Transfer Reactions Research Articles

Redox kinetics of multi-electron transfer reactions of polyoxometalates (POMs) relevant to electrochemical devices

The formal equilibrium potential (E0′) and heterogeneous rate constant (k0) are characteristics of any electron-transfer reaction. The estimation of these characteristics for very fast multiple electron-transfer reactions of polyoxometalates (POMs) relevant to various applications including redox flow batteries, hydrogen storage materials, and electrocatalysis is highly challenging by the conventional electrochemical methods. Therefore, E0′and k0 (k0∼10–2 cm sec‑1) of such reactions (for e.g., that of tungstosilicic acid (SiW12) and phosphotungstic acid (PW12)) separated by small potential windows are estimated from the background current free higher harmonic response of large-amplitude AC voltammetry. For SiW12/PW12 redox species, the E0′ values of processes 1, 2, and 3 estimated from the minima of second harmonic response are -0.326/-0.127, -0.530/-0.380 and -0.691/-0.701 (V vs. Ag/AgCl), respectively. The k0 values of the first redox process (P1) of SiW12 (SiW12/ SiW12-,4.8 × 10–2 cm sec‑1) and PW12 (PW12/PW12-,5.2 × 10–2 cm sec‑1) estimated from the large-amplitude AC voltammetry are further validated through the impedance measurement (2.1 × 10–2 and 2.4 × 10–2 cm sec‑1). The uniqueness of large-amplitude AC voltammetry over conventional DC techniques and impedance spectroscopy is illustrated. The relevance of k0 values in the context of electrocatalytic processes and RFBs system is also presented.

Effective lateral dispersion of momentum, heat and mass in bubbling fluidized beds

The lateral dispersion of bed material in a bubbling fluidized bed is a key parameter in the prediction of the effective in-bed heat transfer and transport of heterogenous reactants, properties important for the successful design and scale-up of thermal and/or chemical processes. Computational fluid dynamics simulations offer means to investigate such beds in silico and derive effective parameters for reduced-order models. In this work, we use the Eulerian-Eulerian two-fluid model with the kinetic theory of granular flow to perform numerical simulations of solids mixing and heat transfer in bubbling fluidized beds. We extract the lateral solids dispersion coefficient using four different methods: by fitting the transient response of the bed to (1) an ideal heat or (2) mass transfer problem, (3) by extracting the time-averaged heat transfer behavior and (4) through a momentum transfer approach in an analogy with single-phase turbulence. The method (2) fitting against a mass transfer problem is found to produce robust results at a reasonable computational cost when assessed against experiments. Furthermore, the gas inlet boundary condition is shown to have a significant effect on the prediction, indicating a need to account for nozzle characteristics when simulating industrial cases.

A study of electrochemiluminescence mechanism of Rubrene/TPrA system in an aqueous solution via stochastic collision electrochemistry in an emulsion reactor

BackgroundElectrochemiluminescence (ECL) is an electrochemically induced process in which radicals generated at the electrode surface undergo exergonic electron transfer reaction to form excited states and luminesce. ECL, with high sensitivity and superior spatiotemporal control, has been widely applied in bioanalysis and light-emitting devices. The ECL signal of rubrene (Rub) was observed in Rub/TPrA oil-in-water (o/w) emulsions, which was inconsistent with the theory of ion-transfer coupled electron-transfer in Rub emulsion droplets, and the conventional ECL mechanism in Rub/TPrA system couldn't explain this phenomenon. ResultsChoosing the toluene oil-in-water emulsion droplets as reactors, we put forward and verified a new ECL mechanism of Rub in aqueous solution on the basis of cyclic voltammograms, single-entity electrochemistry, ECL detection techniques and COMSOL finite element simulation. The new mechanism involved that Rub was reduced to Rub•- by the highly reducing species TPrA•, Rub•- was then oxidized to the excited state Rub∗ by the stable intermediate TPrA•+, and finally Rub∗ was inactivated by emitting photons. In simulation, the standard oxidation rate constant of TPrA in the emulsion droplets was deduced as 1.5 × 10−4 cm/s, and the deprotonation rate of TPrA•+ was about 200 s−1. Besides, emulsion droplets colliding on Au ultramicroelectrode (UME) were found to be able to amplify ECL signals. SignificanceThe newly proposed ECL mechanism of Rub/TPrA emulsion reactors broke the solubility problem of Rub in an aqueous, promoting the research and application of the organic luminophore Rub in bioanalysis. With the ECL signals amplification capability, the o/w emulsion reactors are promising to future design of ECL biosensors with higher sensitivity.

Effects of organic ligands and photoactive substances on MOFs-derived Co3O4@MnOx hollow-sphere structure for efficient energy transfer and photothermocatalysis of acetone and NO

A set of MOFs-derived Co3O4@MnOx hollow-sphere were synthesized to develop a catalyst for the photothermal catalytic removal of NO using acetone as a reducing agent. The study systematically investigated the impact of organic ligands and photoactive substances on energy transfer and photothermocatalytic reactions involving acetone and NO under 5 vol % H2O with the catalysts. At 240°C, sample C-5/1 (with an organic ligand added and Co/Mn molar ratio of 5/1) demonstrated 75 % NO conversion and 65 % acetone conversion. The highest catalytic performance was observed in the L-Py sample (with photoactive substance was added), achieving 80 % NO and 69 % acetone conversion at 240°C. The catalyst demonstrated low crystallinity, and the introduction structural defects through ligands adjusted the ratio of active components. Meanwhile, enhanced catalytic performance was attributed to light energy scattering in the inner space of microspheres, resulting in the efficient transfer of 2.17 eV energy with the addition of two photoactive substances. The elevated concentration of surface-active oxygen facilitated oxidation, while Mn/Mn+1 (Mn3+/Mn4+ and Co2+/Co3+) redox cycling supplied surface oxygen in the photothermal low-temperature response. The proposed mechanism for the simultaneous degradation of acetone and NO was elucidated using Density Functional Theory calculations.

Direct Observation of the Reactivity of Electrons toward Gold Nanoparticles in Aqueous Solution.

The catalytic activity of gold nanoparticles (AuNPs) has been widely acknowledged; however, Au NPs are considered to be highly inert as radiosensitizers in biological systems. This apparent discrepancy across different fields complicates the understanding of their interfacial reactivity, particularly in terms of electron transfer reactions. Here, we employ pulse radiolysis to determine the rate constants for the reactions of electrons with AuNPs in aqueous solution. Our investigation of AuNPs with different sizes and surface modifications demonstrates the potential influence of the AuNPs design on electron transfer reactions. These findings address long-standing mechanistic contradictions and underscore the significance of interfacial electron dynamics on AuNPs in both catalytic and biological processes.

Synergistic photoelectrochemical detection of Cd2+ with carbon-bismuth oxybromide composites: Mechanistic insights from DFT calculations

The existences of hazardous heavy metals like cadmium (Cd) in water bodies necessitates rapid, accurate on-site detection strategies. Herein, a novel photoelectrochemical scheme for sensitive detection of Cd2+ was proposed based on the hybrid carbon-bismuth oxybromide materials (C/Bi4O5Br2 and CNTs/BiOBr). The effects of ultraviolet light (UV-light) illumination during the Cd2+ deposition and desorption stages were analyzed, revealing enhanced photocurrent responses and detection sensitivity compared with those non-illumiantion. The optimal sensitivity of 0.42079 μA/ppb (C/Bi4O5Br2 under both deposition and desorption stages) and 0.15634 μA/ppb (CNTs/BiOBr under desorption stage only) were observed with UV illumination within a Cd2+ range of 10–100 ppb. Density functional theory calculation elucidated that Cd2+ adsorption on the semiconductor surface reduced the badgaps of Bi4O5Br2 and BiOBr, which would benefit electron transfer and redox reactions. Additionally, the interaction between Cd and the semiconductor produced a Schottky barrier, which prolonged the lifetime of the photo-generated electron-hole pairs, where the electrons migrated on the semiconductor surface formed electron capture traps and induced band bending, therefore facilitated the electrons in the conduction band to react with Cd2+ deposited on the electrode surface. The study provides mechanistic insights into the photoelectrochemical processes in enhancng precise and sensitive on-site heavy metal ions detection.

Comparison of the Efficiency of B-O and B-C Bond Formation Pathways in Borane-Catalyzed Carbene Transfer Reactions Using α-Diazocarbonyl Precursors: A Combined Density Functional Theory and Machine Learning Study.

Lewis acidic boranes, especially tris(pentafluorophenyl)borane [B(C6F5)3], have emerged as metal-free catalysts for carbene transfer reactions of α-diazocarbonyl compounds in a variety of functionalization reactions. The established mechanism for how borane facilitates carbene generation for these compounds in the scientific community is based on the formation of a B-O (C=O) intermediate (path O). Herein, we report an extensive DFT study that challenges the notion of a ubiquitous path O, revealing that B-C(=N=N) bond formation (path C) for certain diazocarbonyl substrates proves to be the preferred pathway. This study elucidates, through the introduction of 22 various substituents on each side of the α-diazocarbonyl backbone, how the electron-donating and -withdrawing properties of substituents influence the competition between these B-O and B-C pathways. To elucidate the impact of the electronic features of diazo substrates on the competition between the O and C pathways in the studied dataset, we employed a machine learning approach based on the Random Forest model. This analysis revealed that substrates with higher electron density on the diazo-attached carbon, lower electron density on the carbonyl carbon, and more stable HOMO orbitals tend to proceed via path C. Furthermore, this study not only demonstrates that borane efficiency in facilitating N2 release is greatly affected by the nature of substituents on both sides of the α-diazocarbonyl functionality but also shows that for some substrates, borane is incapable of catalyzing the release of molecular nitrogen.

Pyrolysis combined with KOH activation to turn waste apple pruning branches into high performance electrode materials with multiple energy storage functions

In this paper, porous activated carbon is successfully prepared from waste apple pruning branches (PGZ), which demonstrates an ultra-high specific capacity of 505 F g −1 at a current density of 1 A g −1 with excellent rate performance (215 F g −1 at 50 A g−1). The assembled supercapacitor also exhibits excellent specific capacitance of 320 F g −1 (at 0.5 A g−1) and 160 F g −1 (at 20 A g−1), with a high energy density of 12.03 Wh kg −1 at a power density of 250.45 W kg −1 in 6 M KOH. In 1 M Na2SO 4 and 1 M Et4 NBF4/AC electrolytes, high energy densities of 18.8 Wh kg −1 and 44.1 Wh kg −1 could be achieved. It also exhibits high reversible lithium storage capacity of 636.2 mAh g −1 at 0.2 C and retains 390 mAh g −1 after 1000 cycles. Even at 0.8 C, the storage capacity is still as high as 327 mAh g −1, with 282 mAh g −1 retained after 1000 cycles. These excellent electrochemical properties are attributed to the hierarchical porous structure of the sample prepared under the optimum conditions. The large pores in the hierarchical structure will lead to high-speed capacitive properties due to their low ion transport resistance while the small mesopore and micropore provide a large electrode and electrolyte interface, which can facilitate charge transfer reaction. These outstanding performances highlights the first example of using waste apple pruning branches as a sustainable source of raw materials for the preparation of high value-added porous carbon materials with multiple energy storage functions.

Integrated electrochemical and chemical system for ampere-level production of terephthalic acid alternatives and hydrogen

2,5-Furandicarboxylic acid (FDCA), a critical polymer platform molecule that can potentially replace terephthalic acid, coupled hydrogen coproduction holds great prospects via electrolysis. However, the electrosynthesis of FDCA faces challenges in product separation from complex electrolytes and unclear electrochemical and nonelectrochemical reactions during the 5-hydroxymethylfurfural (HMF) oxidation. Herein, an electrochemical/chemical integrated system of alkaline HMF-H2O co-electrolysis is proposed, achieving distillation-free synthesis of high-purity FDCA by acidic separation/purification and hydrogen coproduction. This system achieves ampere-level current densities of 812 and 1290 mA cm−2 at potentials of 1.50 and 1.60 V, with nearly 100% FDCA yield and HMF conversion in only 6 min at 1.50 V. The electrooxidation of HMF involves a coupling of electrochemical and nonelectrochemical reactions, wherein the aldehyde group is dehydrogenated and oxidized, followed by dehydrated and oxidized of the hydroxyl group, ultimately forming FDCA. Concurrently, nonelectrochemical reactions of intermolecular electron transfer occur in HMF and aldehyde group-containing intermediates.

Enhanced Recovery of Lithium and Cobalt from Spent Lithium-Ion Batteries Using Ultrasound-Assisted Deep Eutectic Solvent Leaching

This study investigates the ultrasound-assisted leaching of Li and Co from spent batteries using a deep eutectic solvent (DES) composed of polyethylene glycol and thiourea. The synergistic effect of ultrasound and DESs was explored to enhance the efficiency of Li and Co recovery. The experimental results demonstrated that ultrasound significantly accelerates the leaching process, achieving up to four times higher recovery rates compared to traditional methods. Optimal leaching conditions were identified at a solid-to-liquid ratio of 0.02 g/g, a temperature of 160 °C, and periodic ultrasound exposure. Under these conditions, the leaching efficiency reached 74% for Li and 71% for Co within 24 h. A kinetic analysis revealed that the ultrasound application shifts the rate-limiting step from a mixed control of mass transfer and chemical reactions to predominantly chemical reaction control, reducing the activation energy by approximately 27%.

Research on the corrosion mechanism of Q345R steel under water-oil two-phase flow with the HCl and NH4Cl corrosive medium in low-temperature system of petrochemical plants

The serious corrosion failure phenomenon of HCl and NH4Cl in the water-oil two-phase flow are usually occurred in the low-temperature system of petroleum refinery facilities. In this paper, the corrosion mechanism of these corrosive medium in two-phase flow environment was investigated in detail by using corrosion weight loss, electrochemical measurement methods, surface analysis techniques, and numerical research methods. The results indicate that the corrosion rate of Q345R steel in an HCl-NH4Cl coupling medium falls between the rates observed with each medium alone. The stirring of the corrosive fluid creates an unstable oil-in-water emulsion. The formation of an oil film on the surface of Q345R steel slows down the corrosion process and alters the surface corrosion morphology when the oil phase was not originally present. Increasing the proportion of the water phase accelerates the corrosion rate, and the stronger wettability of the oil phase makes the loose γ-FeOOH products easier to cover the surface, which can effectively prevent the mass transfer and corrosion reaction process.

Enhancing the activity and sulfur resistance of CuFeAlOx catalyst via the structure effect for the simultaneous removal of Hg0 and NO at wide temperature

The efficient strategy for improving SO2 resistance and catalytic activity is structural modification. Herein, the CuFeAlOx catalysts with different structures, including one-dimensionally disordered mesoporous nanoparticles structure (CuFeAl-N), one-dimensionally ordered mesoporous nanoparticles structure (CuFeAl-C), three-dimensionally ordered porous honeycomb-like structure (CuFeAl-P) and three-dimensionally ordered porous flower-like structures (CuFeAl-CP), were synthesized via a template method to investigate structure effect on activity and sulfur resistance of the catalyst for simultaneously removing NO and Hg0 at wide temperature. The results showed that the various surface characteristics resulted in distinct behaviours with regards to SO2 tolerance. CuFeAl-CP and CuFeAl-C exhibits excellent SO2 resistance, but CuFeAl-N catalyst presents poor SO2 resistance. The CuFeAl-CP with the flower-like structure possesses large specific surface area, which can expose more active sites and exhibited highly dispersed active component. More importantly, it reacts with SO2 to generate reactive sulfate providing additional acid sites, which significantly promotes high-temperature catalytic performance. One-dimensionally ordered mesoporous and three-dimensionally ordered porous effectively facilitates mass transfer of reactants and ammonium sulphate decomposition, thereby inhibiting surface sulfation and ammonium sulfate species deposition. This work lays the foundation for developing highly efficient SCR catalysts that are tolerant to SO2.

Promoting Water Dissociation and Weakening Active Hydrogen Adsorption to Boost the Hydrogen Transfer Reaction over a Cu-Ag Superlattice Electrocatalyst.

The prerequisite for electrocatalytic hydrogenation reactions (EHRs) is H2O splitting to form surface hydrogen species (*H), which occupy catalytic sites and lead to mismatched coverage of *H and reactants, resulting in unsatisfactory activity and selectivity. Thus, modulating the splitting pathway of H2O is significant for optimizing the EHR process. Herein, a Cu-Ag alloy with a superlattice structure of staggered-ordered Cu and Ag is theoretically predicted and experimentally proven to undergo a pathway for H2O splitting called the hydrogen transfer reaction (HTR) in the water layer, which involves the formation of *H, the capture of *H by a water cluster to form H*(H2O)x and subsequent hydrogenation reactions by H*(H2O)x. Taking acetylene hydrogenation as a model case, the as-proposed HTR pathway could lead to a relaxation hydrogenation process to modulate the matching degree of C2H2 and *H, thus enabling a 91.2% C2H4 Faradaic efficiency at a partial current density of 0.38 A cm- 2, greatly outperforming its counterpart without a superlattice structure.

Copolymerization of ethylene and isoprene initiated by metallocene catalyst

In this study, we explore the dynamic nature of metallocene catalysts during ethylene/isoprene E/IP) copolymerization, with a focus on the influence of various reaction parameters. Challenges, why do olefinic catalysts show lower activity and molecular weight (Mw) at higher temperatures and low activity with higher diene content? Firstly, we investigate the observed phenomena of decreased catalyst activity and Mw at elevated temperatures using 1.25 μmole of the metallocene. Notably, a substantial increase in active sites from 30 °C to 40 °C, reaching a peak of 89 %. Surprisingly, further temperature increments lead to a noticeable decline in active sites. At 30 °C, the active site primarily engages in the insertion of IP through 3,4 connections, with no detectable cis-1,4 or trans-1,4 connections, which suggests a lack of stereoselectivity at this temperature. At 40–50°C, cis/trans-1,4 connections and active sites are approaching a higher level. This implies a reduction in chain transfer reactions, making catalytic active sites more favorable to cis/trans-1,4 connections. Secondly, we observe a remarkable impact of IP concentration in the E/IP copolymers, active centers, and activity show stability when the amount of IP was 0.116–0.48 mol/L and then started to decline when the amount of IP 0.96 mol/L, indicating a threshold beyond which deactivation occurs. Increasing IP concentration not only reduces activity and active sites but also fails to reactivate dormant polyethylene sites. The Mw and active centers of copolymers progressively decrease with elevated IP concentration, suggesting a faster chain transfer reaction with IP compared to E.

Schiff base substituted non-peripheral symmetrical cupper, cobalt, and manganese phthalocyanines: Synthesis, design, electrochemistry, and spectroelectrochemistry

Novel CoII (nANTHCoPc), CuII (nANTHCuPc), and MnIIICl (nANTH-MnClPc) phthalocyanines were obtained by substituting the 3-(4-((1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylimino)methyl)phenoxy) Schiff base compound (nANTHOH) obtained by the acid-catalyzed condensation reaction of 4-aminoantipyrine and 4-hydroxybenzaldehyde at non-peripheral positions. By using various spectroscopic techniques, (NMR, MALDI-TOF, FT-IR, and UV–Vis), the structures of green-colored phthalocyanine compounds and precursor phthalonitrile compounds were identified. The electrochemical responses of cobalt (II) (nANTHCoPc), cupper (II) (nANTHCuPc), and manganese (III) (nANTH-MnClPc) phthalocyanines were determined, and their redox responses were analyzed based on the different metal centers. The results indicated that using redox-active Co2+ and Mn3+ cations instead of Cu2+enhanced the redox richness of the complexes due to the observation of extra metal-based electron transfer reactions in addition to the Pc-based ones. In-situ spectroelectrochemical analyses of the complexes were used to support the peak assignments of the redox processes and the spectrum and color of the electrogenerated species during the redox reactions. Supported these redox mechanisms. Multi-electron transfer processes and distinct color changes during these processes indicate the possible usage of these complexes in various electrochemical and opto-electrochemical processes. Metal-based electron transfer reactions illustrated different spectral changes than those of the Pc-based ones, and these spectral changes significantly differed the color of the anionic and cationic species.

Simulating Cavity-Modified Electron Transfer Dynamics on NISQ Computers.

We present an algorithm based on the quantum-mechanically exact tensor-train thermo-field dynamics (TT-TFD) method for simulating cavity-modified electron transfer dynamics on noisy intermediate-scale quantum (NISQ) computers. The utility and accuracy of the proposed methodology is demonstrated on a model for the photoinduced intramolecular electron transfer reaction within the carotenoid-porphyrin-C60 molecular triad in tetrahydrofuran (THF) solution. The electron transfer rate is found to increase significantly with increasing coupling strength between the molecular system and the cavity. The rate process is also seen to shift from overdamped monotonic decay to under-damped oscillatory dynamics. The electron transfer rate is seen to be highly sensitive to the cavity frequency, with the emergence of a resonance cavity frequency for which the effect of coupling to the cavity is maximal. Finally, an implementation of the algorithm on the IBM Osaka quantum computer is used to demonstrate how TT-TFD-based electron transfer dynamics can be simulated accurately on NISQ computers.

Research on the solution of the thermo-hydro-mechanical-chemical coupling model based on the unified finite volume method framework

Heat extraction from hot dry rock (HDR) reservoirs involves complex thermal–hydraulic-mechanical-chemical (THMC) coupling processes, which pose significant challenges for efficient geothermal energy utilization. The current frameworks that combine the finite volume method (FVM) and finite element method (FEM) for THMC modeling based on the embedded discrete fracture model (EDFM) are separate, leading to complex implementations and hindering the development of efficient solutions. To address these issues, we propose an FVM-based THMC coupling model that solves fluid flow, heat transfer, and chemical reactions using the finite volume method (FVM), while mechanical deformation is addressed using the extended finite volume method (XFVM). The reaction module incorporates PHREEQC for multicomponent reactions under high-temperature and high-pressure conditions. The model is validated against experimental data for mineral reactions under high-temperature and high-pressure conditions, as well as XFEM and COMSOL simulations for displacement fields, confirming its accuracy and computational performance. Application results show that the temperature deviation between multicomponent and single-component models can reach up to 14 °C, underscoring the importance of incorporating multicomponent water–rock reactions in THMC coupling. This model accurately captures the spatiotemporal evolution of THMC processes and efficiently predicts long-term heat production in enhanced geothermal systems (EGS) reservoirs. It could significantly advance the ability to achieve more accurate and reliable predictions for the engineering development and efficient utilization of EGS reservoirs.

Solar-driven purification: Removing pharmaceutical contaminants from water using carbon-doped NASICON photocatalyst

Pharmaceutical contaminants in water pose significant risks to aquatic ecosystems and human health. This work synthesized a novel NASICON@C composite (sodium super ionic conductor embedded with carbon) as a visible-light-driven photocatalyst for eliminating paracetamol from water. Characterization confirmed a well-dispersed composite with hexagonal morphology, surface porosity, and strong visible light absorption. The carbon phase enabled visible light harvesting while the NASICON facilitated charge transfer and redox reactions. Photocatalytic testing showed dramatic paracetamol degradation within 30 min under visible irradiation using NASICON@C. 99.7 % of the initial 100 mg L−1 paracetamol was eliminated in neutral pH conditions. The ion-conducting NASICON framework promoted efficient charge carrier separation and transfer to enable the oxidation reactions. The NASICON@C catalyst displayed excellent stability over five reuse cycles. The synergistic integration of carbon and NASICON phases in this composite photocatalyst makes it a promising and sustainable platform for visible light-driven pharmaceutical contaminant removal from water sources.

Mass Transfer Resistance and Reaction Rate Kinetics for Carbohydrate Digestion with Cell Wall Degradation by Cellulase.

This paper introduces an enzymatic approach to estimate internal mass-transfer resistances during food digestion studies. Cellulase has been used to degrade starch cell walls (where cellulose is a significant component) and reduce the internal mass-transfer resistance, so that the starch granules are released and hydrolysed by amylase, increasing the starch hydrolysis rates, as a technique for measuring the internal mass-transfer resistance of cell walls. The estimated internal mass-transfer resistances for granular starch hydrolysis in a beaker and stirrer system for simulating the food digestion range from 2.2 × 107 m-1 s at a stirrer speed of 100 rpm to 6.6 × 107 m-1 s at 200 rpm. The reaction rate constants for cellulase-treated starch are about three to eight times as great as those for starch powder. The beaker and stirrer system provides an in vitro model to quantitatively understand external mass-transfer resistance and compare mass-transfer and reaction rate kinetics in starch hydrolysis during food digestion. Particle size analysis indicates that starch cell wall degradation reduces starch granule adhesion (compared with soaked starch samples), though the primary particle sizes are similar, and increases the interfacial surface area, reducing internal mass-transfer resistance and overall mass-transfer resistance. Dimensional analysis (such as the Damköhler numbers, Da, 0.3-0.5) from this in vitro system shows that mass-transfer rates are greater than reaction rates. At the same time, SEM (scanning electron microscopy) images of starch particles indicate significant morphology changes due to the cell wall degradation.

Synergistic effect of oxygen defects and calabash-like hollow carbon matrix enables VO2 as high-performance cathode for zinc ion battery

Vanadium dioxide (VO2) materials exhibit significant theoretical specific capacity, which is ascribed to multi-electron transfer reactions and unique tunneled structures. However, the low electronic conductivity and sluggish reaction kinetics of VO2 have impeded its further development. Hence, in this study, we employed a synergistic strategy of defect engineering and compositing with a calabash carbon matrix to reduce Zn2+ diffusion barriers and accelerate electron transfer. The VO2 cathode provided a high specific capacity at a low rate of 303 mA h g−1 at 0.1 A g−1 after 191 cycles, along with good rate performance (168 mA h g−1 at 10 A g−1) and satisfactory long-term stability (170 mA h g−1 at 1 A g−1 after 1100 cycles). The exhaustive structural analyses indicated that oxygen vacancies accelerated the Zn2+ diffusion rate, while a uniform calabash-like hollow carbon matrix improved electronic conductivity during cycling. Moreover, ex-situ measurements demonstrated that during discharge, the composite cathode transformed to layered Zn3+x(OH)2V2O7·2H2O, which then facilitated the subsequent intercalation of Zn2+. This cooperative strategy advances the practical application of aqueous zinc ion batteries by leveraging vanadium-based electrodes.