Electrocatalytic Oxygen Evolution Reaction Research Articles

Biogenic Bovine Serum Albumin/Zn3(PO4)2/Cr2O3 hybrid electrocatalyst for improved oxygen evolution reaction

The fabrication of nanostructured protein-inorganic hybrid materials is crucial for the development of advanced multifunctional materials. Protein-inorganic mesoporous composites are gaining attention due to their remarkable properties, including large surface areas and active surface functional groups. We have successfully synthesized mesoporous BSA/Zn3(PO4)2/Cr2O3 catalysts to improve the kinetics of the oxygen evolution reaction (OER) in electrocatalytic water splitting for sustainable energy generation. This approach utilizes BSA in the synthesis process and is environmentally friendly. By adjusting the BSA quantity, we could control the yield of BSA/Zn3(PO4)2/Cr2O3 mesoporous. We employed various techniques, including FE-SEM, XRD, and FTIR, to analyze the morphology and structural characteristics of the biogenic BSA/Zn3(PO4)2/Cr2O3 electrocatalyst. Our comprehensive evaluation of the electrocatalytic OER activity of the BSA/Zn3(PO4)2/Cr2O3 hybrid structure demonstrated its remarkable performance. The biologically synthesized catalyst exhibited exceptional OER efficiency, maintaining a high current density of 10 mA cm−2 at very low overpotentials (only 216 mV) under alkaline conditions. The elongated peptide backbone of BSA significantly facilitated ion and electron transport, contributing to improved OER activity. The synergistic interaction between various amino acids from BSA and the metal ions within Zn3(PO4)2/Cr2O3 can be attributed to this enhancement, highlighting the potential of this hybrid structure in electrocatalytic OER applications.

Effects of Ir‐Incorporation and Nanostructuring in β‐MnO2 for an Enhanced Electrocatalytic Oxygen Evolution Reaction

Effects of Ir‐Incorporation and Nanostructuring in β‐MnO2 for an Enhanced Electrocatalytic Oxygen Evolution Reaction

Lignin-assisted electronic modulation on NiSe/FeOx heterointerface for boosting electrocatalytic oxygen evolution reaction

The development of productive and durable non-precious metal catalysts for the sluggish oxygen evolution reaction (OER) is critical for water splitting. Herein, a novel NiSe-FeOx heterojunction encapsulated in lignin-derived carbon layer (NiSe-FeOx@LC) was synthesized via hydrothermal self-assembly and in-situ pyrolysis. NiSe-FeOx@LC exhibited excellent OER performance with an overpotential of 265 mV at 50 mA·cm−2, a Tafel slope of 83 mV·dec−1, as well as long-term stability. Both experimental and DFT calculation results indicated that the doping of FeOx into NiSe@LC successfully optimized the dual interface structure between NiSe and FeOx, thereby promoted the d-bands orbital hybridization, that facilitated electron transfer. Besides, the carbon coating effectively protected the NiSe-FeOx components from leaching and agglomerating during the reaction. This study provides insight into the significance of lignin-derived carbon-encapsulated metallic catalyst for electrocatalytic OER process.

ZIF‐67 Derived Co‐LDH Nanocubes for Oxygen Evolution Reaction

AbstractTo address the substantial energy needs of the quickly evolving modern civilization, efforts are still needed to provide sustainable renewable energy sources. The electrocatalytic Oxygen evolution reaction (OER) is one of the essential technologies used in the various hydrogen production techniques. ZIF‐67 nanocubes (ZIF‐67 NCs) were synthesized in an aqueous solution and used as sacrificial templates. Cobalt nitrate hexahydrate was added under water bath conditions, resulting in the evolution of numerous small layered layers of cobalt hydroxide. This ultimately led to the formation of multilayered, three‐dimensionally crosslinked Co‐LDH with a porous networked cubic morphology. Hydrolysis of Co2+ at different concentrations produces different degrees of weak acidic environments, and the loose LDH on the cubic structure of the best catalyst, Co‐LDH‐1, exposes more active cobalt sites for the OER, which results in a high electrochemically active surface area, with an overpotential of 354 mV and a Tafel slope of 79.06 mV dec−1 at a current density of 10 mA cm−2, and good stability and low activation under alkaline condition also has good stability and low activation energy. It provides us an easy and practical plan for logically creating ZIF‐derived hydroxide materials, leading to the development of affordable and effective electrocatalysts.

Recent Developments in Nickel-Based Layered Double Hydroxides for Photo(-/)electrocatalytic Water Oxidation.

Layered double hydroxides (LDHs), especially those containing nickel (Ni), are increasingly recognized for their potential in photo(-/)electrocatalytic water oxidation due to the abundant availability of Ni, their corrosion resistance, and their minimal toxicity. This review provides a comprehensive examination of Ni-based LDHs in electrocatalytic (EC), photocatalytic (PC), and photoelectrocatalytic (PEC) water oxidation processes. The review delves into the operational principles, highlighting similarities and distinctions as well as the benefits and limitations associated with each method of water oxidation. It includes a detailed discussion on the synthesis of monolayer, ultrathin, and bulk Ni-based LDHs, focusing on the merits and drawbacks inherent to each synthesis approach. Regarding the EC oxygen evolution reaction (OER), strategies to improve catalytic performance and insights into the structural evolution of Ni-based LDHs during the electrocatalytic process are summarized. Furthermore, the review extensively covers the advancements in Ni-based LDHs for PEC OER, including an analysis of semiconductors paired with Ni-based LDHs to form photoanodes, with a focus on their enhanced activity, stability, and underlying mechanisms facilitated by LDHs. The review concludes by addressing the challenges and prospects in the development of innovative Ni-based LDH catalysts for practical applications. The comprehensive insights provided in this paper will not only stimulate further research but also engage the scientific community, thus driving the field of photo(-/)electrocatalytic water oxidation forward.

Transition Metal Ions Synergistic Bilayer H2O Pillared MXene Directing In Situ Ordered Embedding Growth of Highly Efficient NiFe Alloy Catalysts

AbstractEfficient, stable, and inexpensive electrocatalysts are essential to overcome the high overpotential and slow kinetics of the oxygen evolution reaction (OER) process during water electrolysis applications. 2D transition metal carbides (MXene) show great potential in functional heterogeneous interface engineering for electrocatalytic OER. However, it is still a challenge to regulate the interlayer space and realize the heterogeneous layer‐by‐layer ordered embedding for MXene. Herein, a simple hydrothermal‐assisted strategy is proposed to prepare highly conductive Ti3C2Tx MXene supported by synergized Ni2+, Co2+, and Fe3+ with bilayer H2O, which significantly enlarges the interlayer distances and improves the interlayer ion concentrations. Benefiting from modulated interface chemistry, embedded metal ions undergo multi‐directional in situ growth on the MXene substrate, thereby forming a stable 0D/2D@2D nano‐hybrid material (NiFe/MX‐HT). Combining density functional theory calculations with experiments demonstrates that MXene offers a framework for electron transfer, enhances the exposure of active sites, modulates the electronic structure, and greatly reduces the energy barrier of the rate‐determining step in the process of OER. Thus, NiFe/MX‐HT requires only 230 mV to achieve 10 mA cm−2 and maintains stability even after operating at 100 mA cm−2 for 150 h. This work offers new insights into exploring various functional MXene‐based heterogeneous materials.

Synthesis of Ni-doped 1T/2H MoS2 nanoparticles as an efficient and stable bifunctional electrocatalyst for overall water-splitting

In advancing hydrogen fuel production through water-splitting, we focus on the optimisation of 1T/2H phases of MoS2 nanoparticles to enrich the overall water-splitting performance which has garnered significant interest. We propose a straightforward hydrothermal method to develop a 1T/2H MoS2 catalyst by introducing Ni. Morphological and chemical investigations evidenced the generation of the metal/semiconductor MoS2 nanoparticles. Further, the electrocatalytic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) have been demonstrated, and the optimised 1 m mol nickel-doped MoS2 catalyst (MSN-1) exhibits remarkable performance in both HER and OER, with a low overpotential of 117 and 250 mV respectively at a current density of 10 mA cm−2, and superior stability in alkaline medium (about 20 h). Additionally, it exhibits promising bifunctional activity with an overpotential of approximately 1.36 V at a current density of 10 mA cm−2, maintaining stability for 20 h in a 1.0 M KOH medium. These outcomes emphasise that MSN-1 has the potential as a practical bifunctional electrocatalyst with significant applications on the horizon.

Craved Ni3S2–Sm2O3 heterojunction with enhanced electrocatalytic stability and oxygen evolution reaction

Craved Ni3S2–Sm2O3 heterojunction with enhanced electrocatalytic stability and oxygen evolution reaction

Charge engineering in black phosphorene with tunable electronic structures as efficient oxygen evolution electrocatalyst

The unique electronic structure of layered black phosphorus (BP) makes it an ideal candidate material for electrocatalytic oxygen evolution reaction (OER). Charge doping effectively improves the environmental stability and catalytic activity of BP by providing electron transfer channels and reducing charge transfer barrier. Therefore, based on the first principles calculation, this paper theoretically discusses how the intrinsic charge doping without introducing impurities changes the electronic structure and improves the catalytic activity of BP. It is found that charge engineering can effectively regulate and change the electronic structure and work function by stimulating the hybridization between different P-p orbitals, while maintaining the direct bandgap semiconductor characteristics of monolayer BP system. More importantly, in the catalytic process of OER, electrons and hole doping as free charges provide different donor and acceptor energy levels for the system depending on the doping concentration, and affect the adsorption capacity of monolayer BP to different reaction intermediates. At a certain doping concentration, the carrier mobility increases significantly, and the optimal Gibbs free energy and overpotential can be achieved in monolayer BP. These results provide new opportunities and possibilities for designing charge-engineered BP catalysts with adjustable electronic structure and excellent OER activity.

Polyaniline layered N-doped carbon-coated iron oxide nanocapsules for extremely active Li-ion battery anode and oxygen evolution reaction

We report the effective synthesis of polyaniline (PANi)-layered nitrogen-doped carbon-coated Fe3O4 (FNC@PANi) nanocapsules (NCs) for electrocatalysis of oxygen evolution reaction (OER) as well as anode material for lithium (Li)-ion batteries (LIBs) via a simple hydrothermal method and oxidative polymerization technique. The prepared FNC@PANi NCs revealed a dual core-shell structure, in which an intermediate carbon layer allowed excellent electrical conduction between the Fe3O4 NCs and PANi. The dual core-shell structure also allowed the Fe3O4 NCs to expand freely during the Li-ion insertion/extraction and OER processes without breaking the outer layer, thus providing a high surface area (147.85 m2 g−1) and enhanced electrical conductivity. These properties facilitate the application of the dual core-shell FNC@PANi NCs as an advanced electrode material for LIBs, delivering a high reversible specific capacity of 1556.48 mAh g−1 at 0.1 A g−1, excellent rate performance (896.96 mAh g−1 at 1 A g−1), and durable cycling life (680.12 mAh g−1 at 5 A g−1 for 3000 cycles). The dual core-shell FNC@PANi NCs exhibited high electrocatalytic activity in the OER, with a small Tafel slope of 108.7 mV dec−1 owing to synergistic effects between the copious active sites of the Fe3O4 NCs and the carbon core-shell structure and a modest overpotential of 219 mV at 10 mA cm−2. The electrodes showed excellent stability over 10 h, as determined by chronopotentiometry at 10 mA cm−1. The resultant dual-core-shell FNC@PANi NCs are efficient iron-oxide-based electrode materials for LIBs and OER electrocatalysts.

Unraveling the competition between the oxygen and chlorine evolution reactions in seawater electrolysis: Enhancing selectivity for green hydrogen production

Selective oxidation of water without production of chlorine during the electrolysis of seawater is a critical impediment towards obtaining green hydrogen. Indeed, understanding the complex competitive mechanisms of oxygen and chlorine formation at the anode is an analytic challenge. An argument for direct seawater electrolysis is presented with a dissection of the complications that arise at the anode in the presence of seawater ionic constituents such as the chloride ion. Electrolyser system durability and the impact on the current and voltage efficiencies are discussed. Critical challenges at the anode under the acidic conditions of proton exchange membrane water electrolysis interrelate the thermodynamic and kinetic constraints of the oxygen evolution reaction (OER) and the chlorine evolution reaction (CER) to elucidate the heterogenous mechanisms of the OER and the CER and the crucial stability predicament under selective OER electrocatalysis. The selectivity circumstances resolved by Density Functional Theory computations shed insight onto the reaction conditions that select for the preferred OER adsorbate chemisorption on the surface and substantiates the observed overpotentials required for the OER and CER; experimental rotating ring disk electrode analysis further indicate competitive adsorption of OER and CER reactants under an assumed Langmuir isotherm model. Identifying the rate determining step and breaking the scaling relationship of the AEM OER pathway may both improve the stability of the catalyst and achieve lower OER overpotentials. Critical insight is given into designing the heterogeneous electrocatalyst structure with selective facets, additional point defects, and augmented active site density through single atom catalysts. An argument for the utilization of ruthenium for its high natural ubiquity and modulable valence states that can facilitate atomic configurations with optimal active site d-band center energies to promote selective adsorbate binding is presented. Studies of in-situ filtration of the chloride ion under acidic conditions highlight the utility of manganese oxide and silica; the augmentation of the conductivity through manipulation of polaronic interactions; and the design of heterogeneous electrocatalysts with self-healing characteristics demonstrated in select molecular catalysts that may decrease the overpotential of the OER and achieve selectivity. It is with the hope that these design strategies provide insights into future research efforts to uncover an electrocatalytic surface selective for OER evolution under the perilous acidic conditions and reveal an effective solution as serendipitous as the abundancy of a natural resource such as seawater.

Ceria-Optimized Oxygen-Species Exchange in Hierarchical Bimetallic Hydroxide for Electrocatalytic Water Oxidation.

The utilization of rare earth elements to regulate the interaction between catalysts and oxygen-containing species holds promising prospects in the field of oxygen electrocatalysis. Through structural engineering and adsorption regulation, it is possible to achieve high-performance catalytic sites with a broken activity-stability tradeoff. Herein, this work fabricates a hierarchical CeO2/NiCo hydroxide for electrocatalytic oxygen evolution reaction (OER). This material exhibits superior overpotentials and enhanced stability. Multiple potential-dependent experiments reveal that CeO2 promotes oxygen-species exchange, especially OH- ions, between catalyst and environment, thereby optimizing the redox transformation of hydroxide and the adsorption of oxygen-containing intermediates during OER. This is attributed to the reduction in the adsorption energy barrier of Ni to *OH facilitated by CeO2, particularly the near-interfacial Ni sites. The less-damaging adsorbate evolution mechanism and the CeO2 hierarchical shell significantly enhance the structural robustness, leading to exceptional stability. Additionally, the observed "self-healing" phenomenon provides further substantiation for the accelerated oxygen exchange. This work provides a neat strategy for the synthesis of ceria-based complex hollow electrocatalysts, as well as an in-depth insight into the co-catalytic role of CeO2 in terms of oxygen transfer.

Formation of FeNi-based nanowire-assembled superstructures with tunable anions for electrocatalytic oxygen evolution reaction

Anion modification has been considered as a strategy to improve water splitting efficiency upon oxygen evolution reaction (OER). However, constructing a novel catalysis system with high catalytic activity and precise structures is still a huge challenge due to the tedious procedure of precursor synthesis and anion selection. Here, a bimetallic (FeNi) nanowire self-assembled superstructure was synthesized using the Hoffmann rearrangement method, and then functionalized with four anions (P, Se, S, and O). Notably, the Fe3Se4/Ni3Se4 catalyst shows a high conductivity, enhances the adsorption of intermediate products, accelerates the rate-determining step, and consequently results to improved electrocatalytic performance. Using the Fe3Se4/Ni3Se4 catalyst exhibits enhanced performance with overpotential of 316 mV at 10 mA/cm2, in stark contrast to Fe2P/Ni2P (357 mV), Fe7S8/NiS (379 mV), and Fe3O4/NiO (464 mV). Moreover, the formation mechanism of superstructure and the relationship between electronegativities and electrocatalytic properties, are elucidated. Accordingly, this work provides an efficient approach to Hoffmann-type coordination polymer catalyst for oxygen evolution towards a near future.

Controllable Phase Separation Engineering of Iron-Cobalt Alloy Heterojunction for Efficient Water Oxidation.

The tailor-made transition metal alloy-based heterojunctions hold a promising prospect for the electrocatalytic oxygen evolution reaction (OER). Herein, a series of iron-cobalt bimetallic alloy heterojunctions are purposely designed and constructed via a newly developed controllable phase separation engineering strategy. The results show that the phase separation process and alloy component distribution rely on the metal molar ratio (Fe/Co), indicative of the metal content dependent behavior. Theoretical calculations demonstrate that the electronic structure and charge distribution of iron-cobalt bimetallic alloy can be modulated and optimized, thus leading to the formation of an electron-rich interface layer, which likely tunes the d-band center and reduces the adsorption energy barrier toward electrocatalytic intermediates. As a result, the Fe0.25Co0.75/Co heterojunction exhibits superior OER activity with a low overpotential of 185 mV at 10 mA cm-2. Moreover, it can reach industrial-level current densities and excellent durability in high-temperature and high-concentration electrolyte (30 wt % KOH), exhibiting enormous potential for industrial applications.

Research progress on electronic and active site engineering of cobalt‐based electrocatalysts for oxygen evolution reaction

AbstractElectrocatalytic water splitting has been identified as a potential candidate for producing clean hydrogen energy with zero carbon emission. However, the sluggish kinetics of oxygen evolution reaction on the anode side of the water‐splitting device significantly hinders its practical applications. Generally, the efficiency of oxygen evolution processes depends greatly on the availability of cost‐effective catalysts with high activity and selectivity. In recent years, extensive theoretical and experimental studies have demonstrated that cobalt (Co)‐based nanomaterials, especially low‐dimensional Co‐based nanomaterials with a huge specific surface area and abundant unsaturated active sites, have emerged as versatile electrocatalysts for oxygen evolution reactions, and thus, great progress has been made in the rational design and synthesis of Co‐based nanomaterials for electrocatalytic oxygen evolution reactions. Considering the remarkable progress in this area, in this timely review, we highlight the most recent developments in Co‐based nanomaterials relating to their dimensional control, defect regulation (conductivity), electronic structure regulation, and so forth. Furthermore, a brief conclusion about recent progress achieved in oxygen evolution on Co‐based nanomaterials, as well as an outlook on future research challenges, is given.

Accurately Modulating Binuclear Metal Nodes of Metal-Organic Frameworks for Oxygen Evolution.

The accurate manipulation of the species and locations of catalytic centers is crucial for regulating the catalytic activity of catalysts, which is essential for their efficient design and development. Metal-organic frameworks (MOFs) with coordinated metal sites are ideal materials for investigating the origin of catalytic activity. In this study, we present a Ni2-MOF featuring novel Ni-based binuclear nodes with open metal sites (OMSs) and saturated metal sites (SMSs). The nickel was replaced by iron to obtain Ni1Fe1-MOF. In the electrocatalytic oxygen evolution reaction, Ni1Fe1-MOF exhibited an overpotential and Tafel slope of 370 mV@10 mA cm-2 and 87.06 mV dec-1, respectively, which were higher than those of Ni2-MOF (283 mV@10 mA cm-2 and 39.59 mV dec-1, respectively), demonstrating the superior performance of Ni1Fe1-MOF. Furthermore, theoretical calculations revealed that iron as an SMS may effectively regulate the electronic structure of the nickel catalytic center to reduce the free energy barrier ΔG*OH of the rate-determining step.

Promoting Oxygen Evolution Electrocatalysis by Coordination Engineering in Cobalt Phosphate.

Understanding the structure-activity correlation is an important prerequisite for the rational design of high-efficiency electrocatalysts at the atomic level. However, the effect of coordination environment on electrocatalytic oxygen evolution reaction (OER) remains enigmatic. In this work, the regulation of proton transfer involved in water oxidation by coordination engineering based on Co3(PO4)2 and CoHPO4 is reported. The HPO4 2- anion has intermediate pKa value between Co(II)-H2O and Co(III)-H2O to be served as an appealing proton-coupled electron transfer (PCET) induction group. From theoretical calculations, the pH-dependent OER properties, deuterium kinetic isotope effects, operando electrochemical impedance spectroscopy (EIS) and Raman studies, the CoHPO4 catalyst beneficially reduces the energy barrier of proton hopping and modulates the formation energy of high-valent Co species, thereby enhancing OER activity. This work demonstrates a promising strategy that involves tuning the local coordination environment to optimize PCET steps and electrocatalytic activities for electrochemical applications. In addition, the designed system offers a motif to understand the structure-efficiency relationship from those amino-acid residue with proton buffer ability in natural photosynthesis.

Bridging OER Electrocatalysis and Tumor Therapy: Utilizing Piezoelectric‐Hole‐Induced OER Electrocatalysis for Direct Oxygen Generation to Address Hypoxia

AbstractIn addressing the challenge of hypoxia within the tumor microenvironment (TME), a significant obstacle to effective cancer therapy, this research introduces a pioneering nanozyme engineered to utilize water and oxygen as reactants. Utilizing ultrasonic piezoelectricity, this nanozyme converts these substrates into oxygen (O2) and reactive oxygen species, thereby amplifying oxidative stress without relying on endogenous H2O2. This approach involves the strategic engineering of porous ZnSnOv:Mn nanosheets (named MZSO NSs), which are distinguished by oxygen‐rich vacancies and enhanced piezoelectric properties. This breakthrough represents the initial attempt to merge catalytic activities akin to catalase (CAT) with the electrocatalytic oxygen evolution reaction (OER), confirmed through both enzymatic reactions and electrochemical voltammetric analysis. The predominant mechanism of ultrasound‐augmented oxygen generation in MZSO is identified as piezoelectric hole‐induced OER. Supporting theoretical analyses clarify the synergistic impact of oxygen vacancies and Mn doping on the dynamics of carriers and the OER process, leading to a notable increase in catalytic efficiency. These findings highlight the potential of piezoelectric‐enhanced OER electrocatalysts to alleviate hypoxia in the TME, providing novel insights into the development of piezoelectric acoustic sensitizers for the treatment of cancer.

Organic-inorganic hybrid interfaces with π-d electron coupling for preventing metal and sulfur leaching toward enhanced oxygen evolution reaction

Transition metal sulfides (TMSs) catalysts with high catalytic oxygen evolution reaction (OER) activity have been extensively studied, especially Fe and Co-based sulfides. Fe and Co active sites with a strong synergistic effect, which can adjust the electron density distribution and effectively improve the electrocatalytic OER activity. However, TMSs have poor stability in alkaline environment caused by metal ions and sulfur elements are facilitated to dissolve. In this work, TMSs was modified by polyaniline (PANI) to inhibit the precipitation of iron, cobalt, and sulfur elements and enhance its stability under alkaline conditions. Moreover, π-d structure can also be formed by the coating of PANI, which can further adjust its own electronic structure on the basis of stabilizing the TMSs structure, so as to improve the electrochemical performance, rendering them to stably operate at harsh environment for more than 90 h. These findings offer new guidance for improving the electrocatalytic stability of TMSs.

Ligand-Induced Electronic Structure Modulation of Self-Evolved Ni3S2 Nanosheets for the Electrocatalytic Oxygen Evolution Reaction.

Modulating the electronic structure of the electrocatalyst plays a vital role in boosting the electrocatalytic performance of the oxygen evolution reaction (OER). In this work, we introduced a one-step solvothermal method to fabricate 1,1-ferrocene dicarboxylic acid (FcDA)-decorated self-evolved nickel sulfide (Ni3S2) nanosheet arrays on a nickel foam (NF) framework (denoted as FcDA-Ni3S2/NF). Benefiting from the interconnected ultrathin nanosheet architecture, ligand dopants induced and facilitated in situ structural reconstruction, and the FcDA-decorated Ni3S2 (FcDA-Ni3S2/NF) outperformed its singly doped and undoped counterparts in terms of OER activity. The optimized FcDA-Ni3S2/NF self-supported electrode presents a remarkably low overpotential of 268 mV to achieve a current density of 10 mA cm-2 for the OER and demonstrates robust electrochemical stability for 48 h in a 1.0 M KOH electrolyte. More importantly, in situ electrochemical Raman spectroscopy reveals the generation of catalytically active oxyhydroxide species (NiOOH) derived from the surface construction during the OER of pristine FcDA-Ni3S2/NF, contributing significantly to its superior electrocatalytic performance. This study concerns the modulation of electronic structure through ligand engineering and may provide profound insight into the design of cost-efficient OER electrocatalysts.