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1.
J Environ Sci (China) ; 149: 638-650, 2025 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-39181674

RESUMO

High ammonia-nitrogen digestate has become a key bottleneck limiting the anaerobic digestion of organic solid waste. Vacuum ammonia stripping can simultaneously remove and recover ammonia nitrogen, which has attracted a lot of attention in recent years. To investigate the parameter effects on the efficiency and mass transfer, five combination conditions (53 °C 15 kPa, 60 °C 20 kPa, 65 °C 25 kPa, 72 °C 35 kPa, and 81 °C 50 kPa) were conducted for ammonia stripping of sludge digestate. The results showed that 80% of ammonia nitrogen was stripped in 45 min for all experimental groups, but the ammonia transfer coefficient varied under different conditions, which increased with the rising of boiling point temperature, and reached the maximum value (39.0 mm/hr) at 81 °C 50 kPa. The ammonia nitrogen removal efficiency was more than 80% for 30 min vacuum stripping after adjusting the initial pH to above 9.5, and adjustment of the initial alkalinity also affects the pH value of liquid digestate. It was found that pH and alkalinity are the key factors influencing the ammonia nitrogen dissociation and removal efficiency, while temperature and vacuum mainly affect the ammonia nitrogen mass transfer and removal velocity. In terms of the mechanism of vacuum ammonia stripping, it underwent alkalinity destruction, pH enhancement, ammonia nitrogen dissociation, and free ammonia removal. In this study, two-stage experiments of alkalinity destruction and ammonia removal were also carried out, which showed that the two-stage configuration was beneficial for ammonia removal. It provides a theoretical basis and practical technology for the vacuum ammonia stripping from liquid digestate of organic solid waste.


Assuntos
Amônia , Temperatura , Eliminação de Resíduos Líquidos , Amônia/química , Concentração de Íons de Hidrogênio , Vácuo , Eliminação de Resíduos Líquidos/métodos , Nitrogênio , Esgotos/química , Pressão
2.
Perit Dial Int ; : 8968608241260024, 2024 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-39091083

RESUMO

BACKGROUND: Variation in residual volume between peritoneal dialysis dwells creates uncertainty in ultrafiltration determination, dialysis efficiency, and poses a risk of overfill if the residual volume is large. Measuring the dilution of a marker molecule during fluid fill offers a convenient approach, however, estimation accuracy depends on the choice of dilution marker. We here evaluate the feasibility of creatinine and urea as dilution markers compared to albumin-based residual volumes and three-pore model estimations. METHOD: This clinical, retrospective analysis comprises 56 residual volume estimations from 20 individuals, based on the dilution of pre-fill dialysate creatinine, urea and albumin concentrations during the dialysis fluid fill phase. Outcomes were compared individually. Bias induced by ultrafiltration, marker molecule mass-transfer and influence of fluid glucose contents was quantified using the three-pore model. Linear regression established conversion factors enabling conversion between the various marker molecules. RESULTS: Creatinine-based calculations overestimated residual volumes by 115 mL (IQR 89-149) in 1.5% dwells and 252 mL (IQR 179-313) in 4.25% glucose dwells. In hypertonic dwells, ultrafiltration was 52 mL (IQR 38-66), while intraperitoneal creatinine mass increased by 67% during fluid fill, being the leading cause of overestimation. Albumin-based volumes conformed strongly with three-pore model estimates. Correction factors effectively enabled marker molecule interchangeability. CONCLUSIONS: Mass-transfer of low molecular weight marker molecules is associated with residual volume overestimation. However, by applying correction factors, creatinine and urea dilution can still provide reasonable estimates, particularly when the purpose is to exclude the presence of a very large residual volume.

3.
Appl Mech (Basel) ; 5(1): 91-101, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-39170914

RESUMO

In this work, we explore a simplified model based on both analytical and computational methods for the study of film-boiling droplet motion on microscale ratchets. We consider a specific ratchet design with the length periods and depth of ratchets much smaller than the size of the droplet. We conclude based on our modeling that for the ratchet configuration considered in this paper, the conduction within the vapor film is the dominant means of heat transfer in comparison with convection and radiation. Furthermore, we demonstrate a more manageable two-dimensional model in which analytical approaches coupled with computational approaches yield reasonably accurate results in comparison to the actual experiments.

4.
Heliyon ; 10(15): e35105, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-39170329

RESUMO

The use of solar greenhouses in China is increasing because they permit environmental conditions to be controlled. Studies of the heat transfer processes in the leaves of plants cultivated within solar greenhouses are needed. Here, we studied heat transfer processes in 'Shine Muscat' grapevine leaves under moderate deficit irrigation (MDI), severe deficit irrigation (SDI), and full irrigation (FI) treatments under varying weather conditions. The stomatal conductance, leaf temperature, and transpiration rate of both shade and sun grapevine leaves were measured, and the effects of ambient temperature and relative humidity on these variables were determined. A thermal physics model of the leaves was established to explore the heat dissipation process. On sunny days, the transpiration heat transfer of sun leaves in the MDI, SDI, and FI treatments was 2.62 MJ m-2·day-1, 2.44 MJ m-2·day-1, and 3.86 MJ m-2·day-1and 0.818 MJ m-2·day-1, 0.782 MJ m-2·day-1, and 1.185 MJ m-2·day-1 on rainy days, respectively. There was a significant difference in transpiration heat transfer under fully irrigated and deficit irrigation conditions under different weather conditions. Furthermore, transpiration heat transfer accounted for 41.49 % and 25.03 % of the total heat transfer of sun leaves in the FI treatment and 33.94 % and 29.43 % of the total heat transfer of shade leaves on rainy days, respectively, indicating that relative humidity plays a key role in determining transpiration heat transfer and leaf temperature and that its effect was greater on sun leaves than on shade leaves.

5.
Ultrason Sonochem ; 109: 107019, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39126989

RESUMO

The electrodeposition process confronts significant challenges arising from mass transfer limitation and residual stress. To address these issues, an innovative method, combining megasonic agitation with coaxial jet electrodeposition, is introduced. This approach aims to enhance mass transfer and mitigate residual stress. First, an electrodeposition nozzle device was designed, and the liquid-phase mass transfer during electrodeposition was analyzed through finite element simulation. Simulation results indicate that the mass transfer coefficient increases with rising megasonic power density. Notably, when the megasonic power density reached 20 W/cm2, the mass transfer coefficient increased from 0.45 × 10-7 m/s to 18.63 × 10-7 m/s, compared to electrodeposition without megasonic agitation. Secondly, electrodeposition experiments were conducted both with and without megasonic assistance. X-ray diffraction (XRD) was employed to measure the residual stress values of the electrodeposited layers. The results reveal that samples processed with megasonic assistance exhibit lower residual stress values compared to those without. Specifically, at a megasonic power density of 10 W/cm2, the residual stress was 94.3 MPa, representing a 37.7 % reduction compared to the residual stress of 151.5 MPa observed in samples without megasonic agitation. Overall, the findings demonstrate that coaxial megasonic agitation can effectively enhance the liquid-phase mass transfer capability during electrodeposition and reduce the residual stress of the electroplated layer. This innovative method presents a promising avenue for improving electrodeposition processes and achieving superior material properties.

6.
Environ Sci Technol ; 2024 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-39190653

RESUMO

Peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs), as a promising technology for water decontamination, are constrained by low reaction kinetics due to limited reaction selectivity and mass transfer. Herein, we designed a nanoconfined FeCo2O4-embedded ceramic membrane (FeCo2O4-CM) under flow-through pattern for PMS activation. Confining PMS and FeCo2O4 within nanochannels (3.0-4.7 nm) enhanced adsorption interactions (-7.84 eV vs -2.20 eV), thus boosting mass transfer. Nanoconfinement effect regulated electron transfer pathways from PMS to FeCo2O4-CM by modulating the active site transformation to ≡Co(III) in nanoconfined FeCo2O4-CM, enabling selectively generating 1O2. The primary role of 1O2 in the nanoconfined system was confirmed by kinetic solvent isotope experiments and indicative anthracene endoperoxide (DPAO2). The system enabled 100% removal of atrazine (ATZ) within a hydraulic retention time of 2.124 ms, demonstrating a rate constant over 5 orders of magnitude higher than the nonconfined system (3.50 × 103 s-1 vs 0.42 min-1). It also exhibited strong resilience to pH variations (3.3-9.0) and coexisting substances, demonstrating excellent stability indicated by consistent 100% ATZ removal for 14 days. This study sheds light on regulating electron transfer pathways to selectively generate 1O2 through the nanoconfinement effect, boosting the practical application of PMS-based AOPs in environmental remediation and potentially applying them to various other AOPs.

7.
J Food Sci ; 2024 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-39164807

RESUMO

Baking is a healthier alternative to frying, since texture, color, smell, and flavor are developed, without adding oil. The objective was to estimate the moisture content in potato slices, during baking using Fick's law of diffusion to model internal moisture transport and to assess the impact on quality attributes. Moisture transport kinetics were examined at three baking temperatures of 120, 130, and 140°C. Fick's law was employed to estimate average moisture content using different methods: considering both a constant (method of slopes by subperiods, MSS; and method of successive approximations, MSA) and a variable (represented as a quadratic function of time, QFT) behavior of effective diffusivity (De). Three quality variables were analyzed: water activity (aw, dew point hygrometry), total color difference (∆E, colorimetry), and fracturability (F, universal testing machine). The diffusivity estimated with the time-varying De method provided a more realistic description of moisture migration during baking. The aw, ∆E, and F for baked potato slices ranged from 0.234 to 0.276, 17.9 to 24.6, and 5.20 to 5.49 N, respectively. These attributes imply improved stability and extended shelf life, showing typical colors and texture changes for baked snacks. These changes are linked to variations in diffusivity, influenced by the size and quantity of micropores within the food structure. This study could allow an accurate prediction of mass transfer by considering variable De, facilitating the optimization of baking conditions. PRACTICAL APPLICATION: The analysis of the moisture content using Fick's law, considering a time-varying diffusivity, enables the optimization of the baking process for foods. This helps minimize the occurrence of defective products.

8.
Bioresour Technol ; 409: 131247, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39122127

RESUMO

This study presents a bidirectional flow tidal bioreactor designed to enhance H2-driven CO2 biomethanation. The bioreactor alternated biofilms between immersion in nutrient solution and exposure to H2/CO2, creating alternating dry and wet states. This tidal operation minimized liquid film thickness during dry periods and ensured uniform nutrient distribution during wet periods. Bidirectional H2/CO2 supply was used to reduce biofilm thickness heterogeneity across the reactor height. CO2 biomethanation remained stable with an empty bed residence time of 9.7 min, achieving a methane (CH4) formation rate of 26.8 Nm3 CH4/(m3·d). The product gas contained 95.0 ± 2.5 % CH4, with a H2/CO2 conversion efficiency of 90.8 %. Tidal operation mitigated the buildup of dissolved and suspended organics, such as organic acids and detached biofilms. Dominant bacteria in biofilms included fermentative species like Petrimonas and H2-utilizing homoacetogens like Sporomusa. Enriched hydrogenotrophic methanogens, particularly Methanobacterium, were observed. Overall, this study highlights the bioreactor's effectiveness in improving CO2 biomethanation.


Assuntos
Biofilmes , Reatores Biológicos , Dióxido de Carbono , Hidrogênio , Metano , Dióxido de Carbono/metabolismo , Metano/metabolismo , Hidrogênio/metabolismo , Bactérias/metabolismo
9.
Chemosphere ; : 143174, 2024 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-39181465

RESUMO

Air pollution is a long-standing environmental challenge as well an important economic subject. Hydrogen sulfide is one the major pollutants in the industrial releases. This review focuses on the thermochemical treatment of hydrogen sulfide based on the most recent works to date regarding its removal. By analyzing fundamental steps in chemical reaction engineering, some useful factors are emphasized since they are often neglected in scientific studies, catalysts design and process scale-up. From processing side, the fluid flow conditions including velocity, H2S concentration, relative humidity, temperature and pressure strongly influence the kinetic behavior and so the catalytic performance of the H2S removal reactor. From material side, the catalyst properties including nature, porosity, pore types, size, sites distribution and layer structuration largely influence the removal performance via among others the accessibility to catalytic sites, pores connection and mass transfer resistance. Plasma-assisted catalytic removal of H2S combines many novelties in comparison with a classical thermo-catalytic process. From patents review, we can see that main concerns are about electrodes mounting, reactor lifetime and modular design to solve the problems in the industrial practice. We attempt to provide for scientists, engineers and industrialists a guidance on the design of catalysts and processes for H2S removal which could be applied in laboratorial studies and industrial processes as well.

10.
Sci Rep ; 14(1): 19711, 2024 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-39181913

RESUMO

The study examined mass transfer coefficients in a structured CO2 absorption column using machine learning (ML) and response surface methodology (RSM). Three correlations for the fractional effective area (af), gas phase mass transfer coefficient (kG), and liquid phase mass transfer coefficient (kL) were derived with coefficient of determination (R2) values of 0.9717, 0.9907 and 0.9323, respectively. To develop these correlations, four characteristics of structured packings, including packing surface area (ap), packing corrugation angle (θ), packing channel base (B), and packing crimp height (h), were used. ML used five models, represented as random forest (RF), radial basis function neural network (RBF), multilayer perceptron (MLP), XGB Regressor, and Extra Trees Regressor (ETR), with the best models being radial basis function neural network (RBF) for af (R2 = 0.9813, MSE = 0.00088), RBF for kG (R2 = 0.9933, MSE = 0.00056), and multilayer perceptron (MLP) for kL (R2 = 0.9871, MSE = 0.00089). The channel base had the most impact on af and kL, while crimp height affected kG the most. Although the RSM method produced adequate equations for each output variable with good predictability, the ML method provides superior modeling capabilities.

11.
Food Res Int ; 193: 114826, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39160039

RESUMO

Herein, goji berries were pretreated with sodium carbonate (Na2CO3) and then dried via ultrasound-assisted air drying or microwave drying. Water migration and phenolic chemistry of goji berries were studied under drying. A three-dimensional ellipsoid water transport model, accounting for porosity and temperature fluctuations, was established to explore the intricacies of the drying mechanism. Generally, microwave drying promoted interior water transport compared to ultrasound drying. Among all the drying methods, microwave drying at 240 W (MW-240 W) exhibited the highest De (from 7.34 × 10-9 to 9.61 × 10-9 m2/s) and kc (6.78 × 10-4 m/s) values. The goji berries received a considerably high water content gradient between its surface and center within the first 2 s of all the drying treatments. Microwave drying diminished the water content gradient earlier than air drying and ultrasound-assisted air drying treatments. Furthermore, most correlations observed among phenolics, oxidase activity, and cell wall pectin did not align with the established theories, highlighting the highly nonlinear nature of phenolic chemistry during goji berry drying. This study provides a three-dimensional model to study the mass transfer mechanism of goji berries and analyzes the evolution of polyphenols during the drying process.


Assuntos
Dessecação , Frutas , Lycium , Micro-Ondas , Fenóis , Dessecação/métodos , Frutas/química , Fenóis/química , Lycium/química , Manipulação de Alimentos/métodos , Água/química , Porosidade , Ondas Ultrassônicas , Ultrassom
12.
Food Res Int ; 193: 114808, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39160056

RESUMO

The digestion of starch-based foods in the intestinal tract is important for human health. Modeling the details enhances fundamental understanding and glycemic prediction accuracy. It is, however, a challenge to take granular properties into account. A multiscale digestion model has been proposed to characterize mass transfer and hydrolysis reaction at both the intestine and particle scales, seamlessly integrating inter-scale mass exchange. A specific grid scheme was formulated for the shrinkage and transport of the particle computational domain. By incorporating additional glycemic-related processes, e.g., intestinal absorption, a dietary property-based glycemic prediction system has been developed. Its effectiveness was validated based on a human tolerance experiment of cooked rice particles. The model-based investigation comprehensively reveals the impact of initial size on digestion behavior, specifically in terms of enzyme distribution and particle evolution. This work also demonstrates the significance of modeling both particle-scale diffusion and intestine-scale transport, a combination not previously explored. The results indicate that ignoring the former mechanism leads to an overestimation of the glycemic peak by at least 50.8%, while ignoring the latter results in an underestimation of 16.3%.


Assuntos
Digestão , Modelos Biológicos , Amido , Amido/química , Amido/metabolismo , Humanos , Oryza/química , Índice Glicêmico , Tamanho da Partícula , Hidrólise , Absorção Intestinal
13.
Chembiochem ; : e202400345, 2024 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-39087277

RESUMO

Converting fatty acids into specialty chemicals is sustainable but hindered by the low efficiency and thermal instability of current oleic acid hydratases, along with mass transfer limitations in emulsion reactions. This study introduces an optimized continuous flow micro-reactor (CFMR) that efficiently transforms oleic acid at low (15 g·L-1) and high (50 g·L-1) concentrations, improving reaction efficiency and overcoming key conversion barriers. The first CFMR model showed reaction speeds surpassing traditional batch stirred tank reactors (BSTR). Optimizations were performed on three key components: liquid storage, mixer, and reaction section of the CFMR, with each round's best conditions carried into the next. This achieved a space-time yield of 597 g·L-1·d-1 at a 15 g·L-1 oleic acid load. To further enhance the yield, we optimized the emulsifier system to solve incomplete emulsification and developed a two-component feed microreactor (TCFMR) that addressed substrate and product inhibition at high loads, reaching a 91% conversion of 50 g·L-1 oleic acid in 30 minutes, with a space-time yield of 2312 g·L-1·d-1. These advancements represent significant progress in utilizing fatty acids and advancing sustainable chemical synthesis.

14.
Adv Mater ; : e2405493, 2024 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-39136062

RESUMO

Overall water splitting is a promising technology for sustainable hydrogen production, but the primary challenge is removing bubbles from the electrode surface quickly to increase hydrogen production. Inspired by the directional fluid transport properties of natural biological surfaces like Nepenthes peristome and Morpho butterfly's wings, here a strategy is demonstrated to achieve highly efficient overall water splitting by a bubble-guidance electrode, that is, an anisotropic groove-micro/nanostructured porous electrode (GMPE). Gradient groove micro/nanostructures on the GMPE serve as high-speed bubble transmission channels and exhibit superior bubble-guidance capabilities. The synergistic effect of the asymmetric Laplace pressure generated between microscale porous structure and groove patterns and the buoyancy along the groove patterns pushes the produced bubbles directionally to spread, transport, and detach from the electrode surface in time. Moreover, the low adhesive nanosheet arrays are beneficial to reduce bubble size and increase bubble release frequency, which cooperatively improve mass transfer with the microscale structure. Notably, GMPE outperforms planar-micro/nanostructured porous electrode (PMPE) in hydrogen/oxygen evolution reactions, with GMPE||GMPE showing better water splitting performance than commercially available RuO2||20 wt.% Pt/C. This work improves electrodes for better mass transfer and kinetics in electrochemical reactions at solid-liquid-gas interfaces, offering insight for designing and preparing gas-involved photoelectrochemical electrodes.

15.
Water Res ; 265: 122293, 2024 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-39167972

RESUMO

Sorption-based atmospheric water harvesting holds promise for alleviating water scarcity, but current prototypes have not shown significant increases in practical yields despite efforts in the enlarged engineering scale. This is due to weakened heat and mass transfer with a packed sorbent bed. In this work, the desiccant-coated adsorbers were employed to fabricate the water harvesting device that incorporates internal fluid for cooling and heating during sorption and desorption. Featured with an internal cooling effect, practical water productivity could be improved by 1.75-9.96 times with a low desorption temperature (45-62 °C). The continuous water harvesting system could produce 0.77-3.98 Lwater/kgsorbent/day with a thermal energy consumption of 7.7-30.4 MJ/kg in wide climates from 20 % to 80 % RH, providing a reference for device design in the engineering view. The demonstration revealed that using natural cooling in the sorption stage has great benefits in improving water harvesting performance, which can be integrated into the building sectors or a wider range of scenarios.

16.
Sci Rep ; 14(1): 16245, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-39009602

RESUMO

Chemical bioreactions play a significant role in many of the microfluidic devices, and their applications in biomedical science have seen substantial growth. Given that effective mixing is vital for initiating biochemical reactions in many applications, micromixers have become increasingly prevalent for high-throughput assays. In this research, a numerical study using the finite element method was conducted to examine the fluid flow and mass transfer characteristics in novel micromixers featuring an array of pillars. The study utilized two-dimensional geometries. The impact of pillar configuration on mixing performance was evaluated using concentration distribution and mixing index as key metrics. The study explores the effects of pillar array design on mixing performance and pressure drop, drawing from principles such as contraction-expansion and split-recombine. Two configurations of pillar arrays, slanted and arrowhead, are introduced, each undergoing investigation regarding parameters such as pillar diameter, gap size between pillar groups, distance between pillars, and vertical shift in pillar groups. Subsequently, optimal micromixers are identified, exhibiting mixing efficiency exceeding 99.7% at moderate Reynolds number (Re = 1), a level typically challenging for micromixers to attain high mixing efficiency. Notably, the pressure drop remains low at 1102 Pa. Furthermore, the variations in mixing index over time and across different positions along the channel are examined. Both configurations demonstrate short mixing lengths and times. At a distance of 4300 µm from the inlet, the slanted and arrowhead configurations yielded mixing indices of 97.2% and 98.9%, respectively. The micromixers could provide a mixing index of 99.5% at the channel's end within 8 s. Additionally, both configurations exceeded 90% mixing indices by the 3 s. The combination of rapid mixing, low pressure drop, and short mixing length positions the novel micromixers as highly promising for microfluidic applications.

17.
Water Res ; 262: 122101, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-39032329

RESUMO

Fluorinated pharmaceuticals pollution has become an ever-increasing environmental concern due to its negative impacts. Photoelectrocatalytic (PEC) degradation system is a desirable approach to tackle the pollution problems. However, photogenerated charge separation and interfacial mass transfer are the main bottlenecks for improving the PEC degradation performance. Herein, we report a TiO2 photoanode with tuned (101)/(110) facets in situ grown on a Ti mesh substrate for PEC degradation of fluorinated pharmaceuticals. The exposure of (101) facets facilitates efficient photogenerated charge separation and the desorption of generated •OH radical. Besides, the three-dimensional (3D) architecture of photoanode promotes macroscopic mass transfer. This system performed complete defluorination of 5-fluorouracil and more than 75 % total organic carbon (TOC) removal efficiency. The apparent reaction rate constant of high (101) facet-exposed TiO2 grown on Ti mesh is up to 6.96 h-1, 6‒fold faster than that of photoanode with low (101) facet-exposed TiO2 grown on Ti foil. It is demonstrated that a large-sized PEC system of 1200 cm2 can degrade 100 L of synthetic fluorinated pharmaceutical wastewater with more than 80 % elimination efficiency. This work showcases the facet and substrate modulated strategy of fabricating high-performed photoanode for PEC wastewater purification.


Assuntos
Águas Residuárias , Poluentes Químicos da Água , Águas Residuárias/química , Poluentes Químicos da Água/química , Preparações Farmacêuticas/química , Titânio/química , Catálise , Eletrodos , Eliminação de Resíduos Líquidos/métodos , Técnicas Eletroquímicas
18.
Environ Sci Technol ; 58(32): 14585-14593, 2024 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-39072735

RESUMO

Alcohols are promising fuels for direct alcohol fuel cells and are common scavengers to identify reactive oxygen species (ROS) in electro-Fenton (EF) systems. However, the side impacts of alcohols on oxygen reduction reactions and ROS generation are controversial due to the complex interactions between electrodes and alcohol-containing electrolytes. Herein, we employed synchrotron-Fourier-transform infrared spectroscopy and electron paramagnetic resonance technologies to directly observe the changes of chemical species and electrochemical properties on the electrode surface. Our studies suggested that alcohols exhibited different limiting degrees on proton (H+) mass transfer toward the catalytic surface, following an order of methanol < ethanol < isopropanol < tert-butyl alcohol (TBA). In addition, the formation of hydrophobic TBA clusters at high concentrations (>400 mM) resulted in a significant reduction in ionic conductivity and an elevation in charge transfer resistance, which impedes H+ mass transfer and raises the energy barrier for 2e- oxygen reduction reaction processes. Moreover, the organic radical •CH2(CH3)2CH2OH produced by the interaction of Fe3+ and •OH with the alcohol in the EF system serves as a crucial intermediate in facilitating H2O2 regeneration, which complicates the quenching effect of alcohols on •OH identification. Therefore, it is recommended that methanol should be used as the scavenger instead of TBA and the concentration should be less than 400 mM in EF systems.


Assuntos
Álcoois , Peróxido de Hidrogênio , Peróxido de Hidrogênio/química , Álcoois/química , Oxirredução , Ferro/química , Espécies Reativas de Oxigênio/química
19.
Int J Biol Macromol ; 278(Pt 1): 133946, 2024 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-39029825

RESUMO

The incorporation of active compounds into polymeric matrices using traditional methods has several drawbacks mainly due to the high volatility and thermal sensitivity of these substances. A solution to this problem could be the incorporation of bioactive compounds forming inclusion complexes as a strategy to improve the chemical stability, bioactivity and achieve controlled release. In this work, ß-cyclodextrin/carvacrol inclusion complex was prepared by spray drying to be incorporated into poly(lactic acid) (PLA) and Mater-Bi® films by supercritical CO2 impregnation. The impregnation process was carried out at pressures of 10, 15 and 20 MPa and at 40 °C. Both polymers showed the highest amount of incorporated inclusion complex at 15 MPa, where the percentage of impregnation varied from 0.6 % to 7.1 % in Mater-Bi® and PLA, respectively. Release tests for PLA films impregnated with inclusion complex showed a slow release of the active compound, which did not reach equilibrium after 350 h under the experimental conditions. This prolonged release was not observed in Mater-Bi® due to the lower incorporation of the inclusion complex. The release rate was described herein by a comprehensive phenomenological model considering the decomplexation kinetics combined with the equilibrium and mass transfer expressions.

20.
ACS Appl Mater Interfaces ; 16(32): 42363-42371, 2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39078706

RESUMO

The mass transport and ion conductivity in the catalyst layer are important for fuel cell performances. Here, we report an in situ-grown ultrathin catalyst layer (UTCL) to reduce the oxygen mass transport and a surface ionomer-coated gas diffusion layer method to reduce the ion conducting resistance. A significantly reduced catalyst layer thickness (ca. 1 µm) is achieved, and coupled with the ionomer introduction method, the ultrathin catalyst layer is in good contact with the membrane, resulting in high ion conductivity and high Pt utilization. This ultrathin catalyst layer is suitable for both proton exchange membrane fuel cells and anion exchange membrane fuel cells, giving peak power densities of 2.24 and 1.11 W cm-2, respectively, which represent an increase of more than 30% compared with the membrane electrode assembly (MEA) fabricated by using traditional Pt/C power catalysts. Electrochemical impedance spectra and limiting current tests demonstrate the reduced charge transfer, mass transfer, and ohmic resistances in the ultrathin catalyst layer membrane electrode assembly, resulting in the promoted fuel cell performances.

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