Low Tafel Slope Research Articles

Fluorine-Induced Lattice Oxygen Participation in 2D Layered Double Hydroxide/MXene Hybrids for Efficient Oxygen Evolution.

In oxygen evolution reaction (OER), the participation of lattice oxygen can break the limitation of adsorption evolution mechanism, but the activation of lattice oxygen remains a critical challenge. Herein, a surface fluorinated highly active 2D/2D FeNi layered double hydroxide/MXene (F-LDH/MX) is demonstrated, boosting OER with the enhanced lattice-oxygen-mediated path. The introduction of fluorine promotes the self-evolution of catalyst in an alkaline environment, even without an external current. It further accelerates the formation of active metal oxyhydroxides with abundant oxygen vacancies under the operating potential. The introduced oxygen vacancy activates the lattice oxygen, increasing the proportion of lattice oxygen mechanism in OER. Owing to the synergistic effects of the 2D/2D hierarchical structure and the modulated active surface, F-LDH/MX possesses excellent electrochemical performances, including a low overpotential of 251 mV at 10 mA cm-2, a low Tafel slope of 40.28 mV dec-1, and robust stability. The water electrolyzer system with F-LDH/MX as the anode offers the benchmark current density at a low cell voltage of 1.53 V, while the Zn-air battery with F-LDH/MX as the air electrode exhibits a higher power density of 75.43 mW cm-2. This study presents a promising strategy to design highly active electrocatalysts for energy conversion and storage.

FeCoNi-based Alloy Coatings as Low Overpotential Electrocatalysts for Alkaline Water Electrolysis.

Developing efficient, stable and low-cost electrocatalysts is a viable approach to solve the current energy crisis. It is found that increasing the surface area of the electrodes can effectively promote the electrocatalytic efficiency. Herein, the atmospheric plasma spraying (APS) technology was used to prepare FeCoNi-Ni3C alloy coating by adding Ni3C powder to FeCoNi powder with an equal molar ratio. The atomic ratios of Ni3C in the powder are 25 %, 50 %, and 75 %, respectively. The results prove that the pores on the surface of the coating have increased after Ni3C doping, which can provide more active sites in the electrocatalytic process to promote the electrocatalytic reaction. By controlling the proportion of Ni3C, the porosity of the coating surface can be effectively regulated. In 1.0 M KOH electrolyte and 10 mA cm-2, the50 at.% Ni3C coatingshows an overpotential of 105 mV and 212 mV for HER and OER, respectively. It is worth noting that the 50 at.% Ni3C coating has a low Tafel slope of 45.78 mV dec-1(HER) and 44 mV dec-1(OER). Furthermore, the 50 %at. Ni3C coating catalyst has a low potential of 1.664 V at 10 mA cm-2in a water-splitting system.

Electronic Synergistic Effects on the Stability and Oxygen Evolution Reaction Efficiency of the Mesoporous LiMn2-xMxO4 (M = Mn, Fe, Co, Ni, and Cu) Electrodes.

Stable porous manganese oxide-based electrodes are essential for clean energy generation and storage because of their high natural abundance and health safety. This investigation focuses on mesoporous LiMn2-xMxO4 (where M is Fe, Co, Ni, and Cu and x is 0, 0.1, 0.3, 0.5, and 0.67) electrodes and thin/thick films. The mesoporous electrodes and films are fabricated by coating clear and homogeneous ethanol solutions of the salts (LiNO3, [Mn(OH2)4](NO3)2, and [M(OH2)x](NO3)2) and surfactants (P123 and CTAB) and calcining at elevated temperature (denoted as F-LiMn2-xMxO4, G-LiMn2-xMxO4, and meso-LiMn2-xMxO4, respectively). The electrochemical properties, stability, and oxygen evolution reaction (OER) performance of the F/G-LiMn2-xMxO4 electrodes are investigated in alkaline media using a three electrode setup. The F-LiMn1.33M0.67O4 electrodes (where M is Mn, Fe, Co, and Ni) exhibit low Tafel slopes of 60, 43, 44, and 32 mV/dec, respectively. While all the Mn-rich and F-LiMn2-xFexO4 electrodes degrade via Mn(VI) disproportionation reaction, the 33% Co electrode shows high stability during the OER. The nickel-based electrodes are stable with as little as 15% Ni and display excellent OER performance over 25% Ni, albeit undergoing a transformation that accumulates Ni(OH)2 species on the electrode surface. Copper in the F-LiMn2-xCuxO4 electrodes is homogeneous at low Cu percentages but forms a CuO phase above 15% Cu, undergoes degradation, and displays a weak OER performance. In short, Co and Ni stabilize the F-LiMn1.33Co0.67O4 and F-LiMn1.7Ni0.3O4 electrodes, which display excellent OER performance.

Water-Driven Stacking Structure Transformation of Ultrathin Ru Nanosheets for Efficient Hydrogen Evolution Reaction.

Ultrathin crystalline materials are a class of popular materials that can potentially exhibit fascinating physical and chemical properties dictated by their unique stacking freedom. However, it is challenging to achieve the controllable synthesis over their stacking structure for ultrathin crystalline materials. Herein, water is employed as a key regulatory factor to realize phase engineering in ultrathin nanosheets (NSs), thereby altering stacking faults to achieve distinct stacking arrangements. Ruthenium (Ru) NSs with consistent specific surface areas but different stacking manners are fabricated through the systematic regulation of water. Based on this, it is demonstrated that the hydrogen evolution reaction (HER) performance can be significantly influenced by their stacking structures. Further in-depth investigations reveal that the distinct stacking structures of Ru NSs, featuring a limited area of side facets, will influence the energy barrier of sluggish Volmer step in HER. Ru NSs with ABC stacking exhibit an accelerated Volmer process with outstanding catalytic activity, demonstrating a remarkably low overpotential (25mV at 10mAcm-2) and Tafel slope (29mVdec-1) than most of the reported HER catalysts. The work will advance the understanding of controllable synthesis methods and illuminate the structure-activity relationships in ultrathin crystalline nanomaterials.

Molecular complex inspired design of an efficient copper(II)-containing robust porous polymers for electrochemical water oxidation

Homogeneous copper-bipyridine complexes have been reported as effective catalysts for water oxidation, demonstrating significant potential as alternatives to precious metal-based complexes. However, these complexes face long-term stability and product separation challenges similar to many homogeneous catalysts. Meanwhile, recent studies have underscored the potential of metalated polymer networks, which integrate the structural advantages of polymers with the functional benefits of metal species, making them highly attractive for various applications. Herein, we integrated copper-bipyridine units into porous polymer networks to overcome the limitations of copper-bipyridine complexes. We prepared a series of copper-incorporated polymers (TpBpy-Cux) for electrochemical water oxidation. The electrochemical properties of these polymers were tuned by varying the copper content, with TpBpy-Cu3 presenting the best performance among the samples studied. TpBpy-Cu3 demonstrated a low Tafel slope of 69 mV/decade, achieved a high Faradaic efficiency (FE) of 94 %, and exhibited exceptional stability over 1000 cyclic scans. This study offers insights into the design and optimization of metal-incorporated porous polymer networks building on the foundational understanding of their molecular counterparts for advanced catalytic applications.

Recycled industrial waste silicon steel as high-performance electrode for oxygen evolution reaction using electroless plating surface modification

Exploring the large-area, cost-effective, and high-performance electrocatalyticoxygen evolution reaction (OER) electrode for water splitting is of great significance. Inspiring from the ‘waste to resource’ toward the circular economy, herein, the waste silicon steels (SS) were transformed into high-performance CoxFe3-xP/SS OER electrode through a facile electroless plating method. The plating layer of CoxFe3-xP not only endows the CoxFe3-xP/SS with outstanding electrocatalytic OER activity but also improves the corrosion resistance and stability of CoxFe3-xP/SS. The obtained Co2Fe1P/SS electrode exhibits the lowest overpotential of 244 mV at a current density of 10 mA/cm2 in 1 M KOH with a low Tafel slope of 48.7 mV/dec. Even at high current densities and in 6 M KOH and alkaline seawater (seawater + 1 M KOH), the Co2Fe1P/SS electrode also shows relatively low overpotentials, as well as high long-term durability. Specially, a large-area Co2Fe1P/SS OER electrode(40 × 40 cm2)was successfully prepared via the electroless plating approach. Toward the CoxFe3-xP/SS, the bimetallic Co-Fe synergies and phosphating effect promote the exposure of active sites and charge transfer. In addition, generated M(OH)x/MOOH (M = Co or Fe) species during OER activation could synergize with CoxFe3-xP and contribute excellent catalytic activity and stability.

The Effect of Saccharin on SnNi Alloy: the Electrodeposition and its Electrocatalytic Activity in Ethanol Oxidation Reaction

The development of Direct Ethanol Fuel Cell (DEFC) has attracted much attention, as alternative energy sources due to its various advantages. However, among its various advantages, DEFC has several problems, such as the kinetics of the ethanol oxidation reaction. Transition metal-based catalysts such as nickel and tin are considered as potential catalysts for DEFC due to their oxophilic properties that can improve catalytic activity. In this study, the effect of saccharin on SnNi bimetallic alloy catalyst synthesized by electrodeposition method on copper wire substrate was investigated. SnNi samples were characterized by several techniques, including X-ray diffraction, Scanning electron microscopy, and energi dispersive X-ray spectrocopy. Saccharin addition had a significant effect on the morphology, crystallite size, and composition of the catalyst. The presence of saccharin causes the formation of more uniform particles and has a smaller size. The sample with the addition of saccharin had a smaller charge transfer resistance value 4.82 Ω, lower tafel slope by 115 mV/dec, and show higher jf/jb ratio by 0.55. Furthermore, as the current density decreases, the SnNi catalyst with saccharin has a slow decrease rate and higher stability than the SnNi catalyst without saccharin.

S−S Bond Strategy at Sulfide Heterointerface: Reversing Charge Transfer and Constructing Hydrogen Spillover for Boosted Hydrogen Evolution

AbstractDeveloping efficient electrocatalyst in sulfides for hydrogen evolution reaction (HER) still poses challenges due to the lack of understanding the role of sulfide heterointerface. Here, we report a sulfide heterostructure RuSx/NbS2, which is composed of 3R‐type NbS2 loaded by amorphous RuSx nanoparticles with S−S bonds formed at the interface. As HER electrocatalyst, the RuSx/NbS2 shows remarkable low overpotential of 38 mV to drive a current density of 10 mA cm−2 in acid, and also low Tafel slope of 51.05 mV dec−1. The intrinsic activity of RuSx/NbS2 is much higher than that of Ru/NbS2 reference as well as the commercial Pt/C. Both experiments and theoretical calculations unveil a reversed charge transfer at the interface from NbS2 to RuSx that driven by the formation of S−S bonds, resulting in electron‐rich Ru configuration for strong hydrogen adsorption. Meanwhile, electronic redistribution induced by the sulfide heterostructure facilitates hydrogen spillover (HSo) effect in this system, leading to accelerated hydrogen desorption at the basal plane of NbS2. This study provides an effective S−S bond strategy in sulfide heterostructure to synergistically modulate the charge transfer and adsorption thermodynamics, which is very valuable for the development of efficient electrocatalysts in practical applications.

A‐site Regulated (PrBa)xCo1.5Fe0.5O6‐δ Double Perovskite Oxides: Highly Active and Durable Electrocatalysts for the Enhanced Oxygen Evolution Reaction

Oxygen evolution reaction (OER) represents a significant bottleneck in many energy technologies such as electrochemical water splitting, metal‐oxygen (O) batteries, and solid oxide fuel cells (SOFCs), because of the complexity of the reaction process. Double perovskite oxides (ABO3), recognized for their compositional flexibility, have emerged as excellent OER activity and stability. This study investigates the catalytic potential of B‐site ordered double ABO3 with (PrBa)xCo1.5Fe0.5O6‐δ (PBCF‐x, x=0.9‐1.1) in alkaline media. The results reveal that PBCF‐0.9, characterized by an A‐site deficient composition, exhibits exceptional OER activity. It demonstrates a low Tafel slope of 76.12 mV⋅dec‐1 and a low overpotential (η) of 270 mV at 10 mA⋅cm‐2. Notably, the intrinsic OER activity of PBCF‐0.9 is 25% higher than that of the stoichiometric PBCF‐1.0. Additionally, PBCF‐0.9 exhibits remarkable durability, as evidenced by its stable performance during a 6‐hour chronopotentiometry (CP) test and minimal microstructural changes. These results underscore the effectiveness of A‐site deficiency in optimizing the structure of double ABO3 for improved OER performance. This approach presents a promising strategy for designing highly efficient, stable, and inexpensive catalysts for energy‐related applications.

Tailored IrO2@ZIF-67 nanocomposites for efficient oxygen evolution reaction: Insights into catalyst design and performance enhancement

The pursuit of effective electrocatalysts for the oxygen evolution reaction (OER) is crucial for advancing sustainable energy technologies. Efficient OER catalysts play a vital role in the development of water splitting systems, which are fundamental for producing hydrogen—a clean and renewable energy source. The synthesis of IrO2 nanoparticles embedded in ZIF-67 nanostructures has been explored to improve the performance of OER electrocatalysts. The resulting IrO2@ZIF-67 composite catalyst demonstrates a remarkable overpotential of 220 mV and 290 mV at current densities of 10 and 50 mA cm⁻2, alongside a low Tafel slope of 58 mV dec⁻1, significantly outperforming the pristine ZIF-67 catalyst. Integrating IrO2 nanoparticles into the ZIF-67 matrix significantly enhances both the catalytic activity and durability of the material. Extensive electrochemical testing reveals that the IrO2@ZIF-67 catalyst maintains exceptional stability, operating consistently for over 50 h at a current density of 50 mA cm⁻2 without significant degradation. This enhanced performance is attributed to the synergistic effects between the highly active IrO2 nanoparticles and the robust ZIF-67 framework, which collectively facilitate efficient charge transfer and improve structural integrity during prolonged OER operation. These findings highlight the potential of IrO2@ZIF-67 nanostructures as a promising electrocatalyst for sustainable water splitting applications, providing a pathway towards the development of more efficient and durable OER catalysts.

Exploring pyrolusite β-MnO2 as a robust support for noble metal catalysts in proton exchange membrane water electrolysis

Proton exchange membrane water electrolysis (PEMWE) represents a promising avenue for producing hydrogen sustainably. Nonetheless, its widespread adoption encounters hurdles owing to the sluggishness of the oxygen evolution reaction (OER) and the expensive noble metal catalysts, particularly iridium (Ir). Our investigation addresses these challenges by examining pyrolusite β-MnO2 as a robust substrate for noble metal catalysts, including iridium (Ir) and ruthenium (Ru), within PEMWE systems. We illustrate that nanostructured β-MnO2 effectively supports Ir and Ru catalysts, resulting in significantly improved catalytic activity for acidic OER compared to conventional IrO2 catalysts. The morphology shows nanorod structures with thicknesses ranging of 30–60 nm. The catalytic activity exhibits a lower overpotential of 215 mV and a higher Ir mass activity of 2268.7 A·gIr−1. The catalyst also exhibits lower Tafel slope value (37.82 mV/dec) and higher reaction kinetics. The catalyst also shows durability for the 12h under corrosive acidic OER conditions. The enhancements in performance can be attributed to the distinctive nanostructure of the Mn1-xTixO2 (MTO) support, which facilitates the even distribution of Ir and Ru catalysts. Additionally, the incorporation of titanium in pyrolusite β-MnO2 enhances the electrochemical durability of the MTO support under challenging acidic OER conditions.

Ir Doping Modulates the Electronic Structure of Flower-Shaped Phosphides for Water Oxidation.

Electrolysis of water to produce hydrogen is an efficient, clean, and environmentally friendly hydrogen production method with unlimited development prospects. However, its overall efficiency is hampered by the slow oxygen evolution reaction (OER) with complex electron transfer processes. Therefore, designing efficient and low-cost OER catalysts is the key to solving this problem. In this paper, Ir-doped Co2P/Fe2P (abbreviated as Ir-CoFeP/NF) was grown on nickel foam through the strategies of low amount noble-metal doping and mild phosphating. Phosphide derived from a floral metal-organic framework (MOF) exhibits regular three-dimensional (3D) morphology and large active area, avoiding the stacking of active sites. The addition of Ir can effectively adjust the electronic structure, change the position of the d-band center, and increase active sites, thus enhancing the catalytic activity. Hence, the optimized catalyst exhibits unexpected electrocatalytic OER activity with an ideal overpotential of 213 mV at 10 mA cm-2, as well as a low Tafel slope of 40.63 mV dec-1. Coupling with Pt/C for overall water splitting (OWS), the entire device only needs an ultralow cell voltage of 1.50 V to achieve a current density of 10 mA cm-2. Besides, the OWS can be maintained for more than 70 h. This study demonstrates the superiority of Ir-doped phosphide in accelerating water oxidation.

Spatially Immobilized PtPdFeCoNi as an Excellent Bifunctional Oxygen Electrocatalyst for Zinc–Air Battery

AbstractDeveloping efficient oxygen electrocatalysts with low cost, high catalytic activity, and robust stability remains a formidable challenge for rechargeable zinc–air batteries (ZABs). Herein, highly dispersed ultrasmall PtPdFeCoNi high‐entropy alloy nanoparticles with a size of ≈ 2 nm and randomly distributed multimetallic single atoms spatially immobilized on the 3D hierarchically ordered porous nitrogen‐doped carbon skeleton (denoted as PtPdFeCoNi/HOPNC) are successfully synthesized via ultra‐rapid Joule heating process. The spatial immobilization on 3D HOPNC skeleton is the key to the high dispersion of multi‐active sites of oxygen electrocatalysts, and the formed hierarchical pore structure is conducive to the successful construction of the rapid mass transfer channel. As a result, the as‐prepared PtPdFeCoNi/HOPNC exhibits a positive half‐wave potential of 0.866 V versus RHE for oxygen reduction reaction (ORR), a low overpotential of 310 mV at 10 mA cm−2 for oxygen evolution reaction (OER), and low Tafel slopes for both ORR and OER. Furthermore, ZAB using PtPdFeCoNi/HOPNC as bifunctional oxygen catalysts exhibits excellent rate performances and superior cycling stability, surpassing that of a commercial Pt/C‐RuO2 mixture. The spatial immobilization strategy of HOPNC provides a new idea for the design and synthesis of efficient catalysts for various applications.

Achieving High OER Performance by Tuning the Co/Mn Content in Prussian Blue Analogues.

The need for efficient, economical, and clean energy systems is increasing, and as a result, interest in water-splitting techniques to produce green hydrogen is also increasing. However, the sluggish kinetics of the oxygen evolution reaction (OER) hinders the practical application and widespread use of water-splitting technologies; therefore, to address this challenge, it is essential to develop cost-effective and efficient OER catalysts. In this work, we have synthesized an inexpensive and tunable FeCoMn Prussian blue analogue (PBAs) as an efficient OER catalyst via a straightforward process. The ratio of the Co and Mn to optimize the electrochemical performance, and as a result, the FeCo0.41Mn0.42 PBA catalyst demonstrated the best electrochemical performance (260/304 mV overpotential at 10/50 mA cm-2, a low Tafel slope of 48 mV dec-1 and a good stability of 72 h at 10 mA cm-2). Additionally, X-ray absorption spectroscopy (XAS) measurements and density functional theory (DFT) calculations suggest that the FeCo0.41Mn0.42 PBA possesses the optimized electronic density distribution at the active site (Co), and the doping of Mn and Fe can not only increase the electricity conductivity but also activate the critical H2O deprotonation step.

Exploring multimetal interactions between FeNi3 alloy and Lu3Ga5O12 metal oxide for improved water splitting performance

The production of energy from fossil fuels generates greenhouse gases, leading to global warming and various environmental impacts. Extensive research into sustainable alternative fuels has identified hydrogen (H2) as a viable option. With net zero carbon emissions, hydrogen presents a promising solution for sustainable and renewable energy. This study employs a simple gel-matrix method to fabricate Ni-Fe alloy-based nanocomposites in alkaline media (1 M KOH). Achieving outstanding performance in hydrogen generation through the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with impressive turn-over frequencies (TOF) of 2.98 s−1 at 177 mV and 1.48 s−1 at 219 mV. Nanocomposite’s unique structure enhances electroactive surface area (347.5 cm2/gram), extending electrocatalytic active sites and durability to 60 h. It shows excellent performance, characterized by low Tafel slopes of 50 mV/dec and 37 mV/dec, and minimal overpotentials of 219 mV for the oxygen evolution reaction (OER) and 177 mV for the hydrogen evolution reaction (HER), reaching a current density of 10 mA cm−2. This study presents a method for synthesizing high-performance, sustainable metal-alloy/garnet hybrid electrocatalysts, offering a new frontier in design of next-generation materials for advanced energy conversion technologies.

Atomically dispersed ruthenium single-atom alloy catalysts enabling efficient iodide oxidation reaction electrolysis in acidic media

Single-atom catalysts exhibit immense potential across diverse reactions, yet their synthesis and stability in acidic environments pose significant challenges. Herein, we introduce a facile one-step hydrothermal approach to fabricate Ru single-atom alloy catalysts (Ru SAAC) through the reaction of Ru and Ti precursors, followed by annealing in an argon atmosphere. Analysis via extended X-ray absorption fine structure spectroscopy and aberration-corrected scanning transmission electron microscopy confirms the atomically dispersed Ru alloy catalyst anchored on a TiO2 support. Remarkably, Ru SAAC demonstrates exceptional electrocatalytic performance in the iodide oxidation reaction (IOR), achieving a benchmark current density of 10 mA/cm2 at a mere voltage of 0.64 V in acidic conditions within a three-electrode electrolyzer setup. Surpassing nanoscale Ru/TiO2 and RuO2/TiO2 counterparts, Ru SAAC exhibits the highest voltage efficiency (84.4%), lowest Tafel slope (36 mV/dec), and lowest overpotential (100 mV) under identical experimental conditions. This method enables facile control over Ru morphology. It enhances the kinetics and thermodynamic favorability of Ru SAAC in acidic media, opening avenues for synthesizing diverse transition metal-based single-alloy catalysts for varied applications.

CuO and spinel CuCo2O4 supported on mesoporous nanocubes with dual redox-active centers for electrocatalytic H2O2 reduction and sensing

The copper hexacyanoferrate (CuHCF) nanocube and its cobalt-substituted analogue (CoCuHCF) possess numerous micropores; however, they demonstrate limited electrocatalytic performance for H2O2 reduction. Heat treatment of CuHCF in air (CuHCF-ht) results in the formation of CuO and Fe3O4 with noticeable aggregation. In contrast, the heat treatment of CoCuHCF in air (CoCuHCF-ht) preserves its nanocube structure while also forming a spinel CuCo2O4 phase. The partial substitution of cobalt ions for copper ions in CuHCF enhances both thermal and structural stability, leading to the transformation of micropores into mesopores during heat treatment. This transformation improves electrolyte accessibility and structural integrity. The CoCuHCF-ht electrode features dual redox-active centers (Cu+/Cu2+ couple) derived from the CuO and CuCo2O4 phases, serving as catalytic redox mediators for H2O2 reduction. This dual redox activity results in superior performance for H2O2 reduction compared to CuHCF-ht, which only exhibits a single pair of Cu+/Cu2+ couple from CuO as an active mediator. This enhanced performance is evidenced by a lower Tafel slope, a higher catalytic rate constant, and improved mass transfer of analytes. The CoCuHCF-ht catalyst, characterized by dual redox-active centers in mesoporous nanocubes, demonstrates a high sensitivity of 234.03 μA mM−1 cm−2 and a low limit of detection (0.26 μM), along with high selectivity, stability, repeatability, and reproducibility.

Nanostructured Fe-Doped Ni3S2 Electrocatalyst for the Oxygen Evolution Reaction with High Stability at an Industrially-Relevant Current Density.

A novel oxygen evolution reaction (OER) electrocatalyst was prepared by a synthesis strategy consisting of the solvothermal growth of Ni3S2 nanostructures on Ni foam, followed by hydrothermal incorporation of Fe species (Fe-Ni3S2/Ni foam). This electrocatalyst displayed a low OER overpotential of 230 mV at 100 mA·cm-2, a low Tafel slope of 43 mV·dec-1, and constant performance at an industrially relevant current density (500 mA·cm-2) over 100 h in a 1.0 M KOH electrolyte, despite a minor loss of Fe in the process. Based on a detailed characterization by (in situ) Raman spectroscopy, (quasi-in situ) XPS, SEM, TEM, XRD, ICP-AES, EIS, and Cdl analysis, the high OER activity and stability of Fe-Ni3S2/Ni foam were attributed to the nanostructuring of the surface in the form of stable nanosheets and to the combination of Ni3S2 granting suitable electrical conductivity with newly formed NiFe-based (oxy)hydroxides at the surface of the material providing the active sites for OER.

Facile synthesis of nitrogen-containing multiwalled carbon nanotubes as a worth metal-free electrocatalyst for hydrogen evolution reaction and semicarbazide oxidation

Studies of metal-free carbon nanostructures prove effective in energy and environmental applications due to their molecular tunability and vast chemical space. Herein, we synthesize nitrogen-containing multi-walled carbon nanotubes (N-MWCNTs) via. acid-catalysed incorporation of 3, 4-diaminopyridine into multi-walled carbon nanotubes (MWCNTs), and demonstrating their efficacy in electrocatalytic hydrogen evolution reaction (HER) and semicarbazide (SCB) oxidation for energy and environmental waste management, respectively. Successful synthesis is further confirmed by analysis techniques, i.e. Fourier transform infrared (FTIR) spectral analysis shows the diminishing OH frequency around 3250 cm−1 in MWCNTs after functionalization and the formation of an OC–NH bond in N-MWCNTs at 1710 cm−1. X-ray diffraction (XRD) confirms the incorporation of N-species, while Raman spectroscopic analysis indicates an increase in the ID/IG ratio MWCNTs (∼1) to N-MWCNTs (∼1.25), suggesting more defective sites in the N-MWCNTs nanocomposite. X-ray photoelectron spectroscopy (XPS) reveals peaks at 399.38, 400.49, and 402.05 eV, attributed to pyridinic-N, aromatic amide-N, and protonated amine groups, respectively. N₂ adsorption-desorption studies shows a high Brunauer-Emmett-Teller (BET) surface area for N-MWCNTs (119.22 m2/g) compared to MWCNTs (74.94 m2/g). Linear sweep voltammetry (LSV) profiles demonstrate enhanced activity of N-MWCNTs for both HER and SCB oxidation at an ultralow potential of E = −0.55 V vs RHE at 10 mA/cm2, with a lower Tafel slope of 108 mV.dec−1. Moreover, the electrochemical sensing studies indicates on N-MWCNTs were demonstrating an efficient electron transfer to SCB with the lower detection limit of 0.004 μmol. This work provides carbon-based metal-free electrocatalysts for energy harvesting and environmental management.

Enhanced electrocatalytic OER activity following electrochemical pre-cathodic treatment of Mn-substituted nickel ferrite

In this study, the electronic engineering of a high-valent active site for enhanced oxygen evolution reaction (OER) was achieved through the electrochemical pre-cathodic treatment method (EPCTM). This method involves applying a cathodic potential to the drop-cast working electrode of Mn-substituted nickel ferrite (Ni1−xMnxFe2O4; where x = 0.0, 0.2, and 0.4) electrocatalysts. X-ray photoelectron spectroscopy analysis revealed an increase in the ratios of Ni3+/Ni2+ and Mn3+/Mn2+ in Ni1−xMnxFe2O4 after EPCTM followed by OER, leading to an enhancement in electrochemical OER current density at 600 mV overpotential by 3.65 times for x = 0.0, 5.56 times for x = 0.20, and 4.72 times for x = 0.40. This enhancement was further supported by a decrease in the slope of the anodic Tafel equation after EPCTM, indicating improved efficiency of the interaction between the working electrode and electrolyte, as a lower Tafel slope suggests better charge exchange at the electrode–electrolyte interface. The positive slope in the Mott–Schottky (MS) plot for all Ni1−xMnxFe2O4 samples confirmed the p-type nature of the electrocatalysts. Additionally, the significant decrease in the slope of the linear portion of the MS plot indicated an increase in carrier concentration after electrochemical pre-cathodic treatment in all Ni1−xMnxFe2O4 samples. This increase in p-type carrier concentration supports the observed increase in the Ni3+/Ni2+ ratio for OER after EPCTM.