Alkaline Oxygen Evolution Reaction Research Articles

Nanoengineered Cobalt Electrocatalyst for Alkaline Oxygen Evolution Reaction

The alkaline oxygen evolution reaction (OER) remains a bottleneck in green hydrogen production owing to its slow reaction kinetics and low catalytic efficiencies of earth abundant electrocatalysts in the alkaline OER reaction. This study investigates the OER performance of hierarchically porous cobalt electrocatalysts synthesized using the dynamic hydrogen bubble templating (DHBT) method. Characterization studies revealed that electrocatalysts synthesized under optimized conditions using the DHBT method consisted of cobalt nanosheets, and hierarchical porosity with macropores distributed in a honeycomb network and mesopores distributed between cobalt nanosheets. Moreover, X-ray photoelectron spectroscopy studies revealed the presence of Co(OH)2 as the predominant surface cobalt species while Raman studies revealed the presence of the cubic Co3O4 phase in the synthesized electrocatalysts. The best performing electrocatalyst required only 360 mV of overpotential to initiate a current density of 10 mA cm−2, exhibited a Tafel slope of 37 mV dec−1, and stable OER activity over 24 h. The DHBT method offers a facile, low cost and rapid synthesis approach for preparation for highly efficient cobalt electrocatalysts.

Combustion Growth of NiFe Layered Double Hydroxide for Efficient and Durable Oxygen Evolution Reaction.

NiFe layered double hydroxide (LDH) with abundant heterostructures represents a state-of-the-art electrocatalyst for the alkaline oxygen evolution reaction (OER). Herein, NiFe LDH/Fe2O3 nanosheet arrays have been fabricated by facile combustion of corrosion-engineered NiFe foam (NFF). The in situ grown, self-supported electrocatalyst exhibited a low overpotential of 248 mV for the OER at 50 mA cm-2, a small Tafel slope of 31 mV dec-1, and excellent durability over 100 h under the industrial benchmarking 500 mA cm-2 current density. A balanced Ni and Fe composition under optimal corrosion and combustion contributed to the desirable electrochemical properties. Comprehensive ex-situ analyses and operando characterizations including Fourier-transformed alternating current voltammetry (FTACV) and in situ Raman demonstrate the beneficial role of modulated interfacial electron transfer, dynamic atomic structural transformation to NiOOH, and the high-valence active metal sites. This study provides a low-cost and easy-to-expand way to synthesize efficient and durable electrocatalysts.

Directional movement of electron induced by interfacial coupling in CuS@NiCo-LDHs for efficient alkaline oxygen evolution reaction

Heterojunction has the characteristics of adjusting catalyst structure, improving oxygen evolution kinetics and breaking the elevated reaction barrier of oxygen evolution process. In this paper, a heterostructure catalyst of NiCo-LDHs nanosheets encapsulated CuS hollow nano-octahedrals has been reported, which has better stability and higher mass transfer efficiency compared with two-dimensional nanosheets. Density functional theory (DFT) calculations indicate that the heterostructure strengthens the orbital hybridization of metal 3d and O 2p, at the same time, the heterointerface coupling induces the directional movement of electrons from NiCo-LDHs to CuS, which together provide abundant high-valence Ni and Co active sites, promote the conversion of *OH to *O species, thus reducing the energy required for the reaction. Hence, CuS@NiCo-LDHs exhibits excellent OER performance and good stability in 1 M KOH. When the current density is 10 mA/cm2, the overpotential and Tafel slope of this catalyst is only 253 mV and 56 mV/dec, respectively. This study furnishes the construction of heterogeneous structures and the catalyst exploitation with serviceable insights.

Carbon-Based Composites for Oxygen Evolution Reaction Electrocatalysts: Design, Fabrication, and Application.

The four-electron oxidation process of the oxygen evolution reaction (OER) highly influences the performance of many green energy storage and conversion devices due to its sluggish kinetics. The fabrication of cost-effective OER electrocatalysts via a facile and green method is, hence, highly desirable. This review summarizes and discusses the recent progress in creating carbon-based materials for alkaline OER. The contents mainly focus on the design, fabrication, and application of carbon-based materials for alkaline OER, including metal-free carbon materials, carbon-based supported composites, and carbon-based material core-shell hybrids. The work presents references and suggestions for the rational design of highly efficient carbon-based OER materials.

Operando Spectroscopic Monitoring of Metal Chalcogenides for Overall Water Splitting: New Views of Active Species and Sites

AbstractMetal‐based chalcogenides exhibit great promise for overall water splitting, yet their intrinsic catalytic reaction mechanisms remain to be fully understood. In this work, we employed operando X‐ray absorption (XAS) and in situ Raman spectroscopy to elucidate the structure–activity relationships of low‐crystalline cobalt sulfide (L−CoS) catalysts toward overall water splitting. The operando results for L−CoS catalyzing the alkaline hydrogen evolution reaction (HER) demonstrate that the cobalt centers in the bulk are predominantly coordinated by sulfur atoms, which undergo a kinetic structural rearrangement to generate metallic cobalt in S−Co−Co−S moieties as the true catalytically active species. In comparison, during the acidic HER, L−CoS undergoes local structural optimization of Co centers, and H2 production proceeds with adsorption/desorption of key intermediates atop the Co−S−Co configurations. Further operando characterizations highlight the crucial formation of high‐valent Co4+ species in L−CoS for the alkaline oxygen evolution reaction (OER), and the formation of such active species was found to be far more facile than in crystalline Co3O4 and Co‐LDH references. These insights offer a clear picture of the complexity of active species and site formation in different media, and demonstrate how their restructuring influences the catalytic activity.

Operando Spectroscopic Monitoring of Metal Chalcogenides for Overall Water Splitting: New Views of Active Species and Sites.

Metal-based chalcogenides exhibit great promise for overall water splitting, yet their intrinsic catalytic reaction mechanisms remain to be fully understood. In this work, we employed operando X-ray absorption (XAS) and in situ Raman spectroscopy to elucidate the structure-activity relationships of low-crystalline cobalt sulfide (L-CoS) catalysts toward overall water splitting. The operando results for L-CoS catalyzing the alkaline hydrogen evolution reaction (HER) demonstrate that the cobalt centers in the bulk are predominantly coordinated by sulfur atoms, which undergo a kinetic structural rearrangement to generate metallic cobalt in S-Co-Co-S moieties as the true catalytically active species. In comparison, during the acidic HER, L-CoS undergoes local structural optimization of Co centers, and H2 production proceeds with adsorption/desorption of key intermediates atop the Co-S-Co configurations. Further operando characterizations highlight the crucial formation of high-valent Co4+ species in L-CoS for the alkaline oxygen evolution reaction (OER), and the formation of such active species was found to be far more facile than in crystalline Co3O4 and Co-LDH references. These insights offer a clear picture of the complexity of active species and site formation in different media, and demonstrate how their restructuring influences the catalytic activity.

Chemical etching to boost medium-entropy metal oxide for oxygen evolution reaction in alkaline

It is crucial to improve the catalytic activity of medium-entropy materials by adjusting the surface electronic structure of medium-entropy materials. In this research, we utilize a chemical etching method for synthesizing a medium-entropy metal oxide E-FeCoNiZn with abundant defects. Owing to the etching of Zn, a special form of electron-transfer by means of electron-accepting-donating is introduced, which greatly optimizes OER activity. The E-FeCoNiZn displays a superior OER activity with a low overpotential of 259 mV at 10 mA cm−2 and a small Tafel slope of 37.1 mV dec-1 in 1 M KOH solution, outperformingtheperformanceofFeCoNiZn and Ni-foam,whilemaintainingexcellentstabilityover48 h. Theoretical calculations demonstrate that the introduction of defects regulates the surface electronic structure of the E-FeCoNiZn via modifying the number of electrons transferred and then optimize the OER activity. Thisworkprovidesa newstrategyfordesigning medium-entropy materials possessing high catalytic activity.

Constructing NiO/Co3O4/KNbO3 heterostructure with NiO and Co3O4 particles coupled on KNO3 cubes for high-performance urea-assisted alkaline oxygen evolution reaction

In this study, a novel NiO/Co3O4/KNbO3 heterostructured electrocatalyst with NiO and Co3O4 particles coupled on KNO3 cubes was constructed using simple sol–gel and calcination processes. The formation of multiple interfaces between NiO, Co3O4, and KNbO3 in the heterostructure contributed to a synergistic effect, adjusted the electronic structure, and generated abundant active sites at the interfaces. As a result, the NiO/Co3O4/KNbO3 electrocatalyst exhibited remarkable urea electrolysis performance, including a low potential of 1.67 V at 100 mA cm-2 and a small Tafel slope of 29 mV dec-1. Furthermore, the change in the overpotential was negligible even after a rigorous stability test of 3000 cycles, highlighting its exceptional durability and reliability. This study provides a novel structural engineering strategy for achieving efficient hydrogen production and purification from urea-containing wastewater.

Enhance the performance of OER electrocatalyst via synergistic oxygen vacancies and NiFe2O4-phosphorene heterostructure

The exfoliated black phosphorus nanosheets (EBP, phosphorene) is considered as a highly anticipated electrocatalyst for oxygen evolution reaction (OER) because of its unique electron structure. However, the poor stability and conductivity of EBP limit its application potential. In this paper, a heterostructure of EBP and nickel ferrite with oxygen vacancies (NFO-V-EBP) is designed by using a simple ultrasound and electronic regulation of EBP. NFO-V forms P-Ni bonds and P-O-M (M=Ni/Fe) bonds by interacting with the active lone pair electrons on the surface of EBP, which passivates EBP to improve its stability and provide more active sites. In situ Raman testing is used to assist in demonstrating the cooperative effect of EBP and oxygen vacancy, which reduced the potential barrier of OER reaction. NFO-V-EBP heterostructure exhibits excellent electrocatalytic performance for alkaline OER, showing overpotential of 243 mV at current density of 10 mA cm-2 and Tafel slope of 39 mV dec-1. It also has excellent long-term stability, at a density of 10 mA cm-2 with no significant increase in overpotential observed after nearly 100 hours under the chronoamperometric method.

Novel amorphous FeOOH-modified Co9S8 nanosheets with enhanced catalytic activity in oxygen evolution reaction

Efficient oxygen evolution reaction (OER) is vital for water electrolysis and advanced hydrogen energy production. However, the sluggish kinetics of this reaction require significant overpotentials, leading to high energy consumption. Therefore, developing OER electrocatalysts with exceptional performance and long-term durability is crucial for enhancing the energy efficiency and cost-effectiveness of the hydrogen production process. In this research, novel FeOOH/Co9S8 catalysts were prepared through a two-step hydrothermal reaction followed by one-step electrodeposition on nickel foam for an alkaline OER. The as-obtained catalysts possessed abundant non-homogeneous interfaces between FeOOH and Co9S8 nanosheets, conducive to optimized coordination environments of Fe and Co sites by redistributing interfacial charges. This synergy strengthened the chemisorption of oxygenated intermediates, leading to accelerated reaction kinetics, abundant active sites, and enhanced OER performance. The optimized electrocatalyst FeOOH/Co9S8-15 achieved a current density of 10 mA cm−2 at an overpotential of 248 mV and good stability for over 140 h. This study presents a novel approach for producing compelling and durable alkaline dielectric OER electrocatalysts, which will be helpful in the future manufacturing of advanced energy devices.

Unique sandwich-cookie-like nanosheet array heterojunction bifunctional electrocatalyst towards efficient overall water/seawater splitting

Construction of multi-component heterostructures is an effective strategy for electrocatalysts to improve both the hydrogen evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) activity at the anode. Herein, an efficient bifunctional electrocatalyst towards overall water/seawater splitting (OW/SS) is reported with strategy of heterostructure construction (ruthenium/nickel phosphorus) on nickel hydroxide (Ni(OH)2). With the unique hydrolysis layer (Ni(OH)2), the processes of H2O hydrolysis and the adsorption/desorption of H*/O-containing intermediates (OH, O, OOH) were greatly boosted by Ru and P sites, which acted as the catalytic active centers of OER and HER, respectively. In addition, the electronic structure reconfiguration was realized through the strong interaction between multi-interfaces. For alkaline HER at the current density of 10 mA cm−2, the overpotential of Ru-P-Ni(OH)2/NF (denoted as RNPOH/NF) was 98 mV, whereas just 230 mV of overpotential was essential to stimulate alkaline OER at the current density of 20 mA cm−2. Specifically, as a bifunctional electrocatalyst towards overall water splitting, RNPOH/NF deserves cell voltages of 1.7/1.92 V and 1.75/1.94 V, respectively, to activate current densities of 50/100 mA cm−2 in alkaline water/seawater systems, together with a good durability of 12 h. This work contributes insights to the development of bifunctional electrocatalysts for overall water/seawater splitting.

Cost-efficient sunlight-driven thermoelectric electrolysis over Mo-doped Ni5P4 nanosheets for highly efficient alkaline water/seawater splitting

Thermoelectric water spitting to hydrogen systems has great potential in the production of environment-friendly fuel using renewable solar energy in the future. In this work, we prepared porous nanosheet Mo doping Ni5P4 catalysts on nickel foam with efficient hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performance in alkaline media. DFT calculations and experimental studies have shown that Mo doping deadeneds the interaction between H and O atomic orbitals of transition state water molecules, effectively weakening the activation energy of H2O dissociation. Therefore, Mo doping is favorable for enhancing HER activity with overpotential at 10 mA cm–2 of 93 mV and Tafel slope of 40.1 mV dec–1 in 1 M KOH. Besides, it exhibits high alkaline OER activity with an ultra-low overpotential of 200 mV at 10 mA cm–2. Moreover, this catalyst only needs 1.537 V in a dual-electrode configuration of the electrolytic cell, which is much lower than the commercial Pt/C-RuO2 couple (1.614 V). In addition, we have developed and constructed a solar thermoelectric generator (TEG) that is capable of floating on water. This TEG has a continuous power output and an exceptionally long lifespan, providing a stable power supply to the synthesized catalyst electrolyzer. It can produce a maximum power output of over 90 mW, meeting the requirement of converting solar radiation heat into usable electricity. As a result, the system achieves productivity of 0.11 mL min–1 H2. This solar thermal energy conversion technology shows the possibility of large-scale industrial production of H2 and provides a new idea for exploring heat source utilization.

Coupling nano and atomic electric field confinement for robust alkaline oxygen evolution

The alkaline oxygen evolution reaction (OER) is a promising avenue for producing clean fuels and storing intermittent energy. However, challenges such as excessive OH– consumption and strong adsorption of oxygen‐containing intermediates hinder the development of alkaline OER. In this study, we propose a cooperative strategy by leveraging both nano‐scale and atomically local electric fields for alkaline OER, demonstrated through the synthesis of Mn single atom doped CoP nanoneedles (Mn SA‐CoP NNs). Finite element method simulations and density functional theory calculations predict that the nano‐scale local electric field enriches OH‐ around the catalyst surface, while the atomically local electric field improves *O desorption. Experimental validation using in situ attenuated total reflection infrared and Raman spectroscopy confirms the effectiveness of the nano‐scale and atomically electric fields. Mn SA‐CoP NNs exhibit an ultra‐low overpotential of 189 mV at 10 mA cm–2 and stable operation over 100 hours at ~100 mA cm–2 during alkaline OER. This innovative strategy provides new insights for enhancing catalyst performance in energy conversion reactions.

Coupling nano and atomic electric field confinement for robust alkaline oxygen evolution.

The alkaline oxygen evolution reaction (OER) is a promising avenue for producing clean fuels and storing intermittent energy. However, challenges such as excessive OH- consumption and strong adsorption of oxygen-containing intermediates hinder the development of alkaline OER. In this study, we propose a cooperative strategy by leveraging both nano-scale and atomically local electric fields for alkaline OER, demonstrated through the synthesis of Mn single atom doped CoP nanoneedles (Mn SA-CoP NNs). Finite element method simulations and density functional theory calculations predict that the nano-scale local electric field enriches OH- around the catalyst surface, while the atomically local electric field improves *O desorption. Experimental validation using in situ attenuated total reflection infrared and Raman spectroscopy confirms the effectiveness of the nano-scale and atomically electric fields. Mn SA-CoP NNs exhibit an ultra-low overpotential of 189 mV at 10 mA cm-2 and stable operation over 100 hours at ~100 mA cm-2 during alkaline OER. This innovative strategy provides new insights for enhancing catalyst performance in energy conversion reactions.

Boron modification promoting electrochemical surface reconstruction of NiFe-LDH for efficient and stable freshwater/seawater oxidation catalysis

Transition metal-based electrocatalysts generally take place surface reconstruction in alkaline conditions, but little is known about how to improve the reconstruction to a highly active oxyhydroxide surface for an efficient and stable oxygen evolution reaction (OER). Herein, we develop a strategy to accelerate surface reconstruction by combining boron modification and cyclic voltammetry (CV) activation. Density functional theory calculations and in-situ/ex-situ characterizations indicate that both B-doping and electrochemical activation can reduce the energy barrier and contribute to the surface evolution into highly active oxyhydroxides. The formed oxyhydroxide active phase can tune the electronic configuration and boost the OER process. The reconstructed catalyst of CV-B-NiFe-LDH displays excellent alkaline OER performance in freshwater, simulated seawater, and natural seawater with low overpotentials at 100 mA cm−2 (η100: 219, 236, and 255 mV, respectively) and good durability. This catalyst also presents outstanding Cl− corrosion resistance in alkalized seawater electrolytes. The CV-B-NiFe-LDH||Pt/C electrolyzer reveals prominent performance for alkalized freshwater/seawater splitting. This study provides a guideline for developing advanced OER electrocatalysts by promoting surface reconstruction.

Understanding highly active and durable Fe-decorated Co(OH)2 catalysts in alkaline oxygen evolution reaction by in situ XANES studies

The activation and degradation mechanisms of CoFe layered double hydroxide (CoFe-LDH) and Fe-decorated Co(OH)2 (Fe-Co(OH)2) have been investigated using in situ X-ray absorption spectroscopy coupled with cyclic voltammetry (CV) in 0–0.9 V (vs Hg/HgO). A series of CoFe-LDH samples have been prepared by co-electrodeposition with varying Co/Fe ratios. Fe-decorating on Co(OH)2 has been applied using 10 ppm of Fe in 1.0 M KOH. Electrochemical impedance spectroscopy (EIS) and CV cycles confirm the degradation of Co(OH)2 and CoFe-LDH due to the irreversible redox of Co(OH)2/CoOOH, and Fe extraction. In contrast, Fe-decorated Co(OH)2 shows high activity and stability in the OER. In situ XANES analysis suggests that the Fe-decorating allows the Co(OH)2 to remain as γ-CoOOH even under potential fluctuations.

High-entropy MnCoCuZnAlSe2 nanosheet arrays for highly efficient alkaline oxygen evolution reaction

The oxygen evolution reaction is the primary obstacle in the electrochemical breakdown of water; whereas transition metal selenides exhibit remarkable OER activity, their stability is compromised by the oxidative dissolution of selenium. The high-entropy materials can provide a feasible strategy to solve this problem due to their multi-element synergy and entropy stabilization effect. Here, we designed novel high-entropy MnCoCuZnAlSe2 electrocatalysts with ultra-low overpotential (190 mV@10 mA cm−2) and exceptional endurance (500 h@10 mA cm−2), which outperform other selenide and IrO2 catalysts. The high entropy effect was experimentally confirmed to inhibit selenium dissolution and improve the stability of transition metal selenides. Calculations using Density Functional Theory suggest that cobalt is actually MnCoCuZnAlSe2's true active center. The extraordinary OER properties of high-entropy selenides offer great opportunities for the design of ideal catalysts for practical applications.

Efficient Alkaline Water Oxidation Electrocatalysis Enabled via the Modulation of Sn‐containing Anions towards NiFe Oxyhydroxide

Despite being considered as efficient non‐noble metal‐based electrocatalysts for alkaline oxygen evolution reaction (OER), NiFe (oxy)hydroxides (NiFeOxHy) typically fall short of meeting practical requirements. To address this challenge, herein, we introduce a facile in situ electrochemical incorporation technique to form Sn‐doped NiFe‐layered double hydroxide (NiFeSn‐LDH) precatalysts. Subsequently, under the alkaline OER process, the precatalyst evolves into stannate ion‐adsorbed NiFe oxyhydroxides (NiFeOOH). The presence of these stable stannate oxyanions plays a key role in mitigating Fe leaching, optimizing the electronic structure of NiFeOOH, and improving its reaction kinetics, thereby significantly enhancing alkaline OER performance. Notably, the nickel foam‐supported NiFeSn‐LDH demonstrated impressive results delivering a large current density of 100 mA cm−2 at an overpotential as low as ~260 mV and maintaining the industrial‐relevant ~500 mA cm−2 current density over 5 days with negligible activity decay, surpassing the performance of most of the transition metal‐based electrocatalysts. Comprehensive advanced characterization of the precatalysts, before and after the OER reactions, has been performed to uncover stable residual stannate ions at the surface of NiFeOxHy and to determine their pivotal role in promoting alkaline OER.

Short-time potentiostatic assisted borate to induce the generation of ultrathin NiFe LDH active phase for industrial-level water oxidation

Self-supported NiFe-based oxygen evolution reaction (OER) catalysts with high activity and durability are essential for the industrialization of green hydrogen. Herein, Boron-interfered NiFe LDH nanosheets (B2-NiFe-(a-10)) with abundant wrinkle structure are prepared by introducing nonmetallic sources into the surface reconstruction of layered double hydroxide (NiFe LDH) through a novel short-time potential constant activation strategy. It enhances interactions with the electrolyte, decreases Arrhenius activation energy (Ea), accelerates efficient charge transfer and O2 escape rate. The as-reconstructed B2-NiFe-(a-10) exhibits outstanding alkaline OER activity with an ultralow overpotential of 290 mV at 100 mA cm−2 and excellent durability (100 h). Additionally, density functional theory calculations further reveal that the interaction optimizes the adsorption of oxygenated intermediates (*OH→*O), induces the center of the d-band toward the Fermi energy level, and lowers the dissociation barrier of H2O. Moreover, the anion-exchange membrane water electrolyzer (AEMWE) achieves a current density of 1 A cm−2 at 1.97 V.

Structural Reconstruction Chemistry for Alkaline Oxygen Evolution Catalysts

AbstractDeveloping efficient and stable catalysts for energy conversion processes such as alkaline oxygen evolution reaction is one of the key measures to solve the energy shortage problems. During alkaline oxygen evolution, several electrocatalysts would undergo structural reconstruction from the pre‐catalyst state to the real‐catalyst state. The structural reconstruction may modify the quantity and characterizations of the active sites, thus affecting the configuration and adsorption strength of the reaction key intermediates, which directly influence the activity and stability of the electrocatalysts. Understanding the structural transformation chemistry is essential for the rational design of highly efficient and stable electrocatalysts. In this review, we have deeply discussed the role and regulation strategies of structural reconstruction. Then, on this basis, we described some characterization technologies to probe the structural reconstruction of catalysts during alkaline OER. Finally, we put forward some views on the future research direction of this vital field.