of H‐PUA and H‐RPUF was 219.0 kJ mol−1 and 111.5 kJ mol−1, respectively. The data obtained from the three models all show that Ea of thermal degradation of H‐PUA is higher than that of H‐RPUF, and it is less likely to decompose.

Thermal performance analysis of optimized biomass conversion in developing organic waste biorefinery to achieve sustainable development goals

To make energy sector sustainable, waste to energy system should be used, as statistics of the International Energy Agency (IEA) shows that the lack of renewable energy and environmental degradation are the major pressing problems confronting the global community. However, in south Asian regions, the situation escalates as a result of severe dependency on conventional energy sources, coupled with the limitations and challenges involved in maintaining a green environment and Waste-to-Energy (WtE) strategies. In this region, energy majorly relies on imported conventional fuel. In addition to harming the environment, imported fossil fuel has also increased the risk of geopolitical unrest. In the current research, rice husk is used as a bio-organic waste that is produced in large volumes and a significant byproduct of agro-based biomass sector. In this research, sample composition of rice husk is demineralized in 5% hydro-chloric acid for different burning ratios and the modified thermo-chemical methodology was used to the acidified rice husk at three different heating rates (20 °C min−1, 30 °C min−1 and 40 °C min−1) respectively in thermogravimetric analyzer (TGA). Proximate, thermal and kinetic analysis was used for observing the degradation patterns of demineralized rice husk. Proximate analysis revealed that the leaching of rice husk has successfully infused HCl, resulting in substantial rise in fixed carbon (FC) and calorific value (CV) by 10.53 % and 10.82 % respectively, along with decrease in the carbon footprint of about 60.55%. Thermogravimetric (TG) and derivative thermogravimetric (DTG) curves have shown decreasing behavior of conversion efficiency to the increase in flow rate, with the maximum drop of 12.7 % observed at 40 °C. With the use of the TGA equipment, the conversion efficiency was evaluated based on the sample's peak weight loss. The current study has reported synergistic effect of flow and heating rate on the degradation temperatures, activation energy and reactivity of acidified rice husk. Lowest activation energy 180.46 kJ permole with highest reactivity of 0.01192345 %*min °C was observed at 40 ml and 20 °C combination. Accordingly, degradation temperatures of burning profiles increased due to lower convective cooling and higher temperature gradient within the particle of rice husk sample. In addition, pre-exponential data and slopes of TG curves have validated the results of activation energy obtained from TGA experimentation. The sustainable biomass conversion approach is envisioned to significantly refine the waste bio refinery system to achieve SDGs.

Effect of beeswax and petroleum wax on the thermal degradation behavior, kinetics, and thermodynamics of low‐grade coal

AbstractThe co‐pyrolysis behavior of low‐grade coal with two different feedstocks (beeswax and petroleum wax) at different compositions (w/w) [(75:25), (50:50), (25:75)] is investigated by using a thermogravimetric (TG) analyzer under the non‐isothermal condition at a constant heating rate of 20°C/min from an ambient temperature to 900°C under nitrogen atmosphere. The kinetic and thermodynamic analysis for the thermal decomposition of the sample parameters was carried out by applying the model fitting Coats–Redfern method to the thermogravimetry data of different feedstocks. The activation energy of thermal degradation of coal is found to be 55.8 kJ/mole. A decrease in activation energy is observed by the addition of 25% and 50% waxes in the blended sample and the blended sample with 25% wax and 75% coal has the lowest activation energy. The activation energy for coal‐beeswax blend (75:25) is 35.718 KJ/mol, but it is 34.237 KJ/mol for coal‐petroleum wax blend (75:25). The value of ∆H decreases by the addition of waxes and follows the order (Coal: Feedstock) {(75:25) &lt; (50:50) &lt; (25:75)}, while that of value of ∆S increases by the addition of waxes and follows the order {(75:25) &gt; (50:50) &gt; (25:75)}. However, the value of ΔG does not significantly shift as the blend ratio of the feedstocks is altered. The addition of both feedstocks with the coal sample showed some degree of synergy. The result illustrates that the co‐pyrolysis of coal with wax be energy economical than individual pyrolysis and this study would give precious scope to design a more efficient conversion system.

Field‐representative evaluation of PID‐polarization in TOPCon PV modules by accelerated stress testing

AbstractPotential‐induced degradation‐polarization (PID‐p) can reduce module power, but how to project the extent to which PID‐p may occur in field conditions considering the factors of system voltage, condensed moisture, temperature, and illumination has not been clarified. Using tunnel oxide passivated contact (TOPCon) modules, this work demonstrates a method to test full‐size crystalline silicon PV modules for PID‐p to provide field‐representative results. In initial screening tests with positive or negative 1000 V electrical bias applied at 60°C for 96 h using Al foil electrodes on the glass surfaces, the module type exhibited reversible PID‐p only on the front face when the cell circuit was in negative voltage potential. No PID was detected on the rear after testing in either polarity. We then evaluated the PID‐p sensitivity on the front side under different UV irradiances while maintaining the glass surface wet to estimate real‐world susceptibility to PID‐p. The magnitude of the observed behavior was fit using a previously developed charge transfer and depletion by light model. Whereas power loss with −1000 V applied to the cell circuit at 60°C for 96 h in the dark was about 30%, testing the module front under 0.051 W·m−2 nm−1 at 340 nm UVA irradiation using fluorescent tubes, the mean degradation was only 3%. When the modules were tested in the dark for PID‐p with in situ dark current–voltage (I‐V) characterization, the thermal activation energy for degradation was 0.71 eV; for recovery in the dark, it was 0.58 eV. Whereas recovery from the degraded state at 60°C in the dark without voltage bias was 5% absolute in 38 h, rapid recovery of about 5% absolute was observed with 1000 W·s/m2 exposure at 25°C using a flash tester.

Effect of trimethylene carbonate segments on the structure and properties of poly(L‐lactide‐glycolide‐trimethylene carbonate) terpolymers for biodegradable vascular stents

AbstractThe total biodegradable vascular stent made of poly(L‐lactide‐glycolide‐trimethylene carbonate) terpolymers with excellent performances has the potential to be used in a new generation of medical implant devices. In this work, the properties and structure of terpolymers were investigated, which were found to be controlled by the composition of the copolymer chain. The amorphous trimethylene carbonate segments not only disturbed the sequence regularity of the L‐lactide segment, but also reduced the crystallization ability of the material. Furthermore, it is the flexible segments in the terpolymer chains that improve the plastic flow capacity, increase the flexibility of chains as well as reduce the apparent activation energy of thermal degradation of materials. Such a chain structured terpolymer exhibited good extrudability and buildability in 3D printing and formed a vascular stent with a cohesion entanglement characteristic microstructure during the process. The crush resistance with radially applied load and crush resistance with parallel plates of stent were 2561.4 mm Hg and 0.24 N/mm, respectively.

A novel sugarcane residue-derived bimetallic Fe/Mn-biochar composite for activation of peroxymonosulfate in advanced oxidation process removal of azo dye: Degradation behavior and mechanism

Metal-biochar composites with varying Fe/Mn ratios were synthesized for activating peroxymonosulfate (PMS) oxidative degradation of azo dye Orange G (OG) were investigated. The 1Fe2Mn-BC composite based on 1:2 molar ratio impregnation of Fe/Mn salt concentrations of efficient sugarcane harvest residue showed the best catalytic performance under aqueous pH 3–10 and had the least impacts from coexistence of inorganic anions and humic acids. The OG degradation by 1Fe2Mn-BC/PMS system optimized at catalyst:oxidant:pollutant ratio of 1:1.25:0.5 on g/L basis was found to follow pseudo-first-order kinetic and achieved 100 % degradation efficiency within 30 min. Apparent activation energy for OG degradation by 1Fe2Mn-BC/PMS was 16.91 kJ mol−1, and increasing reaction temperature from 293 to 313 K enhanced degradation rate constant by 49 %. Electron paramagnetic resonance (EPR) and radical quenching experiments revealed dominant non-radical 1O2 and radical O2− pathways in the OG oxidation removal by the 1Fe2Mn-BC/PMS system, although SO4− and OH radicals also participated. XPS spectra of 1Fe2Mn-BC before and after OG degradation indicated dominant surface composition of Fe(III) and Mn(II) valence states over other FeMn-biochar composites. The novel optimized one-step pyrolysis Fe/Mn bimetal biochar composite provides an efficient PMS activation for advanced oxidation process (AOP) treating of azo dyes in wastewater decontamination.

Porous‐structured vermiculite/polybutylene adipate terephthalate composite films: The morphology, mechanical properties, and nonisothermal degradation kinetics

AbstractTo examine the impact of vermiculite (VMT) on the environmental and physical aspects of polybutylene terephthalate (PBAT), the thermal degradation behavior of VMT/polybutylene terephthalate polyadipate (VMT/PBAT) composite films was investigated by using the thermogravimetric analysis (TGA). To ensure precise calculation of the specific activation energy values of VMT/PBAT composite films in thermal degradation performance experiments, the Kissinger method (K‐method) and Flynn–Wall–Ozawa method (FWO method) were utilized. Additionally, the reaction mechanism was analyzed using the Coats–Redfern equation (CR equation). The introduction of VMT into the PBAT co‐polyester structure leads to an increase in the thermal degradation activation energy Ek of composite films.; the apparent activation energies were calculated by the Coats–Redfern method for different reaction mechanisms, and the interfacial diffusion reaction mechanism of the composite film was determined, with a thermal degradation reaction principle properties of g(α) = [1 − (1 − α)]2 and the number of reaction steps of 2.Highlights VMT/PBAT composite films prepared using a simple method. Analyzing nonisothermal degradation kinetics using K‐method and FWO method. Analyzing the degradation mechanisms using the Coats–Redfern equation. Addition of VMT enhances the thermal degradation properties of composite films. Addition of VMT reduces the mechanical properties of the composite film.

Pretreatment greatly facilitates ethyl levulinate production from catalytic alcoholysis of Napier grass stem

The inhibition effect of impurities in the raw lignocellulosic biomass greatly impedes its direct acid-catalyzed alcoholysis process to produce downstream chemicals. Previous literatures widely investigated the inhibition problems of lignin content and cellulose crystallite in the raw biomass for the production of alkyl levulinate (AL), while the effect of inorganic matters on this process only received cursory attention. In this contribution, the vital importance of ash removal in raw material for efficient catalytic alcoholysis of cellulose fraction been highlighted. Moreover, it has been found that the facile pretreatment of Napier grass stem greatly facilitates the acid-catalyzed alcoholysis of its cellulose fraction towards ethyl levulinate (EL), a versatile commodity chemical. EL yield as high as 72.1 % can be accomplished from the NaOH-pretreated Napier grass stem in ethanol/γ-valerolactone co-solvent medium over Al(OTf)3 at 170 ℃ for 150 min, which is almost ten times that from the pristine one in ethanol medium. It is also interesting to note that a facile and green water prewashing treatment can efficiently remove the inorganic component of the raw biomass, which thus largely promotes the conversion of Napier grass stem to EL. The activation energies of cellulose degradation and glucopyranoside alcoholysis after pretreatment decreased to 62.4 kJ/mol and 68.6 kJ/mol, respectively. This work presents a highly-reliable strategy for valorizing grass lignocellulosic feedstock to produce bio-based ester compounds.

Thermochemistry of pyrolyzed rutin and its esters prepared from facile biocatalytic route

Pyrolysis of quercetin-3-O-rutinoside or rutin and its esters were investigated. Purified ester samples were prepared from lipase-catalyzed esterification of the parent flavonoid i.e., rutin using acyl donors with different carbon chain length. X-ray diffraction revealed the presence of crystalline peaks in the rutin esters. The degradation activation energies (Ea) as a function of conversion degree a were determined using Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa methods, with corroborative results. Disparity in Ea implies distinct thermal degradation routes. For all studied compounds, degradation is a non-spontaneous process. The presence of acyl moieties and their corresponding carbon chain length in relation to thermodegradation profiles, Ea, entropy (?S) and enthalpy (?H) changes of the pyrolysis are discussed.

Encapsulation of Bioactive Compounds from Germinated Mung Bean by Freeze-Drying, Release Kinetics, and Storage Stability.

This research explores the application of germinated mung bean extract, rich in GABA (Gamma-aminobutyric acid) and polyphenols, in enhancing human health. Recognizing the instability of these bioactive compounds in environmental conditions, encapsulation emerges as a pivotal technique to broaden their applications in food and pharmaceuticals. Utilizing response surface methodology and Box-Behnken design, the freeze-drying formulation for encapsulating the aqueous extract was optimized. Second-order polynomial models were developed, exhibiting statistical adequacy in predicting key variables such as encapsulation efficiency for GABA (EE-GABA) and total polyphenol content (EE-TPC), as well as encapsulation yield for GABA (EY-GABA) and total polyphenol content (EY-TPC). The established optimal formulation was validated, resulting in predicted values for EE-GABA, EE-TPC, EY-GABA, and EY-TPC. The release kinetics of encapsulated particles were investigated, highlighting the suitability of the Korsmeyer-Peppas and Higuchi models. Assessing the stability of the encapsulated powder under varying temperatures and humidities revealed degradation rates, half-life, and activation energy, with moisture equilibrium established at 4.70%, indicative of long-term stability. In conclusion, the encapsulated germinated mung bean powder demonstrates high stability, making it a promising candidate for integration into food products and functional ingredients.

Melt crystallization and thermal degradation profile of the antichagasic drug nifurtimox

Despite nifurtimox (NFX) being a traditional drug for treating Chagas disease, some of its physicochemical properties are still unknown, especially its thermal behavior, which brings important outcomes regarding stability and compatibility. In this work, a comprehensive study of NFX’s thermal properties was conducted to assist incremental innovations that can improve the efficacy of this drug in novel pharmaceutical products. For this purpose, thermal analyses associated with spectroscopy and spectrometry techniques were used. DSC analyses revealed that the melt crystallization of the NFX led to its amorphous form with the possible formation of a minor fraction of a different crystalline phase. Coats-Redfern method using TGA results indicated the activation energy of NFX non-isothermal degradation as 348.8 ± 8.2 kJ mol−1, which coincides with the C-NO2 bond dissociation energy of the 2-nitrofuran. Investigation of the isothermal degradation kinetics using FTIR 2D COS showed the possible detachment of radical NO2 and ethylene from the NFX structure, which could affect its mechanism of action. A preliminary mechanism for the thermal degradation of this drug was also proposed. The results enhanced the understanding of NFX's thermal properties, providing valuable insights, especially for developing NFX-based pharmaceutical products that involve thermal processing.

Effects of green and innovative pretreatment techniques on kinetic parameters of sunflower seed husk

The effects of green pretreatment processes, such as ultrasonic process (US) and deep eutectic solvent (DES), applied to the biomass on kinetic parameters are as important as their effects on characteristic properties. Process conditions and course of reaction progression depend on the knowledge about kinetic parameters, activation energy and reaction model of thermal degradation in scale-up studies. Therefore, in this study, the change in the kinetic parameters with US applied with both distilled water and DES (glycerol:sodium acetate) at 100 W power and 20 kHz frequency for 10 minutes to sunflower seed husk (SSH) was revelaed. Isoconversional methods Kissinger-Akahira-Sunose (KAS) and Flynn- Wall-Ozawa (FWO) were preferred for the evaluation of activation energy of SSH and pretreated SSH at 15°C/min, 20°C/min and 25°C/min heating rates. US pretreatment with DES instead of water resulted in increment of average activation energy values (Ea) from 113.13 to 143.65 kJ/mol in the KAS method. Ea values for all SSH samples changed in the range of 87.72-143.65 kJ/mol and higher Ea values was obtained with KAS method for pretreated SSH samples. Consequently, the use of DES in US pretreatment was more effective to change kinetic parameters of SSH compared to water.

Thermally activated natural chalcopyrite for Fenton-like degradation of Rhodamine B: Catalyst characterization, performance evaluation, and catalytic mechanism

In this work, catalytic activity of natural chalcopyrite (CuFeS2) was improved by thermal activation. The modified chalcopyrite was used as efficient catalyst for degradation of organic dye Rhodamine B (RhB) through advanced oxidation process (AOP). Effects of catalyst dosage, H2O2 concentration, reaction temperature, solution pH, anions, and natural organic matter on the degradation efficiency of RhB were investigated. This study revealed that thermal activation at 300 °C changed the chemical valency of surface elements rather than transforming the major chemical phase of natural chalcopyrite. The Fenton-like degradation of RhB was significantly improved by thermally activated chalcopyrite. RhB degradation could be obtained under broad pH and showed high resistance to natural organic matter and anions. Under optimal conditions of H2O2 43.0 mM, catalyst 0.75 g/L, initial pH 5.1, and reaction temperature 25 °C, the degradation of RhB reached 96.7% at 50 min. Based on the rate constant of reaction kinetics, the activation energy for RhB degradation was calculated to be 9 kJ/mol. Radical scavenging experiments and electron paramagnetic resonance (EPR) technique demonstrated that RhB degradation was dominated by the generated hydroxyl radicals in activated chalcopyrite/H2O2 system. The formation of surface sulfates resulted from thermal activation induced the dissolved copper or iron ions, and promoted H2O2 activation and facilitated RhB degradation by reactive hydroxyl radicals. This work provides an in-depth understanding of the mechanism behind thermal activation to enhance the activity of natural chalcopyrite, offering a theoretical basis for utilizing natural minerals for Fenton-like treatment of organic wastewater towards cleaner production.