Interfacial Reaction Research Articles

Electrochemical Behaviors of Ultramicro Triangular Pipettes.

Ultramicro pipettes with circular orifices have practically become common probes in exploring the microscopic world, yet the versatility of differently shaped pipettes is undermined in the pore family. Herein, ultramicro triangular pipettes with a pseudotriangular-shaped orifice were fabricated by laser-pulling triangular quartz capillaries and characterized by microscopic and electrochemical methods. Then, the differences in the electrochemical behaviors of triangular and circular pores were revealed through experiments and simulations. A liquid/liquid interface was supported first at a triangular pipette, and the facilitated potassium ion transfer reactions exhibited steady-state voltammetric responses. An empirical equation for triangular pores between the diffusion-limited current and the side length (a) of the orifice was evaluated, and the corresponding mass transfer coefficient of ion ingress was estimated as mTri = 8.05D/a. As for ion egress transfer, the tip angle and pore shape would affect the diffusion regime and the ion distribution, where the mass transfer would be enhanced at the corners of a triangular pipette with a large tip angle. Triangular submicropores and nanopores were employed to detect particle translocations at a high capture rate, though the events had broader distributions and lower charges than those of circular pores. These findings demonstrate the shape effect in triangular pores that promotes the mass transfer rate of interfacial ion transfer reactions and the capture rate of ionic blockades. The universal laser-pulling method could make ultramicro pores of arbitrary shapes accessible in fundamental studies and applicable as chemical sensors.

Synergistic Effect of Anchoring Transitional/Interstitial Sites on Boosting Structural and Electrochemical Stability of O3-Type Layered Sodium Oxides.

O3-type layered oxides are considered promising cathode materials for next-generation high-energy-density sodium-ion batteries (SIBs). However, they face challenges, such as low rate capacity and poor cycling stability, which arise from structural deformation, sluggish Na+ diffusion kinetics, and interfacial side reactions. Herein, a synergistic substitution strategy for transitional and interstitial sites was adopted to improve the structure stability and Na+ diffusion kinetics of the O3-type NaNi0.2Fe0.4Mn0.4O2. Simulation results indicate that Co3+/B3+ codoping effectively lowers the Na+ migration energy barrier. In addition, the synergistic effect of Co3+/B3+ codoping provides ultralow lattice strain during repeated Na+ deintercalation/intercalation. In situ characterization verified that the complex phase transformation during charge and discharge was suppressed, thereby significantly improving the structural stability. At 1 and 3 C, the capacity retention of the modified O3-Na(Ni0.2Fe0.4Mn0.4)0.96Co0.04B0.02O2 (NFMCB) improved from 29.6% and 1.7% to 86.7% and 88.6% after 200 cycles, respectively. Even at 10 C, it could still produce 107.2 mAh·g-1. Furthermore, full cells assembled with this material and commercial hard carbon exhibit a high energy density of 316.2 Wh·kg-1 and a capacity retention of 80.8% after 200 cycles at 1 C. It is expected that this strategy will facilitate the commercialization of O3-type layered oxides.

Nonthermal Effect of Microwave Processing Enhances Interface Reactivity and Microchannel Integrity: Low-Temperature Rapid Bonding of PMMA Microfluidic Devices

Nonthermal Effect of Microwave Processing Enhances Interface Reactivity and Microchannel Integrity: Low-Temperature Rapid Bonding of PMMA Microfluidic Devices

Kinetics of manganese extraction from pyrolusite using reduction leaching of acidic wastewater from steel plants

ABSTRACT Acidic wastewater from steel works was selected to reduce pyrolusite. The effects of leaching parameters such as the ratio of FeCl2 to MnO2, leaching temperature, liquid–solid ratio and initial HCl concentration in acidic wastewater on the leaching rate of manganese were investigated. The results show that under the conditions including the molar ratio of FeCl2 and MnO2 ( m FeC l 2 / m Mn O 2 ) at 2.2, the leaching temperature of 363 K, a leaching time of 180 min, an L/S ratio of 11:1, and an initial HCl concentration in acidic wastewater of 2.5 mol/L, the leaching rate of manganese in pyrolusite was 97.14%. An unreacted shrinking core model was employed to explore the kinetics of manganese in pyrolusite arising from the reduction leaching of acidic wastewater from steel plants. The results imply that the rate-determining step changed in the leaching process; among which, the first stage (0–100 min) of leaching was subject to the control of interfacial chemical reactions; the second stage (100–180 min) was controlled by internal diffusion. The apparent activation energy of the two stages was 15.57 and 125.48 kJ/mol respectively, and the apparent rate equations were respectively: 1 – ( 1 – r ) 1 / 3 = 0.39 ( m FeC l 2 / m Mn O 2 ) 1.18 [ HCl ] 0.21 ( V L / M S ) 0.62 exp ( − 15.57 / RT ) t 1 – 3 [ ( 1 – r ) / ( 1 – r 1 ) ] 2 / 3 + 2 [ 1 – ( 1 – r 1 ) ( r – r 1 ) 1 / 3 ] = 2.22 × 10 16 ( m FeC l 2 / m Mn O 2 ) 5.81 [ HCl ] exp ( − 125.48 RT ) t

Irrigation System-Inspired Open-/Closed-Pore Hybrid Porous Silicon-Carbon Materials for Lithium-Ion Battery Anodes.

Porous silicon-carbon (Si-C) nanocomposites exhibit high specific capacity and low electrode strain, positioning them as promising next-generation anode materials for lithium-ion batteries (LIBs). However, nanoscale Si's poor dispersibility and severe interfacial side reactions historically hamper battery performance. Inspired by irrigation systems, this study employs a charge-driven Si dispersion and stepwise assembly strategy to fabricate an open-/closed-pore hybrid porous Si-C composite. Polydimethyl diallyl ammonium chloride (PDDA) is used to functionalize Si nanoparticles, inducing strong electrostatic repulsion for uniform dispersion. Subsequently, the PDDA functional layer on Si nanoparticle surfaces facilitates the stepwise self-assembly of acetic acid and chitosan, resulting in Si nanoparticles encapsulated within closed pores during carbonization. Simultaneously, the PDDA functional layers transform into a graphene coating on the Si nanoparticles. Conversely, regions of homogeneous acetic acid/chitosan, distant from the PDDA-functionalized Si nanoparticles, form an open-pore structure. The dual shielding effect of closed carbon pores and the graphene coating effectively isolates Si from the electrolyte, preventing interfacial side reactions. Open carbon pores enhance electrolyte-active material contact, reducing Li+ transport distances. The resulting composite material (PDDA@Si/C) demonstrated excellent cycling stability and superior rate performance as a LIB anode.

Silver‐Based Supportless Membrane Electrode Assemblies for Electrochemical CO2 Reduction

ABSTRACTMost commonly, electrochemical CO2 reduction is performed in a three‐compartment setup employing gas diffusion electrodes (GDEs) to decrease mass transport limitations of the gaseous reactant CO2 to the reaction interface. However recently, there has been a rising number of investigations on suitable membrane electrode assemblies (MEAs) to overcome ohmic potential losses caused by the electrolyte gaps in the systems. While the significant majority of MEAs exhibited in literature is based on catalyst‐coated gas diffusion layers, this work presents an approach that does not require a likewise support. On the basis of a catalyst suspension similar to mixtures already employed for GDE production on industrial level, a method to directly transfer the resulting catalyst layers to the membrane is developed. The Faradaic efficiency of carbon monoxide, i.e. target product formation of GDEs manufactured according to a similar procedure, can be matched or even exceeded for individual modifications of the exchange MEAs. Simultaneously, the cell potentials can be remarkably decreased in this setup. By gradual adaptation of the fabrication procedure, the influence of important manufacturing parameters is unraveled, also discussing the effect of hydrogen permeation through the membrane.

In-situ interfacial reactions in boron nitride-reinforced zinc implants for achieving strength and toughness

In-situ interfacial reactions in boron nitride-reinforced zinc implants for achieving strength and toughness

Photothermally-activated suspended aerogel triggers a biphasic interface reaction for high-efficiency and additive-free hydrogen generation.

The need for a sustainable hydrogen supply has sparked significant efforts to develop effective liquid hydrogen carriers with high hydrogen content that can be safely stored and undergo controlled hydrogen release. However, a major challenge lies in the ultralow hydrogen evolution rate caused by the direct dehydrogenation of liquid hydrogen carriers. Conventionally, accelerant additives are employed to improve the dehydrogenation rate, but this strategy inevitably sacrifices the hydrogen storage density. Therefore, achieving high-efficiency hydrogen release and high storage density remains a daunting task. Herein, we develop an innovative photothermally-activated suspended biphasic reaction strategy, which absorbs solar radiation and re-radiates infrared photons to induce photothermal evaporation and in situ dehydrogenation of liquid hydrogen carriers, fundamentally circumventing the employment of additives. Furthermore, by leveraging this phase transition-induced biphasic reaction design, the strategy improves the required reaction temperature and drastically lowers hydrogen transport resistance. Therefore, an impressive hydrogen evolution rate of 386 mmol g-1 h-1 is achieved from pure formic acid with an ultrahigh hydrogen storage density of 53 g L-1, representing a threefold improvement in rate compared to state-of-the-art strategies. Our approach introduces a fresh perspective for the dehydrogenation of liquid hydrogen carriers, encompassing formic acid, hydrazine hydrate, and so on, and concurrently guarantees exceptional hydrogen release capabilities and excellent hydrogen storage density.

Growth of InxGa1−xAs Films on GaAs (100): Inserting an Ultrathin InxGa1−xAs Buffer Using a Surface Technology

ABSTRACTThe mechanism of the In‐catalyzed reaction of GaAs with In metal to form InxGa1−xAs was explained by comparing the interfacial reactions of metallic In and GaAs at high and low temperatures. Specifically, GaAs dissolved in In metal at the defects under the catalysis of In, and then In diffused into the GaAs crystals to replace Ga in the lattices. Based on this mechanism, a new method was developed for preparing an InxGa1−xAs buffer layer on GaAs by combining the ion‐sputtering method and annealing. The buffer layer and its effect on the quality of the epitaxial layer grown on GaAs were verified and analyzed by transmission electron microscopy, X‐ray diffraction, Hall effect measurements, and Raman scattering. The buffer layer was found to adopt the original dislocations on the GaAs surface, which prevented substrate dislocations from entering the epitaxial layer and reduced the dislocations generated due to the mismatch between the substrate and buffer layer. When the composition of the epitaxial layer is similar to that of the buffer layer, the quality of the epitaxial layer is significantly improved.

Mxene and GaIn Alloy Nanostructures Regulate Zn Surface Ion Deposition for High-Performance Zinc-Ion Battery.

Zinc is an ideal energy storage material because of its low toxicity, nonflammability, and good biocompatibility. However, the commercial application is seriously hindered due to problems such as dendrite growth, hydrogen evolution, and interface passivation caused by "dead zinc" in the process of cyclic deposition. Herein, a nanoscale deposition dispersion model is designed in order to achieve directional deposition and uniform distribution of zinc ions for the growth of interfacial dendrites. Liquid metal GaIn was combined with Mxene for this nanostructure, which provides a rapid ion transfer channel to achieve lower overpotentials, a more uniform electric field distribution, and stronger corrosion resistance in a core-shell structure to achieve interface reaction suppression. The material was coated on the surface of the zinc metal as an artificial protective layer. It has a better cycle life at 1 mA·cm-2 compared with the bare Zn metal anode, achieving a long cycle time of 1100 h and an ultralow voltage lag (28.1 mV). It maintains the stability for 1000 cycles at 1 mA·cm-2 after assembling the complete battery. This provides a way to improve the performance of zinc-ion secondary batteries and paves the way for the next generation of energy storage devices.

Controllable SiOx Coating Layer Promotes High Stable Si Anode for Lithium-Ion Batteries.

Silicon (Si) is considered as one of the most promising candidates for next-generation lithium-ion batteries with high energy density. The main problems are the severe volume expansion and continuous interfacial side reaction of Si that hinder its further application. It can be an effective way by constructing a robust coating layer outside of Si to impede/alleviate the above effect. SiOx with high mechanical strength can largely promote the electrochemical performance of Si. Herein, Si@SiOx material with high specific surface area, high porosity, and controllable coating was synthesized via a simple solid-liquid reaction by LiOH solution etching effect. The etching/oxidation mechanism of Si under alkaline conditions was thoroughly investigated. The surface oxide layer of Si was beneficial to the formation of a solid electrolyte interphase (SEI) with excellent stability and high Li+ conductivity, while its high-porosity structure reduces the volume expansion of the material by approximately 110%. Under the synergistic effect of etching-oxidation, the modified material exhibited superior electrochemical properties. When employed as anode materials, the specific capacity was as high as 3101.5 mAh g-1 and maintained at 841.0 mAh g-1 after 500 cycles at 1 A g-1.

A self-assembly capsule-like solvation structure electrolyte for lithium metal batteries

The localized high-concentration electrolyte can be achieved by diluting a high-concentration electrolyte with an anti-solvent, which inherits the original solvation structural characteristics and reduces harmful interfacial reactions, resulting in an electrolyte with unique functions suitable for lithium metal batteries. Here, we design a localized high-concentration electrolyte with a capsule-like solvation structure and non-flammable properties to obtain stable-cycle and safe lithium metal batteries. The weak coordination and dipole-dipole interactions of fluorinated ether molecules promote the self-assembly of capsule-like solvated sheaths, encapsulating cations/anions and polar solvent molecules within the solvation sheath, which improves the oxidative stability of the electrolyte system and promotes the reduction of anions. A high-quality solid electrolyte layer was derived at the electrode interfaces, leading to rapid Li+ transport and dendrite-free lithium deposition. Consequently, a Coulombic efficiency of 99.7% is achieved, and the assembled Li||NCM811 battery exhibits a long cycle life of more than 400 cycles at 0.5C with a capacity retention of 83%. This work provides a promising approach for developing non-flammable electrolytes suitable for high-voltage lithium metal batteries.

Spatial Confinement Effect of Mineral‐Based Colloid Electrolyte Enables Stable Interface Reaction for Aqueous Zinc–Manganese Batteries

AbstractThe rational design of inorganic colloid electrolytes enables the manipulation of the solvation structure of Zn2+ ions and addresses zinc dendrite formation and manganese dissolution in aqueous zinc–manganese batteries. In this study, magnesium aluminosilicate (MAS) powder is used to fabricate a mineral‐based colloid electrolyte for Zn//α‐MnO2 batteries. According to theoretical calculations, MAS has a stronger binding energy with Zn2+/Mn2+ ions than with H2O molecules, suggesting the possibility of regulating the solvation structure of Zn2+/Mn2+ ions in a MAS–colloid electrolyte. Based on the experimental results, a high ionic conductivity, wide operating voltage, low activation energy barrier, and stable pH environment is achieved in the MAS–colloid electrolyte. As expected, long‐term cyclic stability can be maintained for 3500 h at 0.2 mA cm−2 in Zn//Zn cells, and high capacities of 255.5 and 239.8 mAh g−1 are retained at 0.2 and 0.5 A g−1 after 100 cycles in Zn//α‐MnO2 batteries, respectively. This performance is attributed to the spatial confinement effect of MAS on the active H2O molecules, which effectively reshapes the solvation structure of Zn2+ ions, guaranteeing reversible zinc deposition, suppressing active manganese dissolution, and ensuring stable interfacial reactions. This work will drive the development of mineral‐based electrolytes in zinc‐based batteries.

Synergistic promotion mechanism and structure-function relationship of nonmetallic atoms doped carbon nanodots driving Tagetes patula L. to remediate cadmium-contaminated soils

Phytoremediation is an economical and effective strategy to remove cadmium (Cd) from polluted environments. To improve its efficiency, nanotechnology has been proposed to collaborate with hyperaccumulators in the remediation of Cd-polluted soils. However, the intricate structure-function relationship and the underlying regulatory mechanisms by which nanomaterials regulate Cd migration and conversion within the soil-plant system remained unrevealed. In this study, functional carbon nanodots (FCNs) were modified by doping with nitrogen and (or) sulfur elements. The synthesized nonmetallic atoms-doped FCNs were utilized to investigate their structure-function relationship and the regulatory mechanisms underlying their role in the phytoremediation of Cd-polluted soils by Tagetes patula L. FCNs-based nanomaterials can regulate the migration and bioaccumulation of Cd in the soil-plant system, which exhibits an obvious structural dependency. Specifically, the synergistic application of sulfur doped FCNs and Tagetes patula L. had the highest Cd removal efficiency of 53.2%, which was 20.1% higher than Tagetes patula L. alone. The uptake and migration of Cd in the soil-plant system are regulated by FCNs-based nanomaterials through both direct and indirect mechanisms, involving interfacial reactions, plant physiology regulation and environmental influence. This study not only sheds light on the fate of FCNs-based nanomaterials and Cd in the soil-plant system, but also provides innovative nanotools for reinforcing phytoremediation efficiency in contaminated soils.

Upcycling of waste diamond wire sawing silicon powders to prepare Al-50Si composite by hot-pressing sintering

The disposal of waste diamond wire sawing silicon powders (DWSSP) generated during solar-grade silicon wafer production is crucial for the sustainable development of the photovoltaic industry. To achieve the resourceful utilization of DWSSP, a method to prepare Al-50Si composite by upcycling DWSSP through hot-pressing sintering (HPS) was proposed. The effects of hot-pressing sintering temperature, pressure, and current on the densification of DWSSP and Al powders were investigated by finite element modeling analyses and experiments validation. The numerical simulation results showed that pressure-assisted sintering triggered the percolation effect of interparticle currents coupled with localized high Joule heat, accelerating the interfacial reaction between DWSSP and Al powders. It was found that the Vickers hardness and density of the prepared Al-50Si composite increased and then decreased at sintering temperatures of 450 to 500°C and showed a positive correlation at pressures of 50 to 200MPa. Optimal conditions of 475 °C sintering temperature, 150MPa sintering pressure, and 5min holding time yielded Al-50Si composite with a density of 2.36g/cm3 and a Vickers hardness of 201 HV0.1. The findings demonstrate the application of HPS method allows for the grave-to-cradle waste management of DWSSP and the preparation of recycled Al-50Si composite for its high value-added utilization.

Enhanced strength and ductility of boron nitride nanosheet reinforced cu composites through constructing an interfacial three-dimensional structure

To address the poor wettability and weak interface bonding between boron nitride nanosheet (BNNS) and Cu, BNNS/CuTi composites were prepared through matrix microalloying by adding 1 wt% Ti. Solid-state interfacial reactions resulted in the formation of TiN transition layers and TiB whiskers (TiBw), collectively constructed a BNNS-(TiN&TiB)-Cu interfacial three-dimensional structure (I-3DS). The coherent I-3DS significantly reduced the interfacial energy, improved the interfacial stability, and achieved a favorable combination of strength and ductility in BNNS/CuTi composites. The 0.1 wt% BNNS/CuTi composite achieved an ultimate tensile strength (UTS) of 485 MPa, representing increases of 114 % and 62 % over pure Cu and 0.1 wt% BNNS/Cu composite, respectively. The interlocking structure formed by I-3DS and Cu doubled the theoretical interface shear strength limit and improved load transfer efficiency. This study offered new insights into the innovative design of high-performance Cu matrix composites (CMCs) by constructing I-3DS.

Nanochannel geometry-depended behaviors on ion selectivity for salinity gradient energy harvesting

Nanofluidic osmotic energy, which can be directly converted into electricity, is considered a clean and sustainable energy that effectively utilizes salinity gradients. The rational construction of nanochannel is of great significance to ion transport and osmotic energy conversion, but there is currently little attention paid to naturally formed rough and irregular channels. In this study, a model that considers the effects of nanochannel cone angle and waveform surface on interface reaction coupling was established for osmotic energy conversion. The results indicate that cone angle and waveform have a significant effect on osmotic energy conversion. It is found that the reduction of cone angle and the addition of waveform will improve ion selectivity and increase energy conversion efficiency, and ion rectification effect of corrugated cylindrical channel is the most obvious. Meanwhile, enlarging waveform dimensions leads to a significant overlap of electric double layer, resulting in a growth in cation transference number and selectivity, thereby enhancing the system's energy conversion efficiency, which can reach 49.62%. At low concentration ratios, the waveform dimensions are inversely proportional to the maximum output power, whereas at high concentration ratios, increasing the waveform dimensions and applying the waveform at channel entrance can efficiently improve the maximum output power.

Polymetallic red mud direct materialization strategy towards zero waste emission: Electromagnetic wave absorption conversion and sodium solidification

Red mud is an industrial hazardous alkaline solid waste, whereas it is rich in polymetallic components showing a high comprehensive utilization value. Direct materialization of red mud towards zero waste emission is a more reasonable and environmentally friendly strategy. In this work, a novel materialization approach of red mud via converting the polymetallic constituents into functional ferrite material by phase reconstruction with MnO2 was proposed. The mineral phase reconstruction, microstructure evolution, reaction interface observation, electromagnetic property, and the materialization conversion mechanism were investigated. It was found that the complicated phases in red mud were transferred to simple forms including the magnetic ferrites (Ca/Na/Al/Ti-bearing Mn ferrite) and weakly magnetic silicates ((Na,Al,Ca)2SiO3) after phase reconstruction. The reconstructed red mud after sintering at 1200 ℃ for 120min in air atmosphere had satisfactory electromagnetic property. Magnetism study demonstrated the soft magnetic property with maximum saturation magnetization of 34.22emu/g and coercivity of only 7.0Oe. Compared with the original red mud, effective electromagnetic wave absorption with reflection loss (RL) values of the reconstructed red mud below -20 dB were satisfied across a wider frequency bandwidth of 5-18GHz, and the minimum RL value was lower as -32.4dB with a thinner veneer thickness of 15mm, highlighting its excellent electromagnetic wave absorption performance. Moreover, Na solidification behaviors indicated that Na was solidified in the sintered product, which can reduce the possible environmental hazards of red mud alkalinity. The novel materialization treatment with zero waste emission exhibits a favorable application prospect with a large red mud batching ratio about 50wt%.

Synergistic Behavior and Kinetics of Yttrium Extraction from Nitric Acid Using a Binary System of Cyanex 572 and Cyanex 302

This study explores the extraction of Y(III) from nitric acid solutions using a kerosene-based blend of Cyanex 572 (H₂B₂) and Cyanex 302 (H₂A₂). Slope analysis suggests that the extracted species formed in the presence of this mixture is likely YH₄A₃B₄. Separation factors for Y(III) relative to other rare earth elements, specifically Nd(III) and La(III), demonstrate the effectiveness of the Cyanex 572 and Cyanex 302 mixture for selective separation. To gain deeper insights into the extraction mechanism, a kinetic study was conducted using a Lewis cell. The extraction kinetics of Y(III) from the nitric acid medium were analyzed by applying pseudo-first-order rate constants. Results indicate that the process is diffusion-controlled and involves an interfacial reaction. This conclusion is supported by investigating the effects of stirring speed, temperature, extractant concentration, and nitrate and hydrogen ion concentrations on the extraction rate. From the experimental data, a rate equation was derived, and the rate-determining step was identified using interfacial reaction model predictions. Additionally, an extraction model is proposed to elucidate the underlying mechanisms.

Zn2+ flux regulator to modulate the interface chemistry toward highly reversible Zn anode

The persistent challenges of diminished coulombic efficiency (CE) and the formation of Zn dendrites at the Zn anode interface substantially hinder the cycle life of aqueous Zn-ion batteries (AZIBs), thereby impeding their widespread deployment. To address these issues, multifunctional 2-amino-5-guanidino-pentanoic acid (AGPA) additive is introduced into the electrolyte, as a novel Zn2+ flux regulator (ZFR) to improve the reversibility and durability of Zn anodes. The distinctive zincophilicity of amino groups empowers such ZFR with a higher adsorption energy, enabling the construction of a multifunctional molecular adsorption layer on Zn electrode surface. Simultaneously, leveraging the exceptional nucleophilic characteristics of polar carboxyl groups, AGPA molecules tend to form chelating bonds with Zn2+ for manipulating the interface chemistry and solvation chemistry. The functional groups in ZFR work in synergy to attract zinc ions for homogenizing Zn2+ flux and suppress the interfacial side reactions, resulting in uniform dendrite-free Zn deposition. Consequently, the Zn//Zn symmetrical cell achieves an extended cycle life of 5500 h. Moreover, the ZFR enables stable operation of the full batteries with an ultra-long cycling lifespan of 6000 cycles at 5 A/g, showcasing the effectiveness of ZFR in advancing the commercialization of AZIBs.