Electrochemical Activity Research Articles

Interstitial Oxygen Acts as Electronic Buffer Stabilizing High-Entropy Alloys for Trifunctional Electrocatalysis.

Understanding the effect of elements' oxygen affinity is essential for comprehending high-entropy alloys' (HEAs) complete properties. However, the origin of HEAs' oxygen-containing structure and stability remains poorly understood, primarily due to their diverse components, hindering synthesis and analysis. Herein, the O-doping HEAs (HEA-O) have demonstrated outstanding performance and stability in electrolyzed water and Zinc-air batteries which can be reassembled after being stable for more than 1600h when the zinc consumption is over. The experiment and DFT simulation demonstrate that Cr with strong oxygen affinity can introduce more oxygen into the system of HEAs. Consequently, interstitial oxygens act as electronic buffers making the binding energy of other metal elements move to a higher level. Additionally, O-doping lowers the d-band center promoting electrochemical activity and increasing vacancy formation energies of metal active sites leading to super stability. The study provides significant insights into the design and comprehension of interstitial oxygen-doped HEAs.

Partial‐Oxidation Enabling Homologous Ru/RuO2 Heterostructures With Proper d‐Dand Center as Efficient and Durable Cathode Catalysts for Ultralong Cycle Life in Li–O2 Batteries

AbstractThe sluggish cycle kinetics is one of the major obstacles to the commercial application of Li–O2 batteries (LOBs), despite their large theoretical energy density. Efficient and long‐term durable cathode catalysts are urgently desired to strengthen their cycle stability and rate performance. Density functional theory calculations reveal that Ru/RuO2 Mott–Schottky heterostructures can manipulate the adsorption capacities of intermediates by modulating the d‐band center and redistribute interfacial charges, enabling efficient redox kinetics, reducing overpotentials, and optimizing the growth pathway of discharge products. Herein, a wet impregnation approach followed by partial oxidization of Ru nanodots to construct homologous Ru/RuO2 heterostructures as advanced cathode catalysts for boosting the electrochemical activities of LOBs is employed. They exhibit superior electrochemical performance, including high discharge specific capacity (17 120 mAh g−1 at 200 mA g−1), small overpotential (0.96 V), and ultralong cycle lifetime of 1209 cycles (>2400 h) at 500 mA g−1. Over 1260‐h stable cycle in air atmosphere at 500 mA g−1 demonstrates the potential application prospects of the Ru/RuO2 heterostructures in Li‐air batteries. Multiple ex/in situ measurements and theoretical calculation are conducted to investigate the optimizing mechanism of electrochemical performances.

High entropy 2D metals sulfides: Fast synthesis, exfoliation and electrochemical activity in overall water splitting at alkaline pH

Novel simple and efficient method for synthesis of 2D high entropy sulfides of iron group metals is described. The method utilizes inorganic salts as precursors and CS2 as a sulfurizing agent, which makes it possible to achieve high entropy composition through combination of freezing of the precursor solution, subsequent freeze-drying step, sulfurization, and exfoliation in liquid nitrogen. The created material was investigated as a catalyst for electrochemical water splitting at different pH. Measured overpotentials at 10 and 100 mA*cm−2 current densities for hydrogen evolution reaction (HER) were found to be 49 and 315 mV respectively, while for oxygen evolution reaction (OER) theoverpotentials required for reaching 10 and 100 mA*cm−2 current densities were 370 and 591 mV respectively, both in 1 M KOH solution. The Tafel slopes for HER were found to be 235, 105, and 111 mV/dec in basic, neutral, and acidic conditions, respectively, while only 63 mV/dec for OER in basic conditions. The calculated values of the turnover frequency were 0.62 s−1 for HER and 0.10 s−1 for OER. We also confirmed the key role of high entropy in the catalytic activity of the material by excluding individual elements from the composition of the HES.

Functionalized polyaniline nanofibrils on lamellar structured zirconium for effective bone mineralization

The surface physiology of certain implant material has the ability to promote implant–cell signalling process through which a stable environment is formed. The formation of this favourable environment hastens the process of biomineralization and regeneration. In this context, Zirconium (Zr) when treated with alkali undergoes a surface modification which results in the development of a lamellar structured Zirconium (ATZ). Further, encapsulation of polyaniline (PAni) on ATZ was achieved through the electropolymerization technique which results in an effective and homogeneous electrodeposition of PAni nanofibrils on ATZ surface. A high resolution scanning electron microscope analysis (HR-SEM), phase analysis and functional group analysis were carried out confirming the semi-crystalline PAni nanofibrils braided on the ATZ surface. Potentiodynamic polarization studies of the coated sample exhibited higher Ecorr (−0.060 V) and lower icorr (0.007 µA/cm2) values signifying its better corrosion resistance behaviour in higher potentials coupled with lower electrochemical activity in the SBF medium. The porosity of PAni/ATZ nanofibril was 0.007 % and it provides an effective platform for implant-tissue attachment. The In-vitro biomineralization studies proved the bioactivity of PAni/ATZ which forms well-matured HAp spherules over the surface. Further, hemocompatibility studies of PAni/ATZ expressed a hemolytic rate of ∼0.39 % which denotes it’s biocompatible and non-hemolytic behaviour with the blood cells. Further, the coated sample on gram-positive and gram-negative bacteria causes demise of bacterial cell wall and exhibits higher inhibition percentage. In addition, a standard MTT assay of PAni/ATZ provides an effective support in maintaining cell viability and aids in proliferation of MG-63 cells. Thus, the results demonstrate that the nanoscale surface architecture of PAni/ATZ could serve as a potential and conducive environment for bone-implant interaction on the implant material for better osseointegration.

Dual Ion Co-insertion Induced Spontaneous and Reversible Phase Conversion Chemistry for Unprecedented Zn2+ Storage.

Prussian blue analogues are highly promising electrode materials due to their versatile electrochemical activity and low cost. However, they often suffer from severe structural damage caused by the Jahn-Teller distortion and dissolution of high-spin outer metal ions, resulting in poor cycle life. Material modification and electrolyte regulation have been the common approaches to address this issue, albeit with very limited success. We report here a novel and efficient strategy to preserve structural stability by co-inserting Co2+ and Zn2+ ions in KCo[Fe(CN)6]. This co-insertion induced a spontaneous and reversible phase conversion by the replacement of low-spin inner ion (Fe3+), which efficiently relieves structural damage caused by Jahn-Teller distortion and metal-ion dissolution, leading to an outstanding Zn2+ storage capacity and an exceptional improvement of cycle life with a capacity retention of 97.7% over 4400 cycles at 40 C. We also demonstrated the enhancement of co-intercalation on ion migration using a combined approach of experimental and density functional theory (DFT) calculations. This work provides an important progress to solve the cycle stability of Prussian blue analogues towards their practical application as electrode materials for aqueous batteries.

Dual Ion Co‐insertion Induced Spontaneous and Reversible Phase Conversion Chemistry for Unprecedented Zn2+ Storage

Prussian blue analogues are highly promising electrode materials due to their versatile electrochemical activity and low cost. However, they often suffer from severe structural damage caused by the Jahn‐Teller distortion and dissolution of high‐spin outer metal ions, resulting in poor cycle life. Material modification and electrolyte regulation have been the common approaches to address this issue, albeit with very limited success. We report here a novel and efficient strategy to preserve structural stability by co‐inserting Co2+ and Zn2+ ions in KCo[Fe(CN)6]. This co‐insertion induced a spontaneous and reversible phase conversion by the replacement of low‐spin inner ion (Fe3+), which efficiently relieves structural damage caused by Jahn‐Teller distortion and metal‐ion dissolution, leading to an outstanding Zn2+ storage capacity and an exceptional improvement of cycle life with a capacity retention of 97.7% over 4400 cycles at 40 C. We also demonstrated the enhancement of co‐intercalation on ion migration using a combined approach of experimental and density functional theory (DFT) calculations. This work provides an important progress to solve the cycle stability of Prussian blue analogues towards their practical application as electrode materials for aqueous batteries.

Facile synthesis of green graphite-based (Ni/Cu/N) MOF composite for a methanol oxidation reaction

Recently, direct methanol fuel cells (DMFCs) have been regarded as the greatest energy-producing owing to their low operating temperature, high production rate of methanol, and low greenhouse gas emission. However, the energy conversion efficiency of the DMFCs is still unsatisfactory due to the slow kinetics of the fuel oxidation reaction. So, an economic electrocatalyst with high efficiency and good stability is still needed. Herein, low-cost nanocomposites of (Ni/Cu/N) MOF and palm pollen-derived G-graphite were prepared with different ratios namely, (1:1), (1:2), and (2:1) through a solvothermal reaction. The nanocomposites were characterized via X-ray diffraction (XRD), Scanning electron Microscopy (SEM), Fourier transform infrared (FTIR), Thermal gravimetric analysis (TGA), and, (Brunauer–Emmett–Teller) technique (BET). Electrodes have been tested as electro-catalysts for methanol-oxidation reaction (MOR) in a basic medium. As revealed from the cyclic voltammetry measurements, all electrodes exhibit a good response to MOR, being the nanocomposite with the ratio between (Ni/Cu/N) MOF and G-graphite (2:1) is the best with an oxidation peak current density of 55 mA/cm2 at a scan rate of 50 mV/s, with an onset potential of 0.35 V, and stability reaches 96 %. The electrochemical impedance spectroscopy (EIS) test showed that the ratio (2:1) has the lowest charge transfer resistance, RCT, of 5.21 Ω which confirms its higher electrochemical activity. This superior performance of the (Ni/Cu/N) MOF and G-graphite (2:1) over other reported MOF-based electrocatalysts is attributed to the synergistic effect of the (Ni/Cu/N) MOF electrocatalyst, wherein Ni and Cu provide redox electrocatalytic active sites for MOR while the G-graphite contributes towards the chemical stability and electrical conductivity of the electrode, respectively. The good activity and stability of the prepared electrodes suggest the potential use of these electrodes as electrocatalysts for MOR in direct methanol fuel cells (DMFCs).This study opens the venue for valorizing the natural wastes derived graphitic material as stable supporting material in Mof based composites electrodes for MOR.

Radiation-Synthesized Metal-Organic Frameworks with Ligand-Induced Lewis Pairs for Selective CO2 Electroreduction.

The electrochemical activation of inert CO2 molecules through C─C coupling reactions under ambient conditions remains a significant challenge but holds great promise for sustainable development and the reduction of CO2 emission. Lewis pairs can capture and react with CO2, offering a novel strategy for the electrosynthesis of high-value-added C2 products. Herein, an electron-beam irradiation strategy is presented for rapidly synthesizing a metal-organic framework (MOF) with well-defined Lewis pairs (i.e., Cu- Npyridinic). The synthesized MOFs exhibit a total C2 product faradic efficiency of 70.0% at -0.88V versus RHE. In situ attenuated total reflection Fourier transform infrared and Raman spectra reveal that the electron-deficient Lewis acidic Cu sites and electron-rich Lewis basic pyridinic N sites in the ligand facilitate the targeted chemisorption, activation, and conversion of CO2 molecules. DFT calculations further elucidate the electronic interactions of key intermediates in the CO2 reduction reaction. The work not only advances Lewis pair-site MOFs as a new platform for CO2 electrochemical conversion, but also provides pioneering insights into the underlying mechanisms of electron-beam irradiated synthesis of advanced nanomaterials.

Manipulation of d-Orbital Electron Configurations in Nonplanar Fe-Based Electrocatalysts for Efficient Oxygen Reduction.

Manipulation of the spin state holds great promise to improve the electrochemical activity of transition metal-based catalysts. However, the underlying relationship between the nonplanar metal coordination environment and spin states remains to be explored. Herein, we report the precise regulation of nonplanar Fe atomic d-orbital energy level into an irregular tetrahedral crystal field configuration by introducing P atoms. With the increase of P coordination number, the spin magnetic moment decreases linearly from 3.8 μB to 0.2 μB, and the high spin content decreases linearly from 31% to 5%. Significantly, a volcanic curve between the spin states of Fe-based catalysts (Fe-NxPy) and oxygen reduction reaction (ORR) activity has been unequivocally established based on the thermodynamic results. Thus, the Fe-N3P1 catalyst with a 19% medium spin state experimentally exhibits the optimal reaction activity with a high half-wave potential of 0.92 V. These findings indicate that regulating electron spin moments through coordination engineering is a promising catalyst design strategy, providing important insights into spin catalysis.

The effect of glass sealing stabilization on LSM–YSZ cathode poisoning and oxygen reduction reaction processes in solid oxide fuel cell

AbstractThe perovskite structure and electrochemical activity of (La0.80Sr0.20)0.95MnO3−x–(Y2O3)0.08(ZrO2)0.92 (LSM–YSZ) composite cathode can be significantly affected by volatile boron species originated from sealing glass–ceramics. Herein, we investigate the impact of doping the varying Er2O3 content (ranging from 0 to 4%) into an aluminoborosilicate glass to mitigate boron volatilization, its interaction with the LSM–YSZ cathode and consequent effects on its electrochemical performance. The results reveal that the volatility of boron species can be significantly suppressed by introducing Er oxide into the glass network by enhancing the conversion of [BO3] to [BO4] units, thereby increasing the binding energy of boron and strengthening of the glass structure. Moreover, the electrocatalytic performance for the O2 reduction reaction on the LSM–YSZ/8YSZ/LSM–YSZ symmetric cells is studied under open‐circuit conditions in the presence and absence of glass sealants. The analyses utilizing electrochemical impedance spectroscopy (EIS) and distribution of the relaxation times (DRT) analysis indicate that the electrocatalytic performance of LSM–YSZ cathodes can be enhanced in the presence of glass with 4% Er2O3 (GE4). This enhancement in the electrocatalytic activity of the LSM–YSZ electrode for the oxygen reduction reaction (ORR) is attributed to formation of the thin layer on the electrode surface, leading to a notable reduction in the polarization resistance (Rp) from 0.81 Ω cm2 in the glass absence to 0.45 Ω cm2 in the presence of GE4. However, DRT analysis demonstrates that the prolonged exposure of the cathode to GE4 causes a deterioration in cell performance primarily due to the blocking the cathode active sites, which impedes dominant cathode processes of oxygen dissociative adsorption/desorption and charge transfer and consequently reducing kinetics of the ORR.

Digital Twin Reveals the Impact of Carbon Binder Domain Distribution on Performance of Lithium‐Ion Battery Cathodes

The rising demand for high‐performance lithium‐ion batteries (LIBs) emphasizes the need for precise electrode design. The carbon binder domain (CBD) within electrodes, crucial for electron transport and structural integrity, can impede lithium‐ion transport and reduce electrochemically active sites. This study leverages digital twin technology to investigate the impact of CBD distribution along the electrode thickness on LIB cathode performance. Virtual LIB cathodes with varying CBD configurations are generated, and their performance using 3D heterogeneous electrochemical modeling is evaluated. The results reveal that a steep CBD gradient significantly diminishes charge capacity compared to a mild gradient, particularly at higher current rates. This reduction is attributed to an increased tortuosity factor and an uneven distribution of electrochemical activity, which adversely affect mass transport and electrochemical reaction dynamics. These effects are more pronounced at lower porosities and higher loading levels. These findings highlight that optimizing CBD distribution is critical for advancing electrode design and enhancing LIB cathode performance.

Snowflake Iron Oxide Architectures: Synthesis and Electrochemical Applications

The synthesis and characterization of iron oxide nanostructures, specifically snowflake architecture, are investigated for their potential applications in electrochemical sensing systems. A Raman spectroscopy analysis reveals phase diversity in the synthesized powders. The pH of the synthesis affects the formation of the hematite (α-Fe2O3) and goethite (α-FeOOH). Scanning electron microscopy (SEM) images confirm the distinct morphologies of the particles, which are selectively obtained through recrystallization during the elongated reaction time. An electrochemical analysis demonstrates the differing behaviors of the particles, with synthesis pH affecting the electrochemical activity and surface area differently for each shape. Cyclic voltammetry measurements reveal reversible dopamine detection processes, with snowflake iron oxide showing lower detection limits than a mixture of snowflakes and cube-like particles. This research contributes to understanding the relationship between iron oxide nanomaterials’ structural, morphological, and electrochemical properties. It offers practical insights into their potential applications in sensor technology, particularly dopamine detection, with implications for biomedical and environmental monitoring.

Facile synthesis and electrochemical properties of sheet-rod-sheet structured NiCo2S4/EG/Ti3C2Tx nanocomposites

Electrode materials with outstanding stability and electrochemical activity are ideal for high-performance supercapacitors. Herein, we developed a simple two-step method for fabricating NiCo2S4/EG/Ti3C2Tx nanocomposites with a sheet(2D)-rod(1D)-sheet(2D) structure. The NiCo2S4 rods were embedded into the expanded graphite (EG) sheets via an in-situ hydrothermal method, then the Ti3C2Tx sheets were assembled with NiCo2S4/EG by an electrostatic self-assembly method. The obtained NiCo2S4/EG/Ti3C2Tx nanocomposites exhibited a synergistic effect among the components. The addition of EG inhibited the volumetric effect of NiCo2S4 during charging and discharging processes, while the high conductivity of Ti3C2Tx promoted charges transfer. The rod-like structure of NiCo2S4 effectively inhibited the self-stacking of Ti3C2Tx sheets. Consequently, the optimized composite exhibited an excellent specific capacitance of 1837.9 F·g−1 at a current density of 1 A·g−1. Additionally, the composite electrode exhibited a capacitance retention of 73.5 % during 10,000 charging-discharging cycles at a current density of 20 A·g−1.

Enhancing the electrochemical performance of graphite sheet electrodes for ketamine detection

Flexible graphite sheets (GS) have been a promising material for developing electrochemical sensors. In this work, we showed that the electrochemical activation protocol (+1.4 V followed by -1.0 V vs. Ag|AgCl|KCl(sat.) both at 200 s) in alkaline medium (0.5 mol l-1 NaOH) enhances the electrochemical activity of GS. Before the treatment, cyclic voltammetric profile of inner-sphere [Fe(CN)6]3-/4- redox couple at 50 mV s-1 exhibited an ill-defined voltammetric profile (ΔEp = 800 mV) while an increase in the reversibility was achieved (ΔEp = 225 mV) after the treatment. Additionally, the lower charge transfer resistance (Rct) measured by Electrochemical Impedance Spectroscopy (EIS) and a higher heterogeneous electron transfer constant (k0) corroborate with the enhancement in the electrochemical performance of treated GS electrodes. The SEM images revealed an irregular pattern with number of grooves, indicating a partially surface exfoliation and AFM analysis displayed an increase in the roughness. These findings agreed with the estimation of electroactive area which increased 3-times after the treatment. As proof of concept, ketamine (KET), an anesthetic often used as drug of abuse, was determined in synthetic saliva and veterinary pharmaceutical samples using treated GS electrodes and square wave voltammetric measurements. Linear range of 5.0–100.0 µmol l-1 with a limit of detection value of 2.1 µmol l-1 was obtained for KET. Appropriate recovery values (∼105 %) for the analysis of samples were achieved.

In-situ carbon integration on atomically dispersed platinum metal oxide nanocomposites for hydrogen evolution reaction

In this study, a novel in-situ carbon growth technique by a modified sol gel synthesis method is presented. The carbon support developed on a transition metal oxide composite transforms the electronic conductivity and is engineered for hydrogen evolution reaction by a dispersion of unit atomic concentration of platinum. Through two different synthesis techniques, platinum dispersion is implemented on the metal oxide-carbon system, one by direct sol-gel technique and another by chemical reduction technique, whereby a homogeneous dispersion of the noble metal on the composite is achieved. Carbon-based cerium oxide and titanium oxide composites are used as the base material, and one atomic percentage of platinum metal is ensured while synthesizing each of the carbon composites. The functionality of these catalysts towards hydrogen evolution reaction in a 0.5 M H2SO4 acidic media revealed the synthesis technique's uniqueness and the effect of metal support interaction that plays a vital role in the electrocatalytic activity. The intrinsic activity of the titania system, along with enhanced metal support interaction due to highly enriched platinum availability on the surface of the substrate, provides for strong electrochemical activity. The titanium oxide carbon composite with platinum dispersed by hydrazine reduction exhibited the finest activity with an overpotential of just 44 mV at j = 10 mA/cm2 and a tafel slope of 118 mV/dec. The gas chromatographic analysis on platinum supported titania catalyst showcased better performance by a margin of four times than the commercial three weight percentage platinum supported carbon.

Cobalt vanadate intertwined in carboxylated multiple-walled carbon nanotubes for simultaneous electrochemical detection of ascorbic acid, dopamine and uric acid

Low-cost transition metal vanadate-based electrochemical sensors have attracted a lot of attention recently. A cobalt vanadate and carboxylated multi-walled carbon nanotube composite (CoV/MWCNTs-COOH) was prepared by an ultrasonic-assisted assembly method. The uniform and dense MWCNTs-COOH attached to the surface of CoV not only combines the large surface area and superior conductivity of MWCNTs-COOH with the excellent electrochemical activity of CoV, but also enhances the redox reaction between CoV/MWCNTs-COOH composite and the analyte through synergistic effect of hydrogen bonding and electrostatic interaction. The electrochemical behaviors of CoV/MWCNTs-COOH composite modified glassy carbon electrode (CoV/MWCNTs-COOH/GCE) were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV). The simultaneous electrochemical sensing of ascorbic acid (AA), dopamine (DA) and uric acid (UA) on CoV/MWCNTs-COOH/GCE possesses good peak current signals with well-defined peak potentials. The linear ranges of AA, DA, and UA at CoV/MWCNTs-COOH/GCE are 1.0–100.0 μM, and the limits of detection (LODs; S/N = 3) are 0.4 μM, 0.03 μM, and 0.1 μM, respectively. The practicality of the designed sensor was further confirmed by the good recoveries obtained in the simultaneous measurement of actual samples including fetal bovine serum, human serum, urine, and Vitamin C tablets. Overall, the developed electrochemical sensor shows potential therapeutic applications for simultaneous determination of AA, DA and UA in biological fluids.

Potential-dependent kinetics of oxygen chemisorption as the crucial step of oxygen reduction reaction: GCDFT study

Nitrogen-doped carbon materials (NCMs) are widely regarded as promising alternatives to expensive platinum-based electrocatalysts for the oxygen reduction reaction (ORR). While NCMs exhibit considerable electrochemical activity in alkaline media, their performance in acidic environments remains a significant challenge. However, acidic conditions are commercially desirable for ORR’s catalysis in proton-exchange membrane fuel cells (PEMFCs). The dramatic pH dependence of NCM effectiveness has sparked ongoing debate, with several factors under consideration, including surface protonation, variations in hydrogen binding energy, differences in proton donors, and interface structure. In this work, we present a grand canonical density functional theory (GCDFT) study of the chemisorption step on pristine and nitrogen-doped graphene. Through nudged elastic band (NEB) calculations at various electrode potentials, we propose a potential-dependent (and thus pH-dependent) mechanism of oxygen chemisorption at graphitic nitrogen (Ngr) defects, offering new insights into the pH dependency of the onset potential in NCM catalysts.

Enhanced carbon host with N-reinforced S-sites to catalyze rapid iodine conversion kinetics for Zn-I2 battery

Aqueous zinc-iodine (Zn-I2) battery is a promising energy storage system in the establishment of a low-carbon, clean society, but they are limited by unsatisfied reversible capacity and poor cycle life. Ultimately, this is due to the poor iodine conversion kinetics and the shuttle effect of the intermediate polyiodide. Herein, a N-reinforced S-site carbon host (labeled as NS-YP80F) is designed to resolve these issues. DFT calculation shows that the electrochemical activity of the NS-YP80F with abundant S-site can be further enhanced by introducing N-atom at the original S-site. The synergistic effect of N-reinforced S-site carbon host cannot only enhance the adsorption of polyiodide to avoid the shuttle effect, but also induce the smooth conversion of iodine through enhanced catalytic mechanism. Consequently, the Zn-I2 battery with NS-YP80F@I2 cathode shows high reversible capacity (127 mAh g−1 at 1C) and stable cycling lifespan (15,000 cycles) with a high current density of 50 C. This strategy achieved a breakthrough in the electrochemical activity of the heteroatom doping carbon hosts, and provided a simple and effective solution for optimizing the performance of Zn-I2 battery.

Exploring the Effect of Ball Milling on the Physicochemical Properties and Oxygen Evolution Reaction Activity of Nickel and Cobalt Oxides

Ball milling is commonly used to reduce catalyst particle size. However, little attention is paid to further changes that ball milling can cause to the rest of the catalysts’ physicochemical properties, which can impact their intrinsic catalytic activity. The effect of ball milling on the physicochemical properties of NiCoO2, NiO, CoO, and NiO:CoO mixtures is reported and correlated with their electrochemical oxygen evolution reaction (OER) activity. It is also shown that particle fragmentation is an inherent consequence of ball milling, but some oxides can also experience a phase transformation. In the case of rocksalt‐structured CoO, it is partially or entirely transformed to spinel‐structured Co3O4. Additionally, NiCo2O4 with a spinel structure can be formed by ball milling NiO and CoO simultaneously (both rocksalt structures), but only in the absence of water. The changes impact the electrochemical activity of the initial oxides. Ball milled NiCoO2 exhibits the highest activity with a mean potential of 1.563 V at 10 mA cm−2, demonstrating the advantage of having Ni and Co in the same structure. Although NiCo2O4 is also a binary oxide, the results indicate that its metal coordination environment makes it intrinsically less active than NiCoO2 for the OER in alkaline media.

Tailoring phases of ferrihydrite/α-Fe2O3@C nanocomposites using syringyl and guaiacyl-rich biomass-derived carbon nanodots for electrochemical application

Biomass-derived carbon nanodots (CNDs) hold promise as effective reducing agents for metal oxide nanoparticles yet understanding the intricate interplay with CND structure remains challenging. This study explores the impact of lignin types, specifically syringyl (S), and guaiacyl (G) units in CNDs on metal oxide phases and their electrochemical activity toward dopamine oxidation. We design phases of ferrihydrite/α-Fe2O3@C nanocomposites, using hazelnut carbon nanodots (HS-CNDs (S-rich)) and beetroot carbon nanodots (BS-CNDs (G-rich)) via a one-pot hydrothermal technique. Our findings show S units in HS-CNDs promote α-FeOOH/α-Fe2O3@CHS, while G units in BS-CNDs favor α (β)-FeOOH/α-Fe2O3@CBS. In contrast to α(β)-FeOOH/α-Fe2O3@CBS, α-FeOOH/α-Fe2O3@CHS exhibits superior electrochemical performance in dopamine oxidation due to its larger electrochemical active surface area, higher absorbance capacity, and shortened electron transfer length. Moreover, α-FeOOH/α-Fe2O3@CHS nanocomposites demonstrate remarkable dopamine selectivity, achieving rapid detection response in 10 s with a low LOD of 4 nM within a broad linear range (0.05–0.3 μM), demonstrating impressive reproducibility (97.5 %), stability (96.4 %), and works in real-time human urine detection with a recovery rate of ranging from 94.57 % and 102.2 %. Therefore, the utilization of biomass-derived CNDs, particularly S and G units-rich CNDs, in tailoring the phases of ferrihydrite/α-Fe2O3@C nanocomposites for electrochemical dopamine detection is promising.