Alkaline Oxygen Evolution Reaction Research Articles

Cathodic corrosion induced selective nano-crystallization of Nickel oxo/hydroxo complex on (NiFeCr)SiB amorphous ribbon for alkaline oxygen evolution reaction and methanol oxidation reaction

The study focuses on the development and optimization of (Ni87Fe4Cr9)78Si8B14 amorphous ribbons as self-supported electro-catalysts for oxygen evolution reaction (OER) and methanol oxidation reaction (MOR). Electro-catalytically active nano α-Ni(OH)2 phase (5–10nm) was generated in the amorphous ribbon surface through potentiostatic cathodic corrosion for different time intervals (0–120 min). The X-ray diffraction and scanning electron microscopy results shows the favourable occurrence of dense nanocrystallization of α-Ni(OH)2 between 45 and 90 min of corrosion time. For OER in 1 M KOH, the 60-min surface modified ribbon exhibits an overpotential of 295 mV at 10 mA/cm2 current density and tafel slope of 51 mV dec−1. In case of MOR in 1 M KOH +1 M MeOH, the 90-min corroded ribbon shows lowest potential of 1.38 V vs RHE, at 10 mA/cm2 and tafel slope of 34 mV dec−1. In addition to superior electro-catalytic activity, the optimal surface-modified ribbons show superior long-term stability for OER and MOR studies, indicating its potential application in hydrogen generation and direct methanol fuel cell.

Dynamics of precatalyst conversion and iron incorporation in nickel-based alkaline oxygen evolution reaction catalysts

Dynamics of precatalyst conversion and iron incorporation in nickel-based alkaline oxygen evolution reaction catalysts

Construction of Co-Ni3B/GDY heterostructured electrocatalyst for boosting oxygen evolution in alkaline media

Water splitting as the clean technology for hydrogen production garnered the widespread attention. The high overpotential required for oxygen evolution reaction (OER) is the central dilemma. Herein, Co-Ni3B/graphdiyne heterostructure on copper foam (Co-Ni3B/GDY/CF) was constructed for boosting alkaline OER. Detailed electrochemical analysis showed that Co-Ni3B/GDY/CF was an exceptional OER electrocatalyst with the low overpotentials of 270 and 335mV at 20 and 100mAcm−2 in 1.0M KOH solution, respectively, as well as high turnover frequency of 0.80s−1 at 400mV. Moreover, its catalytic performance outperformed the benchmarked RuO2/CF when the current density exceeded 200mAcm−2. Importantly, the equipped electrolyser Pt/C/CF||Co-Ni3B/GDY/CF showed low cell voltage (1.53V@10mAcm−2) and long-term durability. These results demonstrated that a synergistic effect at the heterointerface between GDY and Co-Ni3B was achieved, which regulated the electronic configuration, accelerated the charge transfer and increased the active surface areas. Furthermore, the density functional theory calculations revealed that Co-Ni3B/GDY with incomplete charge transfer lowered the energy barrier of the rate-determining step and optimized adsorption/desorption behavior of the intermediates, thereby effectively promoting O2 evolution.

Kinetic analysis of the self-discharge of the NiOOH OER active phase in KOH electrolyte: insights from in-situ Raman and UV–Vis reflectance spectroscopies

NiOOH has been established as the active phase of NiO-based electrocatalysts in the alkaline Oxygen Evolution Reaction (OER). Here, we investigate the self-discharge behavior of NiOOH electrodes under open circuit potential (OCP) conditions in 1 M KOH electrolyte by monitoring phase changes via in-situ Raman and UV–Vis reflectance spectroscopies and performing kinetic analyses on the OCP and spectroscopic data. Our findings reveal a linear phase change from NiOOH to Ni(OH)2 over time, indicative of a 0th-order reduction reaction. Contrarily, the OCP evolution associated with this phase reduction displayed a combination of linear and exponential decay patterns as a result of various kinetics, including Faradaic processes and diffusion-controlled mechanisms, influencing the self-discharge potential over 1.25 V (vs RHE). An additional linear region at lower potentials (<1.25 V (vs RHE)) suggests that charge redistribution due to the phase change from α-Ni(OH)2 to β-Ni(OH)2 dominates the self-discharge, a behavior confirmed by in-situ UV–Vis reflectance spectroscopy. These findings highlight the effectiveness of combining in-situ Raman and UV–Vis spectroscopy with electrochemical data for real-time monitoring of electrochemical processes, here potential-dependent electrocatalyst phase changes, leading to a more detailed and accurate understanding of the dynamic behavior, phase change kinetics, and self-discharge behaviors of solid electrocatalysts that can guide the design of more efficient and durable energy storage and conversion materials.

Atomic Manipulation to Create High-Valent Fe4+ for Efficient and Ultrastable Oxygen Evolution at Industrial-Level Current Density.

Manipulating the electronic structure of a catalyst at the atomic level is an effective but challenging way to improve the catalytic performance. Here, by stretching the Fe-O bond in FeOOH with an inserted Mo atom, a Fe-O-Mo unit can be created, which will induce the formation of high-valent Fe4+ during the alkaline oxygen evolution reaction (OER). The highly active Fe4+ state has been clearly revealed by in situ X-ray absorption spectroscopy, which can both enhance the oxidation capability and lead to an efficient and stable adsorbate evolution mechanism (AEM) pathway for the OER. As a result, the obtained Fe-Mo-Ni3S2 catalyst exhibits both superior OER activity and outstanding stability, which can achieve an industrial-level current density of 1 A cm-2 at a low overpotential of 259 mV (at 60 °C) and can stably work at the large current for more than 2000 h. Moreover, by coupling with commercial Pt/C, the Fe-Mo-Ni3S2∥Pt/C system can be used in the anion exchange membrane cell to acquire 1 A cm-2 for overall water splitting at 1.68 V (2.03 V for 4 A cm-2), outperforming the benchmark RuO2∥Pt/C system. The efficient, low-cost, and ultrastable OER catalyst enabled by manipulating the atomic structure may provide potential opportunities for future practical water splitting.

Unveiling the Aggregation of M-N-C Single Atoms into Highly Efficient MOOH Nanoclusters during Alkaline Water Oxidation.

M-N-C-type single-atom catalysts (SACs) are highly efficient for the electrocatalytic oxygen evolution reaction (OER). And the isolated metal atoms are usually considered real active sites. However, the oxidative structural evolution of coordinated N during the OER will probably damage the structure of M-N-C, hence resulting in a completely different reaction mechanism. Here, we reveal the aggregation of M-N-C materials during the alkaline OER. Taking Ni-N-C as an example, multiple characterizations show that the coordinated N on the surface of Ni-N-C is almost completely dissolved in the form of NO3 -, accompanied by the generation of abundant O functional groups on the surface of the carbon support. Accordingly, the Ni-N bonds are broken. Through a dissolution-redeposition mechanism and further oxidation, the isolated Ni atoms are finally converted to NiOOH nanoclusters supported by carbon as the real active sites for the enhanced OER. Fe-N-C and Co-N-C also have similar aggregation mechanism. Our findings provide unique insight into the structural evolution and activity origin of M-N-C-based catalysts under electrooxidative conditions.

Unveiling the Aggregation of M−N−C Single Atoms into Highly Efficient MOOH Nanoclusters during Alkaline Water Oxidation

AbstractM−N−C‐type single‐atom catalysts (SACs) are highly efficient for the electrocatalytic oxygen evolution reaction (OER). And the isolated metal atoms are usually considered real active sites. However, the oxidative structural evolution of coordinated N during the OER will probably damage the structure of M−N−C, hence resulting in a completely different reaction mechanism. Here, we reveal the aggregation of M−N−C materials during the alkaline OER. Taking Ni−N−C as an example, multiple characterizations show that the coordinated N on the surface of Ni−N−C is almost completely dissolved in the form of NO3−, accompanied by the generation of abundant O functional groups on the surface of the carbon support. Accordingly, the Ni−N bonds are broken. Through a dissolution‐redeposition mechanism and further oxidation, the isolated Ni atoms are finally converted to NiOOH nanoclusters supported by carbon as the real active sites for the enhanced OER. Fe−N−C and Co−N−C also have similar aggregation mechanism. Our findings provide unique insight into the structural evolution and activity origin of M−N−C‐based catalysts under electrooxidative conditions.

Electrospun Co-MoC Nanoparticles Embedded in Carbon Nanofibers for Highly Efficient pH-Universal Hydrogen Evolution Reaction and Alkaline Overall Water Splitting.

The construction of highly efficient and self-supported electrocatalysts with abundant active sites for pH-universal hydrogen evolution reaction (HER) and alkaline water splitting is significantly challenging. Herein, Co and MoC nanoparticles embedded in nitrogen-doped carbon nanofibers (Co-MoC/NCNFs) which display a bamboo-like morphology are prepared by electrospinning followed by the carbonization method. The electrospun MoC possesses an ultrasmall size (≈5nm) which can provide more active sites during electrocatalysis, while the introduction of Co greatly optimizes the electronic structure of MoC. Both endow the Co-MoC/NCNFs with superior HER performances over a wide pH range, with low overpotentials of 86, 116, and 145mV to achieve a current density of 10mAcm-2 in alkaline, acidic, and neutral media, respectively. Additionally, the catalyst exhibits remarkable alkaline oxygen evolution reaction (OER) activity with an overpotential of 254mV to reach 10mAcm-2. Density functional theory calculations confirm that electron transfer from Co to MoC regulates the adsorption free energy for hydrogen, thereby promoting HER. Moreover, an electrolyzer assembled with Co-MoC/NCNFs requires only a cell voltage of 1.59V at 10mAcm-2 in 1m KOH. This work opens new pathways for the design of high-efficiency electrocatalysts for energy conversion applications.

Dual Cocatalytic Sites Synergize NiFe Layered Double Hydroxide to Boost Oxygen Evolution Reaction in Anion Exchange Membrane Water Electrolyzer

AbstractNickel‐iron layered double hydroxide (LDH) is a promising cost‐efficient catalyst to replace noble metals for alkaline oxygen evolution reaction (OER), yet its intrinsic activity under high current density conditions is not satisfactory, which greatly constrains the industrial application of NiFe LDH catalysts. Herein, a new class of integrated Co and W co‐doped NiFe LDH catalysts is reported with dual cocatalytic sites for alkaline OER catalysis. The optimized Co2.8, W3.8‐NiFe LDH integrated catalyst has superior alkaline OER activity (255 mV@1000 mA cm−2) and excellent catalytic stability (200 h@500 mA cm−2). The turnover frequency value of Co2.8, W3.8‐NiFe LDH can reach 4.02 s−1 at 1.49 V versus RHE, which is 9.6 times higher than that of NiFe LDH and superior to the noble metal catalysts. Moreover, it can achieve 1.0 A cm−2 at 1.86 V and maintain 300‐h stable operation in anion exchange membrane water electrolyzer. Theoretical and experimental studies indicate that W sites promote the *OH adsorption and Co sites favor protons desorption of OH*. These dual cocatalytic sites jointly promote *O coverage, effectively accelerating alkaline OER kinetic.

Hard X-ray Photoelectron Spectroscopy Probing Fe Segregation during the Oxygen Evolution Reaction.

NiFe electrocatalysts are among the most active phases for water splitting with regard to the alkaline oxygen evolution reaction (OER). The interplay between Ni and Fe, both at the surface and in the subsurface of the catalyst, is crucial to understanding such outstanding properties and remains a subject of debate. Various phenomena, ranging from the formation of oxides/(oxy)hydroxides to the associated segregation of certain species, occur during the electrochemical reactions and add another dimension of complexity that hinders the rational design of electrodes for water splitting. In this work, we have developed the procedure for the quantification of chemical depth profiling by XPS/HAXPES measurements and applied it to two NiFe electrodes with different porosities. The main outcome of this study is related to the surface reconstruction of the electrodes during the OER, followed at two different depths by means of X-ray photoelectron spectroscopy. We find that Fe initially segregates at the surface when exposed to ambient conditions, resulting in the formation of an inactive FeOx phase. In addition, the porosity of the catalyst plays a significant role in the segregation process and thus in the performance of the electrode. In particular, the higher porosity of the nanostructured sample is responsible for a more pronounced diffusion of Fe from the subsurface to the surface with a more effective suppression of the activity of the Ni1-xFexOOH phase. These results highlight the importance of the fact that the chemical state of the surface of a multielement system is a snapshot in time, dependent on both external parameters, such as the applied potential and the adjacent electrolyte, and the underlying bulk properties accessible with HAXPES.

Supersaturated Doping-Induced Maximized Metal-Support Interaction for Highly Active and Durable Oxygen Evolution.

Metal-support interaction (MSI) is pivotal and ubiquitously used in the development of next-generation catalysts, offering a pathway to enhance both catalytic activity and stability. However, owing to the lattice mismatch and poor solubility, traditional catalysts often exhibit a metal-on-support heterogeneous structure with limited interfaces and interaction and, consequently, a compromised enhancement of properties. Herein, we report a universal and tunable method for supersaturated doping of transition-metal carbides via strongly nonequilibrium carbothermal shock synthesis, characterized by rapid heating and swift quenching. Our results enable ∼20 at. % Ni2FeCo doping in Mo2C, significantly surpassing the thermodynamic equilibrium limit of <3 at. %. The supersaturation ensures more catalytically active NiFeCo doping and sufficient interaction with Mo2C, resulting in the maximized MSI (Max-MSI) effect. The Max-MSI enables outstanding activity and particularly stability in alkaline oxygen evolution reaction, showing an overpotential of 284 mV at 100 mA cm-2 and stable for 700 h, while individual Ni2FeCo and Mo2C only last less than 70 and 10 h (completely dissolved), respectively. In particular, the SD-Mo2C catalyst also exhibits excellent durability at 100 mA cm-2 for up to 400 h in 7 M KOH. Such a significantly improved stability is attributed to the supersaturated doping that led to each Mo atom strongly binding with adjacent heteroatoms, thus elevating the dissolution potential and corrosion resistance of Mo2C at a high current density. Additionally, the highly dispersed NiFeCo also facilitates the formation of dense oxyhydroxide coating during reconstruction, further protecting the integrated catalysts for durable operation. Furthermore, the synthesis has been successfully scaled up to fabricate large (16 cm2) electrodes and is adaptable to nickel foam substrates, indicating promising industrial applications. Our strategy allows the general and versatile production of various highly doped transition-metal carbides, such as Ni2FeCo-doped TiC, NbC, and W2C, thus unlocking the potential of maximized or adjustable MSI for diverse catalytic applications.

Trace Amount of Ir Decorated NiFe Phosphide In-Situ Grown on Carbon Cloth as Cost-Effective Electrocatalyst for Oxygen Evolution Reaction.

Cost-effective electrocatalysts is a key constituent to establish the balance of cost and catalytic efficiency for oxygen evolution reaction (OER) via water electrolysis in the area of energy conversion and storage. NiFe phosphide decorated with trace amount of iridium (Ir) species in-situ grown on carbon cloth was prepared by a facile wet chemistry approach followed by a phosphorization post-treatment at a relative low temperature. The optimal electrocatalyst, Ir2-NiFePx/CC, exhibits excellent OER activity, with an low overpotential of 190 mV at 10 mA cm-2 for alkaline OER, and a desirable long-term durability over 90 h. The outstanding OER performance stems from the structural evolution via phosphorization process, Ir decoration with more high-valence stated Ir4+ species, and tight connection between individual components of the electrode, which gives rise to the strong activity to the active sites and faster reaction kinetics in the alkaline OER process. Mover, the Ir loading was as low as approximately ~1.7 wt % (0.29 mg cm-2), showing promissing propective in cost-effective OER.

Activating and Stabilizing Lattice Oxygen via Self-Adaptive Zn-NiOOH Sub-Nanowires for Oxygen Evolution Reaction.

Efficient and durable catalysts for the oxygen evolution reaction are essential for realizing the large-scale application of water electrolysis technologies. Here, we report a novel Zn-doped NiOOH subnanowires (Zn-NiOOH SNWs) catalyst synthesized via the electrochemical reconstruction of Zn-NiMoO4 SNWs. The inclusion of Zn triggers a transition in the oxygen evolution reaction mechanism of NiOOH from the adsorbate evolution mechanism to the lattice oxygen mechanism, resulted from Zn's adaptive adjustment of coordination types, which also improves the reaction energetics, thereby enhancing the stability and activity. Furthermore, the subnanowire structure provides further stabilization of the lattice oxygen in Zn-NiOOH, preventing its destructive dissolution. Remarkably, Zn-NiOOH SNWs display a current density of 10 mA cm-2 with an overpotential of only 179 mV and maintain stable operation at 200 mA cm-2 for 800 h with minimal changes in overpotential, establishing them as one of the most effective catalysts involving lattice oxygen for the alkaline oxygen evolution reaction. When utilized as the anode in an alkaline water electrolyzer, our Zn-NiOOH SNWs catalyst demonstrates stability exceeding 500 h under a water-splitting current of 200 mA cm-2, indicating promising potential for practical applications.

Regulating Local Coordination Sphere of Ir Single Atoms at the Atomic Interface for Efficient Oxygen Evolution Reaction.

Single-atom catalysts dispersed on an oxide support are essential for overcoming the sluggishness of the oxygen evolution reaction (OER). However, the durability of most metal single-atoms is compromised under harsh OER conditions due to their low coordination (weak metal-support interactions) and excessive disruption of metal-Olattice bonds to enable lattice oxygen participation, leading to metal dissolution and hindering their practical applicability. Herein, we systematically regulate the local coordination of Irsingle-atoms at the atomic level to enhance the performance of the OER by precisely modulating their steric localization on the NiO surface. Compared to conventional Irsingle-atoms adsorbed on NiO surface, the atomic Ir atoms partially embedded within the NiO surface (Iremb-NiO) exhibit a 2-fold increase in Ir-Ni second-shell interaction revealed by X-ray absorption spectroscopy (XAS), suggesting stronger metal-support interactions. Remarkably, Iremb-NiO with tailored coordination sphere exhibits excellent alkaline OER mass activity and long-term durability (degradation rate: ∼1 mV/h), outperforming commercial IrO2 (∼26 mV/h) and conventional Irsingle-atoms on NiO (∼7 mV/h). Comprehensive operando X-ray absorption and Raman spectroscopies, along with pH-dependence activity tests, identified high-valence atomic Ir sites embedded on the NiOOH surface during the OER followed the lattice oxygen mechanism, thereby circumventing the traditional linear scaling relationships. Moreover, the enhanced Ir-Ni second-shell interaction in Iremb-NiO plays a crucial role in imparting structural rigidity to Ir single-atoms, thereby mitigating Ir-dissolution and ensuring superior OER kinetics alongside sustained durability.

Synergistic effects of feni bimetal-doped biochar on oxygen evolution reaction kinetics: A one-step, low-temperature pyrolysis approach

As the hydrogen energy sector progresses, water electrolysis technology played a crucial role in producing green hydrogen. A major challenge in this endeavor lied in the oxygen evolution reaction (OER), where the overpotential has consistently been high leading to an increase in the energy demand. This study developed a one-step pyrolysis technique to transform metal-supported biomass into FeNi/NC catalysts having enhanced crystallinity and defect sites. This process without activation step using strong acids or bases reduced the operational procedures and the treatment of intermediate products, which reduced the technical difficulty. As the pyrolysis temperature increases, the metal ions in the biochar gradually formed stable metal oxides, which catalyze the alkaline OER and markedly boosted catalytic efficiency. Crucially, the abundance of lattice oxygen and oxygen vacancies in the catalyst played a key role in enhancing the OER kinetics. Notably, the catalyst pyrolyzed at 750 °C demonstrated good performance, with an overpotential of 270 mV at a concentration of 10 mA cm−2 of the density of current, which was superior to RuO2(η10=315 mV) and IrO2(η10=300 mV). Overall, this study reported an approach for the fabrication of high-performance OER catalysts and the strategic utilization of biomass resources for application in clean energy technologies.

Boosting the bifunctional catalytic activity of Co3O4 on silver and nickel substrates for the alkaline oxygen evolution and reduction reactions

Developing an efficient bifunctional catalyst for oxygen reduction (ORR) and evolution reactions (OER) is a crucial step for the wide commercialization of alkaline water electrolyzers. However, a proper assessment and comparison of various catalysts is still challenging due to the different catalyst substrates and loadings. In this work, Co3O4 spinel nanoparticles (NPs) were investigated as a bifunctional catalyst at different substrates of glassy carbon or Ag bulk substrate or Ni particles and with different loadings. For Co3O4 (800 µg cm-2)/Ag electrode, not only the overpotential for ORR was 50 mV lower than the bare Ag electrode, but also the OER overpotential was 40 mV lower than the sole Co3O4. Besides, less than 1% peroxide intermediate was detected during ORR using the rotating ring disc electrode (RRDE) method, suggesting a 4-electron O2 reduction. Tafel slopes of 70 and 60 mV dec‑1 at Co3O4/Ag were obtained for ORR and OER, respectively. The improved bifunctional activity could be attributed to a synergistic effect between Co3O4 and the Ag support. For the loading effect, it is revealed that the number of accessible sites of Ag surface decreases with increasing the Co3O4 loading, as evaluated from lead-underpotential deposition measurements. Interestingly, after running ORR/OER cycles, the surface area increased by 4–6 times. This surface roughening was also confirmed by SEM and EDX. The study was extended to Co3O4+Ni mixed catalyst to validate the effect of the support on this induced synergism. Hence, this work provides a simple route for designing potential effective catalytic interfaces and contributes to unravelling the influence of the substrate and loading on the catalyst activity for water electrolyzers.

Self-supported FeCoNi(OHy)Ox oxy-hydroxide doped with Cr and Cu as robust low-loading catalyst for the alkaline oxygen evolution reaction

Self-supported FeCoNi(OHy)Ox oxy-hydroxides co-doped with Cr and Cu were obtained from a CrFeCoNiCu low ordered high entropy precursor synthesised by electrodeposition onto carbon cloth fibres (act-CrFeCoNiCu/CC). For comparison a dopant-free FeCoNi(OHy)Ox catalyst (act-FeCoNi/CC) was also synthesised following the same route. No heat treatment was performed to retain their low ordered structure. When assessed towards the oxygen evolution reaction (OER) in alkaline electrolyte, act-CrFeCoNiCu/CC and act-FeCoNi/CC catalyst reached a comparable current density of 10 mA cm−2 at ca. 1.6 VRHE (η10 of 380–390 mV). Nevertheless, Cr and Cu co-doping translated into improved stability. Evident degradation was observed during OER for act-FeCoNi/CC after 12 h operating at 100 mA cm−2, whereas no signs of degradation were detected for act-CrFeCoNiCu/CC under the same reaction conditions. The latter catalyst even delivered a constant potential for 160 h at 50 mA cm−2 aided to the stabilizing effect of Cr and Cu co-doping.

Development of a free-standing flexible electrode for efficient overall water-splitting performance via electroless deposition of iron-nickel-cobalt on polyacrylonitrile-based carbon cloth

Developing cost-effective and highly efficient electrodes for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is crucial, particularly for alkaline OER and HER. Herein, electroless plating of iron-nickel–cobalt (Fe–Ni–Co) electrocatalyst on a flexible polyacrylonitrile (PAN)-based carbon cloth (CC) was performed to synthesize a free-standing catalytic electrode for bifunctional electrocatalysts. The three-dimensional porous backbone of PAN-based CC and the synergistic effect between Fe-Ni-Co and corresponding hydroxides result in outstanding OER and HER activities, that is low overpotentials of 230 and 150 mV at 10 mA cm−2 and Tafel slopes of 63 and 57.1 mV dec–1, respectively. Additionally, a complete alkaline electrolyzer was constructed using Fe-Ni-Co plated PAN-based CC as both the cathode and anode. When operated at 10 mA cm−2, this setup enabled efficient water splitting at a low potential of 1.57 V. This study provides new opportunities for the development of advanced Fe-Ni-Co electrocatalyst with superior bifunctional OER and HER performance and cost-effectiveness that are suitable for integration into PAN-based CC via electroless plating.

Bimetal Metaphosphate/Molybdenum Oxide Heterostructure Nanowires for Boosting Overall Freshwater/Seawater Splitting at High Current Densities.

Exploring excellent non-noble bifunctional electrocatalysts for freshwater/seawater splitting at high current densities has attracted extensive interest owing to strong anodic oxidation and severe chloride corrosion challenges. Herein, hierarchical bimetal Ni-Co metaphosphate/molybdenum oxide heterostructure nanowires (NiCoMoPO) are rationally designed and fabricated to efficiently boost oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline freshwater/seawater, where the favorable electronic structure from heterostructures, signified by X-ray absorption spectra, endows NiCoMoPO with the enhanced intrinsic activity, while its hierarchical nanowire structure and heterostructures provide abundant active sites. Additionally, the PO3 - improves the chloride-corrosion resistance and efficiently facilitates the OER kinetics verified by theoretical and experimental studies. Therefore, NiCoMoPO drives 1000mA cm-2 at low overpotentials of 467 and 442mV for OER and HER in alkaline freshwater respectively, as well as a small cell voltage of 2.135V for overall freshwater splitting with robust durability of 300h. Impressively, due to the strong corrosion resistance, at 500mA cm-2 of overall seawater splitting, NiCoMoPO maintains almost 2.096V for 1200h, indicating promising practical applications. This work sheds light on the rational design and fabrication of outstanding electrocatalysts at high current densities of seawater/freshwater splitting.

Green mediated sol-gel synthesis of MxCu1-xO (M = La,Ce x = 0.02–0.06) as an efficient catalyst for electrocatalytic oxygen evolution reaction

The imperative for advancing contemporary human society lies in the essential requirement to create energy generation systems that are sustainable, environmentally friendly, and exceptionally efficient. The development of efficient electrocatalysts, that are environmentally benign, economically viable and easily available, for alkaline oxygen evolution reaction is a significant research area in this regard. The present study focuses on a green mediated sol–gel auto-combustion process for the synthesis of lanthanum and cerium doped copper oxide nanoparticles with excellent electrocatalytic activity. Citric acid and polyols enriched lemon juice serves as the medium for the synthesis of various metal doped copper oxide nanoparticles. The extensive electrochemical studies using these catalysts reveals that, among the various doped samples, 5% lanthanum and 5% cerium doped catalysts exhibited the best performance in oxygen evolution reaction. Doping was found to enhance electrical conductivity and create oxygen vacancies, which enhanced the electrocatalytic activity of the catalysts. Specifically, the 5% lanthanum-doped copper oxide showed an overpotential of 340 mV, while the cerium-doped material exhibited an overpotential of 337 mV at a current density of 10 mA cm−2 in 1 M KOH. Moreover, the lanthanum-doped sample displayed a Tafel slope of 49 mV dec−1, whereas the cerium-doped sample had a Tafel slope of 60 mV dec−1 with better durability. Additionally, the chronopotentiometric studies revels the stability and long-term performance of LCO5 and CCO5, maintaining consistent potential of 1.58 V throughout 5 h at a current density of 10 mA cm−2. This study is conclusive evidence that the incorporation of rare earth elements improves the conductivity and overpotential of pristine copper oxide nanoparticles, making them highly effective in the oxygen evolution reactions.