Efficient Electrocatalyst For Oxygen Evolution Reaction Research Articles

CoO supported NiFe layered double hydroxide sandwich-like nanosheets on hierarchical carbon framework for efficient electrocatalytic oxygen evolution.

Exploration of greatly efficient and steady non-noble oxygen evolution reaction (OER) electrocatalysts is of great significance in improving the overall efficiency of energy density systems such as regenerative fuel cells, water electrolyzes, and metal-air batteries. Herein, inspired by hierarchical 3D porous structures with open microchannels of natural wood, CoO@NiFe LDH sandwich-like nanosheets were anchored on the carbonized wood (CW) via electrodeposition and calcination strategies. The strong interactions between CoO nanosheets and NiFe LDH nanosheets endow CoO@NiFe LDH/CW electrocatalyst with high catalytic properties toward the OER comparable to CoO/CW and NiFe LDH/CW. The optimized CoO@NiFe LDH/CW electrocatalyst demonstrates good OER catalytic performance with an overpotential of 230 mV at 100 mA cm-2. This work presents an innovative approach to utilize renewable resources for constructing advanced free-standing catalysts.

Correlating Structural Disorder in Metal (Oxy)hydroxides and Catalytic Activity in Electrocatalytic Oxygen Evolution

AbstractUnderstanding the correlation between the structural evolution of electrocatalysts and their catalytic activity is both essential and challenging. In this study, we investigate this correlation in the context of the oxygen evolution reaction (OER) by examining the influence of structural disorder during and after dynamic structural evolution on the OER activity of Fe−Ni (oxy)hydroxide catalysts using operando X‐ray absorption spectroscopy, alongside other experiments and theoretical calculations. The Debye–Waller factors obtained from extended X‐ray absorption fine structure analyses reflect the degree of structural disorder and exhibit a robust correlation with the intrinsic OER activities of the electrocatalysts. The enhanced OER activity of in situ‐generated metal (oxy)hydroxides derived from different pre‐catalysts is linked to increased structural disorder, offering a promising approach for designing efficient OER electrocatalysts. This strategy may inspire similar investigations in related electrocatalytic energy‐conversion systems.

Correlating Structural Disorder in Metal (Oxy)hydroxides and Catalytic Activity in Electrocatalytic Oxygen Evolution.

Understanding the correlation between the structural evolution of electrocatalysts and their catalytic activity is both essential and challenging. In this study, we investigate this correlation in the context of the oxygen evolution reaction (OER) by examining the influence of structural disorder during and after dynamic structural evolution on the OER activity of Fe-Ni (oxy)hydroxide catalysts using operando X-ray absorption spectroscopy, alongside other experiments and theoretical calculations. The Debye-Waller factors obtained from extended X-ray absorption fine structure analyses reflect the degree of structural disorder and exhibit a robust correlation with the intrinsic OER activities of the electrocatalysts. The enhanced OER activity of in situ-generated metal (oxy)hydroxides derived from different pre-catalysts is linked to increased structural disorder, offering a promising approach for designing efficient OER electrocatalysts. This strategy may inspire similar investigations in related electrocatalytic energy-conversion systems.

Facile and scalable synthesis of Ni3S2/Fe3O4 nanoblocks as an efficient and stable electrocatalyst for oxygen evolution reaction

This study employed a one-step hydrothermal process to synthesize Ni3S2/Fe3O4 nanoblocks in situ on nickel foam (NF). The resulting Ni3S2/Fe3O4/NF catalyst demonstrates exceptional electrocatalytic activity for the oxygen evolution reaction (OER) and robust long-term stability. It achieves a low overpotential of only 220 mV for a current density of 10 mA cm−2 with a Tafel slope of 54.1 mV dec−1 and remains stable in 1.0 M KOH for 66 h. The binder-free self-supported three-dimensional nanoblocks enhance the reaction region and long-term stability. Electronic interactions between Fe3O4 and Ni3S2, coupled with heterogeneous interfaces, optimize the electronic structure, fostering the formation of highly reactive species. Density-functional theory (DFT) calculations confirm that Ni3S2/Fe3O4, with a heterogeneous interfacial structure, modulates the chemisorption of reaction intermediates on the catalyst surface, optimizing the Gibbs free energies (ΔG) of oxygen-containing intermediates. The synergistic effect between the two active materials within the heterogeneous structure enhances OER catalytic performance. This finding offers a valuable approach to designing efficient and stable OER electrocatalysts.

Questing for High-Performance Electrocatalysts for Oxygen Evolution Reaction: Importance of Chemical Complexity, Active Phase, and Surface-Adsorbed Species.

Rational design of advanced electrocatalysts for oxygen evolution reaction (OER) is of vital importance for the development of sustainable energy. Entropy engineering is emerging as a promising approach for the design of efficient OER electrocatalysts. However, other multi-anion/cation electrocatalysts with compositional complexity, particularly the medium-entropy and other non-equimolar cation/anion complex electrocatalysts, have not received noteworthy attention. In this perspective, we review and highlight the importance of compositionally complex catalysts and propose a concept of chemical complexity to correlate the OER catalytic activity with the contributions from the pairwise cation-anion interactions. Then, we offer a new view on the active catalytic sites being the hydroxylated reacting interface in an alkaline solution. Further, we argue that the common discrepancies between computationally predicted OER activities and experimental results stem from lack of considerations of surface-adsorbed species in modeling the active catalytic phases or sites. This perspective would facilitate achieving a renewed and profound understanding of the OER mechanism and promote efficient design of OER electrocatalysts for renewable energy conversion and storage.

In-based coordination polymer-derived carbon nanoribbons with abundant CoP nanoparticles in carbon nanotubes for water oxidation.

The sluggish oxygen evolution reaction (OER) in overall electrocatalytic water splitting poses a significant challenge in hydrogen production. A series of transition metal phosphides are emerging as promising electrocatalysts, effectively modulating the charge distribution of surrounding atoms for OER. In this study, a highly efficient OER electrocatalyst (CoP-CNR-CNT) was successfully synthesized through the pyrolysis and phosphatization of a Co-doped In-based coordination polymer, specifically InOF-25. This process resulted in evenly dispersed CoP nanoparticles encapsulated in coordination polymer-derived carbon nanoribbons. The synthesized CoP-CNR-CNT demonstrated a competitive OER activity with a smaller overpotential (η10) of 295.7 mV at 10 mA cm-2 and a satisfactory long-term stability compared to the state-of-the-art RuO2 (η10 = 353.7 mV). The high OER activity and stability can be attributed to the high conductivity of the carbon network, the abundance of CoP particles, and the intricate nanostructure of nanoribbons/nanotubes. This work provides valuable insights into the rational design and facile preparation of efficient non-precious metal-based OER electrocatalysts from inorganic-organic coordination polymers, with potential applications in various energy conversion and storage systems.

Low-Pressure Plasma-Processed NiCo Metal–Organic Framework for Oxygen Evolution Reaction and Its Application in Alkaline Water Electrolysis Module

Ar, Ar/H2 (95:5), and Ar/O2 (95:5) plasmas are used for treating the NiCo metal–organic framework (MOF), and the plasma-processed NiCo MOF is applied for catalyzing the oxygen evolution reaction (OER) in a 1 M KOH electrolyte. Linear sweep voltammetry measurements show that after plasma treatment with Ar/H2 (95:5) and Ar gases, the overpotential reaches 552 and 540 mV, respectively, at a current density of 100 mA/cm2. The increase in the double-layer capacitance further confirms the enhanced oxygen production activity. We test the Ar plasma-treated NiCo MOF as an electrocatalyst at the OER electrode and Ru as an electrocatalyst at the hydrogen evolution reaction (HER) electrode in the alkaline water electrolysis module. The energy efficiency of the electrolyzer with the Ar plasma-processed NiCo-MOF catalyst increases from 54.7% to 62.5% at a current density of 500 mA/cm2 at 25 °C. The alkaline water electrolysis module with the Ar plasma-processed catalyst also exhibits a specific energy consumption of 5.20 kWh/m3 and 4.69 kWh/m3 at 25 °C and 70 °C, respectively. The alkaline water electrolysis module performance parameters such as the hydrogen production rate, specific energy consumption, and energy efficiency are characterized at temperatures between 25 °C and 70 °C. Our experimental results show that the NiCo MOF is an efficient OER electrocatalyst for the alkaline water electrolysis module.

Recent strategies for improving the catalytic activity of ultrathin transition metal sulfide nanosheets toward the oxygen evolution reaction

Hydrogen is considered as one of the clean secondary energy sources required in industry and daily life. Electrocatalytic hydrogen production is believed to be the most reliable method for converting renewable energy into chemical energy. Two-dimensional (2D) transition metal disulfides (TMDs), as an emerging electrocatalysts, have been widely investigated for oxygen evolution reaction (OER) in water splitting. Herein, this review summarizes the recent progress and the strategies of ultrathin TMDs for improving the OER electrocatalytic activities. The basic catalytic mechanism of OER is first introduced, and then the catalytic characteristics of 2D TMDs are presented. Importantly, this review specifically concentrates on strategies to improve catalytic activity such as phase engineering, defect/vacancy engineering, heterostructure, doping effect, and catalyst support material. It can be concluded that these regulatory strategies can largely enhance the electrocatalytic performance by increasing the active site exposure and improving the electrocatalytic kinetics. In addition, the challenges and perspectives of 2D TMDs catalysts are presented, which offers valuable guidance in designing efficient and low-cost OER electrocatalysts for future energy applications. We hope that this review will inspire future studies and bridge the gap between strategy design and practical application.

Engineering high-valence metal-enriched cobalt oxyhydroxide catalysts for an enhanced OER under near-neutral pH conditions.

Understanding water splitting in pH-neutral media has important implications for hydrogen production from seawater. Despite their significance, electrochemical water oxidation and reduction in neutral electrolytes still face great challenges. This study focuses on designing efficient electrocatalysts capable of promoting the oxygen evolution reaction (OER) in neutral media by incorporating high-valence elements into transition-metal hydroxides. The as-prepared and optimized two-dimensional Mo-Co(OH)2 nanosheets, which undergo operando transformation into oxyhydroxide active species, demonstrated an overpotential of 550 mV at 10 mA cm-2 with a Tafel slope of 110.1 mV dec-1 in 0.5 M KHCO3. In situ X-ray absorption spectroscopy revealed that the incorporation of high-valence elements facilitates the generation of CoOOH active sites at low potential and enhances electron transfer kinetics by altering the electronic environment of the Co center. This study offers new insights for developing more efficient OER electrocatalysts and provides fresh ideas for seawater utilization through the study of the reaction mechanism of the near-neutral-pH OER.

Recent progress in hierarchical nanostructures for Ni-based industrial-level OER catalysts.

Exploring efficient and low-cost oxygen evolution reaction (OER) electrocatalysts reaching the industrial level current density is crucial for hydrogen production via water electrolysis. In this feature article, we summarize the recent progress in hierarchical nanostructures for the industrial-level OER. The contents mainly concern (i) the design of a hierarchical structure; (ii) a Ni-based hierarchical structure for the industrial current density OER; and (iii) the surface reconstruction of the hierarchical structure during the OER process. The work provides valuable guidance and insights for the manufacture of hierarchical nanomaterials and devices for industrial applications.

MXene boosted MOF-derived cobalt sulfide/carbon nanocomposites as efficient bifunctional electrocatalysts for OER and HER.

The development of effective bifunctional electrocatalysts that can realize water splitting to produce oxygen and hydrogen through oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is still a great challenge to be addressed. Herein, we report a simple and versatile approach to fabricate bifunctional OER and HER electrocatalysts derived from ZIF67/MXene hybrids via sulfurization of the precursors in hydrogen sulfide gas atmosphere at high temperatures. The as-prepared CoS@C/MXene nanocomposites were characterized using a series of technologies including X-ray diffraction, gas sorption, scanning electronic microscopy, transmission electronic microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy. The synthesized CoS@C/MXene composites are electrocatalytically active in both HER and OER, and the CSMX-800 composite displayed the highest electrocatalytic performance towards OER and HER among all the produced samples. CSMX-800 exhibited overpotentials of 257 mV at 10 mA cm-2 for OER and 270 mV at 10 mA cm-2 for HER. Moreover, it also possesses small Tafel slope values of 93 mV dec-1 and 103 mV dec-1 for OER and HER, respectively. The enhanced electrocatalytic performance of the MXene-containing composites is due to their high surface area, enhanced conductivity, and faster charge transfer. This work demonstrated that CoS@C/MXene based electrocatalyst has great potential in electrochemical water splitting for hydrogen production, thus reducing carbon emissions and protecting the environment.

Tailoring iridium-palladium nanoparticles with Ir-rich skin: a highly durable anode electrocatalyst for acidic water electrolysis via a facile microwave-assisted chemical reduction method.

Electrochemical water splitting under acidic conditions is a clean way towards producing hydrogen fuels. The slow kinetics of the oxygen evolution reaction (OER) at the anode is currently a bottleneck for commercial acceptance of this technology. Therefore, arriving at more efficient and sustainable OER electrocatalysts is highly desirable. We here demonstrate the synthesis of iridium-palladium (IrPd) alloy nanoparticles (2-5 nm) with variable average composition (Ir : Pd = 1 : 0, 1 : 1, 1 : 3, 1 : 6, 1 : 9 and 0 : 1) using a facile one-pot microwave-assisted chemical reduction method. The IrPd nanoparticles show structure- and composition-dependent OER performance in acidic media. Utilizing different reduction strengths and precursor ratios, successful alloy catalysts were prepared with Ir-rich skin and sublayers of different Pd compositions. Their structures were revealed using high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and hydrogen underpotential deposition (Hupd) studies. It turned out that (1) the alloy OER catalyst also has a high electrochemically active surface area for hydrogen adsorption/desorption, (2) the OER performance is strongly dependent on the surface Ir contribution and (3) the intact Ir skin is essential for electrocatalyst stability.

Zn-facilitated surface reconstruction of Ni-MOF for an enhanced oxygen evolution reaction.

Facilitating the surface reconstruction of pre-catalysts has been considered an effective strategy for constructing low-cost and highly efficient OER electrocatalysts. Metal doping is a feasible way to activate the surface reconstruction, thus enhancing the OER performance. Herein, we report a facile hydrothermal method to synthesize a series of Zn-doped Ni-MOF on nickel foam (NiZn-MOF/NF) as promising pre-catalysts toward the oxygen evolution reaction (OER). The Zn leaching of NiZn-MOF/NF can promote the surface self-reconstruction of NiZn-MOF/NF into oxygen-vacancy-rich NiOOH after electrochemical activation. Benefiting from the optimized electronic structure, abundant defects, more accessible active sites, and enhanced electrical conductivity, the reconstructed metal oxyhydroxide hybrids exhibit better electrocatalytic activity than the catalysts transformed from Ni-MOF/NF without Zn doping. The optimized NiZn-MOF/NF-OH as an OER catalyst has an overpotential of 336 mV at 100 mA cm-2, and a Tafel slope of 65.9 mV dec-1, as well as stability over 12 h. This work reveals that Zn cation-doping/leaching induces the surface reconstruction of pre-catalysts for enhanced oxygen catalytic activity, which provides a new approach for the development of advanced electrocatalysts.

Highly hydrophilic and surface defect-rich MOF-74-PA15 obtained by phytic acid etching as a robust catalyst for the oxygen evolution reaction.

Water splitting is an energy conversion process of vital importance. The oxygen evolution reaction (OER), as the half-reaction of water splitting, has very slow kinetics due to the complex quaternary electron transfer process involved, which greatly impedes the efficiency of energy conversion. The rational construction and modification of metal-organic frameworks (MOFs) offer a novel alternative for developing efficient OER electrocatalysts. In this study, MOF-74-PA15 with abundant surface defects and high hydrophilicity was successfully in situ constructed by etching MOFs for different reaction times using phytic acid (PA). The etching of PA increases the active area, and improves the hydrophilicity, allowing tighter contact between the material and the electrolyte. As a result, MOF-74-PA15 exhibits the most optimal OER catalytic performance in all the samples. The overpotential is 250 mV in 1 M KOH at 100 mA cm-2, with the lowest Tafel slope (35.59 mV dec-1). Furthermore, MOF-74-PA15 exhibits excellent stability. It maintains stability for 72 hours at a current density of 50 mA cm-2. This study presents a novel and feasible solution for modifying MOFs as electrocatalytic water splitting catalysts.

Multi-interface anchoring enables atomic-level dispersion of Ru for efficient water oxidation

Although noble metal-based catalysts are expensive, they are still the most promising oxygen evolution reaction (OER) electrocatalysts. Therefore, it is desirable to reduce the load of the precious metal without affecting the OER performance of the catalyst. In this work, we have innovatively proposed a strategy of interfacial anchoring of Ru atoms and successfully achieve the dispersion of precious metal ruthenium atoms in cross-growing NiS and NiSe multifaceted structures. The dispersion of Ru ensures Ru–NiS/NiSe/NF more active sites and more adequate contact with the electrolyte, which further improves the oxygen production property of the catalyst. As a direct outcome, the target catalyst (Ru–NiS/NiSe/NF) only requires low overpotential of 453 mV to excite a current density of 1000 mA cm−2. Meanwhile, it can remain stable to catalyze the OER for more than 50 h (200 mA cm−2), which gives it great application potential in future large-scale electrolytic water processes. This work provides a new perspective for the efficient utilization of precious metal for designing the efficient and stable OER electrocatalyst.

In Situ Electrochemical Restructuring B-Doped Metal-Organic Frameworks as Efficient OER Electrocatalysts for Stable Anion Exchange Membrane Water Electrolysis.

Metal organic frameworks (MOFs) are promising as effective electrocatalysts toward oxygen evolution reaction (OER). However, the origin of OER activity for MOF-based electrocatalysts is still unclear because of their structure reconstruction during electrocatalysis process. Here, a novel MOF (B-MOF-Zn-Co) with spherical superstructure is developed by hydrothermal treatment of zeolitic imidazolate framework-Zn, Co (ZIF-Zn-Co) using boric acid. The resultant B-MOF-Zn-Co shows high OER activity with a low overpotential of 362mV at 100mA cm-2. Remarkably, B-MOF-Zn-Co displays excellent stability with only 3.6% voltage delay over 300h at 100mA cm-2 in alkaline electrolyte. Surprisingly, B-MOF-Zn-Co thoroughly transforms into B-doped CoOOH (B-CoOOH) during electrolysis process, which isserved as actual active material for high OER electrocatalytic performance. The newly-formed B-CoOOH possesses lower energy barrier of potential-determining step (PDS) for OOH* formation compared with CoOOH, benefiting for high OER activity. More importantly, B-MOF-Zn-Co based anion exchange membrane water electrolytic cell (AEMWE) demonstrates continuously durable operation with stable current density of 200mA cm-2 over 300h, illustrating its potential application in practice water electrolysis. This work offers an in situ electrochemical reconstruction strategy for the development of stable and effective OER electrocatalysts toward practice AEMWE.

Direct Capturing and Regulating Key Intermediates for High-Efficiency Oxygen Evolution Reactions.

Developing efficient oxygen evolution reaction (OER) electrocatalysts can greatly advance the commercialization of proton exchange membrane (PEM) water electrolysis. However, the unclear and disputed reaction mechanism and structure-activity relationship of OER pose significant obstacles. Herein, the active site and intermediate for OER on AuIr nanoalloys are simultaneously identified and correlated with the activity, through the integration of in situ shell-isolated nanoparticle-enhanced Raman spectroscopy and X-ray absorption spectroscopy. The AuIr nanoalloys display excellent OER performance with an overpotential of only 246mV to achieve 10mA cm-2 and long-term stability under strong acidic conditions. Direct spectroscopic evidence demonstrates that * OO adsorbed on IrOx sites is the key intermediate for OER, and it is generated through the O-O coupling of adsorbed oxygen species directly from water, providing clear support for the adsorbate evolution mechanism. Moreover, the Raman information of the * OO intermediate can serve as a universal "in situ descriptor" that can be obtained both experimentally and theoretically to accelerate the catalyst design. It unveils that weakening the interactions of * OO on the catalysts and facilitating its desorption would boost the OER performance. This work deepens the mechanistic understandings on OER and provides insightful guidance for the design of more efficient OER catalysts.

Activating Co sites activity in Co(OH)2via VN coupling to facilitate highly efficient oxygen evolution reaction

The quest for efficient electrocatalysts to drive the oxygen evolution reaction (OER) is paramount for renewable energy technologies such as water electrolysis. This study focuses on augmenting the catalytic activity of cobalt hydroxide (Co(OH)2) electrocatalysts by strategically coupling them with vanadium nitride (VN) heterostructures (Co(OH)2/VN@C). The synergistic effect between Co(OH)2 and VN is explored to achieve a remarkable improvement in the OER performance that the hybrid Co(OH)2/VN@C exhibits a low overpotential of 319 mV at a current density of 10 mA cm−2 and a small Tafel slope of 65 mV dec−1. Through characterization techniques and electrochemical measurements, we unveil the intricate interplay at the atomic level that triggers the activation of Co sites by V element, leading to an exceptional enhancement in catalytic activity and excellent stability. This work not only sheds light on the fundamental mechanisms involved in the Co(OH)2/VN heterostructure interaction but also presents a promising strategy for designing highly efficient OER electrocatalysts.

High Entropy Induced γ-NiOOH Formation in Layered Double Hydroxide as Highly-Active and Ultra-Stable Electrocatalyst for Oxygen Evolution Reaction

Developing a low-cost and highly efficient oxygen evolution reaction (OER) electrocatalyst and understanding the underlying reaction mechanism are critical for sustainable renewable energy conversion and storage. In this study, high entropy layered double hydroxide (LDH) was self-supported on nickel foam using a simple hydrothermal method. The resulting binder-free high entropy LDH consisting of five different transition metals of Fe, Ni, Co, Mn, and Cr exhibits an excellent OER activity in alkaline condition with a low overpotential of 218 mV at a current density of 50 mA cm-2. It is superior to the binary, ternary, and quaternary-metal LDH counterparts. We demonstrate that the high entropy LDH possesses ultra-stable electrochemical stability at a high current density of 400 mA cm-2 for 600 h. The modulation of electronic structure facilitates the formation of the highly active γ-NiOOH and the shifting of the d-band center, resulting the outstanding OER performance. The excellent catalytic activity and stability of the high entropy LHD make it is as a highly potential candidate for commercial use.

Graphene Architecture-Supported Porous Cobalt-Iron Fluoride Nanosheets for Promoting the Oxygen Evolution Reaction.

The design of efficient oxygen evolution reaction (OER) electrocatalysts is of great significance for improving the energy efficiency of water electrolysis for hydrogen production. In this work, low-temperature fluorination and the introduction of a conductive substrate strategy greatly improve the OER performance in alkaline solutions. Cobalt-iron fluoride nanosheets supported on reduced graphene architectures are constructed by a one-step solvothermal method and further low-temperature fluorination treatment. The conductive graphene architectures can increase the conductivity of catalysts, and the transition metal ions act as electron acceptors to reduce the Fermi level of graphene, resulting in a low OER overpotential. The surface of the catalyst becomes porous and rough after fluorination, which can expose more active sites and improve the OER performance. Finally, the catalyst exhibits excellent catalytic performance in 1 M KOH, and the overpotential is 245 mV with a Tafel slope of 90 mV dec-1, which is better than the commercially available IrO2 catalyst. The good stability of the catalyst is confirmed with a chronoamperometry (CA) test and the change in surface chemistry is elucidated by comparing the XPS before and after the CA test. This work provides a new strategy to construct transition metal fluoride-based materials for boosted OER catalysts.