Tafel Slope Research Articles

Self‐supported thin‐film electrode consisting of transition metal borides for highly efficient hydrogen evolution

AbstractTransition metal borides (TMBs) are a new class of promising electrocatalysts for hydrogen generation by water splitting. However, the synthesis of robust all‐in‐one electrodes is challenging for practical applications. Herein, a facile solid‐state boronization strategy is reported to synthesize a series of self‐supported TMBs thin films (TMB‐TFs) with large area and high catalytic activity. Among them, MoB thin film (MoB‐TF) exhibits the highest activity toward electrocatalytic hydrogen evolution reaction (HER), displaying a low overpotential (η10 = 191 and 219 mV at 10 mA cm−2) and a small Tafel slope (60.25 and 61.91 mV dec−1) in 0.5 M H2SO4 and 1.0 M KOH, respectively. Moreover, it outperforms the commercial Pt/C at the high current density region, demonstrating potential applications in industrially electrochemical water splitting. Theoretical study reveals that both surfaces terminated by TM and B atoms can serve as the active sites and the H* binding strength of TMBs is correlated with the p band center of B atoms. This work provides a new pathway for the potential application of TMBs in large‐scale hydrogen production.

High‐Performance MCNTs@MoS2(1‐x)Se2x Nanocomposites in Catalytic Hydrogen Evolution

AbstractAdvances in electrocatalysis require the development of high specific surface area materials with high electron conductivity. In this study, a series of MCNTs@MoS2(1‐x)Se2x nanocomposites has been prepared for application in catalytic hydrogen evolution. A uniform growth of MoS2(1‐x)Se2x nanoflower spheres on MCNTs has been achieved, circumventing stacking and aggregation. The introduction of the conducting material accelerated the electron transport rate in the electrode reaction. Structural characterization has confirmed that S doping increased the specific surface area of the catalyst, exposing more edge defects. As a result, the MCNTs@MoS2(1‐x)Se2x nanocomposites exhibited enhanced catalytic activity. Electrochemical tests have established that MCNTs@MoS1.5Se0.5 possessed the lowest overpotential (146 mV) at a current density of 10 mA/cm2 with the smallest Tafel slope (45.1 mV/dec).

Roles and influencing mechanisms of guar gum and polyethylene glycol in copper electrodeposition

ABSTRACT In this paper, the effects of the organics guar gum and polyethylene glycol (PEG) additives on Cu electrodeposition cell voltage, energy consumption and surface morphology were evaluated. Furthermore, the influences of guar gum and PEG on the kinetics of Cu electrodeposition were investigated using electrochemical tests such as cyclic voltammetry (CV), linear sweep voltammetry (LSV) and Tafel linear fitting. The results indicated that adding 0.5 mg/L guar gum promoted the Cu electrodeposition. While indicating the lowest overpotential (10 and 100 mA cm−2 were −462 and −561 mV, respectively) and smaller Tafel slope of 50.37 mV dec−1. However, higher concentrations of guar gum and PEG increased cell voltage and energy consumption, with 900 mg/L PEG leading to a 61 kWh energy increase. Elevated organic levels in the electrolyte raised overpotential, inhibiting Cu deposition and causing surface roughness on Cu sheets.

Versatile platform of 3D/2D/1D:ZnFe2O4/NiAl-LDH/MWCNTs nanocomposite for photocatalytic purification of dinoseb and electrocatalytic O2 evolution reaction.

Integrating photocatalysis with electrocatalysis may represent a synergistic approach to address environmental and energy challenges. In this context, we explored synthesizing a series of nanocomposite materials using a solid-state approach involving simple grinding and subsequent thermal treatment for the photocatalytic purification of dinoseb and electrocatalytic oxygen evolution (OER). Interestingly, among the series of synthesized materials, 40 weight percentage of 3D/2D/1D:ZnFe2O4/NiAl-LDH/MWCNTs ternary nanocomposite (40-NZM) showed highly improved dinoseb detoxification and OER efficiencies compared to those of pure materials. Importantly, approximately 98% detoxification of dinoseb was observed within 75 min of irradiation time under a visible light source. Remarkably, the 40-NZM nanocomposite exhibited the highest rate constant value (k = 4.1×10-2 min-1) with a favorable R2 (0.98) parameter. Furthermore, 40-NZM showed promising electrocatalytic OER performance, requiring only 217 mV of overpotential to achieve 10 mAcm-2 of current density with a smaller Tafel slope of 66.6 mVdec-1. Additionally, long-term stability was tested by recording 2000 cyclic voltammetry (CV) cycles. The results revealed that 40-NZM could maintain its catalytic activity for a longer duration as it required only 227 mV to attain 10 mAcm-2 even after 2000 CV cycles. Consequently, these outstanding characteristics of 40-NZM nanocomposite underscore the significant potential for catalytic water purification and sustainable energy conversion.

On the Quest for Oxygen Evolution Reaction Catalysts Based on Layered Double Hydroxides: An Electrochemical and Chemometric Combined Approach

The oxygen evolution reaction (OER) is a crucial process in various energy conversion and storage technologies, such as water electrolysis. Developing efficient and cost‐effective electrocatalysts is essential to achieve the commercialization of devices for the transition toward sustainable energy solutions. Herein, ternary layer double hydroxides (LDHs) are synthesized and characterized as electrocatalysts for OER using a potentiodynamic electrochemical deposition method on Grafoil. A chemometric approach based on experimental design is employed to rationalize the effort in the investigation of the LDHs which are based on Ni, Co, and Fe. The deposited films are characterized using cyclic voltammetry and X‐ray diffraction to determine peak currents and potentials, and crystal size. Furthermore, the electrocatalyst performances are assessed by linear sweep voltammetry in 1M KOH from which the Tafel slope and onset potential are calculated. The obtained data are used to derive models describing the material properties and electrocatalyst performance as a function of the electrolyte composition used during the LDHs electrodeposition. This study provides valuable insights into the relationship between the electrocatalyst composition and its OER activity, enabling the design of more efficient and sustainable electrochemical systems for energy applications.

Engineering MXene Surface via Oxygen Functionalization and Au Nanoparticle Deposition for Enhanced Electrocatalytic Hydrogen Evolution Reaction.

MXene, a family of 2D transition metal carbides and nitrides, presents promising applications in electrocatalysis. Maximizing its large surface area is key to developing efficient non-noble-metal catalysts for the hydrogen evolution reaction (HER). In this study, oxygen-functionalized Ti3C2Tx MXene (Ti3C2Ox) is synthesized and deposited gold nanoparticles (Au NPs) onto it, forming a novel composite material, Au-Ti3C2Ox. By selectively removing other functional groups, mainly -O functional groups are retained on the surface, directing electron transfer from Au NPs to MXene due to electronic metal-support interaction (EMSI), thereby improving the catalytic activity of the MXene surface. Additionally, the interaction between Au NPs and -O functional groups further enhanced the overall catalytic activity, achieving an overpotential of 62 mV and a Tafel slope of 40.1 mV dec-1 at a current density of -10 mA cm-2 in 0.5 m H2SO4 solution. Density functional theory calculations and scanning electrochemical microscopy with ≤150 nm resolution confirmed the enhanced catalytic efficiency due to the specific interaction between Au NPs and Ti3C2Ox. This work provides a surface modification strategy to fully utilize the MXene surface and enhance the overall catalytic activity of MXene-based catalysts.

ZIF-67 derived N doped carbon embedded CoxP for superior hydrogen evolution

Abstract Developing a sustainable non-noble hybrid electrocatalyst for effective electrocatalysis is the most crucial task; particularly in sustainable hydrogen energy production in the realm of energy conversion. In this work, effective thermal pyrolysis process followed by phosphorization strategy was employed to prepare and fabricate ZIF-67 (Zeolitic imidazole) assisted Co2P/N doped carbon electrocatalyst for hydrogen evolution reaction (HER). The optimized Co2P/N–C electrocatalyst exhibited hollow porous nanostructures as confirmed from the scanning electron microscopy. The achieved porous nanostructure improved the efficiency of the charge and mass transportation which is confirmed by the BET analysis, has high surface area value of 94.731 m2/g. In addition, a transition metal atom can regulate reactants adsorption and desorption capacity by modulating Co and P electronic configuration. The electrochemical studies of fabricated ZIF-67 derived Co2P/N–C electrode were analyzed using 1.0 M alkaline potassium hydroxide (KOH) medium in 3 electrode system process. Whilst, optimizing the pyrolysis temperature during the phosphorization will remarkably enhance the favourable characteristics of the hydrogen generation. Notably, the optimized ZIF-67 derived Co2P/NC at 350 °C electrode exhibited low overpotential (135 mV) at minimum 10 mA/cm2 and low 120.3 mV/dec Tafel slope. Besides, electrode stability at 10 mA/cm2 current density was verified by chronoamperometry test. Hence, this study furnishes the potential technique for the development of advanced hybrid MOF electrocatalyst as a successful alternative on large scale.

CuS-NiTe2 embedded phosphorus-doped graphene oxide catalyst for evaluating hydrogen evolution reaction.

The hydrogen evolution reaction (HER), a crucial half-reaction in the water-splitting process, is hindered by slow kinetics, necessitating efficient electrocatalysts to lower overpotential and enhance energy conversion efficiency. Transition-metal electrode materials, renowned for their robustness and effectiveness, have risen to prominence as primary contenders in the field of energy conversion and storage research. In this investigation, we delve into the capabilities of transition metals when employed as catalysts for the HER. Furthermore, we turn our attention to carbon nanomaterials like graphene, which have exhibited tremendous potential as top-performing electrocatalysts. Nevertheless, advancements are indispensable to expand their utility and versatility. One such enhancement involves the integration of phosphorus-doped graphene. Our research focuses on the synthesis of CuS-NiTe2/PrGO, a nanocomposite with a crystalline structure, through a straightforward method. This nanocomposite exhibits enhanced catalytic activity for the HER, boasting a Tafel slope of 57 mV dec-1 in an acidic environment. Consequently, our findings present a straightforward and efficient approach to developing high-performance electrocatalysts for HER.

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.

Polyimide-based triazine-cored covalent organic frameworks supported metal (Fe, Ni, Ru and Rh) nanoparticles for high-efficiency electrocatalytic hydrogen evolution

Covalent organic frameworks (COFs) have great potential in electrocatalytic hydrogen evolution reaction (HER). Nevertheless, it is a challenging task to fabricate COF-based electrocatalysts with low overpotential and high stability for HER in acidic media. Herein, a series of polyimide-based triazine-cored COFs (PIT-COFs) with different aromatic diimides are designed to support metal (Fe, Ni, Ru and Rh) nanoparticles for electrocatalytic HER. PIT-COFs are obtained by the reaction between melamine and aromatic (benzene, biphenyl, naphthalene and perylene) diimides. PIT-COFs based on perylenediimide show the optimal electrocatalytic HER activity in acidic media due to its large π-conjugated structure. Rh@COFMA-PT has a low overpotential value of 70 mV at 10 mA cm−2 and a small Tafel slope of 56.58 mV dec−1, which surpasses numerous previously published HER electrocatalysts. Furthermore, Rh@COFMA-PT exhibits good electrocatalytic stability and still keeps high activity after 3000 cycles. The conjugated nitrogen-rich structures of PIT-COFs and their ability to effectively anchor metal nanoparticles as active sites significantly promote the electron and proton transport during the electrocatalytic HER process. This work offers a guideline for developing effective and stable COF-based HER electrocatalysts with abundant active sites.

Role of Surfactants on Electrocatalytic Activity of Co/Al Layered Double Hydroxides For Hydrogen and Oxygen Generation

AbstractLayered double hydroxides (LDHs) have recently attracted much attention in the scientific community as a prominent catalyst for oxygen evolution reaction (OER) because they are economical, extremely stable, and highly active. Literature on LDH alone and their hybrids for catalyzing water oxidation are readily available, but LDH catalyzing hydrogen evolution reaction (HER) is meager. Here, we synthesized Co/Al‐based LDH systems that efficiently perform as bifunctional electrocatalysts for both HER and OER. Exfoliation of this layered material via anion intercalation into a few layers further enhanced its activity. In this work, we reported the synthesis of Co/Al LDHs via coprecipitation followed by hydrothermal method and different surfactant‐functionalized LDHs (with anionic surfactant: SDS, cationic surfactant: CTAB, and nonionic surfactant: PEG 4000). SDS‐modified LDH (s LDH) showed notable stability and competent results in hydrogen evolution in addition to oxygen evolution. The exfoliation of s LDH caused enhancement in the high specific surface area about 6.8 times compared to pristine LDH, as evident from BET data. The onset potential for HER as obtained from the polarization curve for s LDH is −0.41 V versus RHE, with Tafel slope of 67.4 mV/dec. Similarly, OER onset potential and corresponding Tafel slope are 1.53 V versus RHE at 10 mA/cm2 and 90.2 mV/dec, respectively.

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.

Defect Passivation of Mn2+-Doped CsPbX3(X=Cl,Br) Perovskite Nanocrystals as Electrocatalyst for Overall Water Splitting.

Mn doping has been used to improve the physical chemistry of lead halide perovskite nanocrystals such as CsPbX3, where X is a halogen ion. In this paper, a two-phase method for Mn-doped CsPbX3 nanosheets (where X=Br, Cl), namely water-hexane system, is reported. Compared to conventional catalyst arrays, the band gap of CsPbBr3 nanocrystalline is easily tuned, the carrier diffusion distance is remote, the band edge position of the band structure is favorable for a wide range of electrocatalytic redox reactions, and the catalytic active site is maximally exposed, providing a larger electrolyte contact area. The porous hierarchical structure also accelerates the release of hydrogen bubbles. The results showed that the optimized Mn : CsPbBr3 catalyst exhibited excellent electrolytic performance of aquatic hydrogen in alkaline electrolyte (1 mol/L KOH). The overpotentials of the oxygen evolution reaction (OER) at the current densities of 10 and 100 mA cm-2 are only 114.4 and 505.4 mV, respectively, with a Tafel slope of 43 mV dec-1. At a current density of 10 mA cm-2, the excess potential required for the hydrogen evolution reaction (HER) is 158.6 mV and it exhibits excellent electrochemical stability. The Mn : CsPbBr3 nanocrystalline consists of two electrodes for hydrolysis of water, requiring only a voltage of 1.45 V. This provides implications for the optimization of electrocatalysts in alkaline electrolytes with the aim of developing next generation 2D electrocatalysts for overall water splitting.

NiIr Nanowire Assembles as an Efficient Electrocatalyst Towards Oxygen Evolution Reaction in Both Acid and Alkaline Media.

Oxygen evolution reaction (OER) is the rate-limiting step in water electrolysis due to its sluggish kinetic, and it is challenging to develop an OER catalyst that could work efficiently in both acid and alkaline environment. Herein, NiIr nanowire assembles (NAs) with unique nanoflower morphology were prepared by a facile hydrothermal method. As a result, the NiIr NAs exhibited superior OER activity in both acid and alkaline media. Specifically, in 0.1 M HClO4, NiIr NAs presented a superior electrocatalytic performance with a low overpotential of merely 242 mV at 10 mA cm-2 and a Tafel slope of only 58.1 mV dec-1, surpassing that of commercial IrO2 and pure Ir NAs. And it achieved a significantly higher mass activity of 148.40 A/g at -1.5 V versus RHE. In 1.0 M KOH, NiIr NAs has an overpotential of 291 mV at 10 mA cm-2 and a Tafel slope of 42.1 mV dec-1. Such remarkable activity makes the NiIr NAs among the best of recently reported representative Ir-based OER electrocatalysts. Density functional theory (DFT) calculations confirmed alloying effect promotes surface bonding of NiIr with oxygen-containing reactants, resulting in excellent catalytic properties.

Greenly Synthesized Conducting Polymer Nanotunnels with Metal-Hydroxide Nanobundles in Single Dais for Unmitigated Water Oxidation.

Electrochemical water splitting required efficient electrocatalysts to produce clean hydrogen fuel. Here, we adopted greenway coprecipitation (GC) method to synthesize conducting polymer (CP) nanotunnel network affixed with luminal-abluminal CoNi hydroxides (GC-CoNiCP), namely, GC-Co1Ni2CP, GC-Co1.5Ni1.5CP, and GC-Co2Ni1CP. The active catalyst, GC-Co2Ni1CP/GC, has low oxygen evolution reaction (OER) overpotential (307 mV) and a smaller Tafel slope (47 mV dec-1) than IrO2 (125 mV dec-1). The electrochemical active surface area (EASA) normalized linear sweep voltammetry (LSV) curve exhibited outstanding intrinsic activity of GC-Co2Ni1CP, which required 285 mV to attain 10 mA cm-2. At 1.54 V, the estimated turnover frequency (TOF) of GC-Co2Ni1CP/GC (0.017337 s-1) was found to be 3-fold higher than that of IrO2 (0.0014 s-1). Furthermore, the GC-Co2Ni1CP/NF consumed a very low overpotential (281 mV) with a small Tafel slope of 121 mV dec-1. The ultrastability of GC-Co2Ni1CP for industrial application was confirmed by durability at 10 and 100 mA cm-2 for the OER (GC/NF-8 h, 2.0%/100 h, 2.2%) and overall water splitting (100 h, 3.8%), which implies that GC-Co2Ni1CP had adequate kinetics to address the elevated rates of water oxidation. The effect of pH and addition of tetramethylammonium cation (TMA+) reveal that GC-Co2Ni1CP follows the lattice oxygen mechanism (LOM). The solar-powered water electrolysis at 1.55 V supports the efficacy of GC-Co2Ni1CP in the solar-to-hydrogen conversion. The environmental impact studies and solar-driven water electrolysis proved that GC-CoNiCP has excellent greenness and efficiency, respectively.

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.

Investigating Electrodeposition of Platinum Nanoparticles on Stainless-Steel Mesh Electrodes for Hydrogen Evolution Reaction

Abstract Hydrogen production through electrochemical water splitting is a promising approach for sustainable energy generation, yet developing efficient and durable electrocatalysts remains a critical challenge. This study successfully developed a highly active platinum nanoparticles-decorated stainless-steel mesh (Pt/SSM) electrocatalyst for the hydrogen evolution reaction (HER) using electrodeposition. The Pt nanoparticles exhibited a unique micro-leaf structure on the SSM surface. The Pt/SSM electrocatalyst demonstrated superior HER performance compared to bare SSM, with a remarkably low overpotential of 121 mV and a Tafel slope of 40 mV/dec in 0.5 M H2SO4. This performance was superior to their activity in 0.5 M KOH, attributed to the higher proton concentration, favorable Volmer kinetics, and improved catalyst-electrolyte interactions in the acidic medium. The electrodeposited Pt/SSM electrocatalyst also exhibited more stable HER performance in acidic electrolytes compared to alkaline ones, likely due to the preservation of its morphological integrity in acidic conditions. Overall, this work successfully developed a highly active and durable Pt/SSM electrocatalyst for practical hydrogen production, with the acidic medium providing optimal performance.

Modulating Built‐In Electronic Configuration via Variable Al Doping for Robust Oxygen Evolution Reaction

Transition metal‐based electrocatalysts play a crucial role in the oxygen evolution reaction (OER). However, their heavy reliance on free electrons at the <i>d</i>‐band significantly limits the screening of potentially efficient, earth‐abundant alternatives. Despite extensive exploration of catalyst engineering through multi‐metal cooperation to modulate electron configuration by introducing additional transition metals, practical success remains elusive. Here, we present a straightforward electrodeposition method for preparing amorphous FeCoAl hydroxide catalysts. The introduction of Al contributes external free electrons, enabling a well‐defined electron configuration for intermediate adsorption. Al doping also adjusts the <i>d</i>‐band position of adjacent Co atoms, bringing them closer to the Fermi level and significantly enhancing intrinsic activity at the active sites. Furthermore, Al dopants facilitate rapid mass and charge transfer near the catalyst layer, promoting faster reaction kinetics. Leveraging these properties, the FeCoAl hydroxide catalyst achieves a large current density of 100 mA cm <sup>‐2</sup> at an overpotential of 340 mV, with a small Tafel slope of 29.1 mV dec <sup>‐1</sup>. Our work provides valuable insights for designing efficient electrocatalysts by leveraging free electron‐rich metal doping and expanding the parameter space for catalyst engineering.

Insights Into Electrocatalytic Hydrogenation of Furfural on Nanoparticulate Pd/C Under Acidic Conditions

AbstractIn this work, we present an insight into the mechanism of electrochemical hydrogenation of furfural on carbon supported palladium nanoparticles. By directly coupling electrochemistry with mass spectrometry, we were able to, for the first time, deconvolute the hydrogen evolution reaction and electrochemical hydrogenation by measuring the mass signal for hydrogen and 2‐methylfuran. This approach also allowed us to extract the Tafel slopes for each reaction and get insights into mechanisms. The results indicate that the hydrogenation occurs by a Langmuir–Hinshelwood type process rather than by proton‐coupled electron transfer. Further findings recognize the blocking character of furfuryl alcohol (FA) where the latter or one of its intermediates blocks the electrochemical hydrogenation. Additionally, FA is shown to be a precursor for 2‐methyl furan formation. Accordingly, specific guidelines towards improvement of reaction performance are suggested.

Production of cost-effective green energy using Mn/Gd co-substituted cobalt ferrites hydroelectric cells and their oxygen evolution reaction

A thorough investigation into hydroelectric cells (HECs) composed of spinel ferrites, aiming to generate environmentally friendly electricity through the dissociation of water molecules into H3O+ and OH- ions without producing any harmful by-products has been reported. Utilizing a modified sol-gel auto-combustion synthesis method, we synthesized highly porous Mn2+/Gd3+ co-substituted cobalt ferrites (CFO) with the formula) [Co1-xMnxFe2-yGdyO4, 0≤x≤0.30 and y = 0.10]. X-ray diffraction (XRD) analysis revealed a singular-phase cubic structure, while Rietveld refinement provided essential parameters such as crystallite size, lattice constant, density, porosity percentage, and unit-cell volume. Morphological examination using Field emission scanning electron microscopy (FESEM) confirmed nanoparticle formation with an average size of 60.418 nm, and porosity increasing from 30 % to 51 % with Mn2+ ion doping, indicating enhanced water adsorption. XPS analysis highlighted increased lattice defects due to Mn/Gd co-substitution, boosting water adsorption capacity. Vibrating Sample Measurements showed a rise in Ms value with increasing Mn2+ concentration. Fabricated HECs delivered a maximum output current density of 13.906 mA/cm2, with 20 % Mn-substituted gadolinium cobalt ferrites-based HEC achieved a peak short-circuit current of 9.16 mA. These cells exhibited pseudo-capacitive behaviour, characterized by rapid and reversible faradaic reactions near electrode surfaces, while ionic diffusion mechanisms confirmed ion diffusion over the material's surface. Co1-xMnxGd0.1Fe1.9O4 (x = 0.20) is the optimal composition to get best OER performance having an overpotential of 342 mV at 10 mA/cm2 with a Tafel slope of 48 mV/dec in alkaline medium. This study underscores the potential of Mn2+/Gd3+ co-substituted cobalt ferrite as a promising alternative in green energy conversion applications, potentially replacing conventional fuel and solar cells. It has been concluded that the x = 0.20 is the composition that exhibits the best OER as well as HEC performance.