Charge Transfer Rate Research Articles

Electrochemical Determination of Cysteine Using a 2-(2,5-Dihydroxy-Phenyl)-Naphtho[1,2-d] Oxazole-5-Sulfonic Acid (DHPNOS) and Cerium Oxide Nanoparticle (CeO2NP) Composite Carbon Paste Electrode (CPE)

An electrochemical sensor for the electrocatalytic oxidation of cysteine was designed based upon a 2-(2,5-dihydroxy-phenyl)-naphtho[1,2-d] oxazole-5-sulfonic acid (DHPNOS) and cerium oxide nanoparticle (CN) modified carbon paste electrode (CPE). An investigation of the redox properties of this modified electrode indicates a reduction in oxidative overvoltage and an intense increase in the analytical current. The pH, modifier, and nanoparticles were optimized to 7, 4% weight percent, and 5% weight percent, respectively. The apparent charge transfer rate constant (ks) and transfer coefficient for electron transfer between modifier and electrode were 2.776 s−1 and 0.47, respectively. Using differential pulse voltammetry, a linear range from 1 to40 µM with a detection limit of 0.33 µM was observed in phosphate buffer (pH 7.0). This work introduces a simple approach for selective determination of L-cysteine in the presence of uric acid. Also, based on chronoamperometry, the diffusion coefficient was determined to be 2.61 × 10−5 cm2 s−1. The effect of interferences on L-cysteine peak current were studied. The repeatability and reproducibility of the designed sensor were also measured with relative standard deviation values of 1.00% and 4.45%, respectively. The constructed sensor was employed for the determination of L-cysteine in acetylcysteine tablets.

Mechanistic insights and performance evaluation of ZnFe-Modified bovine manure biochar in activating peroxymonosulfate for efficient thiamethoxam degradation: A combined DFT calculation and degradation pathway analysis

The study explored the degradation of thiamethoxam (THM) in water using modified bovine manure biochar as a catalyst for the first time, due to its potential harm to living organisms and frequent detection in natural water bodies. Experimental findings revealed that the rate constants for peroxymonosulfate (PMS)-catalyzed THM degradation by bovine manure biochar modified with ZnCl2 and K2FeO4 (ZnFeBC) increased by 76.78 times compared to unmodified biochar (BC), achieving a 100% degradation rate within 60 min. ZnFeBC exhibited excellent PMS activation performance across various pH levels. XPS characterization and Density Functional Theory (DFT) calculations have revealed that Fe element cycling occurs on the ZnFeBC surface, resulting in increased charge transfer rates at the reaction interface. The main active sites responsible for PMS activation were found to be Fe0 and Fe3O4. The degradation mechanism of THM by the ZnFeBC/PMS system involved SO4•-, •OH, 1O2 and electron transfer. This catalyst demonstrated strong pH adaptability and outstanding catalytic degradation capabilities for various pollutants, making it highly suitable for widespread wastewater treatment applications, while also providing a new way for resource reutilization of bovine manure.

Harnessing MBene termination for superior anode interfaces in Li/Ca-ion batteries

The elevation of two-dimensional (2D) transition metal borides, specifically MBenes, as anode materials for lithium-ion batteries (LIBs) and calcium-ion batteries (CIBs) can be achieved through strategic functionalization with appropriate groups. Utilizing a first-principles approach, we conducted an in-depth investigation into the electrochemical properties of chlorine-terminated V2B (V2BCl2) as a candidate anode material for LIBs and CIBs. V2BCl2 exhibits metallic behavior, as demonstrated by band structure analysis, which endows it with exceptional conductivity due to the free electron surface of the system, thereby embodying ideal anode characteristics. The dynamic and thermal stability of the system was assessed through comprehensive phonon dispersion analyses and ab-initio molecular dynamics (AIMD) calculations. High net charge transfer rates of Li/Ca ions towards the monolayer, augmented electron localization function (ELF) near system atoms, and the presence of ionic bonds between Ca/Li and the V2BCl2 monolayer contribute to the enhanced conductivity observed in these anode systems. This is corroborated by metrics such as the projected crystal orbital Hamiltonian population (-pCOHP), low diffusion energy barriers (< 0.35 eV) facilitating rapid charging mechanisms, and low open circuit voltages (< 0.32 V) ensuring robust battery performance stability. Furthermore, V2BCl2 exhibits notable specific storage capacities of 875.67 mAh g−1 for Ca ions and 1167.75 mAh g−1 for Li ions, surpassing the benchmarks set by recent MBene systems. These promising results strongly advocate for V2BCl2 as a viable candidate for anode material in both LIB and CIB applications, highlighting its potential significance in advancing battery technology.

Theoretical design and synthesis of Co30Ni60/CC for high selective methanol oxidation assisted energy-saving hydrogen production

The integration of methanol oxidation reaction (MOR) with hydrogen evolution reaction (HER) represents an advanced approach to hydrogen production technology. Nonetheless, the rational design and synthesis of bifunctional catalysts for both MOR and HER with exceptional activity, stability and selectivity present formidable challenges. In this work, firstly, density functional theory (DFT) was utilized to design and evaluate material models with high performance for both MOR and HER. Secondly, guided by DFT, Co30Ni60/CC (CC, carbon cloth) composites with a leaf-like nanosheet structure were successfully fabricated via electrodeposition. In the MOR process, Ni acts as the predominant active center, while Co amplifies the electrochemically active surface area (ECSA) and enhances the selectivity of methanol oxidation. Conversely, in the HER process, Co serves as the primary active center, with Ni augmenting the charge transfer rate. The electrochemical results demonstrate that Co30Ni60/CC exhibits exceptional performance in both MOR and HER at a current density (j) of 10 mA cm−2, with peak potentials of 1.323 V and −95 mV, respectively. Additionally, it shows remarkable selectivity for the oxidiation of methanol to high value-added formic acid. Thirdly, following a 100 h chronopotentiometry (CP) test, the required potential demonstrates an increase of 4.9 % (MOR) and 8.1 % (HER), signifying the superior stability of Co30Ni60/CC compared to those reported in the literature. The exceptional performance of Co30Ni60/CC can be primarily attributed to that the leaf-like nanosheets structure not only exposes a plethora of active sites but also facilitates electrolyte diffusion, the monolithic structure prepared by electrodeposition enhances its stability, and the transfer of electrons from Co to Ni regulates its electronic structure, as corroborated by X-ray photoelectron spectroscopy (XPS) and density of states (DOS) analyses. Finally, at the same j, the voltage required by the Co30Ni60/CC||Co30Ni60/CC electrolytic cell, powered by an electrochemical workstation, is 198 mV lower than that required for alkaline water-splitting. Meanwhile, at higher j (100 mA cm−2), the electrolytic cell exhibits sustained and stable operation for 150 h, enabling high-efficiency hydrogen production and the synthesis of high value-added formic acid.

Carbon cloth-based meteorite-like Co–CuS/MoS2 heterostructure for efficient water electrolysis

Developing low-cost, high-efficiency electrocatalysts is critically important for efficient hydrogen production. In this study, a novel electrocatalyst, Co–CuS/MoS2 nanocomposite, was successfully synthesized via ion exchange on carbon cloth using Evans-Showell type polyoxometalate (NH4)6 [Co2Mo10O38H4]·11H2O (Co2Mo10) as a precursor and thiourea in a hydrothermal reaction. The optimized Co–CuS/MoS2 exhibited outstanding hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activities, with overpotentials of 90 mV and 270 mV at a current density of 10 mA cm−2, respectively, and demonstrated long-term stability in alkaline electrolytes. The superior performance of this catalyst is attributed to the high charge transfer rates between MoS2 and CuS, abundant heterostructure interfaces, and efficient diffusion channels. This study provides a new design strategy for exploring efficient bifunctional electrocatalysts.

Customizing Ionic Liquids Functionalized MOFs Composites with Hydrophobic Interface for Electrochemical CO2 Reduction.

The electrochemical carbon dioxide reduction reaction (CO2RR) to generate feedstocks for chemical products (e.g., carbon monoxide, CO) offers a highly attractive method for achieving the closure of the carbon cycle. Ionic liquids (ILs)-functionalized Cu-based catalyst Cu2O-HKUST-1/IL1/PTFE was developed, configuring metal-organic frameworks(MOFs) based materials with high adsorption and multiple active sites. The modified electrocatalysts exhibited high specific surface area, strong CO2 adsorption capacity, abundant active sites, and fast charge transfer rate. The nucleophilic active site of deprotonation at the C2 site in imidazole ILs further improved the selectivity of proton migration and CO product generation, which was verified through DFT calculations for the low Gibbs free energy of the generated intermediate interactions. In addition, the hydrophobic interface constructed by PTFE facilitated the inhibition of the hydrogen evolution reaction (HER) and significantly improved the efficiency of CO2 electroreduction. The Cu2O-HKUST-1/IL1/PTFE catalyst manifested a high C1 Faraday efficiency (FE) up to 96.5% and in particular 92.7% for FECO at -1.7 V vs RHE. The present work provides an efficient strategy for configuring ILs-functionalized MOFs-based materials with good hydrophobic interfaces to enhance the efficiency of CO2 electroreduction to C1 products.

Unraveling Lattice Dislocation‐Driven Energy Band Convergence Mechanism to Enhance Electrocatalytic Hydrogen Production in Alkaline Seawater

AbstractHydrogen evolution reaction (HER) from seawater electrolysis still faces challenges of low reactivity and chloride ions poison at the active sites, leading to reduced efficiency and stability of electrocatalysts. This study presents edge dislocation strategy aimed at inducing lattice strain in ferric oxide through Mo doping, consequently regulating the catalyst's band structure. Through in situ characterizations and DFT analysis, it is confirmed that lattice strain effectively modulates the band structure, intensifies the hybridization between Mo(d)‐Fe(d)‐O(p) orbitals, thereby accelerating the charge transfer rate of HER. Furthermore, band structure modulated by lattice strain enhances water adsorption capacity, reduces the adsorption energy of Cl−, and optimizes the hydrogen adsorption‐free energy (ΔGH*) for HER. Benefiting from above, the optimized 2%‐Mo‐Fe2O3 catalyst demonstrates HER activity and stability in alkaline seawater electrolysis comparable to that of commercial Pt/C. Additionally, the assembled electrolytic cell utilizing an anion exchange membrane (AEM) maintains long‐term stability for &gt;100 h at 500 mA cm−2, showcasing a sustained catalytic effect.

Study of carbon monoxide adsorption on the α- and γ-graphyne nanosheets for the sensor applications

Recently, graphyne-based gas sensors have drawn a lot of interest. One kind of graphene with acetylene bonds connecting its hexagons is graphyne. In this study, the density functional theory (DFT) method was used to investigate the physical parameters of the surface adsorption of carbon monoxide on the [Formula: see text]- and [Formula: see text]-graphyne nanosheet, taking into account van der Waals (vdW) interactions through the use of the SIESTA computational code. CO molecule adsorbed and optimized in two vertical and horizontal states from the side of carbon and oxygen atoms, at different distances and sites relative to the graphyne sheet. After optimization and finding the adsorption energy, the best adsorption sites, equilibrium distance of the molecule from the surface, electronic structure, charge transfer rate, and bandgap changes were calculated. It was observed that the changes in the electronic structure after the adsorption of CO molecule are insignificant and the [Formula: see text]- and [Formula: see text]-graphyne nanosheets remained zero-gap and narrow-gap semiconductors, respectively. The adsorption of CO molecule on the [Formula: see text]- and [Formula: see text]-graphyne nanosheets is physisorption. The results show that the [Formula: see text]-graphyne nanosheet has a good potential for adsorbing and detecting CO molecules and sensor applications.

Titanium boride nanosheets with photo-enhanced sonodynamic efficiency for glioblastoma treatment

Sonodynamic therapy (SDT) has garnered significant attention in cancer treatment, however, the low-yield reactive oxygen species (ROS) generation from sonosensitizers remains a major challenge. In this study, titanium boride nanosheets (TiB2 NSs) with photo-enhanced sonodynamic efficiency was fabricated for SDT of glioblastoma (GBM). Compared with commonly-used TiO2 nanoparticles, the obtained TiB2 NSs exhibited much higher ROS generation efficiency under ultrasound (US) irradiation due to their narrower band gap (2.50 eV). Importantly, TiB2 NSs displayed strong localized surface plasmon resonance (LSPR) effect in the second near-infrared (NIR II) window, which facilitated charge transfer rate and improved the separation efficiency of US-triggered electron–hole pairs, leading to photo-enhanced ROS generation efficiency. Furthermore, TiB2 NSs were encapsulated with macrophage cell membranes (CM) and then modified with RGD peptide to construct biomimetic nanoagents (TiB2@CM-RGD) for efficient blood-brain barrier (BBB) penetrating and GBM targeting. After intravenous injection into the tumor-bearing mouse, TiB2@CM-RGD can efficiently cross BBB and accumulate in the tumor sites. The tumor growth was significantly inhibited under simultaneous NIR II laser and US irradiation without causing appreciable long-term toxicity. Our work highlighted a new type of multifunctional titanium-based sonosensitizer with photo-enhanced sonodynamic efficiency for GBM treatment. Statement of significanceTitanium boride nanosheets (TiB2 NSs) with photo-enhanced sonodynamic efficiency was fabricated for SDT of glioblastoma (GBM). The obtained TiB2 NSs displayed strong localized surface plasmon resonance (LSPR) effect in the second near-infrared (NIR II) window, which facilitated charge transfer rate and improved the separation efficiency of US-triggered electron-hole pairs, leading to photo-enhanced ROS generation efficiency. Furthermore, TiB2 NSs were encapsulated with macrophage cell membranes (CM) and then modified with RGD peptide to construct biomimetic nanoagents (TiB2@CM-RGD) for efficient blood-brain barrier (BBB) penetrating and GBM targeting. After intravenous injection into the tumor-bearing mouse, TiB2@CM-RGD can efficiently cross BBB and accumulate in the tumor sites. The tumor growth was significantly inhibited under simultaneous NIR II laser and US irradiation without causing appreciable long-term toxicity.

Nickel sulfide nanorods encapsulated in Nitrogen-Doped carbon on nickel foam in situ derived from Saccharomycetes cerevisiae for the selective oxidation of biomass

The design and development of an efficient catalyst for the electrocatalytic oxidation reaction of 5-hydroxymethylfurfural (HMF) require a novel, cost-effective, environmentally friendly, and safe preparation method. In this study, we synthesized nickel sulfide nanorods encapsulated by nitrogen-doped carbon on a nickel foam substrate (Ni3S2@NC/NF), derived in situ from Saccharomyces cerevisiae. The utilization of a gas-phase route facilitated the binding of C, N and S elements to the NF substrate. The resulting Ni3S2@NC/NF catalyst exhibited excellent electrocatalytic performance in the HMF oxidation reaction (HMFOR), achieving a complete conversion of HMF, a selectivity of 95.6 % for 2,5-furandicarboxylic acid, and a Faraday efficiency of 88.9 % at a potential of 1.45 V. Moreover, in situ electrochemical impedance spectroscopy revealed an enhanced charge transfer rate for the Ni3S2@NC/NF catalyst during the interfacial HMFOR. Additionally, the catalyst demonstrated outstanding stability after five cycles of electrolysis. Therefore, this work provides a valuable guide for using microorganisms as sources of C, N, and S in the targeted synthesis of metallic electrocatalysts.

Deliberate Amorphization of Co-MOF for Constructing Crystalline-Amorphous Heterostructures Toward High-Performance Water Electrolysis.

The endowment of metal organic frameworks (MOF) with superior electrocatalytic performance without compromising their structural/compositional superiorities is of great significance for the development of renewable energy devices, yet remains a grand challenge. Herein, a deliberate partial amorphization strategy is developed to construct a heterostructured electrocatalyst consisting of crystalline Co-MOF and amorphous Co-S nanoflake arrays aligned on the carbon cloth (CC) substrate (abbreviated as Co-MOF/Co-S@CC hereafter) through a rapid sulfuration method. The simultaneous implement of crystalline-amorphous (c-a) heterostructure and nanoflake arrayed architecture on CC substrate renders the Co-MOF/Co-S@CC with abundant and tight active sites, accelerated charge transfer rate, regulated electronic structures, and reinforced structural stability. As such, the obtained Co-MOF/Co-S@CC electrode demonstrates outstanding electrochemical hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances with the overpotentials of 64 and 217mV at 10mA cm-2, respectively. Moreover, a two-electrode electrolyzer assembled by Co-MOF/Co-S@CC electrodes exhibits the lower cell voltages and larger current densities than those of Pt/C and RuO2 counterparts, excellent reversibility and prominent long-term stability, representing a great prospect for feasible H2 production. This adopted concept of c-a heterostructure for electronic regulation may bring about insightful inspiration for designing high-performance electrocatalysts for sustainable energy systems.

In Situ Growth of MoS2 Onto Co-Based MOF Derivatives Toward High-Efficiency Quantum Dot-Sensitized Solar Cells.

Quantum dot sensitized solar cells (QDSCs) represent a promising third-generation photovoltaic technology, boasting a high theoretical efficiency of 44% and cost efficiency. However, their practical efficiency is constrained by reduced photovoltage (Voc) and fill factor (FF). One primary reason is the inefficient charge transfer and elevated recombination rates at the counter electrode (CE). In this work, a novel CE composed of a titanium mesh loaded with Co,N─C@MoS2 is introduced for the assembly of QDSCs. The incorporation of nanosized MoS2 enhances the density of catalytic sites, while the Co,N─C component ensures high conductivity and provides a substantial active surface area. Additionally, the titanium mesh's 3D structure serves as an effective electrical conduit, facilitating rapid electron transfer from the external circuit to the composite. These improvements in catalytic activity, charge transfer rate, and stability of the CE significantly enhance the photovoltaic performance of QDSCs. The optimized cells achieve a groundbreaking power conversion efficiency (PCE) of 16.39%, accompanied by a short-circuit current density (Jsc) of 27.26mA cm-2, Voc of 0.818V, and FF of 0.735. These results not only offer a new strategy for designing electrodes with high catalytic activity but also underscore the promising application of the Co,N─C@MoS2 composite in enhancing QDSC technology.

Ag doped TiO2 anchored on metal free g-C3N4 for enhanced solar light activated photodegradation of a dye

Heterogeneous semiconductor photocatalysis has attracted researcher's attention in wastewater treatment owing to the improved surface area, optical properties, and charge transfer rate for boosted degradation of organic pollutants. Thus, the g-C3N4/Ag/TiO2 was prepared following a hydrothermal route for the degradation of azo dye tartrazine (TA) used as a food colourant under solar light. Before application, the composite and pristine materials were interrogated for physicochemical and structural properties using SEM, TEM, EDS, XPS, XRD, UV–vis DRS, PL, BET, Raman, and FTIR spectroscopy. The PL and electrochemical analysis revealed that the CNAT composite had a high charge transfer rate that was coupled with low charge carrier complexation. The degradation efficiency of 91 % was realized in 180 min and the rate of pseudo-first-order kinetics of 0.01143 min−1 was obtained. The CNAT catalyst also displayed high removal efficiency towards a cocktail of naproxen (NPX) and TA. The improved removal efficiencies stem from increased visible usage, reduced charge carrier compounding, and formation of Z-scheme heterojunction with high redox capabilities. The total organic carbon removal reached 95 % while CNAT showed high convincing stability even after four cycles. Given the above results, the hydrothermally prepared composite catalyst can be extended to other organic pollutants such as pharmaceuticals, pesticides, and reduction of inorganics.

Co/CoOx–N–C bifunctional nanocatalyst derived from carbothermally optimized graphene networks with in-situ formed zeolitic imidazolate framework for high performance zinc-air batteries

Rechargeable zinc-air batteries are underpinned by high-performance and durable bifunctional oxygen electrocatalysts. Among the platinum-group metals (PGMs)-free catalysts, the redox-active cobalt-nitrogen-carbon (Co/CoOx–N–C) based materials are promising, however require further structural improvements. This work utilises extremely porous graphene networks (EGO) of hierarchical porosity to in-situ grow ZIF-67 nanocrystals extensively and homogeneously within the porous structure. A simple carbonization of nanoZIF-67@EGO not only generates finely dispersed redox capable Co/CoOx–N–C active sites with the help of residual oxygen functional groups of EGO, but also produces 2-3 dimensional hierarchical porous and conducting structure, readily facilitating high electrochemical surface area. This characteristic structure synergistically contributes to rapid charge and mass transfer rates along with high activity and stability for both ORR and OER. Here, it is worth mentioning that to produce equivalent catalyst material involving different graphitic or template supports requires prolonged and multi-step synthesis routes. The optimized catalyst delivers low potential difference of 0.86 V for bifucntional activity by offering superb ORR half-wave potential of 0.83 V vs RHE and limiting current density of 5.85 mA cm−2 in 0.1 M KOH electrolyte. Zinc-air battery exhibits peak power density of ∼175 mW cm−2 and specific capacity of ∼767 mAh g−1, along with durable cycling round trip efficiency of >63 % (correspond to low voltage gap of ∼0.74 V). These characteristics are better than numerous M–N–C based catalysts reported in the literature. This new strategy holds a great potential to boost the development of diverse MOFs and carbon-based electrocatalysts for a wide range of energy storage and conversion technologies.

Photoinduced charge transfer in small-molecule organic solar cells dependent on external electric field

In this paper, MTDATA is selected as the electron donor and BPhen as the acceptor. The trianiline structure of the donor molecule provides a variety of charge transfer pathways for charge separation. Based on Marcus theory, the photoinduced charge transfer properties of non-fullerene acceptor organic solar cells (NFA-OSCs) in external electric field (Fext) were studied. By analyzing the changes of reorganization energy (λ), Gibbs free energy (ΔG), electron transfer integral (Vda) and charge transfer rate under the influence of Fext, it was found that Fext can effectively regulate the charge transfer. Moreover, the change of charge transfer rate under Fext is similar to Vda, indicating that Vda is the main factor affecting charge transfer rate. To a certain extent, this study provides theoretical support for improving the photoelectric performance of NFA-OSCs.

Advances in the heterostructures for enhanced hydrogen production efficiency: a comprehensive review.

The growing global energy demand and heightened environmental consciousness have contributed to the increasing interest in green energy sources, including hydrogen production. However, the efficacy of this technology is contingent upon the efficient separation of charges, high absorption of sunlight, rapid charge transfer rate, abundant active sites and resistance to photodegradation. The utilization of photocatalytic heterostructures coupling two materials has proved to be effective in tackling the aforementioned challenges and delivering exceptional performance in the production of hydrogen. The present article provides a comprehensive overview of operational principles of photocatalysis and the combination of photocatalytic and piezo-catalytic applications with heterostructures, including the transfer behavior and mechanisms of photoexcited non-equilibrium carriers between the materials. Furthermore, the effects of recent advances and state-of-the-art designs of heterostructures on hydrogen production are discussed, offering practical approaches to form heterostructures for efficient hydrogen production.

Theoretical prediction of holes and electrons mobility in coronene and perchlorocoronene crystals: Application of the Marcus–Jortner–Levich Theory

The study focused on theoretically predicting charge carrier mobilities in coronene and perchlorocoronene crystals using the Marcus–Levich–Jortner approach. By analyzing charge transfer integrals and considering hopping pathways, significant anisotropy in charge transfer was observed. Density functional theory (DFT) calculations at the B3LYP-D3/6-311++G(d,p) and ωB97X-D/6-311++G(d,p) levels were employed to assess the impact of normal modes on reorganization energies and charge transfer rates. Results indicated that perchlorination reduced mobility for both holes and electrons. Notably, maximum mobilities were observed at the melting points: 0.0120 cm2 V−1 s−1 for electrons and 0.0798 cm2 V−1 s−1 for holes in coronene at 455 K, and 0.0032 cm2 V−1 s−1 for electrons and 0.0426 cm2 V−1 s−1 for holes in perchlorocoronene at 560 K. This suggests that both crystals exhibit favorable charge transport characteristics near their respective melting points.

Exploring electrochemical kinetic behaviors and interfacial charge transfer of pure and Ni-doped ZnFe2O4 nanoparticles-based sensing nanoplatform for ultra-sensitive detection of chloramphenicol

ZnFe2O4 (ZFO) nanomaterial was doped with a divalent transition metal cation of Ni2+ (NixZn1-xFe2O4, x=0, 0.2, 0.4, and 0.8) and characterized by various analytical techniques. Powder X-ray diffraction revealed the formation of a single-phase cubic spinel structure, while the stabilization of crystal structure for Ni2+-doped samples was observed. The average crystalline size, d-spacing, and lattice parameters increased with increasing in Ni2+ concentration within NixZn1-xFe2O4, due to differences in the ionic radius, the cation distribution at A-B sites, and the creation of surface oxygen vacancies within ZFO structure. From electrochemical measurements, NixZn1-xFe2O4-based electrodes showed excellent enhancements in charge transfer ability and conductivity with the highest rate constant (0.018 ms−1), the lowest peak-to-peak separation (206 mV), the lowest Rct (118 Ω), and the largest electrochemical active area (0.248 cm2), compared to that of bare SPE. Among them, Ni0.8Zn0.2Fe2O4/SPE provided outstanding electrochemical behaviors and achieved the best sensing performance with the widened concentration linear range from 0.25 to 50 μM and a rather low detection limit of 0.2 μM for chloramphenicol detection. The most important reason for this positive advance comes from the unique synergistic effects of Ni doping into the ZFO host structure. The excellent enhancements in adsorption capacity (Г) (1.4 times higher), number of oxygen vacancies, charge transfer rate constant (approximately 1.15 times higher), and catalytic rate constant (30 times greater) were recorded at Ni-doped ZFO-based electrodes, compared to pure ZFO-based electrode. Furthermore, the detailed hypotheses and possible mechanisms explaining these impressive enhancements were explored. Our work provides insight into the correlation between the Ni-doping and electrochemical characteristics, which has implications for tailoring the electrochemical performance of spinel ferrites across diverse applications and the design of novel spinel ferrite nanomaterials.

Nanoarchitectonics of Fe-Doped Ni3S2 Arrays on Ni Foam from MOF Precursors for Promoted Oxygen Evolution Reaction Activity.

Oxygen evolution reaction (OER) is a critical half-reaction in electrochemical overall water splitting and metal-air battery fields; however, the exploitation of the high activity of non-noble metal electrocatalysts to promote the intrinsic slow kinetics of OER is a vital and urgent research topic. Herein, Fe-doped Ni3S2 arrays were derived from MOF precursors and directly grown on nickel foam via the traditional solvothermal way. The arrays integrated into nickel foam can be used as self-supported electrodes directly without any adhesive. Due to the synergistic effect of Fe and Ni elements in the Ni3S2 structure, the optimized Fe2.3%-Ni3S2/NF electrode delivers excellent OER activity in an alkaline medium. The optimized electrode only requires a small overpotential of 233 mV to reach the current density of 10 mA cm-2, and the catalytic activity of the electrode can surpass several related electrodes reported in the literature. In addition, the long-term stability of the Fe2.3%-Ni3S2/NF electrode showed no significant attenuation after 12 h of testing at a current density of 50 mA cm-2. The introduction of Fe ions could modulate the electrical conductivity and morphology of the Ni3S2 structure and thus provide a high electrochemically active area, fast reaction sites, and charge transfer rate for OER activity.

Interfacial engineering for the construction of iron sulfide/boride nanosheets heterostructure bifunctional electrocatalysts for high-efficiency overall water splitting

Iron-based materials have been extensively studied and applied as electrocatalysts. However, the electronic structure of iron itself is not conducive to effectively activating adsorbed intermediates, leading to slower kinetic steps. In this study, a heterogeneous composite catalyst with a nano-sheet array structure consisting of iron boron/sulfide (FeS@Fe2B/IP) was successfully prepared through a two-step process involving boriding and sulfidation of iron plates. The nanosheet array structure provides numerous catalytic active sites, promotes effective contact between electrolytes and catalytic sites, and enhances the apparent reaction rate of the catalyst. Additionally, the heterogeneous interface of FeS/Fe2B plays a crucial role in regulating the electronic structure of the metal Fe site, improving charge transfer rates, and accelerating electrocatalytic reaction kinetics. Ultimately, FeS@Fe2B/IP demonstrates outstanding water splitting performance, with only 177 and 191 mV overpotential providing 10 mA cm−2 toward HER and OER, respectively. Furthermore, it achieves a high current density of 500 mA cm−2 at 473 and 520 mV overpotentials for HER and OER, respectively. In addition to its excellent performance in water splitting applications, a bipolar alkaline cell was constructed using the FeS@Fe2B/IP bifunctional catalyst. This achieved current densities of 10 and 100 mA cm−2 at potentials of 1.63 and 1.75 V. Moreover, the catalytic stability of the FeS@Fe2B/IP system remained consistent for nearly 50 hours at current densities of 10 and 100 mA cm−2. These results confirm that FeS@Fe2B/IP is indeed a high-performance bifunctional electrocatalytic material which can significantly improve energy utilization efficiency in various applications.