Oxidation Rate Research Articles

Subcritical water delamination: A promising path to efficient recycling of critical minerals

The objective of this study is to degrade the polymer layers within crystalline silicon (c-Si) photovoltaic modules and delaminate the essential valuable minerals for recycling, employing solely the thermodynamic attributes of water under subcritical conditions and abstaining from the utilization of chemical solvents. The c-Si wafer was successfully delaminated from the polymer structures at 200 °C, 100 bar for 30 min in a high-pressure reactor and ground in a planetary ball mill, where the experimental conditions were optimized for energy consumption using a Box-Behnken design. Hydrothermal subcritical delamination process provides structural changes in the polymer layers due to swelling of the ethylene vinyl acetate (EVA) and hardening of the backsheet. The energy consumption measured at the laboratory scale corresponds to the optimum response value of 0.132 kWh, demonstrating the effectiveness of the study under short-term and stable conditions.The c-Si wafer analyzed using techniques such as EDXRF, XRD, TGA, FTIR, and SEM/EDS. 87.5% Si, 1.95% aluminum, 1.12% silver, and 1.23% other metals were recovered from the solar cell. However, an oxidation rate of 6.71% by mass was detected in the c-Si wafer. The recovery rate of valuable minerals by ignoring oxidation is 98.4% of the total mass.

Tailoring oxidation resistance of Cantor alloy by addition of Ta and Al

High-entropy alloys are widely investigated for applications in the nuclear engineering field, the aerospace sector, and various other high-temperature applications. High-temperature oxidation behaviour is a typical issue in such applications. In the current work, an effort is made to tailor the oxidation behaviour of Cantor alloy (CoCrFeMnNi) in the air at 1000 °C with the addition of Ta and Al. Both CoCrFeMnNiTa as well as CoCrFeMnNiAl alloys exhibit considerable resistance to oxide scale spallation as well as develop multi-layered complex oxide scales. CoCrFeMnNiTa primarily forms rutile-type CrTaO4 oxide, which drastically reduces the inward diffusion of oxygen and nitrogen and suppresses the escape of other alloying elements. Nonetheless, the better result is obtained through the Al addition, as evidenced by the comparatively lower oxidation rate constant of CoCrFeMnNiAl in comparison to CoCrFeMnNiTa alloy. This is attributed to the superior oxidation resistance for CoCrFeMnNiAl could be related to the emergence of distinctive Cr2O3 and Al2O3 scales. Additionally, the oxide scale of CoCrFeMnNiTa was not completely smooth and showed some spallation whereas the oxide scales of CoCrFeMnNiAl remained smooth, continuous, and had stronger oxide-substrate interface adhesion.

Carbohydrate storage in cells: a laboratory activity for the assessment of glycogen stores in biological tissues.

Carbohydrates and fats constitute our primary energy sources. The importance of each of these energy substrates varies across cell types and physiological conditions. For example, the brain normally relies almost exclusively on glucose oxidation, while skeletal muscle shifts from lipids towards higher carbohydrate oxidation rates as exercise intensity increases. Understanding how carbohydrate are stored in our cells and which tissues contain significant carbohydrate stores is crucial for health professionals, especially given the role of carbohydrate metabolism in various pathophysiological conditions. This laboratory activity uses a simple and low-cost iodine binding method to quantify glycogen in mouse skeletal muscle and liver samples. By integrating the results of this activity with literature data, students can determine overall glycogen storage in the human body. The primary goal of the activity is to enhance students understanding of the importance and limitations of glycogen stores in energy metabolism.

Tailoring oxygen vacancies by synergy of dual metal cations in LaCo0.8M0.2O3 (M = Cu, Ni, Fe, Mn) towards catalytic oxidation of toluene

Enhancing the catalytic performance of transition metal oxide catalysts is prerequisite for the efficient catalytic oxidation of VOCs. Here the B-site partially substituted LaCoO3 (LaCo0.8M0.2O3, M = Cu, Ni, Fe and Mn) catalysts was synthesized for the catalytic oxidation of toluene. Among these catalysts, LaCo0.8Ni0.2O3 catalyst exhibits remarkable catalytic performance for toluene with T50 = 226 °C and T90 = 239 °C at an initial toluene concentration of 1000 ppm, whose T50 (and T90) reduced by 13 °C (and 34 °C) compared with that of LaCoO3. Confirmed by BET, XPS, and EPR characterizations, Ni substitution improves the specific surface area, Co3+/Co2+ ratio, Oads/Olatt ratio, and oxygen vacancies concentration. This improvement indicates the improvement of adsorption and activation of reactant, mobility of oxygen species, thereby contributing to the superior catalytic performance in toluene oxidation. The B-site of LaCoO3 occupied by dual cations caused the lattice distortion and formation of oxygen vacancies due to the ionic radii difference between Co and Ni cations. Moreover, the apparent activation energy of LaCo0.8Ni0.2O3, as the determining factor for the catalytic oxidation rate, was remarkably reduced. Our findings confirmed the synergy effect of Co and Ni cations at B-site on the enhancement of catalytic activity, which provides a promising strategy for oxygen vacancy engineering.

Successful operation of nitrifying granules at low pH in a continuous-flow reactor: Nitrification performance, granule stability, and microbial community

Acidic nitrification, as a novel process for treating wastewater without sufficient alkalinity, has received increasing attention over the years. In this study, a continuous-flow reactor with aerobic granular sludge was successful operated at low pH (<6.5) performing high-rate acidic nitrification. Volumetric ammonium oxidation rate of 0.4–1.2 kg/(m3·d) were achieved with the specific biomass activities of 5.8–13.9 mg N/(gVSS·h). Stable partial nitritation with nitrite accumulation efficiency over 85% could be maintained at pH above 6 with the aid of residual ammonium, whereas the nitrite accumulation disappeared when pH was below 6. Interestingly, the granule morphology significantly improved during the acidic operation. The increased secretion of extracellular polymeric substances (especially polysaccharides) suggested a self-protective behavior of microbes in the aerobic granules against acidic stress. 16S rRNA gene sequencing analyses indicated that Candidatus Nitrospira defluvii was always the dominant nitrite-oxidizing bacteria, while the dominant ammonia-oxidizing bacteria shifted from Nitrosomonas europaea to Nitrosomonas mobilis. This study, for the first time, demonstrated the improved stability of aerobic granules under acidic conditions, and also highlighted aerobic granules as a useful solution to achieve high-rate acidic nitrification.

Ionic Liquid 1-Octyl-3-Methylimidazolium (M8OI) Is Mono-Oxygenated by CYP3A4 and CYP3A5 in Adult Human Liver

Environmental sampling around a landfill site in the UK previously identified the methylimidazolium ionic liquid, 1-octyl-3-methylimidazolium (M8OI), in the soil. More recently, M8OI was shown to be detectable in sera from 5/20 PBC patients and 1/10 controls and to be oxidised on the alkyl chain in the human liver. The objective of this study was to examine the metabolism of M8OI in humans in more detail. In human hepatocytes, M8OI was mono-oxygenated to 1-(8-Hydroxyoctyl)-3-methyl-imidazolium (HO8IM) then further oxidised to 1-(7-carboxyheptyl)-3-methyl-1H-imidazol-3-ium (COOH7IM). The addition of ketoconazole—in contrast to a range of other cytochrome P450 inhibitors—blocked M8OI metabolism, suggesting primarily CYP3A-dependent mono-oxygenation of M8OI. Hepatocytes from one donor produced negligible and low levels of HO8IM and COOH7IM, respectively, on incubation with M8OI, when compared to hepatocytes from other donors. This donor had undetectable levels of CYP3A4 protein and low CYP3A enzyme activity. Transcript expression levels for other adult CYP3A isoforms—CYP3A5 and CYP3A43—suggest that a lack of CYP3A4 accounted primarily for this donor’s low rate of M8OI oxidation. Insect cell (supersome) expression of various human CYPs identified CYP3A4 as the most active CYP mediating M8OI mono-oxygenation, followed by CYP3A5. HO8IM and COOH7IM were not toxic to human hepatocytes, in contrast to M8OI, and using a pooled preparation of human hepatocytes from five donors, ketoconazole potentiated M8OI toxicity. These data demonstrate that CYP3A initiates the mono-oxygenation and detoxification of M8OI in adult human livers and that CYP3A4 likely plays a major role in this process.

Ionic Liquid 1-Octyl-3-Methylimidazolium (M8OI) Is Mono-Oxygenated by CYP3A4 and CYP3A5 in Adult Human Liver.

Environmental sampling around a landfill site in the UK previously identified the methylimidazolium ionic liquid, 1-octyl-3-methylimidazolium (M8OI), in the soil. More recently, M8OI was shown to be detectable in sera from 5/20 PBC patients and 1/10 controls and to be oxidised on the alkyl chain in the human liver. The objective of this study was to examine the metabolism of M8OI in humans in more detail. In human hepatocytes, M8OI was mono-oxygenated to 1-(8-Hydroxyoctyl)-3-methyl-imidazolium (HO8IM) then further oxidised to 1-(7-carboxyheptyl)-3-methyl-1H-imidazol-3-ium (COOH7IM). The addition of ketoconazole-in contrast to a range of other cytochrome P450 inhibitors-blocked M8OI metabolism, suggesting primarily CYP3A-dependent mono-oxygenation of M8OI. Hepatocytes from one donor produced negligible and low levels of HO8IM and COOH7IM, respectively, on incubation with M8OI, when compared to hepatocytes from other donors. This donor had undetectable levels of CYP3A4 protein and low CYP3A enzyme activity. Transcript expression levels for other adult CYP3A isoforms-CYP3A5 and CYP3A43-suggest that a lack of CYP3A4 accounted primarily for this donor's low rate of M8OI oxidation. Insect cell (supersome) expression of various human CYPs identified CYP3A4 as the most active CYP mediating M8OI mono-oxygenation, followed by CYP3A5. HO8IM and COOH7IM were not toxic to human hepatocytes, in contrast to M8OI, and using a pooled preparation of human hepatocytes from five donors, ketoconazole potentiated M8OI toxicity. These data demonstrate that CYP3A initiates the mono-oxygenation and detoxification of M8OI in adult human livers and that CYP3A4 likely plays a major role in this process.

Effects of " Air Pollution Prevention and Control Action Plan " on PM2.5 and Chemical Compositions in Zhengzhou in Polluted Winters

The Air Pollution Prevention and Control Action Plan （APPCAP） was promulgated in China in 2013. To explore the effectiveness of APPCAP on PM2.5 in winter in Zhengzhou, PM2.5 samples were collected in Zhengzhou Monitoring Center during December 2013 and December 2018. The chemical composition of PM2.5 was analyzed, including EC, OC, water soluble ions, and metal elements. Pollution episodes under different stages were selected to investigate the changes in PM2.5 concentration and composition. The results showed that： ① The average concentration of PM2.5 in winter in Zhengzhou decreased from （215.38 ±107.28） μg·m-3 in 2013 to （77.45 ±49.81） μg·m-3 in 2018, with a decrease rate of 64%. ② The concentrations of EC, K+, SO42-, and Cl- decreased by 85%, 80%, 78%, and 72%, respectively, and the decrease rate in OC, NH4+, and NO3- was 50%, 41%, and 32%, respectively. ③ Compared with those in winter of 2013, the ratios of OC/EC in winter of 2018 increased by 2.6 times, and the proportion of secondary organic carbon in OC increased to 57%； meanwhile, values of sulfur oxidation rate and nitrogen oxidation rate increased by 1.5 and 1.0 times, respectively, indicating heavy secondary pollution in Zhengzhou. ④ The mass ratios of NO3-/SO42-increased from 0.8 ±0.2 in 2013 to 2.5 ±1.0 in 2018, indicating that the contribution of mobile sources increased and surpassed fixed sources as the main source in Zhengzhou. ⑤The comparison results of different stages of the heavy pollution process showed that ρ（PM2.5） decreased significantly in 2018 compared with that in 2013, with the peak concentration decreasing by 61%. The main chemical composition changed from OC, NO3-, SO42-, and NH4+ to OC, NO3-, and NH4+. The results indicated that the primary emission source control in Zhengzhou had achieved remarkable effects, but the contribution of secondary generation to PM2.5 showed an elevated trend； thus, the influence of secondary generation requires further attention in the future.

Algae promotes the biogenic oxidation of Mn(II) by accelerated extracellular superoxide production

Microbial manganese (Mn) oxidation, predominantly occurs within the anaerobic-aerobic interfaces, plays an important role in environmental pollution remediation. The anaerobic-aerobic transition zones, notably riparian and lakeside zones, are hotspots for algae-bacteria interactions. Here, we adopted a Mn(II)-oxidizing bacterium Pseudomonas sp. QJX-1 to investigate the impact of algae on microbial Mn(II) oxidation and verify the underlying mechanisms. Interestingly, we achieved a remarkable enhancement in bacterial Mn(II)-oxidizing activity within the algae-bacteria co-culture, despite the inability to oxidize Mn(II) for the algae used in this study. In addition, the bacterial density almost remains constant in the presence of algal cells. Therefore, the increased Mn(II) oxidation by QJX-1 in the presence of algae cannot be due to the increased biomass. Within this co-culture system, the Mn(II) oxidation rate surged to an impressive 0.23 mg/L/h, in stark contrast to 0.02 mg/L/h recorded within pure QJX-1 system. The presence of algae could inhibit the Fe-S cluster activity of QJX-1 by the produced active substance in co-culture, and result in the acceleration of extracellular superoxide production due to the impairment of electron transfer functions located in QJX-1 cell membranes. Moreover, elevated peroxidase gene expression and heightened extracellular catalase activity not only expedited Mn(II) ions oxidation but also facilitated conversion of intermediate Mn(III) ions into microbial Mn oxides, achieved through the degradation of hydrogen peroxide. Therefore, the acceleration of extracellular superoxide production and the decomposition of hydrogen peroxide are identified as the principal mechanisms behind the observed enhancement in Mn(II) oxidation within algae-bacteria co-cultures. Our findings highlight the need to consider the effect of algae on microbial Mn(II) oxidation, which plays an important role in the environmental pollution remediation.

Diethyl Sulfide Oxidation with Sodium Peroxoborate in Water–Acetonitrile System. Kinetics and Mechanism

In aqueous solutions of acetonitrile (1 vol%), the rate of oxidation of diethyl sulfide with sodium peroxoborate, Na2[B2(O2)2(OH)4]∙6H2O, in the pH range of 8.5–11 is significantly higher than the oxidation rate in water and exceeds the rate of reaction of Et2S with hydrogen peroxide in the H2O–MeCN system. The reaction order with respect to the substrate, which is close to zero, suggests that the limiting stage of the process is the reaction of peroxoborate anions with MeCN, leading to the formation of active boron peroxyimidates, which then react in a rapid stage with Et2S.

FeCo@hydrochar nanocomposites as efficient peroxymonosulfate activator for organic pollutant degradation.

Sulfate radical-based advanced oxidation processes (SR-AOPs) are renowned for their exceptional capacity to degrade refractory organic pollutants due to their wide applicability, cost-effectiveness, and swift mineralization and oxidation rates. The primary sources of radicals in AOPs are persulfate (PS) and peroxymonosulfate (PMS) ions, sparking significant interest in their mechanistic and catalytic aspects. To develop a novel nanocatalyst for SR-AOPs, particularly for PMS activation, we synthesized carbon-coated FeCo nanoparticles (NPs) using solvothermal methods based on the polyol approach. Various synthesis conditions were investigated, and the NPs were thoroughly characterized regarding their structure, morphology, magnetic properties, and catalytic efficiency. The FeCo phase was primarily obtained at [OH-] / [Metal] = 26 and [Fe] / [Co] = 2 ratios. Moreover, as the [Fe]/[Co] ratio increased, the degree of xylose carbonization to form a carbon coating (hydrochar) on the NPs also increased. The NPs exhibited a spherical morphology with agglomerates of varying sizes. Vibrating-sample magnetometer analysis (VSM) indicated that a higher proportion of iron resulted in NPs with higher saturation magnetization (up to 167.8 emu g-1), attributed to a larger proportion of FeCo bcc phase in the nanocomposite. The best catalytic conditions for degrading 100ppm Rhodamine B (RhB) included 0.05g L-1 of NPs, 2mM PMS, pH 7.0, and a 20-min reaction at 25°C. Notably, singlet oxygen was the predominant specie formed in the experiments in the SR-AOP, followed by sulfate and hydroxyl radicals. The catalyst could be reused for up to five cycles, retaining over 98% RhB degradation, albeit with increased metal leaching. Even in the first use, dissolved Fe and Co concentrations were 0.8 ± 0.3 and 4.0 ± 0.5mg L-1, respectively. The FeCo catalyst proved to be effective in dye degradation and offers the potential for further refinement to minimize Co2+ leaching.

The impact of pre-drying and different infrared powers on some quality parameters of apple chips fried by vacuum-combined infrared radiation

In this study, the use of vacuum-combined infrared radiation (VCIR) as a frying technique for the production of apple chips was investigated. The effects of a pre-drying treatment before frying on the quality parameters of apple chips were also evaluated. While the frying time of apple slices decreased by increasing the infrared power, the browning index value, 5-hydroxymethylfurfural (HMF) content, and oxidation ratio were raised. The frying times, oil contents, browning, and oxidation rates of apple chips were decreased with the pre-drying treatment. The sensory analyzes showed that the samples fried by vacuum-combined infrared radiation had the highest scores in all sensory characteristics than deep-fat fried samples. Pre-dried apple samples (41% moisture) fried at 350W infrared power under 400 mmHg vacuum pressure had the highest score for general acceptance. The results showed that VCIR would be an alternative frying method for producing healthier apple chips with less oil content and higher quality.

Improving the transfer of dissolved oxygen in a biological Fe2+ oxidation process using a venturi jet as an intensive aeration system

The low bio-production of Fe3+ as a leaching agent is one of the main limitations to implementing industrial bio-processes at feasibility conditions. The main limitation of the bio-oxidation process of Fe2+ is the low oxygen transfer to the aqueous phase because of the low oxygen solubility. This study assesses the effectiveness of the venturi jet as an innovative and intensive aeration device for overcoming the oxygen limitation in a continuous ferrous oxidation process in a fixed-bed reactor with immobilized acidithiobacillus ferrooxidans, in contrast to the conventional diffuser aeration device. Firstly, the influence of the airflow and the influence of the medium concentration were determined for the following parameters for both aeration devices; Volumetric mass transfer coefficient (kLa), Standard Oxygen Transfer Rate (SOTR), Standard Aeration Efficiency (SAE), and Standard Oxygen Transfer Efficiency (SOTE). Then, both aeration devices were compared in a continuous bio-oxidation process in an up-flow packed bio-reactor (UFPB). The system performance was assessed by monitoring temperature, pH, oxidation-reduction potential, and dissolved oxygen concentration for 69 days. Findings displayed that when aerating with the diffuser, the ferrous oxidation rate was restricted by the low dissolved oxygen availability, being about 1 ppm (1 mg L−1). Under these oxygen-limiting conditions, the maximum ferrous (Fe2+) oxidation rate was 9.09 g L−1 h−1. However, when aerating with the venturi jet, the dissolved oxygen concentration increased up to 2.70 mg L−1, achieving a maximum of 29.11 g L−1 h−1. So, this study has demonstrated that the change in the aeration device has resulted in an improvement in the process, achieving a 3.5-fold increase in the oxidation rate. Furthermore, the venturi jet offered additional advantages over the diffuser, such as requiring less power to deliver the same amount of air, being unaffected by jarosite precipitates, and not requiring a supply of compressed air.

Electrochemical Oxidation Mechanism of Pyrite in a Copper(II)-Citrate-Sodium Thiosulfate Composite System

Pyrite is an important gold carrier during gold leaching, but it is readily oxidized, which causes environmental problems such as acidic mine drainage. Thus, it is necessary to study the oxidation mechanism of pyrite in a gold-leaching electrolyte. The surface oxidation reaction of pyrite is a multi-electron transfer electrochemical oxidation process. Based on this, electrochemical technology was used to explore the electrochemical oxidation mechanism of pyrite in a Cu2+-Cit3−-S2O3 2− system. The surface oxidation products of the pyrite were characterized by Raman spectroscopy and X-ray photoelectron spectroscopy. The experiments showed that the thiosulfate concentration did not change the oxidation mechanism of pyrite at 0.30 V under the conditions of this experiment. Increasing the concentration and potential of thiosulfate accelerated the oxidation rate of pyrite. The electrochemical oxidation of pyrite in the Cu2+-Cit3−-S2O3 2− system occurred in two stages. At low potentials in a passivated state, the process was diffusion-controlled, and the surface oxidation rate was slow. When the potential exceeded 0.50 V, the passivation film on the surface was penetrated, allowing the oxidation reaction on the surface of pyrite to continue. The results of this experiment are useful for deepening the understanding of the oxidation mechanism of pyrite in electrolytes.

Diversity, Methane Oxidation Activity, and Metabolic Potential of Microbial Communities in Terrestrial Mud Volcanos of the Taman Peninsula.

Microbial communities of terrestrial mud volcanoes are involved in aerobic and anaerobic methane oxidation, but the biological mechanisms of these processes are still understudied. We have investigated the taxonomic composition, rates of methane oxidation, and metabolic potential of microbial communities in five mud volcanoes of the Taman Peninsula, Russia. Methane oxidation rates measured by the radiotracer technique varied from 2.0 to 460 nmol CH4 cm-3 day-1 in different mud samples. This is the first measurement of high activity of microbial methane oxidation in terrestrial mud volcanos. 16S rRNA gene amplicon sequencing has shown that Bacteria accounted for 65-99% of prokaryotic diversity in all samples. The most abundant phyla were Pseudomonadota, Desulfobacterota, and Halobacterota. A total of 32 prokaryotic genera, which include methanotrophs, sulfur or iron reducers, and facultative anaerobes with broad metabolic capabilities, were detected in relative abundance >5%. The most highly represented genus of aerobic methanotrophs was Methyloprofundus reaching 36%. The most numerous group of anaerobic methanotrophs was ANME-2a-b (Ca. Methanocomedenaceae), identified in 60% of the samples and attaining relative abundance of 54%. The analysis of the metagenome-assembled genomes of a community with high methane oxidation rate indicates the importance of CO2 fixation, Fe(III) and nitrate reduction, and sulfide oxidation. This study expands current knowledge on the occurrence, distribution, and activity of microorganisms associated with methane cycle in terrestrial mud volcanoes.

Mechanistic insight into microbial interaction and metabolic pattern of anammox consortia on surface-modified biofilm carrier with extracellular polymeric substances

The extremely slow growth rate of anaerobic ammonia oxidation (anammox) bacteria limits full-scale application of anammox process worldwide. In this study, extracellular polymeric substances (EPS)-coated polypropylene (PP) carriers were prepared for biofilm formation. The biomass adhesion rate of EPS-PP carrier was 12 times that of PP carrier, and EPS-PP achieved significant enrichment of E. coli BY63. The 120-day continuous flow experiment showed that the EPS-PP carrier accelerated the formation of anammox biofilm, and the nitrogen removal efficiency increased by 10.5 %. In addition, the abundance of Candidatus Kuenenia in EPS-PP biofilm was 27.1%. Simultaneously, amino acids with high synthesis cost and the metabolites of glycerophospholipids related to biofilm formation on EPS-PP biofilm were significantly up-regulated. Therefore, EPS-PP carriers facilitated the rapid formation of anammox biofilm and promoted the metabolic activity of functional bacteria, which further contributed to the environmental and economic sustainability of anammox process.

Bifunctional sulfur-doped biochar for efficient removal of tetracycline and resistant bacteria via adsorption and peroxydisulfate activation

Sulfur-doped biochar (SBC) was prepared for the efficient removal of tetracycline (TC) and TC-resistant bacteria via the dual functions of adsorption and peroxydisulfate (PDS) activation. One of the prepared SBC/PDS systems was found to remove 93.89 % of TC with 3.11 times the removal efficiency of the system without sulfur doping (i.e., BC/PDS). The SBC/PDS system inactivated approximately 105 CFU/mL of the TC-resistant bacterium Escherichia coli within 90 min, corresponding to 1.14 times the inactivation efficiency of the BC/PDS system. The introduction of sulfur improved the adsorption rate by 3.09 times, likely due to pore filling and hydrogen bonding. The PDS activation of the SBC/PDS system primarily removed TC and E. coli through nonradical oxidation dominated by 1O2 generation, and the main active sites were vacancy defects. TC adsorption may be the key step for determining the reaction rate of nonradical oxidation. A high correlation (R2 = 0.98) was observed between the adsorption capacity and degradation rate constant of different activator systems, which indicated a synergistic effect between the adsorption and oxidation of TC. This study provides a theoretical basis for the development of advanced oxidation processes utilizing bifunctional materials with a nonradical oxidation pathway for the removal of antibiotics and antibiotic-resistant bacteria.

Electrical modeling of an electrochemical sensor operating at the redox cycling mode

In this work, the direct current vs. voltage (DC) characteristics, and the alternate current (AC) impedance of a 1D four-electrode electrochemical cell, operating under redox-cycling conditions, are presented and discussed. The analysis refers to a four-electrode electrochemical system with one positively biased working electrode, one negatively biased working electrode, one auxiliary electrode, and one reference electrode operating in a redox cycling mode. This configuration is useful, for example, for electrochemical biosensors that can benefit from the inherent redox-cycling amplification of the apparatus. An aqueous buffered electrolyte is assumed, containing electrochemically active species that can be oxidized on the anode, with a positive overpotential. Meanwhile, the product of the oxidation reaction can diffuse to the other working electrode which has a negative overpotential, where the product is reduced. The analysis in this paper assumes that oxidation is the dominant mechanism at the anode, reduction is the dominant mechanism at the cathode, and the transport between them is dominated by diffusion. Since it is a 1D model, an ideal lossless redox cycling, i.e. both working electrodes’ currents (anodic and cathodic) are of the same magnitude with opposite signs, is assumed. Next, the small signal (AC) impedance of the electrochemical cell was calculated assuming that the AC signal modifies the oxidation reaction rate at the anode while the reduction reaction rate at the cathode is fixed. The impedance under redox cycling is calculated vs. frequency for various oxidation and reduction rates and both Bodé and Nyquist plots of the impedance are presented. The last part of the paper presents measured data for both DC and AC (i.e. Bodé and Nyquist plots) experiments with interdigitated array (IDA) electrodes, 5 & 10 μm spacing, operating under redox cycling conditions. The DC measurements were conducted in a 6 mM ferricyanide [K3Fe(CN)6] in 0.1 M Phosphate Buffer Saline (PBS) solution, pH 7.4. The AC measurements were conducted in 10 mM & 100 nM ferricyanide (K3Fe(CN)6) in 100 mM KNO3 aqueous electrolyte. A critical discussion follows the results section where the highlights and problems of the models are discussed.

Oxidation behavior of Cu–Ag alloy in-situ manufactured via laser powder bed fusion

The oxidation behavior of copper-silver (Cu–Ag) alloy with the structure of triply periodic minimal surfaces (TPMS) processed by laser powder bed fusion (LPBF) was investigated at 300°C and 600°C. The lightweight TPMSs increase surface area, boosting measurement sensitivity in oxidation studies. The presence of silver enhances oxidation resistance of Cu–Ag alloy compared to that of pure copper by slowing down the oxidation process and thinning the oxide layer. This suggests that silver in the alloy potentially suppresses the outward diffusion of copper from the substrate to the oxide layer. This effect is evident in the oxidation rate curves, where the introduction of silver changes the oxidation kinetics from a linear rate in Cu to a parabolic rate in Cu–2 wt.% Ag at 300°C. Moreover, at 600°C, silver induces a slower parabolic rate in Cu–2 wt.% Ag compared to Cu.

The Impacts of Red Mud on Road Performance and Aging Resistance of Asphalt Mixture

Abstract Red mud as an asphalt modifier has been investigated in some studies, but few studies are further concerned about the effect of red mud on performance of asphalt mixture. In this study, the impact of red mud on road performance and aging endurance of asphalt mixtures was evaluated. Primarily, the optimal asphalt content was determined based on mechanical strength and volumetric properties. Then, the performance evaluations, including Marshall stability, low-temperature splitting, freeze-thaw splitting, indirect tensile fatigue, and thermal-oxidative aging, were executed. The outcomes demonstrate that in comparison with the base asphalt mixture, red mud asphalt mixture exhibits worse high-temperature stability and moisture resistance, and superior temperature shrinkage cracking resistance and fatigue performance. After the surface of red mud has been modified, the adhesion between asphalt mastics and aggregate is strengthened, and the distribution of red mud in asphalt mixture becomes more uniform, which intensifies the rigidity and road performance (except for low-temperature cracking resistance) of asphalt mixture. Furthermore, since red mud absorbs a portion of asphalt content, it can hinder the physical hardening and oxidation rate of asphalt mixture. The anti-aging ability of asphalt mixture is further reinforced by the incorporation of organic red mud.