Mass Transfer Resistance Research Articles

Characterizing Acoustic Behavior of Silicon Microchannels Separated by a Porous Wall.

Lateral flow membrane microdevices are widely used for chromatographic separation processes and diagnostics. The separation performance of microfluidic lateral membrane devices is determined by mass transfer limitations in the membrane, and in the liquid phase, mass transfer resistance is dependent on the channel dimensions and transport properties of the species separated by the membrane. We present a novel approach based on an active bulk acoustic wave (BAW) mixing method to enhance lateral transport in micromachined silicon devices. BAWs have been previously applied in channels for mixing and trapping cells and particles in single channels, but this is, to the best of our knowledge, the first instance of their application in membrane devices. Our findings demonstrate that optimal resonance is achieved with minimal influence of the pore configuration on the average lateral flow. This has practical implications for the design of microfluidic devices, as the channels connected through porous walls under the acoustic streaming act as 760 µm-wide channels rather than two 375 µm-wide channels in the context of matching the standing pressure wave criteria of the piezoelectric transducer. However, the roughness of the microchannel walls does seem to play a significant role in mixing. A roughened (black silicon) wall results in a threefold increase in average streaming flow in BAW mode, suggesting potential avenues for further optimization.

Kinetics studies on the ascorbic acid extraction from roselle (Hibiscus sabdariffa) calyces

The effect of processing conditions of roselle (Hibiscus sabdariffa) calyces on the vitamin C content of the extracts was studied to develop models that best describe the process. The extraction parameters are the processing time (5, 10, 15 mins), process temperature (30oC, 50℃, 75℃ and 100℃), and calyx-water mass ratio (1:50, 1:20 and 1:10). These samples were tested for ascorbic acid using the spectrophotometric method. Statistical analysis was conducted on the experimental results and regression models were developed. A total of six mathematical models were selected for the description of vitamin C extraction from the calyces. The results showed that time, temperature and calyx-water mass ratio have a linear significant effect (p ≤ 0.01); while time-temperature and temperature-ratio had a significant (p ≤ 0.05) interaction effect; time and temperature had a significant (p ≤ 0.05) quadratic effect on the vitamin C content of the extract. Pseudo-first-order gave the highest overall coefficient of determination R2 and lowest overall root mean square error (RMSE). The activation energy of vitamin C ranged from 3 to 8.4 kJ; the effective diffusion coefficient ranged from 1.5×10-9 to 5.0×10-7 m 2 s -1 ; while mass diffusivity ranged from 3.11×10-5 to 8.6×10-4 ms-1 . The Biot number calculated ranged between 33.93 and 541.94 which showed that there is an insignificant external mass transfer resistance.

Facile fabrication of eccentric hollow molecularly imprinted polymers microspheres via miniemulsion one-step seed swelling polymerization

Molecular imprinting technique has been increasingly concerned for preparing tailor-made specific recognition materials. In this work, the molecularly imprinted polymers (MIP) microspheres with eccentric hollow structure were prepared by miniemulsion one-step seed swelling polymerization for specific recognition of bisphenol A (BPA), a typical endocrine disrupter. The obtained MIP microspheres were investigated by TEM and SEM, respectively. The images show that the MIP microspheres are of unique eccentric hollow structure with the average diameter of 210 nm. Due to the presence of hollow structure, most of imprinted sites were distributed in the internal and external surfaces of MIP microspheres and the mass transfer resistance of template molecule decreases significantly. The successful building of imprinted sites was validated by a series of adsorption experiments. The experimental results indicate that the MIP microspheres present fast adsorption rate and could reach adsorption equilibrium within 90 min because of low mass transfer resistance resulted from the hollow structure. Additionally, the MIP microspheres also appear considerable binding capacity, binding selectivity (the imprinting factor of 2.06) and renewability. The binding capacity of MIP could remain at a high level after 5 binding-unbinding cycles. Furthermore, the MIP microspheres present excellent water compatibility and could rebind BPA selectively from aqueous medium because of the adoption of hydrophilic functional monomer and aqueous polymerization environment. Due to these unique characteristics, the MIP microspheres show the application prospect in the fields of environmental protection and detection.

On Comparing Packed Beds and Monoliths for CO2 Capture from Air Through Experiments, Theory, and Modeling.

This study compares the performance of amine-functionalized γ-alumina sorbents in the form of 3 mm γ-alumina pellets and of a γ-alumina wash-coated monolith for CO2 capture for direct air capture (DAC). Breakthrough experiments were conducted on the two contactors to analyze the adsorption kinetics and performance for different gas feeds. A constant pattern analysis revealed dominant mass transfer resistances in the gas film and in the pores, with axial dispersion also observed, particularly at higher concentrations. A 1D, physical model was used to fit the experiments and thus to estimate mass transfer and axial dispersion coefficients, which appear to be consistent with the hypotheses derived from constant pattern analysis. A dual kinetic model to describe mass transfer was found to better describe the tail behavior in the monolith, whereas a pseudo-first-order model was sufficient to describe breakthroughs on packed beds. A substantial two-order magnitude decrease in mass transfer coefficients was noted when reducing the feed concentration from 5.6% to 400 ppm CO2, thus underscoring the significant mass transfer limitations observed in DAC. Comparison between the contactors revealed notably higher mass transfer coefficients in the monolith compared to the packed beds, which are attributed to shorter diffusion lengths and lower equilibrium capacity. While the faster mass transfer coefficients observed in the monolith experiments led to reduced specific energy consumption and increased adsorption productivity compared to the packed bed at 400 ppm, no significant improvement was observed for the same process at the higher concentration of 5.6% CO2 in the feed. This finding highlights the need to tailor the contactor design to the specific gas separation requirements. This research contributes to the understanding and quantification of mass transfer kinetics at DAC concentrations in both packed bed and monolith contactors. It demonstrates the crucial role of the contactor in DAC systems and the importance of optimizing the adsorption step to enhance productivity and DAC performance.

Rapid Synthesis and Microenvironment Optimization of Hierarchical Porous Fe─N─C Catalysts for Enhanced ORR in Microbial Fuel Cells.

Here, an approach to produce a hierarchical porous Fe-N-C@TABOH catalyst with densely accessible high intrinsic active FeNx sites is proposed. The method involves a single-step pyrolysis of Zn/Fe-zeolitic imidazolate framework (Zn/Fe-ZIF-H) with tetrabutylammonium hydroxide (TABOH) micelles, which is obtained by utilizing TABOH as a structural template and electronic mediator at room temperature for a brief duration of 16min. Notably, the yield of Zn/Fe-ZIF-H is 3.5 times that of Zn/Fe-ZIF-N prepared by conventional method. Results indicate that in addition to expediting synthesis and increasing yield of the Zn/Fe-ZIF-H, the TABOH induces a hierarchical porous structure and fosters the formation of more and higher intrinsic active FeNx moieties in Fex-N-C@TABOH, showing that TABOH is a multifunctional template. Crucially, the increased mesoporosity/external surface area and optimized microenvironment of Fe-N-C@TABOH significantly enhance ORR activity by facilitating the formation of high intrinsic active FeNx sites, increasing accessible FeNx sites, and reducing mass transfer resistance. Through structure tailoring and microenvironment optimization, the resulting Fe-N-C@TABOH exhibits superior ORR performance. DFT calculation further validates that the synergistic effect of these two factors leads to low ORR barrier and optimized *OH adsorption energy. This study underscores the importance of structure and electronic engineering in the development of highly active ORR catalysts.

Mechanisms and mass transfer kinetics of Cr(VI) adsorbed by mussel shell incorporated adsorptive membrane

The presence of Cr(VI) results in pollution that threatens human health and aquatic life. Therefore, there is an urgent need for Cr(VI) to be removed from contaminated water. The mussel shell incorporated polyethersulfone (MSPES) membranes designed to form the flat sheet adsorptive membrane (FSAM) crossflow treatment systems was used to remove Cr(VI) from synthetic solution. The physicochemical properties of the MSPES membrane were verified using an atomic force microscope, scanning electron microscope, and water contact angle goniometer. The performance of MSPES2.0 to remove Cr(VI) ions ranged from 15.00 to 16.05 % was higher than that of MSPES2.2 ranged from 10.00 to 10.75 %, which observed for 1.5 h of the experiment. The MSPES2.0 adsorption capacity of 3.2 mg g−1 was higher than the MSPES2.2 adsorption capacity of 1.45 mg g−1. The applicability of Generalized Fulazzaky equations to simulate the experimental data was validated to predict the mechanisms and kinetics of Cr(VI) mass transfer by the MSPES membrane and to determine the resistance of mass transfer for adsorption of Cr(VI) depended on porous diffusion (PD) rate. The Cr(VI) adsorption controlled by PD was verified to provide an insight of how the mass transfer process contributed to advanced FSAM crossflow treatment system.

Comprehensive analysis of water vapor sorption kinetics and mechanisms using biosorbent pellets from canola meal and oat hull

Agricultural residues, specifically canola meal (CM) and oat hull (OH), have been innovatively utilized to develop biosorbents for sorbing water vapor from the air. These biomaterials are comprised of hydrophilic functional groups that effectively perform air dehydration. Air, being non-polar, was used as a model gas in this study to simulate gas dehydration. In the current research, these materials were formed into pellets to produce high-quality biosorbents with controlled size, shape, and enhanced moisture uptake capacity. CM (309.48 mg/g) and OH (233.07 mg/g) pellets had higher or comparable water sorption capacities than commercialized adsorbents used for drying gases. The mixed-order kinetic model described the sorption process well and identified both mass transfer and sorption on active site steps (R 2 > 0.991 and χ 2 < 16.0). Regarding the OH pellet, sorption on active sites was the predominant kinetic mechanism at the beginning, followed by intraparticle diffusion until equilibrium. However, sorption on CM pellets was delayed at 4.2 min at the initial stage, owing to the external mass transfer resistance; then, intraparticle diffusion controlled the process until equilibrium. Adding sodium lignosulfonate (LSNa) lowered the initial sorption rate but enhanced the water uptake and strength of pellets. The addition of LSNa resulted in a 25% and 14% increase in the water uptake capacity of oat hull and canola meal pellets, respectively; conversely, it also caused an increase in the delay time for sorption on CM pellets at the beginning of the process, extending it to 9.50 min.

Measuring Mass Transfer of n-Hexane and 2-Chloroethyl Ethyl Sulfide in Sorbent/Polymer Fiber Composites Using a Volumetric Adsorption Apparatus.

The integration of metal-organic frameworks (MOFs) into composite systems serves as an effective strategy to increase the processability of these materials. Notably, MOF/fiber composites have shown much promise as protective equipment for the capture and remediation of chemical warfare agents. However, the practical application of these composites requires an understanding of their mass transport properties, as both mass transfer resistance at the surface and diffusion within the materials can impact the efficacy of these materials. In this work, we synthesized composite fibers of MOF-808 and amidoxime-functionalized polymers of intrinsic microporosity (PIM-1-AX) and measured the adsorption and mass transport behavior of n-hexane and 2-chloroethyl ethyl sulfide (CEES), a sulfur mustard simulant. We developed a new Fickian diffusion model for cylindrical shapes to fit the dynamic adsorption data obtained from a commercial volumetric adsorption apparatus and found that mass transport behavior in composite fibers closely resembled that in the pure PIM fibers, regardless of MOF loading. Moreover, we found that n-hexane adsorption mirrors that of CEES, indicating that it could be used as a structural mimic for future adsorption studies of the sulfur mustard simulant. These preliminary insights and the new model introduced in this work lay the groundwork for the design of next-generation composite materials for practical applications.

Heat and mass transfer performance analysis of a vertical tubular ammonia/water bubble absorber based on CFD modeling

Bubble absorbers are highly efficient in mass transfer processes, but their popularization is limited by the risks associated with too much ammonia charging. In order to reduce the ammonia charge, it is essential to optimize the heat and mass transfer performance in the absorber. Existing models provide in-depth analysis of bubble motion and morphology, but insufficient attention has been paid to the concentration distribution and interfacial heat and mass transfer resistance. In this study, a two-dimensional axisymmetric vertical tubular ammonia/water bubble absorber was modeled based on Fluent and phase equilibrium, absorption heat data based on Aspen was imported. The relative deviations were 9%, 0.45%, and 4.1% in terms of the completely absorbed height, the liquid phase ammonia mass fraction, and the outlet temperature, respectively. The results showed that the mass transfer deterioration point was at the gas column closure and the heat transfer deterioration point was at the gas column contraction. Variable parameter studies have shown that turbulence effects at the gas–liquid interface can lead to enhancement and deterioration of local heat and mass transfer, which in turn cause local oscillations in the concentration and temperature profiles. While increasing the interphase mass transfer driving force promotes the interphase mass transfer process, it hinders the diffusion mass transfer process within the liquid phase. This effect is particularly pronounced in the absence of intense cooling, leading to an increase in the complete absorbed height.

Development of an Apple Snack Enriched with Probiotic Lacticaseibacillus rhamnosus: Evaluation of the Refractance Window Drying Process on Cell Viability.

The objective of this study was to develop a dried apple snack enriched with probiotics, evaluate its viability using Refractance Window (RWTM) drying, and compare it with conventional hot air drying (CD) and freeze-drying (FD). Apple slices were impregnated with Lacticaseibacillus rhamnosus and dried at 45 °C using RWTM and CD and FD. Total polyphenol content (TPC), color (∆E*), texture, and viable cell count were measured, and samples were stored for 28 days at 4 °C. Vacuum impregnation allowed for a probiotic inoculation of 8.53 log CFU/gdb. Retention values of 6.30, 6.67, and 7.20 log CFU/gdb were observed for CD, RWTM, and FD, respectively; the population in CD, RWTM remained while FD showed a decrease of one order of magnitude during storage. Comparing RWTM with FD, ∆E* was not significantly different (p < 0.05) and RWTM presented lower hardness values and higher crispness than FD, but the RWTM-dried apple slices had the highest TPC retention (41.3%). Microstructural analysis showed that RWTM produced a smoother surface, facilitating uniform moisture diffusion and lower mass transfer resistance. The effective moisture diffusion coefficient was higher in RWTM than in CD, resulting in shorter drying times. As a consequence, RWTM produced dried apple snacks enriched with probiotics, with color and TPC retention comparable to FD.

Preparation and application of chromatographic stationary phase based on two-dimensional materials

The stationary phase is the heart of chromatographic separation technology and a critical contributor to the overall separation performance of a chromatographic separation technique. However, traditional silicon-based materials designed for this purpose usually feature complex preparation processes, suboptimal permeability, pronounced mass-transfer resistance, and limited pH-range compatibility. These limitations have spurred ongoing research efforts aimed at developing new chromatographic stationary phases characterized by higher separation efficiency, adaptable selectivity, and a broader scope of applicability. In this context, the scientific community has made significant strides toward the development of new-generation materials suitable for use as chromatographic stationary phases. These materials include carbon-based nanomaterial arrays, carbon quantum dots, and two-dimensional (2D) materials. 2D-materials are characterized by nanometer-scale thicknesses, extensive specific surface areas, distinctive layered structures, and outstanding mechanical properties under standard conditions. Thus, these materials demonstrate excellent utility in various applications, such as electrical and thermal conductivity enhancements, gas storage and separation solutions, membrane separation technologies, and catalysis. Graphene, which is arguably the most popular 2D-material used for chromatographic separation, consists of a 2D-lattice of carbon atoms arranged in a single layer, with a large specific surface area and efficient adsorption properties. Its widespread adoption in research and various industries is a testament to its versatility and effectiveness. In addition to graphene, the scientific community has developed various 2D-materials that mirror the layered structures of graphene, such as boron nitride, transition-metal sulfides, and 2D porous organic frameworks, all of which offer unique advantages. 2D porous organic frameworks, in particular, have received attention because of their nanosheet morphology, one-dimensional pores, and special interlayer forces; thus, these frameworks are considered promising candidate chromatographic stationary phase materials. Such recognition is especially true for 2D-metal organic frameworks (MOFs) and 2D-covalent organic frameworks (COFs), which exhibit low densities, high porosities, and substantial specific surface areas. The modifiability of these materials, in terms of pore size, shape, functional groups, and layer-stacking arrangements allows for excellent separation selectivity, highlighting their promising potential in chromatographic separation. Compared with their three-dimensional counterparts, 2D-MOFs feature a simple pore structure that offers reduced mass-transfer resistance and enhanced column efficiency. These attributes highlight the advantages of 2D-MOF nanosheets as chromatographic stationary phases. Similarly, 2D-COFs, given their high specific surface area and porosity, not only exhibit great thermal stability and chemical tolerance but also support a wide selection of solvents and operational conditions. Therefore, their role in the preparation of chromatographic stationary phases is considered highly promising. This review discusses the latest research developments in 2D porous organic framework materials in the context of gas- and liquid-chromatographic stationary phases. It introduces the synthesis methods for these novel materials, elucidates their retention mechanisms, and describes the applications of other 2D-materials, such as graphene, its derivatives, graphitic carbon nitride, and boron nitride, in chromatography. This review aims to shed light on the promising development prospects and future directions of 2D-materials in the field of chromatographic separation, offering valuable insights into the rational design and application of new 2D-materials in chromatography.

Features of Electrospark Coatings Formation on a Chromium Substrate Using Ceramic ZrSi2-MoSi2-ZrB2 and HfSi2-MoSi2-HfB2 Electrodes

The work is devoted to the study of the features of mass transfer, structure and properties of electrospark coatings on substrates made of the chromium alloy grade VKh1-17A using SHS-electrode ceramics of the compositions ZrSi2-MoSi2-ZrB2 and HfSi2-MoSi2-HfB2. The coatings were studied using X-ray diffraction, scanning electron microscopy, energy-dispersive analysis, and tribological tests using the “pin-on-disk”; nanoindentation was also carried out. The kinetics of the mass transfer and heat resistance of coatings were determined by the gravimetric method. In accordance with the Palatnik criterion, the formation of coatings occured in the form of an alloy of an anode (electrode) and a cathode (substrate) materials, which ensures high adhesion of the surface layer. The maximum weight gain on the cathode was observed after the first minute of treatment, and subsequently a decrease in the mass of the cathode was noted. As a result of electrospark deposition, coatings with 100% continuity and a thickness of 10–20 µm were deposited on the surface of the chrome alloy VKh1-17A. Zirconium-containing coatings are characterized by a hardness of 18.2 GPa and an elastic modulus of 274 GPa, and coatings obtained using the HfSi2-MoSi2-HfB2 electrode were characterized by a hardness of 16.9 GPa and an elastic modulus of 332 GPa. The use of SHS-electrodes made it possible to increase the hardness of the surface layer of the chromium alloy by 4 times, wear resistance by 1.5 times, and oxidation resistance by 1.6 times at t 1000 °C for 30 hours of testing.

Optimizing COF crystallinity for high-resolution GC separation

This research explores the influence of crystallinity on gas chromatographic (GC) separation using covalent organic frameworks (COFs) as stationary phases. Three COF materials (CTF-DCBs) with varying crystallinity were synthesized and characterized. CTF-DCB-1, with superior crystallinity, demonstrated high-selectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures, while CTF-DCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance. Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance, which resulted in the best separation. Therefore, optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes, achieving high-performance GC stationary phases.

Microstructured gas-liquid-(solid) interfaces: A platform for sustainable synthesis of commodity chemicals.

Gas-liquid-solid catalytic reactions are widespread in nature and man-made technologies. Recently, the exceptional reactivity observed on (electro)sprayed microdroplets, in comparison to bulk gas-liquid systems, has attracted the attention of researchers. In this perspective, we compile possible strategies to engineer catalytically active gas-liquid-(solid) interfaces based on membrane contactors, microdroplets, micromarbles, microbubbles, and microfoams to produce commodity chemicals such as hydrogen peroxide, ammonia, and formic acid. In particular, particle-stabilized microfoams, with superior upscaling capacity, emerge as a promising and versatile platform to conceive high-performing (catalytic) gas-liquid-(solid) nanoreactors. Gas-liquid-(solid) nanoreactors could circumvent current limitations of state-of-the-art multiphase reactors (e.g., stirred tanks, trickle beds, and bubble columns) suffering from poor gas solubility and mass transfer resistances and access gas-liquid-(solid) reactors with lower cost and carbon footprint.

Dimensional Reduction of Metal-Organic Frameworks for Photocatalytic Synthesis of Fused Tetracyclic Heterocycles.

Heterogeneous palladium catalysts with high efficiency, high Pd atom utilization, simplified separation, and recycle have attracted considerable attention in the field of synthetic chemistry. Herein, we reported a zirconium-based two-dimensional metal-organic framework (2D-MOF)-based Pd(II) photocatalyst (Zr-Ir-Pd) by merging the Ir photosensitizers and Pd(II) species into the skeletons of the 2D-MOF for the Pd(II)-catalyzed oxidation reaction. Morphological and structural characterization identified that Zr-Ir-Pd with a specific nanoflower-like structure consists of ultrathin 2D-MOF nanosheets (3.85 nm). Due to its excellent visible-light response and absorption capability, faster transfer and separation of photogenerated carriers, more accessible Pd active sites, and low mass transfer resistance, Zr-Ir-Pd exhibited boosted photocatalytic activity in catalyzing sterically hindered isocyanide insertion of diarylalkynes for the construction of fused tetracyclic heterocycles, with up to 12 times the Pd catalyst turnover number than the existing catalytic systems. In addition, Zr-Ir-Pd inhibited the competitive agglomeration of Pd(0) species and could be reused at least five times, owing to the stabilization of 2D-MOF on the single-site Pd and Ir sites. Finally, a possible mechanism of the photocatalytic synthesis of fused tetracyclic heterocycles catalyzed by Zr-Ir-Pd was proposed.

Devolatilization of high viscous fluids with high gravity technology

Volatile organic compounds (VOCs) are generally toxic and harmful substances that can cause health and environmental problems. The removal of VOCs from polymers has become a key problem. The effective devolatilization to remove VOCs from high viscous fluids such as polymer is necessary and is of great importance. In this study, the devolatilization effect of a rotating packed bed (RPB) was studied by using polydimethylsiloxane as the viscous fluid and acetone as the VOC. The devolatilization rate and liquid phase volume (KLa) have been evaluated. The results indicated that the optimum conditions were the high-gravity factor of 60, liquid flow rate of 10 L·h−1, and vacuum degree of 0.077 MPa. The dimensionless correlation of KLa was established, and the deviations between predicted and experimental values were less than ±28%. The high-gravity technology will result in lower mass transfer resistance in the devolatilization process, enhance the mass transfer process of acetone, and improve the removal effect of acetone. This work provides a promising path for the removal of volatiles from polymers in combination with high-gravity technology. It can provide the basis for the application of RPB in viscous fluids.

Hydrophobic hypercrosslinked polymers prepared by secondary pore-forming method as excellent toluene adsorbents

In this work, inspired by molecular imprinting technology, we developed a secondary pore-forming method to chemically etch three hypercrosslinked polymers which are constructed from three novel hexapolar monomers containing imine groups, resulting in three novel hydrophobic porous hyper-crosslinked polymers (HCPs) pGly-TPA, pP-TPA and pBP-TPA. The structures were determined by FT-IR and solid-state 13C NMR spectroscopic techniques. The specific surface areas of pGly-TPA, pP-TPA and pBP-TPA are 694.1, 197.9 and 497.7 m2/g, respectively. All three porous polymers exhibit high hydrophobic properties with wetting angles of much greater than 90°. The breakthrough adsorption experiments revealed that the three prepared polymers exhibited significant adsorption capacity for toluene (322.05 mg/g for pGly-TPA, 114.43 mg/g for pP-TPA and 279.14 mg/g for pBP-TPA), but showed almost no adsorption for ethyl acetate, cyclohexane, and n-hexane, exhibiting certain molecular size and polarity selectivity. The adsorption behaviors of toluene on pGly-TPA, pP-TPA and pBP-TPA can be fit by the Boltzmann model and the Yoon-Nelson model, suggesting that the fixed bed has low mass transfer resistance. The adsorption rate is controlled by both external diffusion and intraparticle diffusion, as shown by the intraparticle diffusion model analysis. In addition, the adsorption capacity of toluene on pGly-TPA is almost unchanged under high humidity (70 %) or five adsorption–desorption processes, which demonstrates exceptional water-resistance and stability. This work is a reference for preparing novel hydrophobic HCPs using the secondary pore-forming method for removing VOCs from humid air.

Nonconductive Metal Oxide Gas Diffusion Layer for Mitigating Electrowetting during CO2 Electrolysis.

Gas diffusion electrodes (GDEs) are extensively used for high current density electrochemical CO2 electrolysis (ECO2R), enabled by significantly reducing mass transfer resistance of CO2 to the catalyst layer. Conventionally, these GDEs are based upon hydrophobic carbon-based gas-diffusion layers (GDLs) that facilitate the gas transport; however, these supports are prone to flood with electrolyte during electrolysis. This potential-induced flooding, known as electrowetting, is related to the inherent conductivity of carbon and limits the activity of ECO2R. To investigate the effect of electrical conductivity more carefully, a GDE is constructed based on a Cu mesh with a nonconductive microporous GDL applied to this substrate, the latter composed of a mixture of metal oxide and polytetrafluoroethylene. With alumina as the metal oxide, a stable operation is obtained at -200 mA cm-2 with 70% selectivity for ECO2R (with over half toward C2+ products) without flooding as observed by in situ microscopy. On the contrary, with a Vulcan carbon-based GDL, the initial activity is rapidly lost as severe flooding ensues. It is reasoned that electrowetting is averted by virtue of the nonconductive nature of alumina, providing a new perspective on alternative GDL compositions and their influence on ECO2R performance.

A novel naturally aspirated cathode for efficient electrosynthesis of hydrogen peroxide and wastewater purification in electro-Fenton systems

Electrochemical synthesis of hydrogen peroxide (H2O2) has developed rapidly in recent years as an alternative process to the anthraquinone method. However, the low H2O2 production and high energy consumption limit its further application. In this study, we propose a simple method to fabricate a naturally aspirated cathode (NAC), which significantly reduces the mass transfer resistance of oxygen and achieves a high oxygen diffusion coefficient (7.11 × 10-6 m2 s−1) and oxygen utilization efficiency (39.6 %). Additionally, the NAC provides a high density of reaction sites to achieve efficient production of H2O2 (0–84.33 mg h−1 cm−2) at near industrial current densities (0–240 mA cm−2) without external aeration. Meanwhile, the prepared NAC can degrade over 97.5 % of dyes within 10 min during the electro-Fenton process. The NAC exhibits excellent H2O2 production performance and great stability during long-term operation, which offers huge potential for industrial-scale electrochemical H2O2 production and the advanced oxidation processes (AOP) derived from it.

Mesoporous Pdx-Nix aerogels for electrocatalytic evaluation of urea-assisted electrolysis

This work presents the synthesis and evaluation of Pd-Ni aerogels toward the urea oxidation reaction (UOR). The incorporation of Ni led to a 0.13 V reduction in the energy required for the oxidation and reduction of PdO compared to monometallic Pd, both in alkaline medium with and without urea. Varying the Ni ratios in Pd (Pd-Ni 4:1, Pd-Ni 1:1, and Pd-Ni 1:4) led to significant changes in the electrochemical behaviour. In alkaline medium without urea, PdNi 4:1 showed the formation of NiOOH at 1.35 V, which promoted oxygen diffusion on the electrode surface and increased the current density, confirming the increase in the active sites of NiOOH and NiPdOOH and enabling urea-based electrolysis at these sites. While palladium aerogels alone are ineffective for UOR, the presence of nickel plays a key role in enhancing the UOR efficiency. On the other hand, physicochemical characterisation revealed that PdNi 4:1 has a crystal size of 4.37 nm and a larger shift in the 2θ positions of the (111) and (200) planes, which favours electronic changes that were investigated by XPS. These changes affected the electrocatalytic activity, which is primarily related to electronic effects. The results of SEM and TEM studies and nitrogen adsorption-desorption isotherm confirmed that the aerogels are highly porous and have an effective surface area and abundant active sites for reactions that allow efficient mass transfer and low diffusion resistance. TEM observations revealed interconnected nanochains indicating optimal electrocatalytic activity for both ORR and UOR due to high mass transfer. These interconnected networks are crucial for improving electrocatalytic activity in the urea oxidation reaction.