Linear Sweep Research Articles

NiMnO nanoparticle-activated carbon anodes for efficient urea oxidation and energy production in wastewater-driven direct urea fuel cells

The growing concern over urea-containing wastewater from industrial sources necessitates innovative treatment solutions that also offer sustainable energy production. In this study, a novel anode material is developed by decorating activated carbon with NiMnO nanoparticles through thermal treatment under an inert atmosphere. The resulting NiMnO NPs-decorated activated carbon was evaluated for its electrocatalytic performance in the electrooxidation of urea and its application in a direct urea fuel cell (DUFC). X-ray diffraction patterns confirmed the formation of nickel metal and Mn(II) oxide, with activated carbon showing representative peaks. Scanning electron microscopy images revealed well-dispersed nanoparticles on the activated carbon surface, corroborated by uniform elemental distribution from mapping results. Electrochemical measurements using cyclic voltammetry demonstrated that the 30 wt% MnAc sample exhibited the highest electrocatalytic activity among the tested samples (0, 5, 10, 20, 30, 40 and 50 wt% MnAc) with a maximum current density of 123 mA/cm2 at 3.0 M urea concentration and an onset potential of −0.02 V versus Ag/AgCl. Linear sweep voltammetry of the assembled DUFC showed promising open circuit potentials of 0.82 V and maximum power densities reaching 4.9 W/m2, achieved using industrial wastewater from the Egyptian Chemical Industries Company (KIMA) in Aswan, Egypt. The results highlight the efficacy of NiMnO NPs-decorated activated carbon in both urea oxidation and electrical energy generation. This study not only provides a viable method for treating urea-rich industrial wastewater but also presents a sustainable approach to energy production. The findings underscore the potential of this material for future applications in DUFCs, offering significant environmental and economic benefits.

Reversible in situ Control over Monolayer Organization.

Cr2+ and Cr3+ ions are shown to mediate the formation, morphology, and organization of arachidic acid (AA) Langmuir-Blodgett (LB) monolayers. This finding, based on cyclic voltammetry (CV), linear sweep voltammetry (LSV) and fluorescence recovery after photobleaching (FRAP) measurements, show that Langmuir monolayer formation depends on subphase pH and metal ion concentration. Following monolayer deposition on indium tin oxide (ITO), the LB monolayer organization can be modified reversibly through control of the Cr oxidation state, which has not been shown before by other monolayers formed with other divalent metal ions. The dynamics and the mobility of a chromophore (perylene) incorporated into the monolayer sense changes in Cr oxidation state-dependent organization of the LB monolayer. Demonstrating reversible changes in monolayer organization provides an opportunity to control chemical and electron access to the interface support.

Compositional dependence of electrochemical properties in biopolymer blend-based solid electrolytes doped with sodium perchlorate for EDLC applications

Biopolymer-based blends of solid electrolytes capable of conducting sodium ions were prepared via solution casting by incorporating sodium carboxymethyl cellulose (NaCMC) and polyvinyl alcohol (PVA) with varying concentrations of sodium perchlorate monohydrate (NaClO4.H2O), which was used as the dopant. The prepared electrolytes were characterized to reveal their structural, vibrational, electrical, and electrochemical properties that make them promising as solid polymer electrolytes (SPEs). X-ray diffraction (XRD) analysis showed that the amorphous nature of the sample increased with the addition of NaClO4.H2O salt concentrations of up to 30 wt.%. The complexation between the polymers and salt was confirmed by Fourier-Transform Infrared (FTIR) analysis. The SPE exhibited an optimal ionic conductivity of (1.90 ± 0.05) ×10−5 S cm−1, which is three orders higher than that of the pristine polymer blend with (5.31 ± 0.61) ×10−8 S cm−1, as determined by electrochemical impedance spectroscopy (EIS) analysis. Scaling studies conducted based on AC conductivity and tangent loss revealed that these measurements could be represented by a single master curve, which suggests that the optimal sample adheres to the time-temperature superposition principle (TTSP). The temperature dependence of Jonscher's exponent indicates that the conduction mechanism can be effectively represented by the Quantum Mechanical Tunneling model (QMT). Both transference number measurement (TNM) and linear sweep voltammetry (LSV) analyses validated the electrolyte's suitability for energy device applications by demonstrating its high ion transference number and electrochemical potential window of 3.93 V. The optimized SPE film was subsequently utilized in an electrochemical double-layer capacitor (EDLC) device to evaluate its performance as both an electrolyte and separator. The supercapacitor exhibited an impressive energy density of 15.18 Wh kg−1 and a power density of 4512.5 W kg−1, along with remarkable stability in terms of cycle life.

Enhancing of hydroquinone and catechol oxidation using a graphite and graphene composite polymer modified paste electrode

ABSTRACT An innovative electrochemical redox response of hydroquinone (HQN) and catechol (CCL) was analysed using a bare graphite and graphene composite paste electrode (BGGCPE) and polymerised L-leucine modified graphite and graphene composite paste electrode (LCN-MGGCPE) was successfully developed in 0.2 M phosphate buffer solution (PBS) with pH 6.0 at a 0.1 V/s scan rate. Fabricated electrode using simple and cost-effective method, the polymerised LCN-MGGCPE surface shows more electrochemical activity, sensitivity and selectivity towards the determination for HQN and CCL. Cyclic voltammetry (CV), linear sweep voltammetry (LSV), Differential pulse voltammetry (DPV), and electrochemical impudence spectroscopy (EIS) were utilised as analytical techniques while LCN-MGGCPE and BGGCPE surface characterisation were studied using a scanning electron microscopy (SEM) technique. LCN-MGGCPE exhibited superior electrochemical activity compared to BGGCPE towards the oxidation responses of both HQN and CCL. Additionally, the effect of pH studies, scan rate change for HQN, and concentration change of analyte molecule were examined, with the 0.025 to 0.500 V/s scan rate varied and revealing an adsorption-controlled process. The concentration changes of CVs methods ranged from 0.2 to 320 μM, DPVs ranged from 0.2 to 1100 μM and LSVs ranged from 0.2 to 850 μM, the calculated a limit of detection (LOD) of CV, DPV, and LSV, is 0.020 μM, 0.026 μM, and 0.011 μM and a limit of quantification (LOQ) of 0.068 μM, 0.088 μM, and 0.035 μM. The electrochemically developed LCN-MGGCPE shows good reproducibility, repeatability, stability, sensitivity and simultaneous analysis of analyte molecules were studied. This study presents a promising pathway for the growth of effective sensors for the determination of HQN in medicinal and water sample applications.

High-spatial-resolution quasi-distributed acoustic sensing with phase noise suppression based on φ-OFDR

A quasi-distributed acoustic sensor with high-spatial-resolution based on phase-sensitive optical frequency domain reflectometry (φ-OFDR) was demonstrated. The source of noise that affects the accuracy of phase demodulation was analyzed. Two low noise linear frequency sweeps (LFSs) with different sweep ranges obtained by injection-locking method were used to achieve high-spatial-resolution and long-distance sensing. The phase noise caused by laser, intensity and fading noises was effectively suppressed by further combining a femtosecond-laser-inscribed weak reflector array (WRA) and a phase index method (PIM). Vibration signals located a long distance of over 1 km were successfully demodulated with a spatial resolution of 2 cm through the use of 12 GHz LFS and a WRA with an interval of 2 cm. In addition, the 5 mm ultra-high spatial resolution capability of the system had been demonstrated through the use of 52 GHz LFS and a WRA with an interval of 5 mm.

Sewage sludge ash as filler in asphalt mastic: Low-temperature towards high-temperature performance

The sewage sludge ash (SSA) is characterized as a by-product used in the pavement industry to mitigate the environmental risks, enhance the landfill capacity and conserve the non-renewable resources. This research utilized SSA as a filler substitute in asphalt mastic, and its performance-based properties from low towards high temperatures were evaluated. For this goal, the physical and chemical properties of SSA and rock powder (used as base filler) were determined using BET surface area measurement, X-ray fluorescence, and scanning electron microscopy tests. The performance of base and SSA-modified asphalt mastics in four filler/bitumen weight ratios (0.6, 0.8, 1, and 1.2) was investigated using dynamic shear rheometer, multiple stress creep and recovery, linear amplitude sweep, and bending beam rheometer tests across a wide temperature range. The results indicate that SSA has a higher specific surface area, better bitumen absorption, and lower density compared to the base filler. Additionally, unlike the acidic nature of the base filler, SSA possesses strong basic properties, leading to a stronger chemical bond with bitumen and enhanced resistance to aging, particularly at high temperatures. Moreover, the lower density of SSA escalates the amount of filler per unit volume of the SSA-modified asphalt mastic, leading to the increased stiffness and elasticity. This trend improves resistance to permanent deformation and cracking at medium temperatures, although it has an adverse effect on performance of mastic at low temperatures. Moreover, due to the improved performance of SSA-modified asphalt mastic, this study can contribute to the sustainable development of the pavement industry.

The influence of pH electrolyte on the electrochemical deposition and properties of cerium oxide thin films

Thin cerium oxide layers cathodically deposited on zinc were studied. These electrochemically deposited coatings provide effective corrosion protection and require less deposition time compared to chemical conversion coatings. The kinetics of their formation depend on various factors, such as temperature, applied current density, electrolyte composition, pH, and agitation. In this study, the effect of bath solution pH was investigated, with coatings produced at room temperature from aqueous cerium nitrate solutions. Chronopotentiometry, linear sweep voltammetry, and electrochemical impedance spectroscopy (EIS) were used to monitor the deposition process, while scanning electron microscopy and energy-dispersive spectroscopy were performed to characterize the deposits. Corrosion resistance was evaluated through potentiodynamic tests in a 3.5% NaCl solution. The results indicate that the electrolyte pH significantly influences the cerium electrodeposition process. Based on the findings, the cerium oxide coating obtained from a pH 4 solution exhibited lower corrosion current density, higher polarization resistance, and superior anti-corrosion performance.

Facile synthesis of spherical-shaped CeC2–TiO2 nanocomposite electrocatalyst with boosted alkaline OER

Developing noble metal-free multifunctional electrocatalysts to catalyze water oxidation is vital for future renewable energy systems. Herein, through several defect modifications, the CeC2–TiO2 nanocomposite on the strength of enriched oxygen vacancies was successfully fabricated by facile hydrothermal method on SS (stainless steel) substrate, attributed to the conductive ability for fast electron transportation. A well-defined phase growth, vibrational bonding of metal atoms, morphological determination, and elemental composition for synthesized heterostructured electrocatalysts were revealed by XRD, FTIR, TEM, and EDX, respectively. XPS has complied to understand the moderate binding energies of CeC2–TiO2 for OER intermediates, which signifies the strong interactions between electronic states of Ce, C, Ti, and O atoms. With the plentiful catalytic active sites, the resultant CeC2–TiO2 entails low overpotentials of only 169 mV and 108.8 mV/dec Tafel slope to afford 10 mA cm−2 for OER in 1.0 M KOH are tested through cyclic and linear sweep voltammogram measurements, thereby exhibit promising activity in alkaline water electrolysis. EIS measurements revealed a decreased polarization resistance for the composite dominated by the small semicircle diameter, corresponding to the adsorption of intermediates. Finally, observed results strongly recommended that the CeC2–TiO2 catalyst exhibited superior OER performance due to excellent electrical chemical coupling between CeC2 and TiO2.

A comparative study into the effect of spent coffee powder and ash on improving the mechanical properties of bitumen

Nowadays, waste and renewable materials are used to modify bitumen and asphalt, reduce costs, decrease the use of natural resources, and maintain ecological balance, and have thus received much attention. This study aimed to improve the rheological properties of bitumen and reduce spent coffee grounds' (SCG) waste by partially replacing it with SCG powder and ash. SCG powder and ash were added in percentages of 0, 1, 3, 5, and 8 wt percent of bitumen to check the properties of control and modified bitumens. Microstructural properties were evaluated by Fourier transform infrared spectroscopy, thermal gravimetric analysis, X-ray fluorescence spectroscopy (XRF), and scanning electron microscopy (SEM). Penetration, softening point, and ductility tests were performed to check the physical properties of bitumens, along with the storage stability test. Rheological tests (viscosity, bending beam rheometer (BBR), dynamic shear rheometer (DSR), multiple stress creep and recovery (MSCR), and linear amplitude sweep (LAS) were also carried out. According to the BBR results, adding SCG powder up to −12 °C and adding SCG ash up to −6 °C increased the resistance to low temperatures. Based on DSR and MSCR results, SCG, either in the form of ash or powder, increased the resistance to rutting, and adding SCG ash improved the high temperature performance of bitumen by 1 grade. At 64 °C, adding 8 % of SCG powder increased the rutting resistance by 43 %, and adding SCG ash raised the rutting resistance by about 113 %. LAS results also showed that SCG ash outperforms SCG powder in fatigue. Although both SCG powder and ash performed well in high, moderate, and low temperatures, SCG powder performed better in cold regions, and SCG ash performed better in regions with temperate and tropical climates.

Evaluating diffusivity for efficient electrocatalytic conversion of carbon dioxide into multicarbon products using dealloyed hierarchically nanoporous copper

Hierarchical nanoporous copper (Hi-NPC) is a promising catalyst for carbon dioxide reduction reaction (CO2RR) due to its high surface area and excellent mass transport properties. To evaluate the effect of its architecture, eutectic-phased Cu18Al82 and single-phased Cu33Al67 were potentiostatically dealloyed to produce Hi-NPC and homogeneous nanoporous copper (Ho-NPC), respectively. At a comparable overpotential, the Hi-NPC electrocatalyst exhibited a significantly higher C2+ partial current density (jC2+) in CO2RR, reaching 510 mA/cm2, compared to both Ho-NPC (72 mA/cm2) and Cu electrodes (23 mA/cm2). When the current density was normalized by the electrochemically active surface area, the CO production among three electrodes demonstrated similar electrochemical behavior. However, notable differences were observed in the formation of C2H4 and C2H5OH, which can be attributed to the hierarchical structure of Hi-NPC facilitating C–C coupling to form C2 products. Although the Tafel plot indicated the CO2RR kinetics were identical for all three electrodes, linear sweep voltammetry experiments revealed that Hi-NPC exhibited the steepest current variation slope. Furthermore, the improved diffusivity was further confirmed by conducting oxygen reduction reactions with varying partial O2/N2 flow rates and electrochemical impedance spectroscopies. The hydrophobic properties of the electrode under various CO2RR current densities were also evaluated by water contact angle test.

Promoting Surface Reconstruction in Spinel Oxides via Tetrahedral‐Octahedral Phase Boundary Construction for Efficient Oxygen Evolution

AbstractUnderstanding the origin of surface reconstruction is crucial for developing highly efficient lattice oxygen oxidation mechanism (LOM) based spinel oxides. Traditionally, the reconstruction has been achieved through electrochemical procedures, such as cyclic voltammetry (CV), linear sweep voltammetry (LSV). In this work, we found that the surface reconstruction in LOM‐based CoFe0.25Al1.75O4 catalyst was an irreversible oxygen redox chemical reaction. And a lower oxygen vacancy formation energy (EO‐V) could benefit the combination of the activated lattice oxygen atoms with adsorbed water molecular. Motivated by this finding, a strategy of phase boundary construction from Co tetrahedral to octahedral was employed to decrease EO‐V in CoFe0.25Al1.75O4. The results showed that as the Co octahedral occupancy ratio rose to 64 %, a 3.5 nm‐thick reconstructed layer formed on the catalyst surface with a 158 mV decrease in overpotential. Further experiments indicated that the coexistence of tetrahedral‐octahedral (O−T) phase would result in lattice mismatch, promoting non‐bonding oxygen states and lowering EO‐V. Then more active lattice oxygen combined with H2O molecules to generate hydroxide ions (OH−), followed by soluble cation leaching, which enhanced the reconstruction process. This work provided new insights into the relationship between the intrinsic structure of pre‐catalysts and surface reconstruction in LOM‐based spinel electrocatalysts.

Engineering the mass transport properties in potassium-ion intercalated pristine Prussian blue for sustainable potassium-ion batteries

Potassium-ion batteries (PIBs) could be a cheaper and more abundant alternative to lithium-ion batteries, offering faster charging and suitability for large-scale energy storage. Prussian blue (PB) is prepared through a simple wet chemical method, and its intercalation affinity for K+ ions is tested using linear sweep voltammetry (LSV). The diffusion resistance (Rw: ∼116 Ω Hz1/2) and low-frequency region slope (m: ∼0.63) are found high for the third LSV drive (Seg-3), indicating passivation of the PB surface which leads to a double-layer formation. Most of the K+ ions are intercalated into PB until three LSV segments. After that PB surface is passivated and prohibits further LSV-driven K+ ions intercalation. On average, the Seg-3 sample exhibits a 58 % higher lattice strain in comparison to the as-prepared PB. A capacity of 27 mAh g−1 @ 2 mA g−1 in aqueous media is recorded for the Seg-3 sample and a capacity drop of 4 mAh g−1 and Coulombic efficiency of 99.3 % is recorded under 100 cycles. These findings are further comprehensively validated through multi-technique approaches. The observed affinity and single-stage LSV-driven intercalation of K+ ions highlight the perspective of PB as an electrode material for aqueous potassium ion batteries (a-PIBs).

Effects of antioxidants on chemical and rheological properties of asphalt binders from different crude oil sources

Antioxidants can effectively mitigate or delay the oxidative aging degradation of asphalt binder, thereby improving pavement durability. While research has largely concentrated on the application of antioxidants to asphalt binders from a single source, limited studies have explored their effects on binders derived from different crude oil sources. Moreover, the relationship between the chemical and rheological properties of antioxidant-modified asphalt binders remains insufficiently understood. In this study, three antioxidants - zinc diethyldithiocarbamate (ZDC), Irganox 1010 and kraft lignin - were utilized and blended with base binders sourced from three distinct regions globally. Fourier transform infrared spectroscopy (FTIR) was utilized to analyze the impact of these antioxidants on the chemical composition of aged binders. Additionally, dynamic shear rheometer (DSR) and bending beam rheometer (BBR) tests were conducted to assess the high- and low-temperature performance of the antioxidant-modified binders, identifying the most effective antioxidant. The linear amplitude sweep (LAS) test further evaluated the performance of ZDC across binders from different crude oil sources. The results revealed three key findings: first, chemical functional group changes due to antioxidants are not always reflected in rheological performance; second, ZDC demonstrated superior performance across different base binders, as evidenced by improved aging indices, high-temperature rutting resistance, and enhanced fatigue and low-temperature cracking resistance; and third, asphalt binders from different crude oil sources exhibit varying sensitivities to antioxidant type and dosage. This study underscores the necessity of determining optimal antioxidant dosages for different asphalt binders, as the relationship between antioxidant dosage and effectiveness is not straightforward.

Synthesis and electrochemial performances of CuO/MgO nanocomposite as a sensing platform for dopamine

In this line of work, we reported the sensing of Dopamine (DA) with the existence of Ascorbic acid (AA) and Uric acid (UA) by CuO/MgO nanocomposite fabricated to carbon paste electrode (MCPE) by Cyclic voltammetric (CV) and Linear Sweep Voltammetric (LSV) techniques. CuO nanoparticles was symphonized by simple co-precipitation method and MgO was symphonized by mechanochemical method. The characterisation such as scanning electron microscope (SEM), X-Ray diffraction (XRD) and energy dispersive X-Ray spectroscopy (EDS) was reported for both the nanoparticles. Certain parameters inclusive of varying scan rate, concentration of analytes, pH of the solution were developed to the modified electrode. The detection and quantification limits (LOD and LOQ) value was calculated. Simultaneous analysis of DA in the subsistence of AA and UA was failed at unmodified carbon paste electrode (CPE) but a well defined separation of anodic peaks occurred at CuO / MgO nanocomposite fabricated carbon paste electrode. The method has been applied to spiked injection sample and blood serum. Thus the presented method can be successfully employed for the scrutining of DA in the real samples.

Quantification of Deleterious Phase Precipitation in a Hyper Duplex Stainless Steel Aged at 700-950 °C Using Optimized Linear Sweep Voltammetry: Effect of KOH Concentration

Quantification of Deleterious Phase Precipitation in a Hyper Duplex Stainless Steel Aged at 700-950 °C Using Optimized Linear Sweep Voltammetry: Effect of KOH Concentration

In-situ polarization modulation IRRAS investigation of ammonia electrooxidation on Pt-Ir and Pt-Ru nanoparticles prepared on engineered catalyst supports

The catalytic activity and surface reactivity of monometallic Pt and bimetallic Pt-Ir and Pt-Ru nanoparticles, supported on two distinct Engineered Catalyst Supports (ECSs), were investigated for the Ammonia Electrooxidation Reaction (AmER) in alkaline media. XRD measurements confirmed alloy formation between Pt-Ir and Pt-Ru nanoparticles, as indicated by the shift of the (111) reflection to higher 2θ values. Cyclic voltammetry, linear sweep voltammetry, and chronoamperometry experiments were conducted to assess the catalytic activity of the Pt, Pt-Ir, and Pt-Ru electrocatalysts. All bimetallic catalysts exhibited lower onset potentials compared to Pt. The differing Tafel slopes between Pt (74 mV dec⁻¹), Pt-Ir (152 mV dec⁻¹), and Pt-Ru (118–197 mV dec⁻¹) suggest that alloying Pt with Ir or Ru alters the reaction mechanisms. Furthermore, the bimetallic Pt-Ir and Pt-Ru catalysts demonstrated greater tolerance for concentrated ammonia solutions relative to Pt.In-situ Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) provided insights into the formation of N-H species, azide anions (N₃⁻), and N-O compounds. For the Pt-Ru catalyst, an additional peak around ∼3600 cm⁻¹ was observed, corresponding to OH⁻ species. The PM-IRRAS results align with the Gerischer–Mauerer mechanism, indicating that partially dehydrogenated ammonia adsorbates act as active intermediates in the oxidation of ammonia over Pt-Ir and Pt-Ru catalysts.

Nonlinear viscoelastic effect on the fatigue performance of wood tar-based rejuvenated asphalt

The nonlinear viscoelasticity (NLVE) effects of rejuvenated asphalt are often neglected during fatigue degradation, potentially leading to misjudgment of its true fatigue performance. To more accurately quantify the fatigue life of rejuvenated asphalt under NLVE effects, frequency sweep (FS), incremental stress sweep (ISS), and linear amplitude sweep (LAS) tests were used to study two types of rejuvenated asphalt. FS and ISS tests respectively obtained the dynamic modulus |G*|LVE and |G*|NLVE representing the linear viscoelasticity (LVE) and NLVE of rejuvenated asphalt, and incorporated them into the simplified viscoelastic continuum damage (S-VECD) model to establish the fatigue failure criterion and predict the fatigue life of rejuvenated asphalt under high strain levels in LAS tests. The findings indicate that the NLVE-based-S-VECD model quantifies fatigue damage in rejuvenated asphalt lower than the LVE model, and the fatigue life of rejuvenated asphalt increases significantly after considering the NLVE effect. Besides, the failure difference (∆GR) and failure area difference (∆A) defined during the modeling process explain the impact of NLVE on the fatigue failure criterion average pseudo strain energy release rate (GR) of rejuvenated asphalt, validating the necessity of incorporating NLVE into the fatigue performance analysis of rejuvenated asphalt. Therefore, it's necessary to account for the impact of NLVE effect on the fatigue performance of rejuvenated asphalt in engineering practice, which will contribute to the development and application of rejuvenator.

Hydrated molten salt electrolytes effectively promote electrocatalytic NH3 synthesis at low temperatures

In the field of electrocatalytic nitrogen reduction reaction (NRR), molten salt is used as a unique electrolyte due to its advantages of high N2 solubility and wide electrochemical window. However, it has failed to be widely used due to its high reaction temperature (mostly > 200 °C) and low yield. Herein, a novel low-temperature (<100 °C) electrolysis system with hydrated molten salt hybrid electrolyte is designed. This system exhibits an ammonia yield of 1.003 × 10−8 mol s−1 cm−2 (−0.7 V vs. SCE) at 60 °C. Faradaic efficiency (FE) reaches 80.45 % (−0.65 V vs. SCE). The NH3 yield and FE are increased by 18.6 and 2 times compared to the previously reported low-temperature system, respectively. Linear sweep voltammetry (LSV), in situ Raman and in situ Fourier Transform-Infrared (FT-IR) experiments show that solid crystalline water can be used as a hydrogen source to effectively promote NRR while inhibiting the hydrogen evolution reaction (HER). Molecular dynamics (MD) experiments confirm that the electrolyte system maintains a high N2 solubility and mass transfer rate.

In Situ Analysis of Binder Degradation during Catalyst-Accelerated Stress Test of Polymer Electrolyte Membrane Fuel Cells.

High-oxygen-permeability ionomers (HOPIs) are being actively developed to enhance the performance and durability of high-power polymer electrolyte membrane fuel cells (PEMFCs). While methods for evaluating binder performance are well-established, techniques for assessing binder durability and measuring its degradation in situ during the AST process remain limited. This study examines the distribution of relaxation times (DRT) and Warburg-like response (WLR) methods as in situ analysis techniques during the catalyst-accelerated stress test (AST) process. We conducted catalyst-ASTs (0.6-0.95 V cycling) for 20,000 cycles, monitoring changes using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). Contrary to expectations, during the catalyst-AST, the ion transport resistance of the binder decreased, indicating no binder degradation. Scanning electron microscopy/energy dispersive spectrometer (SEM/EDS) analysis revealed that the degradation rate of the catalyst and the support was relatively higher than that of the binder, leading to a reduction in catalyst layer thickness and improved binder network formation. By applying the DRT method during the catalyst-AST process, we were able to measure the increase in oxygen reduction reaction (ORR) resistance and the decrease in proton transport resistance in situ. This allowed for the real-time detection of the reduction in catalyst layer thickness and improvements in ionomer networks due to catalyst and support degradation. These findings provide new insights into the complex interplay between catalyst degradation and binder performance, contributing to the development of more durable PEMFC components.

Performance evaluation of microbial fuel cells for bioelectricity generation: influence of potential scan-rate and real-time external load

AbstractThe electrochemical performance of microbial fuel cells is conventionally assessed through linear sweep voltammetry at predefined potential scan rates. Nevertheless, this approach frequently falls short in representing the long-term behavior of microbial fuel cells under actual external loads, highlighting the need for a standardized evaluation method incorporating both linear sweep voltammetry and external loads. To address this gap, this study evaluates the performance of single-chamber microbial fuel cells under different loads and scan rates. The MFCs were tested with external loads of 1200, 470, and 270 Ω, derived from maximum power points of polarization sweeps at scan rates of 0.1, 0.5, and 1 mV/s at two operational phases. Power estimates at these scan rates were 61.96, 87.88, and 166.68 mW/m2 at current densities of 116.5, 229.6, and 403 mA/m2, respectively. In the initial two hours, average power densities with 1200, 470, and 270 Ω were 73 ± 16.7, 36.3 ± 42, and 88.5 ± 120.1 mW/m2, respectively. Over the long term, the fuel cells under constant loading with resistance estimated at 0.1 mV/s showed average power 73.7% and 89.1% higher than those with resistances estimated at 0.5 mV/s and 1 mV/s, respectively, indicating that higher scan rates lead to overestimation of power. Although initially underestimated, the 0.1 mV/s scan rate more accurately reflected the true long-term performance of the fuel cells. This study emphasizes the importance of using appropriate scan rates for linear sweep voltammetry to obtain realistic long-term performance estimates of microbial fuel cells under real-time loads.