Electrocatalysts For Oxygen Evolution Reaction Research Articles

Dynamic hydrogen bubble template electrodeposition of a self-supported Co-P electrocatalyst for efficient alkaline oxygen evolution reaction

The development of efficient, inexpensive, and earth-abundant electrocatalysts for the oxygen evolution reaction (OER) represents a significant challenge for the large-scale production of hydrogen. The primary obstacle to the advancement of OER is the necessity for a considerably higher overpotential than the theoretical oxygen evolution potential, due to the sluggish kinetics of the electron transfer reaction, which involves a large amount of thermodynamic energy. In this article, amorphous and cauliflower-like Co-P electrocatalysts were in situ grown on nickel foam by dynamic hydrogen bubble template (DHBT) electrodeposition method. The Co-P electrocatalyst with Co/P ratio optimal presented excellent electrocatalytic activities with a low overpotential of 239 mV for OER at 10 mA·cm−2 and long-term stability in 1.0 M KOH. The outstanding OER performance of the catalyst is mainly attributed the synergistic effect of amorphous and cauliflower-like structure, superhydrophilicity surface, and the electronic regulation by adjusting the atomic ratio of Co to P. This research will bring fresh ideas and strategies for developing novel simple, affordable, and efficient electrocatalysts to boost OER kinetics.

Orange peel derived activated carbon supported Ni–Co3O4 as an efficient electrocatalyst for oxygen evolution and reduction reaction in alkaline media

This study focuses on the development of a cost-effective electrocatalyst with excellent activity and stability for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR), which is crucial for water electrolysis and fuel cell technologies. Waste orange peel is utilized as a carbon precursor to synthesize biomass-derived activated carbon (OPAC) with a unique three-dimensional sheet-like microstructure. Subsequently, a simple hydrothermal method is employed to modify the OPAC by introducing Ni-doped Co3O4, leading to the formation of a Ni–Co3O4/OPAC hybrid. We propose the Ni–Co3O4/OPAC hybrid as a highly efficient bifunctional electrocatalyst for both OER and ORR. Co3O4/OPAC and Co3O4 catalysts are also prepared for comparison. Remarkably, the Ni–Co3O4/OPAC hybrid exhibits significantly enhanced OER activity compared to Co3O4/OPAC and Co3O4 catalysts. It demonstrates a lower overpotential of 360 mV and a lower Tafel slope of 55.47 mV/dec, indicative of more efficient electrochemical performance. Moreover, in the ORR analysis, the Ni–Co3O4/OPAC hybrid displays a two-step pathway and achieves a higher ORR limiting current density compared to the Co3O4/OPAC and Co3O4 catalysts. These results highlight the synergistic effects of Ni and Co species, along with the unique properties of the OPAC support, which contribute to the enhanced activity, stability, and electron transfer characteristics of the Ni–Co3O4/OPAC hybrid. Furthermore, the improved electrical conductivity of the Ni–Co3O4/OPAC hybrid makes it a promising candidate for applications in metal-air batteries and other energy conversion devices. The utilization of waste orange peel as a carbon precursor and the facile synthesis method demonstrate the potential for cost-effective and sustainable electrocatalyst production. Overall, the Ni–Co3O4/OPAC hybrid represents a significant advancement in electrocatalyst design and holds promise for advancing the field of energy conversion and storage.

Surface-selenization formed NiFe MOF@NiSex heterogeneous arrays for enhanced oxygen evolution and methanol electrooxidation

Designing reasonable electrocatalysts for oxygen evolution reaction (OER) is a vital issue for water splitting to hydrogen. We report a surface-selenization of NiFe MOF-74 formed NiFe MOF@NiSex arrays through the simple solvothermal method. The NiFe MOF@NiSex heterostructures greatly enhance the charge transfer and cooperativity of active sites and result in strong adsorption capacity for OH– to strongly boost the OER and MOR process. The optimized electrode shows the highly efficient catalytic activity for OER with a low onset potential of 1.31 V vs. RHE and small Tafel slopes of 38.3 mV dec−1 in alkaline media. And it shows the extremely low overpotential of 229 and 329 mV at 100 and 500 mA cm−2. Moreover, its current density can reach more than 500 mA cm−2 at the potentials of 1.645 V vs. RHE at 0.8 M methanol/1 M KOH electrolyte, and it shows very good long-term stability at large current density. This heterogeneous arrays electrocatalysts may play a positive role in energy conversion and storage process.

Understanding the electrocatalytic role of magnesium doped bismuth copper titanate (BCTO) in oxygen evolution reaction

Designing high-efficiency electrocatalysts for water oxidation has become increasingly important in the catalysis field owing to its implications for renewable energy production and storage. The production of hydrogen (H2) from water is hampered by the very sluggish kinetics of the water-splitting process. Enhancement of effective oxygen evolution reaction (OER) electrocatalysts is also required to understand the primary barrier to OER. This article investigates the electrochemical activity of magnesium-doped bismuth copper titanate (Mg-BCTO) as an efficient catalyst for the OER in water electrolysis, a critical step in hydrogen production for sustainable energy. The synthesized materials, including various stoichiometries of Mg-doped BCTO, undergo thorough physical and electrochemical characterization using XRD, FT-IR, Raman, SEM, TEM, XPS, CV, EIS, and Tafel polarization analyses. Remarkably, Mg0.1 doped BCTO demonstrates superior performance, achieving a current density of 10 mA cm−2 at a very low overpotential (η10) of 265 mV and with a Tafel slope of 92 mV dec−1. This finding not only highlights the electrocatalytic efficiency of Mg doped BCTO but also positions it as a promising model for the development of highly active and stable water oxidizing catalysts, contributing to the advancement of clean energy technologies.

Dodecylamine‐Assisted Hydrothermal Synthesis of Carbon‐Supported Ultrafine IrRu Nanoparticles for Oxygen Evolution Electrocatalysis and Overall Water Splitting

AbstractRuthenium (Ru)‐ and iridium (Ir)‐based nanomaterials have always been regarded as efficient electrocatalysts for oxygen evolution reaction (OER) in acidic electrolytes. Herein, we develop a facile dodecylamine‐assisted hydrothermal synthesis for producing carbon‐supported IrRu alloy nanoparticles with controllable Ir/Ru ratios and ultrafine sizes towards high‐efficiency OER and overall water electrolysis. In this strategy, the dodecylamine that serves as a capping and reducing agent enables the final IrRu alloy nanoparticles to possess average sizes <3 nm and high degree of dispersion on carbon substrate. By combining high OER activity of Ru with high acidic robustness of Ir, the as‐prepared IrRu/C nanoparticles at a suitable Ir/Ru ratio of 1/3 show good activity and durability for the OER electrocatalysis and overall water splitting. In specific, the Ir1Ru3/C catalyst exhibits the lowest overpotential of 302 mV at the current density of 10 mA cm−2 and the highest mass activity of 120.5 mA mg−1 at 1.532 V for OER in 0.5 M H2SO4 electrolyte. In addition, a two‐electrode acidic electrolyzer assembled with Ir1Ru3/C at anode and commercial Pt/C at cathode (Pt/C|| Ir1Ru3/C) exhibits a low cell voltage of 1.44 V for achieving the current density of 10 mA cm−2, along with a satisfied 20h durability.

Modulating RuO2 Electrocatalysis via Introducing Lanthanides for Enhanced Acidic Oxygen Evolution

AbstractThe low activity of ruthenium dioxide (RuO2) and the rapid dissolution of the ruthenium (Ru) site during acid oxygen evolution reaction (OER) at high current density restricts its application in proton exchange membrane (PEM) electrolyzers. In this work, a series of rare‐earth (RE) elements doped RuO2 nanorods is developed as high‐performance OER electrocatalysts. X‐ray absorption spectroscopy suggests that RE doping regulates the local coordination environment around Ru sites, lowers the valance of Ru, and shortens the Ru─O─Ru(M) bond length, which enhances structural stability. Among the RE‐RuO2 samples, Sm‐RuO2 exhibits remarkable performance with a low overpotential of 283 mV to reach 100 mA cm−2 and maintained stability for over 140 h at 10 mA cm−2. Moreover, the PEM electrolyzer using Sm‐RuO2 as the anode can be stably operated at 500 mA cm−2 for 15 h. Electrochemical analysis, X‐ray photoelectron spectroscopy, and in situ Raman spectroscopy show that Sm doping lowers the d‐band center, reduces the adsorption energy of O intermediates to enhance the OER activity, and restrains excessive oxidation of Ru sites while stabilizing lattice oxygen during the OER process, thereby enhancing OER stability. This work offers valuable insights into improving the stability of metal oxide catalysts in acidic electrolytes.

Low-Spin Fe3+ Evoked by Multiple Defects with Optimal Intermediate Adsorption Attaining Unparalleled Performance in Water Oxidation.

Electrocatalytic water splitting is long constrained by the sluggish kinetics of anodic oxygen evolution reaction (OER), and rational spin-state manipulation holds great promise to break through this bottleneck. Low-spin Fe3+ (LS, t2g 5eg 0) species are identified as highly active sites for OER in theory, whereas it is still a formidable challenge to construct experimentally. Herein, a new strategy is demonstrated for the effective construction of LS Fe3+ in NiFe-layered double hydroxide (NiFe-LDH) by introducing multiple defects, which induce coordination unsaturation over Fe sites and thus enlarge their d orbital splitting energy. The as-obtained catalyst exhibits extraordinary OER performance with an ultra-low overpotential of 244 mV at the industrially required current density of 500 mA cm-2, which is 110 mV lower than that of the conventional NiFe-LDH with high-spin Fe3+ (HS, t2g 3eg 2) and superior to most previously reported NiFe-based catalysts. Comprehensive experimental and theoretical studies reveal that LS Fe3+ configuration effectively reduces the adsorption strength of the O* intermediate compared with that of the HS case, thereby altering the rate-determining step from (O* → OOH*) to (OH* → O*) of OER and lowering its reaction energy barrier. This work paves a new avenue for developing efficient spin-dependent electrocatalysts for OER and beyond.

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.

An Analysis of the Conceptual and Functional Factors Affecting the Effectiveness of Proton-Exchange Membrane Water Electrolysis

Hydrogen has the potential to decarbonize the energy and industrial sectors in the future, mainly if it is generated by water electrolysis. The proton-exchange membrane water electrolysis (PEMWE) system is regarded as a propitious technology to produce green hydrogen from water using power supplied by renewable energy sources. It offers many benefits, such as high performance, high proton conductibility, quick response, compact size, and low working temperature. Many conceptual and functional parameters influence the effectiveness of PEM, including temperature, pressure of anode and cathode regions, water content and wideness of the layer, and cathode and anode exchange current density. In addition, the anodic half-reaction (known as the oxygen evolution reaction (OER)) and cathodic half-reaction (known as the hydrogen evolution reaction (HER)) perform an important function in the development of PEMWE. The current study aims to present these parameters and discuss their impacts on the performance of PEM. Also, the PEM efficiency is presented. The different methods used to enhance the scattering of OER electrocatalysts and minimize catalyst loading to minimize the price of PEMWE are also highlighted. Moreover, the alternative noble metals that could be used as electrocatalysts in HER and OER to minimize the cost of PEM are reviewed and presented.

Enhanced Electrocatalytic Capacity of Two POM@NH2‐MIL‐101(Fe) Composites for Oxygen Evolution Reaction

AbstractThe development and exploration of efficient bifunctional electrocatalysts for water splitting are in high demand and have garnered significant attention in recent years. Herein, by incorporating the advantages of catalytically active polyoxometalates (POMs) and structural stable metal–organic frameworks (MOFs), two POM@MOFs composite materials, Ni4Mo12@Fe and Co4Mo12@Fe, have been successfully prepared via the encapsulation of POMs anions, [MoV12O30(μ2‐OH)10H2{NiII4(H2O)12}]∙14H2O (noted as Ni4Mo12) and [MoV12O30(μ2‐OH)10 H2{CoII(H2O)3}4]∙12H2O (noted as Co4Mo12), into the cavities of MOFs NH2‐MIL‐101(Fe), respectively. Compared to each individual components, Ni4Mo12@Fe and Co4Mo12@Fe composites, as heterogeneous electrocatalysts, both showed enhanced electrocatalytic capacities for efficient oxygen evolution reaction (OER) under alkaline conditions with overpotentials of 332.64 mV for Ni4Mo12@Fe and 352.64 mV for Co4Mo12@Fe at 10 mA cm−2. Additionally, the enhanced electrocatalytic capacities of these two composites could also achieve towards hydrogen evolution reaction (HER). Such a POMs‐assisted strategy for the formation of POM@MOFs composites, described here, paves a new avenue for the development of highly economical, active nonnoble metal bifunctional electrocatalysts for OER and HER.

High-Entropy Selenides with Tunable Lattice Distortion as Efficient Electrocatalysts for Oxygen Evolution Reaction.

Developing stable and active electrocatalysts is crucial for enhancing the oxygen evolution reaction (OER) efficiency, which sluggish kinetics hinder sustainable hydrogen production. High entropy selenides (HESes) feature with random distribution of multiple metals cations and unique electronic and size effect of Se anion, allowing for precious regulation of their catalytic properties towards high OER activity. In this work, we report a series of high-entropy selenides catalysts with tunable lattice strain for electrocatalytic oxygen evolution. Electrochemical measurements show that the quinary (NiCoMnMoFe)Sex requires only 291 mV to reach 10 mA cm-2 and exhibits a superior stability with negligible current decay during 100 h's continuous operation. By combining experimental measurements and theoretical calculation, the study reveals that the lattice distortion, reflected by the local microstrain near the active site, plays a vital role in boosting the OER activity of HESes.

Regulation of Oxide Pathway Mechanism for Sustainable Acidic Water Oxidation.

The advancement of acid-stable oxygen evolution reaction (OER) electrocatalysts is crucial for efficient hydrogen production through proton exchange membrane (PEM) water electrolysis. Unfortunately, the activity of electrocatalysts is constrained by a linear scaling relationship in the adsorbed evolution mechanism, while the lattice-oxygen-mediated mechanism undermines stability. Here, we propose a heterogeneous dual-site oxide pathway mechanism (OPM) that avoids these limitations through direct dioxygen radical coupling. A combination of Lewis acid (Cr) and Ru to form solid solution oxides (CrxRu1-xO2) promotes OH adsorption and shortens the dual-site distance, which facilitates the formation of *O radical and promotes the coupling of dioxygen radical, thereby altering the OER mechanism to a Cr-Ru dual-site OPM. The Cr0.6Ru0.4O2 catalyst demonstrates a lower overpotential than that of RuO2 and maintains stable operation for over 350 h in a PEM water electrolyzer at 300 mA cm-2. This mechanism regulation strategy paves the way for an optimal catalytic pathway, essential for large-scale green hydrogen production.

Structural Regulation of a Multi-Component Co2P2O7-MoN/NC Electrocatalyst for Efficient Oxygen Evolution Reaction.

Realizing efficient and durable non-precious metal-based electrocatalysts for oxygen evolution reaction (OER) still remains a great challenge. Here, a multi-component composite of Co2P2O7-MoN/NC containing pyrophosphate, nitride, and nitrogen-doped carbon is successfully prepared via a facile two-step synthesis method. Combining the structural regulation between the active metal- and non-metal-based species, Co2P2O7-MoN/NC demonstrates superior activity and durability for OER, requiring an overpotential of 278 mV at a current density of 10 mA cm-2, a Tafel slope of 83.3 mV dec-1, and long-term stability over 100 h in an alkaline solution. Post-characterizations reveal that synergistic effect among stable Co2P2O7, partially dissolved MoN, N-doped carbon, and new-formed CoOOH nanosheets enable structural reconstruction, fast charge transfer, and formation of oxygen-containing intermediates, promoting the OER performance significantly. This work provides a promising pathway to tune multi-components to fabricate efficient transition-metal-based electrocatalysts in energy conversion applications.

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.

Enhancing Oxygen Reduction Reaction Electrocatalytic Performance of Nickel‐Nitrogen‐Carbon Catalysts through Coordination Environment Engineering†

Comprehensive SummarySingle‐atom catalysts (SACs) have attracted significant attention due to their high atomic utilization and tunable coordination environment. However, the catalytic mechanisms related to the active center and coordination environment remain unclear. In this study, we systematically investigated the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalytic activities of NiN4, NiN3, NiN3H2, NiN4X, NiN3X, and NiN3H2X (X denotes axial ligand) through density functional theory (DFT) calculations. This study unveils two distinct reaction pathways for ORR and OER, involving proton‐electron pairs adsorbed from both the solution and the catalyst surface. The overpotential is the key parameter to evaluate the catalytic performance when proton‐electron pairs are adsorbed from the solution. NiN3 and NiN3H2 show promise as pH‐universal bifunctional electrocatalysts for both ORR and OER. On the other hand, when proton‐electron pairs are adsorbed from the catalyst surface, the reaction energy barrier becomes the crucial metric for assessing catalytic activity. Our investigation reveals that NiN3H2 consistently exhibits optimal ORR activity across a wide pH range, regardless of the source of proton‐electron pair (solvent or catalyst surface).

Tracking Water Dissociation on RuO2(110) Using Atomic Force Microscopy and First-Principles Simulations.

The interaction between interfacial water and transition metal oxides is a primary enabling step for the oxygen evolution reaction (OER). RuO2 is a prototypical OER electrocatalyst whose ability to activate interfacial water molecules is essential to its OER activity. We image the dissociation of surface water into OH* and O* on RuO2(110), where * denotes adsorbed species, using atomic force microscopy. Starting from the surface-bound water molecules, which form a one-dimensional network along the rows of Ru surface sites, increasing the oxidative potential strips hydrogen away and transforms the water molecules into OH* and O*. This oxidative step changes the pattern of the adsorbates from one- to two-dimensional. First-principles calculations with interfacial polarization, capacitive charging, and adsorbate interactions attribute this evolution to the cooperative dehydrogenation of adsorbed water and OH* on RuO2. We use these results to map the surface phase diagram of RuO2(110) and provide a quantitative interpretation of its cyclic voltammetry. Our result provides the visualization of the water dissociation on a conductive oxide surface, a critical step in the OER, and demonstrates that the water activation is a collective phenomenon at RuO2(110) electrodes.

Lewis acid sites in hollow cobalt phytate micropolyhedra promote the electrocatalytic water oxidation.

The acid-base microenvironment of the metal center is crucial for constructing advanced oxygen evolution reaction (OER) electrocatalysts. However, the correlation between acidic site and OER performance remains unclear for cobalt-based catalysts. Herein, Lewis acid sites in hollow cobalt phytate micropolyhedra (M-CoPA, M = Cu, Sr) were synthesized by a cation-exchange strategy, and their OER performances were studied systematically. Experimentally, Lewis acid Cu2+ sites with stronger Lewis acidity exhibited superior intrinsic activity and long-term stability in alkaline electrolytes. The spectroscopic and electrochemical studies show Lewis acid sites in hollow cobalt phytate micropolyhedra can modulate the electronic distribution of the adjacent cobalt center and further optimize the adsorption strength of oxygenated species. This study figures out the effect of Lewis acid sites on the OER kinetics and provides an effective way to develop high-efficiency electrocatalysts for energy conversion systems.

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.

Boron doped Fe3S4/Co3S4 decorated with multi-wall carbon nanotubes as an efficient electrocatalyst for oxygen evolution reaction in alkaline media

Designing an exceedingly active and universal electrocatalyst for oxygen evolution reaction is utterly essential for commercial development. Herein, boron-doped cobalt-iron bimetallic sulfide synthesized through an easy single-step hydrothermal route is reported as electrocatalyst. The B-Fe3S4/Co3S4 was further decorated with the multi-wall carbon nano-tubes (MWCNT). The morphology of B-Fe3S4/Co3S4 was sphere like and it was converted to marigold flower-like after decorating it with MWCNT. The catalytic efficiency of Fe3S4/Co3S4 increased by doping with Boron and further increased by decorating with MWCNT. The prepared catalyst B-Fe3S4/Co3S4/MWCNT was tested for oxygen evolution reaction (OER) in alkaline solution and offered 319 mV as overpotential and 60 mV/decas Tafel slope value. In addition to it, the catalyst shows good stability, large Brunauer-Emmett-Teller (BET) surface area (30.24 m2/g), and low value of charge transfer resistance (6.5Ω), indicating that it is efficient catalyst and its high efficiency is associated with its morphology and ternary composite structure. The investigated low cost catalyst is as good as the commercially used high cost noble metal RuO2 catalysts.

Enhanced Heterogeneous Interfacial Coupling of NiCoS@NiCo(CH3COO)x as Efficient and Long-term Stable Electrocatalysts for Oxygen Evolution Reaction

Enhanced Heterogeneous Interfacial Coupling of NiCoS@NiCo(CH₃COO)_<i>x</i> as Efficient and Long-term Stable Electrocatalysts for Oxygen Evolution Reaction