Oxygen Evolution Reaction Mechanism Research Articles

Exploring the Water Oxidation Catalytic Activity of a Mn-Based Magnetic Metal-Organic Framework: The Role of Proton Conductivity and Oxygen Evolution Reaction Overpotential.

The present work evaluates the water oxidation catalytic activity of a Mn-based metal-organic framework (MOF), which we envisioned to reduce the oxygen evolution reaction (OER) overpotential because of its high electrical conductivity, facilitated by solvent-encapsulated structural features. The presence of Mn centers induces interesting magnetic features in the MOF, which exhibits impressive cryogenic magnetic refrigeration with a ΔSM value of 29.94 J kg-1 K-1 for a field change of ΔH = 5T at 2.3 K. To the best of our knowledge, the ΔSM value of the current system ranked the highest position among the published examples. The crystal structure aligns perfectly with the thematic expectations and features as many as ten metal-coordinated water molecules, forming an extensive web of a hydrogen-bonded network while facing toward the porous channel filled with another set of much-anticipated entrapped lattice water molecules. Such structural features are expected to manifest high proton conductivity, and detailed investigation indeed yields the best value for the system at 1.57 × 10-4 S/cm at 95% humidity and 85 °C. In order to evaluate the thematic notion of a one-to-one relationship between OER and improved electrical conductivity, extensive electrocatalytic water splitting (WS) investigations were carried out. The final results show highly encouraging WS ability of the Mn-MOF, showing the electrocatalytic surface area value of the active species as 0.0686 F/g with a turnover frequency value of 0.043 [(mol. O2) (mol. Mn-MOF)-1 s-1]. Another fascinating aspect of the current communication is the excellent synergy observed between the experimental WS outcomes and the corresponding theoretical data calculated using density functional theory (DFT). Consequently, a plausible mechanism of the overall OER and the role of the Mn-MOF as a water oxidation catalyst, along with the importance of water molecules, have also been derived from the theoretical calculations using DFT.

Sonication-Induced Boladipeptide-Based Metallogel as an Efficient Electrocatalyst for the Oxygen Evolution Reaction.

Bioinspired, self-assembled hybrid materials show great potential in the field of energy conversion. Here, we have prepared a sonication-induced boladipeptide (HO-YF-AA-FY-OH (PBFY); AA = Adipic acid, F = l-phenylalanine, and Y = l-tyrosine) and an anchored, self-assembled nickel-based coordinated polymeric nanohybrid hydrogel (Ni-PBFY). The morphological studies of hydrogels PBFY and Ni-PBFY exhibit nanofibrillar network structures. XPS analysis has been used to study the self-assembled coordinated polymeric hydrogel Ni-PBFY-3, with the aim of identifying its chemical makeup and electronic state. XANES and EXAFS analyses have been used to examine the local electronic structure and coordination environment of Ni-PBFY-3. The xerogel of Ni-PBFY was used to fabricate the electrodes and is utilized in the OER (oxygen evolution reaction). The native hydrogel (PBFY) contains a gelator boladipeptide of 15.33 mg (20 mmol L-1) in a final volume of 1 mL. The metallo-hydrogel (Ni-PBFY-3) is prepared by combining 15.33 mg (20 mmol L-1) of boladipeptide (PBFY) with 3 mg (13 mmol L-1) of NiCl2·6H2O metal in a final volume of 1 mL. It displays an ultralow Tafel slope of 74 mV dec-1 and a lower overpotential of 164 mV at a 10 mA cm-2 current density in a 1 M KOH electrolyte, compared to other electrocatalysts under the same experimental conditions. Furthermore, the Ni-PBFY-3 electrocatalyst has been witnessed to be highly stable during 100 h of chronopotentiometry performance. To explore the OER mechanism in an alkaline medium, a theoretical calculation was carried out by employing the first-principles-based density functional theory (DFT) method. The computed results obtained by the DFT method further confirm that the Ni-PBFY-3 electrocatalyst has a high intrinsic activity toward the OER, and the value of overpotential obtained from the present experiment agrees well with the computed value of the overpotential. The biomolecule-assisted electrocatalytic results provide a new approach for designing efficient electrocatalysts, which could have significant implications in the field of green energy conversion.

Shifting the Oxygen-Evolution Reaction Pathway via Cation Engineering to Activate Lattice Oxygen in Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) as promising electrocatalysts have been widely studied, but their performance is limited by conductivity and coordinating saturation. This study proposes a cationic (V) modification strategy and evaluates its effect on the electrocatalytic performance of CoFe-MOF nanosheet arrays. The optimal V-CoFe-MOF/NF electrocatalyst exhibits excellent oxygen-evolution reaction (OER)/hydrogen-evolution reaction (HER) performance (231 mV at 100 mA cm-2/86 mV at 10 mA cm-2) in alkaline conditions, with its OER durability exceeding 400 h without evident degradation. Furthermore, as a bifunctional electrocatalyst for water splitting, a small cell voltage is achieved (1.60 V at 10 mA cm-2). The practicability of the catalyst is further evaluated by membrane electrode assembly (MEA), showing outstanding activity (1.53 V at 10 mA cm-2) and long-term stability (at 300 mA cm-2). Moreover, our results reveal the apparent reconstruction properties of V-CoFe-MOF/NF in alkaline electrolytes, where the partially dissolved V promotes the formation of more active β-MOOH. The mechanism study shows the OER mechanism shifts to a lattice oxygen oxidation mechanism (LOM) after V doping, which directly avoids complex multistep adsorption mechanism and reduces reaction energy. This study provides a cation mediated strategy for designing efficient electrocatalysts.

In situ exploration of oxygen electrocatalysis using core-shell nanostructure-enhanced Raman spectroscopy

Advancements in fuel cells and water electrolyzers have significantly bolstered the utilization of hydrogen energy. Notably, the oxidation and reduction processes of oxygen at the electrode—termed oxygen evolution reaction (OER) and oxygen reduction reaction (ORR)—manifest sluggish reaction kinetics, thus requiring noble metals as catalysts, which considerably impedes system efficiency and cost. The imperative for enhancing reaction rates and diminishing overpotential necessitates the development of effective catalysts, which strongly depends on the mechanistic understanding of these reactions at the molecular level. Therefore, this review summarizes our recent efforts in utilizing in situ enhanced Raman spectroscopy, especially the borrowing surface-enhanced Raman spectroscopy (SERS) strategy, shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), and the SHINERS-satellite strategy, to capture oxygen intermediate species as a bridge to investigate the molecular mechanisms of OER and ORR. Combining in situ SERS with other characterization techniques and theoretical simulation, the structural evolution of active sites and intermediates, including ∗OOH, ∗OH, ∗OO, etc., during OER/ORR has been monitored under reaction conditions, and the reaction mechanisms together with structure-activity correlations have been identified at the molecular level. These findings may provide a pivotal scientific foundation towards the discovery of better materials for electrochemical hydrogen energy.

Bifunctional mechanism of oxygen evolution reaction and oxygen reduction reaction induced by surface reconstruction in Perovskite electrocatalysts

Elucidation of the relationship among crystal structure, material compositions, and electrocatalytic performance is beneficial to the design of electrocatalysts with high activity. Specially, for bifunctional electrocatalysts, there is a lack of the unified understanding of oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) mechanisms. Based on the first-principles calculations, LaCoO3 surface reconstructions with different OH coverage under OER/ORR condition are determined. Thereby, the different reaction pathways for OER and ORR with the cooperation of Co and O sites are revealed, under which Co and lattice O sites are activated dynamically, and an overpotential of 0.35 V for the OER and 0.44 V for the ORR are obtained. Furthermore, the octahedra lattice distortion-related bifunctional mechanism (DRBM) is proposed from electron structure analysis, and the bifunctional activity of different B-site doped LaCoO3 (LaCoMO3) are studied. Based on this mechanism, we find that OER, ORR, and their bifunctional activity of LaCoMO3 all exhibit a volcano trend as a function of the O-B-O bond angle formed by Co and lattice oxygen. Consequently, we predict that Mn, Cr, Fe, and Ti doped LaCoO3 electrocatalysts exhibit remarkable bifunctional activity, which is corroborated by the reported experimental results.

Efficient chlorine evolution of CuO modified RuO2 electrode and its application in preparation of electrochemical disinfectant

Electrochemical chlorine evolution reaction (CER) is one of the most important practical applications of electrochemical reaction, which can be used for electrochemical disinfection. The electrochemical disinfectant of acidic electrolyzed water (AEW) is obtained by electrolyzing extremely dilute chlorine-containing solution in ion-exchange membrane electrolyzer. In the anode area, HClO is produced by CER, which has a strong bactericidal effect. Due to the low concentration of chloride ion, it is necessary to improve the CER selectivity of the electrode in order to improve the efficiency of chlorine electrolysis. In this paper, CuO/RuO2 electrode was prepared by the two-step thermal decomposition method, and the surface morphology and electronic structure of RuO2 electrode were modified. Compared with the ordinary RuO2 electrode, the CER activity of CuO/RuO2 electrode is improved. For the oxygen evolution reaction (OER), the activity of CuO/RuO2 electrode is significantly lower than that of RuO2 electrode. The CER mechanism of CuO/RuO2 electrode is the second electron transfer, and the OER mechanism is the formation and transformation of OHads. The potential difference between CER and OER of CuO/RuO2-3 electrode is 105 mV, which is 52 mV higher than that of RuO2 electrode, so the selectivity of CER of CuO/RuO2 electrode is remarkably improved. During the preparation of AEW, the HClO of AEW2 (prepared by CuO/RuO2-3 electrode) is 0.72 mmol/L, which is 2.5 times that of AEW1 (prepared by RuO2 electrode). In the sterilization experiments on E. coli and B. subtilis, the germicidal efficacy of AEW2 (3.71 and 2.99 log10 CFU/mL) is obviously superior to that of AEW1 (0.76 and 0.61 log10 CFU/mL).

Tracking the role of compressive strain in bowl-Like Co-MOFs structural evolution in water oxidation reaction

Dynamic structural evolution of catalyst active sites is crucial to for transition metal-catalyzed oxygen evolution reaction (OER). Yet, the elucidation of their mechanism behind the compressive-strain-induced reconstruction during OER process remains enigmatic. Here, we construct a bowl-like cobalt-based metal-organic frameworks (BL-Co-MOFs) catalyst with compressive strain to investigate the effect of strain on the structural evolution process and the OER mechanism. In situ techniques directly observe that compressive strain exists in the reconstruction of the potential-driven CoOOH-like active phase with contractile interatomic CoCo distance, promoting a direct OO radical coupling over the Co sites (Co−O−O−Co) during the OER process. This disrupts the constrains of the inherent linear scaling relationship and achieves the kinetic-faster oxide path mechanism (OPM) during OER process. Consequently, the BL-Co-MOFs exhibit a huge mass activity of 12516 A gmetal−1 and a large turnover frequency of 6888 h−1 at a low overpotential of 275 mV (300 mA cm−2).

Introducing phosphorus into spinel nickel ferrite to enhance lattice oxygen participation towards water oxidation electrocatalysis

Oxygen evolution reaction (OER) restricts the efficiency of overall water splitting due to its complex transfer process and sluggish intrinsic kinetics. The novel lattice oxygen oxidation mechanism (LOM) could lift the theoretical scaling limits of the traditional adsorbate evolution mechanism (AEM), but increasing the participation of lattice oxygen still remains a great challenge. Herein, we introduce phosphorus into spinel nickel ferrite as electrocatalyst with an overpotential of 264 mV at 10 mA cm−2 towards water oxidation. Experimental results confirm the enhanced participation of lattice oxygen for OER in P-NiFe2O4. Further theoretical modelling reveals that the incorporated phosphorus results in an upshift of O 2p band center relative to Fermi level and enhances hybridization of the metal-oxygen bond, thus facilitating LOM and accelerating the OER process on spinel NiFe2O4. This work provides some deep insights into the OER mechanism and a sound strategy for improving the electrocatalytic activity of spinel oxides.

Stabilizing Lattice Oxygen through Mn Doping in NiCo2O4-δ Spinel Electrocatalysts for Efficient and Durable Acid Oxygen Evolution.

Design the electrocatalysts without noble metal is still a challenge for oxygen evolution reaction (OER) in acid media. Herein, we reported the manganese (Mn) doping method to decrease the concentration of oxygen vacancy (VO) and form the Mn-O structure adjacent octahedral sites in spinel NiCo2O4-δ (NiMn1.5Co3O4-δ), which highly enhanced the activity and stability of spinel NiCo2O4-δ with a low overpotential (η) of 280 mV at j=10 mA cm-2 and long-term stability of 80 h in acid media. The isotopic labelling experiment based on differential electrochemical mass spectrometry (DEMS) clearly demonstrated the lattice oxygen in NiMn1.5Co3O4-δ is more stable due to strong Mn-O bond and shows synergetic adsorbate evolution mechanism (SAEM) for acid OER. Density functional theory (DFT) calculations reveal highly increased oxygen vacancy formation energy (EVO) of NiCo2O4-δ after Mn doping. More importantly, the highly hydrogen bonding between Mn-O and *OOH adsorbed on adjacent Co octahedral sites promote the formation of *OO from *OOH due to the greatly enhanced charge density of O in Mn substituted sites.

Recent Advancements on Spin Engineering Strategies for Highly Efficient Electrocatalytic Oxygen Evolution Reactions.

Oxygen evolution reaction (OER) is a widely employed half-electrode reaction in oxygen electrochemistry, in applications such as hydrogen evolution, carbon dioxide reduction, ammonia synthesis, and electrocatalytic hydrogenation. Unfortunately, its slow kinetics limits the commercialization of such applications. It is therefore highly imperative to develop highly robust electrocatalysts with high activity, long-term durability, and low noble-metal contents. Previously intensive efforts have been made to introduce the advancements on developing non-precious transition metal electrocatalysts and their OER mechanisms. Electronic structure tuning is one of the most effective and interesting ways to boost OER activity and spin angular momentum is an intrinsic property of the electron. Therefore, modulation on the spin states and the magnetic properties of the electrocatalyst enables the changes on energy associated with interacting electron clouds with radical absorbance, affecting the OER activity and stability. Given that few review efforts have been made on this topic, in this review, the-state-of-the-art research progress on spin-dependent effects in OER will be briefed. Spin engineering strategies, such as strain, crystal surface engineering, crystal doping, etc., will be introduced. The related mechanism for spin manipulation to boost OER activity will also be discussed. Finally, the challenges and prospects for the development of spin catalysis are presented. This review aims to highlight the significance of spin engineering in breaking the bottleneck of electrocatalysis and promoting the practical application of high-efficiency electrocatalysts.

Research Advances of Non-Noble Metal Catalysts for Oxygen Evolution Reaction in Acid.

Water splitting is an important way to obtain hydrogen applied in clean energy, which mainly consists of two half-reactions: hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, the kinetics of the OER of water splitting, which occurs at the anode, is slow and inefficient, especially in acid. Currently, the main OER catalysts are still based on noble metals, such as Ir and Ru, which are the main active components. Hence, the exploration of new OER catalysts with low cost, high activity, and stability has become a key issue in the research of electrolytic water hydrogen production technology. In this paper, the reaction mechanism of OER in acid was discussed and summarized, and the main methods to improve the activity and stability of non-noble metal OER catalysts were summarized and categorized. Finally, the future prospects of OER catalysts in acid were made to provide a little reference idea for the development of advanced OER catalysts in acid in the future.

Tuning Electrocatalytic Water Oxidation Activity: Insights from the Active-Site Distance in LnCu6 Clusters.

Atomically precise metal clusters serve as a unique model for unraveling the intricate mechanism of the catalytic reaction and exploring the complex relationship between structure and activity. Herein, three series of water-soluble heterometallic clusters LnCu6, abbreviated as LnCu6-AC (Ln = La, Nd, Gd, Er, Yb; HAC = acetic acid), LnCu6-IM (Ln = La and Nd; IM = Imidazole), and LnCu6-IDA (Ln = Nd; H2IDA = Iminodiacetic acid) are presented, each featuring a uniform metallic core stabilized by distinct protected ligands. Crystal structure analysis reveals a triangular prism topology formed by six Cu2+ ions around one Ln3+ ion in LnCu6, with variations in Cu···Cu distances attributed to different ligands. Electrocatalytic oxygen evolution reaction (OER) shows that these different LnCu6 clusters exhibit different OER activities with remarkable turnover frequency of 135s-1 for NdCu6-AC, 79s-1 for NdCu6-IM and 32s-1 for NdCu6-IDA. Structural analysis and Density Functional Theory (DFT) calculations underscore the correlation between shorter Cu···Cu distances and improves OER catalytic activity, emphasizing the pivotal role of active-site distance in regulating electrocatalytic OER activities. These results provide valuable insights into the OER mechanism and contribute to the design of efficient homogeneous OER electrocatalysts.

Theoretical study on oxygen evolution reaction mechanism of double rare earth europium-doped graphene under hydroxyl modification in alkaline environment

The development and design of high performance OER catalyst is the key to electrocatalysis technology. Herein, based on density functional theory (DFT), the oxygen evolution reaction mechanism of double rare earth europium-doped graphene under hydroxyl modification in alkaline environment has been systematically studied. Through thermodynamic and kinetic stability analysis, and the optimal reaction path and different adsorption sites of intermediates were compared. Four catalysts with good catalytic activity for OER reaction were selected. The results show that when the two hydroxyl groups are modified, the overpotentials on the optimal pathway for the four catalyst configurations are 0.54 V, 0.50 V, 0.54 V, and 0.61 V, respectively. These catalysts demonstrate excellent catalytic activity for the oxygen evolution reaction (OER). Moreover, these catalysts have good electrical conductivity, and the active site and adsorption intermediates can be stably bonded together. In addition, the scaling relationship between oxygen adsorption free energy and overpotential is described. This work may provide new insights and guidance for future research on rare-earth atom-based OER catalysts.

Catalytic Activity and Electrochemical Stability of Ru1-xMxO2 (M = Zr, Nb, Ta): Computational and Experimental Study of the Oxygen Evolution Reaction.

We use computations and experiments to determine the effect of substituting zirconium, niobium, and tantalum within rutile RuO2 on the structure, oxygen evolution reaction (OER) mechanism and activity, and electrochemical stability. Calculated electronic structures altered by Zr, Nb, and Ta show surface regions of electron density depletion and accumulation, along with anisotropic lattice parameter shifts dependent on the substitution site, substituent, and concentration. Consistent with theory, X-ray photoelectron spectroscopy experiments show shifts in binding energies of O-2s, O-2p, and Ru-4d peaks due to the substituents. Experimentally, the substituted materials showed the presence of two phases with a majority phase that contains the metal substituent within the rutile phase and a second, smaller-percentage RuO2 phase. Our experimental analysis of OER activity shows Zr, Nb, and Ta substituents at 12.5 atom % induce lower activity relative to RuO2, which agrees with computing the average of all sites; however, Zr and Ta substitution at specific sites yields higher theoretical OER activity than RuO2, with Zr substitution suggesting an alternative OER mechanism. Metal dissolution predictions show the involvement of cooperative interactions among multiple surface sites and the electrolyte. Zr substitution at specific sites increases activation barriers for Ru dissolution, however, with Zr surface dissolution rates comparable to those of Ru. Experimental OER stability analysis shows lower Ru dissolution from synthesized RuO2 and Zr-substituted RuO2 compared to commercial RuO2 and comparable amounts of Zr and Ru dissolved from Zr-substituted RuO2, aligned with our calculations.

Stabilizing Lattice Oxygen through Mn Doping in NiCo2O4−d Spinel Electrocatalysts for Efficient and Durable Acid Oxygen Evolution

Design the electrocatalysts without noble metal is still a challenge for oxygen evolution reaction (OER) in acid media. Herein, we reported the manganese doping method to decrease the concentration of oxygen vacancy (Vo) and form the Mn−O structure adjacent octahedral sites in spinel NiCo2O4−δ (NiMn1.5Co3O4−δ), which highly enhanced the activity and stability of spinel NiCo2O4−δ with a low overpotential (η) of 280 mV at j = 10 mA cm−2 and long‐term stability of 80 h in acid media. The isotopic labelling experiment based on differential electrochemical mass spectrometry (DEMS) clearly demonstrated the lattice oxygen in NiMn1.5Co3O4−δ is more stable due to strong Mn‐O bond and synergetic adsorbate evolution mechanism (SAEM) for acid OER. Density functional theory (DFT) calculations reveal highly increased oxygen vacancy formation energy (EVO) of NiCo2O4−δ after Mn doping. More importantly, the highly hydrogen bonding between Mn−O and *OOH adsorbed on adjacent Co octahedral sites promote the formation of *OO from *OOH due to the greatly enhanced charge density of O in Mn substituted sites.

Recent Advances in Iridium-based Electrocatalysts for Acidic Electrolyte Oxidation.

Ongoing research to develop advanced electrocatalysts for the oxygen evolution reaction (OER) is needed to address demand for efficient energy conversion and carbon-free energy sources. In the OER process, acidic electrolytes have higher proton concentration and faster response than alkaline ones, but their harsh strongly acidic environment requires catalysts with greater corrosion and oxidation resistance. At present, iridium oxide (IrO2 ) with its strong stability and excellent catalytic performance is the catalyst of choice for the anode side of commercial PEM electrolysis cells. However, the scarcity and high cost of iridium (Ir) and the unsatisfactory activity of IrO2 hinder industrial scale application and the sustainable development of acidic OER catalytic technology. This highlights the importance of further research on acidic Ir-based OER catalysts. In this review, recent advances in Ir-based acidic OER electrocatalysts are summarized, including fundamental understanding of the acidic OER mechanism, recent insights into the stability of acidic OER catalysts, highly efficient Ir-based electrocatalysts, and common strategies for optimizing Ir-based catalysts. The future challenges and prospects of developing highly effective Ir-based catalysts are also discussed.

Revolutionizing energy evolution: SnS-Sn2S3 layered structures as exceptional electrocatalytic materials for H2 and O2 generation

In this paper, we prepared the SnS-Sn2S3 layered structure using the in-situ solvothermal method for hydrogen evolution (HER) and oxygen evolution reaction (OER). XRD and HRTEM confirm the successful synthesis of the orthorhombic crystal structure of the SnS-Sn2S3. Further, SEM images demonstrate the layered shape of the SnS-Sn2S3 nanostructure, promoting the formation of more active sites on the surface for better electrocatalytic activities. Interestingly, during OER investigation, the SnS-Sn2S3 catalyst depicts an overpotential of 359 mV (10 mA cm−2) and a Tafel slope of 90.1 mV dec-1. However, during HER investigation, the SnS-Sn2S3 catalyst describes an overpotential of 162 mV (-10 mA cm−2) and a Tafel slope of 107.6 mV dec-1. Moreover, the SnS-Sn2S3 catalyst unveils superb stability for 2.3 h at 10 mA cm−2 for OER and 4.0 h at −10 mA cm−2 for HER. The OER and HER reaction mechanisms were also discussed to explore the kinetics rate of SnS-Sn2S3 catalyst.

Few-layer MoAlB nanosheets with Al vacancies enhanced hydroxyl adsorption for improved water oxidation kinetics

Few-layer metal borides (MBenes) have attracted much attention in electrocatalytic energy conversion due to the unique physical features, but the present studies are confined to the related bulk materials and the structure-activity relationship is unclear. Here, we successfully synthetized a few-layer exfoliated MoAlB (denoted as EMAB) material as an oxygen evolution reaction (OER) catalyst through a modified etching and exfoliation method to remove the Al atoms and separate the layers. The enhanced hydroxyl adsorption and reduced surface valence of Mo are responsible for the improved OER activity and stability. Density functional theory simulations indicate the hydroxyl adsorption sites are adjusted when removing the Al atoms. The reactive interface for the MAB is the Al layer, while introducing Al vacancies, the hydroxyls prefer to be firstly adsorbed on the Mo sites, and further adsorbed on Al sites, so the energy barrier is largely reduced to accelerate the reaction. This work expands the OER application and mechanism study of MBenes.

Antagonism effect of residual S triggers the dual-path mechanism for water oxidation

Transition metal chalcogenides (TMCs) are recognized as pre-catalysts, and their (oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation. However, understanding the role of the residual chalcogen in the reconstructed layer is lacking in detail, and the corresponding catalytic mechanism remains controversial. Here, taking Cu1−xCoxS as a platform, we explore the regulating effect and existence form of the residual S doped into the reconstructive layer for oxygen evolution reaction (OER), where a dual-path OER mechanism is proposed. First-principles calculations and operando 18O isotopic labeling experiments jointly reveal that the residual S in the reconstructive layer of Cu1−xCoxS can wisely balance the adsorbate evolution mechanism (AEM) and lattice oxygen oxidation mechanism (LOM) by activating lattice oxygen and optimizing the adsorption/desorption behaviors at metal active sites, rather than change the reaction mechanism from AEM to LOM. Following such a dual-path OER mechanism, Cu0.4Co0.6S-derived Cu0.4Co0.6OSH not only overcomes the restriction of linear scaling relationship in AEM, but also avoids the structural collapse caused by lattice oxygen migration in LOM, so as to greatly reduce the OER potential and improved stability.

Ir Single Atoms Boost Metal-Oxygen Covalency on Selenide-Derived NiOOH for Direct Intramolecular Oxygen Coupling.

This investigation probes the intricate interplay of catalyst dynamics and reaction pathways during the oxygen evolution reaction (OER), highlighting the significance of atomic-level and local ligand structure insights in crafting highly active electrocatalysts. Leveraging a tailored ion exchange reaction followed by electrochemical dynamic reconstruction, we engineered a novel catalytic structure featuring single Ir atoms anchored to NiOOH (Ir1@NiOOH). This novel approach involved the strategic replacement of Fe with Ir, facilitating the transition of selenide precatalysts into active (oxy)hydroxides. This elemental substitution promoted an upward shift in the O 2p band and intensified the metal-oxygen covalency, thereby altering the OER mechanism toward enhanced activity. The shift from a single-metal site mechanism (SMSM) in NiOOH to a dual-metal-site mechanism (DMSM) in Ir1@NiOOH was substantiated by in situ differential electrochemical mass spectrometry (DEMS) and supported by theoretical insights. Remarkably, the Ir1@NiOOH electrode exhibited exceptional electrocatalytic performance, achieving overpotentials as low as 142 and 308 mV at current densities of 10 and 1000 mA cm-2, respectively, setting a new benchmark for the electrocatalysis of OER.