Oxygen Evolution Reaction Research Articles

Ligand engineering enhances (photo) electrocatalytic activity and stability of zeolitic imidazolate frameworks via in-situ surface reconstruction

The current limitations in utilizing metal-organic frameworks for (photo)electrochemical applications stem from their diminished electrochemical stability. In our study, we illustrate a method to bolster the activity and stability of (photo)electrocatalytically active metal-organic frameworks through ligand engineering. We synthesize four distinct mixed-ligand versions of zeolitic imidazolate framework-67, and conduct a comprehensive investigation into the structural evolution and self-reconstruction during electrocatalytic oxygen evolution reactions. In contrast to the conventional single-ligand ZIF, where the framework undergoes a complete transformation into CoOOH via a stepwise oxidation, the ligand-engineered zeolitic imidazolate frameworks manage to preserve the fundamental framework structure by in-situ forming a protective cobalt (oxy)hydroxide layer on the surface. This surface reconstruction facilitates both conductivity and catalytic activity by one order of magnitude and considerably enhances the (photo)electrochemical stability. This work highlights the vital role of ligand engineering for designing advanced and stable metal-organic frameworks for photo- and electrocatalysis.

Tailoring Carrier Dynamics of BiVO4 Photoanode via Dual Incorporation of Au and Co(OH)x Cooperative Modification for Photoelectrochemical Water Splitting

AbstractPhotoelectrochemical solar to hydrogen production is a promising way to achieve carbon neutrality, but severe charge recombination in photoanodes limits the conversion efficiency. Herein, Au nanoparticles and Co(OH)x co‐sensitized bismuth vanadate (BiVO4) to construct AuCo(OH)x/BiVO4 photoanode for significantly enhancing the performance of photoelectrochemical water splitting. This process significantly improves the bulk charge carrier separation efficiency, the surface kinetics of water oxidation, and the electron density of BiVO4 photoanode through Au surface plasmon resonance (SPR) and Co(OH)x oxygen evolution catalysts effect. Additionally, the enhancement of the *O and the *OOH generation accelerate the oxygen evolution reaction kinetics. Consequently, the constructed AuCo(OH)x/BiVO4 photoanode demonstrates an excellent photocurrent of 6.2 mA cm−2 at 1.23 V versus reversible hydrogen electrode and a stable continuous output within 42 h. This work contributes to developing high‐efficiency and high‐stability photoanodes for solar H2 production through SPR effect and oxygen evolution catalysts.

Polyaniline prepared by Fe3O4 catalysed eco-friendly synthesis as electrocatalyst for efficient water electrolysis

Preparing cost-effective and highly active catalysts for electrocatalytic hydrogen evolution reaction is crucial for developing hydrogen-based technologies. Hence, four conductive polyanilines, prepared by the environmentally-friendly approach using Fe3O4 nanoparticles/H2O2 as the catalyst/main oxidant system (PANI/Fe3O4), were investi¬gated for the first time as electrocatalysts for hydrogen evolution reaction (HER) in acidic media (0.1 M H2SO4) by using voltammetry and chronoamperometry. PANI/Fe3O4 electrodes exhibited Tafel slope values in the -171 to -246 mV dec-1 range depending on the synthesis conditions ‒ Fe3O4/aniline mass ratio and polymerization time. The sample PANI/Fe3O4-II(3) prepared with shorter reaction time and higher Fe3O4/aniline mass ratio showed the best electrocatalytic behaviour reflected in the lowest onset potential (-0.286 V), the lowest overpotential to reach a current density of -10 mA cm-2, the highest current density, the lowest HER activation energy (10 kJ mol-1), and the lowest charge-transfer resistance (5.3 Ω) under HER conditions. Materials were characterized by scanning electron microscopy with energy dispersive X-ray spectroscopy, X-ray photo¬electron spectroscopy and electrochemical impedance spectroscopy, and differences in their electrocatalytic HER performance were explained by differences in their content of Fe3O4, surface and electrical properties. Moreover, the possibility of using PANI/Fe3O4-II(3) as HER electrocatalyst in a wider range of pH (i.e. in alkaline media as well) and as a bifunc¬tional electrocatalyst, i.e., for oxygen evolution reaction beside HER, was also examined.

Wet-chemical synthesis of Co3Mo3C-based electrocatalysts for oxygen reduction and evolution reactions

Abstract In recent years, efforts have been made to adapt secondary metal–air batteries for practical rechargeable applications through the development of bifunctional catalysts, which are highly active in both oxygen reduction reaction and oxygen evolution reaction. Molybdenum carbides, known for their high chemical durability and electrical conductivity, are being investigated as electrode materials for hydrogen evolution reactions in water electrolysis. In this study, we found a new wet chemical synthesis of cobalt-molybdenum-based carbides. Especially, the synthesized Mn-doped Co₃(Mo₀.₉Mn₀.₁)₃C catalyst gave a remarkable activity for both oxygen evolution reaction and oxygen reduction reaction, showing significant potential for the advancement of metal–air batteries as secondary batteries.

Effect of cobalt-doped iron oxide as an electrocatalyst for water splitting and photocatalytic hydrogen evolution

Developing cost-effective and efficient electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is a significant challenge for economically viable energy conversion devices, such as electrolyzers, rechargeable metal-air batteries, and regenerative fuel cells. Here, we have synthesized cobalt doped iron oxides (CoFe2O3) with different Co:Fe wt%. Among them, Co[1:3]Fe2O3 catalyst demonstrated outstanding performance and stability positioning it as a standard electrocatalyst for OER and HER, and as a photocatalyst for H2 production. The catalysts were characterized using various techniques, including field emission scanning electron microscopy (FESEM), X-ray diffraction spectroscopy (XRD), and energy dispersive X-ray spectroscopy (EDS) demonstrating successful application in water electrolysis. Specifically, the onset potentials for OER and HER were 1.63 V/RHE and −0.23 V/RHE, respectively. The overpotential (η) required to achieve 10 mA/cm2 for OER (in alkaline medium) and HER (in acidic medium) was 0.44 and −0.3 V/RHE, respectively. Additionally, the developed OER and HER catalyst exhibited high current and potential stability over a 13-hour period. This approach is considered a promising avenue for making water electrolysis for hydrogen (H2) energy viable by minimizing the energy requirements of the electrolytic process. Similarly, the performance of the fabricated catalyst was also examined for the photocatalytic generation of H2 gas in a photo-reactor. Where the highest generation rate of 97.77 mL. (g.min−1) was recorded for Co[1:3]Fe2O3 as a photocatalyst. As a result, the Co[1:3]Fe2O3 catalyst has the potential to function as both a photocatalyst and an electrocatalyst for water splitting.

In Situ Transformed CoOOH@Co3S4 Heterostructured Catalyst for Highly Efficient Catalytic OER Application.

The deprived electrochemical kinetics of the oxygen evolution reaction (OER) catalyst is the prime bottleneck and remains the major obstacle in the water electrolysis processes. Herein, a facile hydrothermal technique was implemented to form a freestanding polyhedron-like Co3O4 on the microporous architecture of Ni foam, its reaction kinetics enhanced through sulfide counterpart transformation in the presence of Na2S, and their catalytic OER performances comparatively investigated in 1 M KOH medium. The formed Co3S4 catalyst shows outstanding catalytic OER activity at a current density of 100 mA cm-2 by achieving a relatively low overpotential of 292 mV compared to the pure Co3O4 catalyst and the commercial IrO2 catalyst. This enhancement results from the improved active centers and conductivity, which boost the intrinsic reaction kinetics. Further, the optimized Co3S4 catalyst exhibits admirable prolonged durability up to 72 h at varied current rates with insignificant selectivity decay. The energy dispersive X-ray spectroscopy (EDX) and Raman spectra measured after the prolonged OER stability test reveal a partial transformation of the active catalyst into an oxyhydroxide phase (i.e., CoOOH@Co3S4), which acts as an active catalyst phase during the electrolysis process.

Interface Engineering of Flower-like Co 2 P/WO 3-x /Carbon Cloth Catalysts with Oxygen Vacancies for Efficient Oxygen Evolution Reaction.

The Constructing an efficient and low-cost oxygen evolution reaction (OER) electrocatalyst is critical for improving the performance of electrolysis in alkaline water. In this study, a self-supported electrocatalyst of flower-like cobalt phosphide and tungsten oxide (Co2P/WO3-x/CC) was prepared on carbon cloth (CC)surface by hydrothermal reaction with solution immersion etching and phosphorization annealing under H2/Ar atmosphere. This strategy can generate oxygen vacancies (OV), improving the speed of charge transfer between cobalt phosphide (Co2P) and tungsten oxide (WO3-x) components. The catalyst greatly increases the electrochemical active surface area, which is beneficial for efficient oxygen evolution. Electrochemical testing studies show that in 1.0 M KOH solution, Co2P-WO3-x/CC catalyst exhibits good OER activity, with a low overpotential of 254 mV at 10 mA cm-2, a small Tafel slope of 58.32 mV dec-1. The synergistic effect of oxygen vacancies and Co2P with WO3-xcan regulate electronic structures, expose more active sites, and cooperatively enhancing the OER activity. This study provides a workable strategy for preparing efficient non-noble metal OER electrocatalysts on engineered interfaces and OV.

Carbon‐ and Nitrogen‐Based Complexes as Photocatalysts for Prebiotic and Oxygen Chemistry during Earth Evolution

AbstractSunlight has long served as primary energy source on our planet, shaping the behavior of living organisms. Extensive research has been dedicated to unraveling the evolutionary pathways involved. When the formation of Earth atmosphere, it primarily consisted of small gas molecules, which are considered crucial for the emergence of life. Recent demonstrations have shown that these molecules can also be transformed into semiconductors, with the potential to harness solar energy and catalyze chemical reactions as photocatalysts. Building upon this research, this minireview focuses on the potential revolutionary impact of photocatalysis on Earth. Initially, it examines key reactions, such as the formation of prebiotic molecules and the oxygen evolution reaction via water oxidation. Additionally, various C−N complexes in photocatalysts are explored, showcasing their roles in catalyzing chemical reactions. The conclusion and outlook provide a potential pathway for the evolution of Earth, shedding light on the significance of metal‐free photocatalysts in development of Earth.

CoFe2O4 nanoparticle embedded carbon nanofibers: A promising non-noble metal catalyst for oxygen evolution reaction

There is a strong demand for noble metal-free durable catalysts to facilitate the advancement of clean, sustainable energy technologies and to replace energy equipment reliant on fossil fuels. In this study, metal-organic framework (MOF)-derived CoFe2O4 (CFO) nanoparticle-embedded electrospun carbon nanofibers (CNFs) were synthesized. Nanofibers were calcined at three different temperatures to obtain optimum electrocatalytic performance in oxygen evolution reaction (OER). Nanofibers annealed at 800 °C (CFO@CNFs 800) displayed a reduced overpotential of 300 mV while maintaining a steady current density of 10 mA cm−2. CFO@CNFs 800 demonstrated Tafel slope 42 mV dec−1 with excellent long-term stability up to 48 h. The synergistic effect of the redox activity of CFO coupled with the high surface area and conductivity of carbon nanofibers is responsible for enhanced OER performance.

Unveiling the Activity Origin of Electrochemical Oxygen Evolution on Heteroatom‐Decorated Carbon Matrix

AbstractChemical modification via functional dopants in carbon materials holds great promise for elevating catalytic activity and stability. To gain comprehensive insights into the pivotal mechanisms and establish structure‐performance relationships, especially concerning the roles of dopants, remains a pressing need. Herein, we employ computational simulations to unravel the catalytic function of heteroatoms in the acidic oxygen evolution reaction (OER), focusing on a physical model of high‐electronegative F and N co‐doped carbon matrix. Theoretical and experimental findings elucidate that the enhanced activity originates from the F and pyridinic‐N (Py−N) species that achieve carbon activation. This activated carbon significantly lowers the conversion energy barrier from O* to OOH*, shifts the potential‐limiting step from OOH* formation to O* generation, and ultimately optimizes the energy barrier of the potential‐limiting step. This wok elucidates that the critical role of heteroatoms in catalyzing the reaction and unlocks the potential of carbon materials for acidic OER.

Unveiling the Activity Origin of Electrochemical Oxygen Evolution on Heteroatom-Decorated Carbon Matrix.

Chemical modification via functional dopants in carbon materials holds great promise for elevating catalytic activity and stability. To gain comprehensive insights into the pivotal mechanisms and establish structure-performance relationships, especially concerning the roles of dopants, remains a pressing need. Herein, we employ computational simulations to unravel the catalytic function of heteroatoms in the acidic oxygen evolution reaction (OER), focusing on a physical model of high-electronegative F and N co-doped carbon matrix. Theoretical and experimental findings elucidate that the enhanced activity originates from the F and pyridinic-N (Py-N) species that achieve carbon activation. This activated carbon significantly lowers the conversion energy barrier from O* to OOH*, shifts the potential-limiting step from OOH* formation to O* generation, and ultimately optimizes the energy barrier of the potential-limiting step. This wok elucidates that the critical role of heteroatoms in catalyzing the reaction and unlocks the potential of carbon materials for acidic OER.

Hierarchical MoO2@MoS2 heterojunction nanosheets anchored with metal-organic framework-derived CoFe alloy as bifunctional catalysts for flexible zinc-air batteries

Crafting a robust, high-performance, non-precious metal-based flexible air electrode is crucial for realizing flexible zinc-air batteries (ZABs). Herein, hierarchical MoO2 and MoS2 heterojunction nanosheets grown on carbon cloth (CC) are prepared through a simple hydrothermal reaction followed by calcination. Afterward, through self-assembly and high-temperature carbonization of zeolitic imidazolate framework-67 (ZIF-67) and Materials of Institute Lavoisier-101 (MIL-101) on the heterojunction nanosheets, a hierarchical structure of nitrogen-doped carbon (NC) encapsulated CoFe alloy nanoparticles (NPs) supported on MoO2@MoS2 heterojunction nanosheets (CC/MoS2@MoO2@CoFe) is obtained. It exhibits remarkable activity and durability for both bifunctional oxygen evolution and reduction reactions (OER/ORR), attributed to the ternary heterojunction formed by NC-coated CoFe alloy NPs uniformly dispersed among the MoO2@MoS2 nanosheets, along with oxygen vacancies at heterogeneous interfaces between MoS2, MoO2, and Co0.72Fe0.28 alloy. As a binder-less self-supporting electrode, the assembled aqueous ZAB demonstrates a maximum power density of 113.6 mW cm–2, surpassing that of Pt/C + RuO2 (75.2 mW cm–2), along with excellent cycling stability. Furthermore, the CC/MoS2@MoO2@CoFe-based flexible ZABs achieve a maximum power density of 54.1 mW cm–2, exhibit good cycling stability for up to 120 cycles, and show outstanding flexibility. This study paves the way for the practical integration of flexible ZABs into wearable electronic devices, heralding a new era of portable power solutions.

Recent Advances in Nickel-Based Perovskite Oxides for the Electrocatalytic Oxygen Evolution Reaction in Alkaline Electrolytes

Recent Advances in Nickel-Based Perovskite Oxides for the Electrocatalytic Oxygen Evolution Reaction in Alkaline Electrolytes

Electrodeposited NiB Films as Bifunctional Electrocatalysts in Alkaline Water Electrolizer

Abstract Sustainable electrochemical energy generation requires cost-effective, noble-metal-free electrocatalysts for hydrogen and oxygen production in electrolyzers. This study used electrodeposition to create crystalline NiB films with different boron (B) contents—Ni-B(1.17 wt.%), Ni-B(1.06 wt.%), Ni-B(0.94 wt.%), and Ni-B(0.89 wt.%)—on FTO substrates. These films were tested as bifunctional electrocatalyst electrodes for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline media. The NiB films' composition and morphology were analyzed using SEM, AFM, XRD, GD-OES, and XPS. Linear sweep voltammetry assessed their electrocatalytic performance. Higher B content in the films promoted the formation of electroactive NiOOH, enhancing the OER. The Ni-B(1.17 wt.%) electrode required an overpotential of 380 mV to reach 10 mA cm⁻² for OER, while the Ni-B(1.06 wt.%) electrode required 146 mV for the same current density for HER. An alkaline water electrolyzer using Ni-B(1.17 wt.%) as the anode and Ni-B(1.06 wt.%) as the cathode achieved a current density of 10 mA cm⁻² at 1.71 V for overall water splitting. The system showed stability over 12 hours of testing. The results indicate that NiB films on FTO substrates are promising, low-cost bifunctional electrocatalysts for alkaline water electrolysis, offering an alternative to noble-metal-based electrocatalysts.

Achievements and Challenges in Surfactants-Assisted Synthesis of MOFs-Derived Transition Metal-Nitrogen-Carbon as a Highly Efficient Electrocatalyst for ORR, OER, and HER.

Metal-organic frameworks (MOFs) are excellent precursors for preparing transition metal and nitrogen co-doped carbon catalysts, which have been widely utilized in the field of electrocatalysis since their initial development. However, the original MOFs derived catalysts have been greatly limited in their development and application due to their disadvantages such as metal atom aggregation, structural collapse, and narrow pore channels. Recently, surfactants-assisted MOFs derived catalysts have attracted much attention from researchers due to their advantages such as hierarchical porous structure, increased specific surface area, and many exposed active sites. This review mainly focuses on the synthesis methods of surfactants-assisted MOFs derived catalysts and comprehensively introduces the action of surfactants in MOFs derived materials and the structure-activity relationship between the catalysts and the oxygen reduction reaction, oxygen evolution reaction, and hydrogen evolution reaction performance. Apparently, the aims of this review not only introduce the status of surfactants-assisted MOFs derived catalysts in the field of electrocatalysis but also contribute to the rational design and synthesis of MOFs derived catalysts for fuel cells, metal-air cells, and electrolysis of water toward hydrogen production.

Carbon nanomaterials for efficient oxygen and hydrogen evolution reactions in water splitting: A review

Water splitting has gained significant attention as a means to produce clean and sustainable hydrogen fuel through the electrochemical or photoelectrochemical decomposition of water. Efficient and cost-effective water splitting requires the development of highly active and stable catalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Carbon nanomaterials, including carbon nanotubes, graphene, and carbon nanofibers, etc., have emerged as promising candidates for catalyzing these reactions due to their unique properties, such as high surface area, excellent electrical conductivity, and chemical stability. This review article provides an overview of recent advancements in the utilization of carbon nanomaterials as catalysts or catalyst supports for the OER and HER in water splitting. It discusses various strategies employed to enhance the catalytic activity and stability of carbon nanomaterials, such as surface functionalization, hybridization with other active materials, and optimization of nanostructure and morphology. The influence of carbon nanomaterial properties, such as defect density, doping, and surface chemistry, on electrochemical performance is also explored. Furthermore, the article highlights the challenges and opportunities in the field, including scalability, long-term stability, and integration of carbon nanomaterials into practical water splitting devices. Overall, carbon nanomaterials show great potential for advancing the field of water splitting and enabling the realization of efficient and sustainable hydrogen production.

Rational Design of Ultrahigh-Loading Ir Single Atoms on Reconstructed Mn─NiOOH for Enhanced Catalytic Performance in Urea-Water Electrolysis.

Investigating advanced electrocatalysts is crucial for improving the efficacy of water splitting to generate environmentally friendly fuel. The discovery of highly effective electrocatalysts, capable of driving oxygen evolution reaction (OER) and urea oxidation reaction (UOR) in urea-alkaline environments, is pivotal for advancing large-scale hydrogen production. This study aims to introduce a new method that involves creating nanosheets of high-loading iridium single atoms embedded in a manganese-containing nickel oxyhydroxide matrix (Ir@Mn─NiOOH). These nanostructures are derived from self-supported hydrate pre-catalyst nanosheets grown on nickel foam and then activated through electrochemical etching pretreatment. The Ir@Mn─NiOOH nanoarchitecture displays outstanding electrocatalytic activity, having a low overpotential of just 258mV and a potential of 1.319V (at 10mAcm-2) for OER and UOR, respectively. Such extraordinary catalytic characteristics of Ir@Mn─NiOOH is mainly owing to the strong synthetic electronic interaction between Ir single atoms and Mn─NiOOH, which can change its electronic characteristics and boost electrochemical catalytic sites. This research presents a new way to produce exceptionally efficient catalysts by adding a synergistic effect to complex multi-electron processes.

Upcycling of waste polyethylene terephthalate (PET) into CoFe@C for highly efficient PV-driven bifunctional seawater splitting via a “waste materialization” strategy

Developing green and efficient techniques to convert plastic wastes into functional materials is attractive and remains highly challenging. This study employs a hydrothermal combining with pyrolysis process for constructing a Co3Fe1@C heterostructure from the polyethylene terephthalate (PET) waste-mediated metal-organic frameworks. The as-obtained Co3Fe1@C shows a core-shell structure and possesses good performance towards water electrolysis. The Co3Fe1@C can attain the current density of 100 mA cm−2 with an overpotential of 250 mV for oxygen evolution reaction (OER). In addition, the bifunctional Co3Fe1@C can realize the overall seawater electrolysis at 50 mA cm−2 with good stability for 280 h driven by a 2.2 V commercial silicon solar cell. Overall, this study demonstrates a green chemistry approach to simultaneous plastic waste upcycling and cost-effective electrocatalyst fabrication, which may stimulate further research on the “waste materialization” approach to converting solid waste into highly efficient catalysts for various chemistry and energy industry applications.

Novel synthesis of CuHCF/B-rGO composites for oxygen evolution reaction activity

In this work, we have focused on the preparation of copper hexacyanoferrate/boron doped rGO composites (abbreviated as CuHCF/B-rGO) by employing simple co-precipitation technique subsequently processed with ultrasonication method. The XRD spectra confirmed the existence of the cubic structure of copper hexacyanoferrate with high crystalline peaks. The prepared nanocomposite morphology was evaluated by scanning electron microscopy (SEM), and confirmed CuHCF nanoparticles formation with flake-like and wrinkled sheets. Pure CuHCF nanostructures revealed good OER action at 430 mV to obtain 10 mA/cm2. The obtained CuHCF product OER activity can be further upgraded by incorporating the electrically conductive boron doped reduced graphene oxide matrix into CuHCF nanostructures, for the reason that the overpotential of the CuHCF/B-rGO was reduced to 380 mV to attain 10 mA/cm2 with 88 mV/dec Tafel slope value. The doping of heteroatom considerably improves charge-transfer resistance of metal hexacyanoferrate, giving a small resistance value of 2.97 Ω, which was lower than that of CuHCF (5.57 Ω) and CuHCF/rGO (4.31 Ω). Furthermore, the catalytic activity of the CuHCF/B-rGO was stable at prolonged hours with a small decay of 12.5%. Therefore, this work offers new approach to stimulate the catalytic performance of metal hexcyanoferrate by highly conductive carbon-based materials for water splitting performance.

Coordination Tuning of FeNi-HMT Frameworks Derived Effective Hybrid Catalysts for Water Oxidation.

FeNi-based hybrid materials are promising oxygen evolution reaction (OER) catalysts for water electrolysis in hydrogen generation. In this work, the coordination tuning of FeNi-HMT frameworks was achieved by simply changing the Fe/Ni ratios using hexamethylenetetramine (HMT) as an organic ligand, and the derived hybrid FeNi catalysts with varied compositions were probed for OER. Incorporating varying amounts of Fe3+ by adjusting the Ni/Fe ratio results in different metal-organic framework (MOF) structures, and higher Fe feed leads to the formation of amorphous structures due to the coordination structure destruction from the weaker coordination capacity of Fe3+ compared to Ni2+ combining with the tertiary amine ligand. Among them, the FeNi-HMT (with the Fe/Ni molar ratio of 1/1) derived catalyst, consisting of Fe0.36Ni0.64 alloy/Ni0.4Fe2.6O4 spinel oxide heterostructures supported by graphitized carbon matrix, exhibits the highest OER performance. The unique structure facilitates significant electron transfer at the alloy/spinel interface due to the large work function difference between each phase. This strong electronic effect downshifts the d-band center of the catalyst and optimizes the binding energies to the crucial oxygenated intermediates, thereby promoting the OER kinetics. This work highlights the importance of the coordination tuning of FeNi-HMT frameworks for highly efficient catalyst development.