Improved Oxygen Evolution Reaction Research Articles

Cutting-Edge PCN-ZnO Nanocomposites with Experimental and DFT Insights into Enhanced Hydrogen Evolution Reaction.

Polymeric carbon nitride (PCN) and PCN-ZnO nanocomposites are promising candidates for catalysis, particularly for hydrogen evolution reactions (HER). However, their catalytic efficiency requires enhancement to fully realize their potential. This study aims to improve the HER performance of PCN by synthesizing PCN-ZnO nanocomposites using melamine as a precursor. Two synthesis methods were employed: thermal condensation (Method 1) and liquid exfoliation (Method 2). Method 1 resulted in a composite with a 2.44 eV energy gap and reduced particle size, with significantly enhanced performance as a bifunctional electrocatalyst for simultaneous hydrogen and oxygen production. In contrast, Method 2 produced a nanocomposite with an enhanced surface area and a minor alteration in the band gap. In alkaline electrolytes, the PCN-ZnO0.4 nanocomposite synthesized with Method 1 exhibited high HER performance with an overpotential of 281 mV, outperforming pristine PCN (382 mV) and ZnO (302 mV), along with improved oxygen evolution reaction (OER) activity. Further analysis in a two-electrode alkaline electrolyzer using PCN-ZnO0.4 nanocomposite as both the anode and cathode demonstrated its promise as a bifunctional electrocatalyst. Density functional theory (DFT) calculations explained the enhanced catalytic activity of the PCN-ZnO nanocomposite, confirming that hydrogen evolution occurs through the Heyrovsky process, consistent with experimental results. Notably, the solar-to-hydrogen (STH) efficiency of the PCN-ZnO nanocomposite was four times greater, at 21.7% compared to 5.2% for the PCN monolayer, underscoring its potential for efficient solar-driven hydrogen production. This work paves the way for future advancements in the design of high-performance electrocatalysts for sustainable energy applications.

Revealing Enhanced Active Oxygen Formation by Incorporating Chromium into Nickel Hydroxide Nanosheets for Improved Oxygen Evolution Reaction.

Nickel-based oxyhydroxides have emerged as promising catalysts for the oxygen evolution reaction (OER) among Earth-abundant metals. While the incorporation of foreign elements is recognized to enhance catalytic activity, the origin of this enhancement is still debated. We synthesize and examine Ni hydroxide nanosheets, both with and without Cr doping, to elucidate the underlying enhancements. Operando UV-vis and Raman spectroscopy are employed to unravel the behavior of the catalysts. The Cr doping facilitates the oxidation of Ni, resulting in the generation of active oxygen species. The enriched active oxygen species improves OER performance through a lattice oxygen-mediated pathway in Fe-free KOH, and further contribute to the creation and increased activity of FeOxHy sites in the presence of Fe impurities. This work provides a mechanistic understanding of the performance enhancement in Ni-based catalysts through Cr doping and suggests a strategy for the design of more efficient catalysts in the future.

Role of active redox sites and charge transport resistance at reaction potentials in spinel ferrites for improved oxygen evolution reaction

Fe and Ni oxide-based systems are often investigated as electrocatalysts for the oxygen evolution reaction (OER) in water electrolysis and the improvement in OER activity is explained by two main reasons, (i) improving bulk electrical conductivity and (ii) synergic effect between Ni and Fe. Among the two factors, the identification of the dominant factor for OER is very important for catalyst engineering in the right direction. In order to have a better understanding, spinel-structured ZnFe2O4 nanoparticles have been synthesized and its bulk conductivity is studied by progressively varying Ni doping. The conductivity of the synthesised compounds follows the order of ZnFe2O4 > Ni0.3Zn0.7Fe2O4 > Ni0.5Zn0.5Fe2O4 > Ni0.7Zn0.3Fe2O4 > NiFe2O4. The oxygen evolution studies reveal that NiFe2O4 is highly active with an onset potential of 1.57 V versus reversible hydrogen electrode (RHE) and Tafel slope of 102 mV/dec. With the increase in Ni doping, the structure changes from spinel to inverse spinel as confirmed by X-ray diffraction and Raman spectra. Further, the contribution from Ni redox sites in addition to Fe ion sites and FexNi1−xOOH species formation, causes improved OER performance. This study uniquely proves that the OER activity majorly relies on redox/active metal sites, FexNi1−xOOH species and charge transfer resistance at OER potential rather than the bulk electrical conductivity of spinel ferrites. This conclusion is supported by voltammetry and impedance studies of five different spinel ferrites.

Exploring the Phase Transformation of Tri-Metallic Prussian Blue Analogue Pre-Catalyst for Improved Oxygen Evolution Reaction

The development of non-noble metal electrocatalyst with high-efficiency and clear underlying of the related reaction mechanism towards the sluggish oxygen evolution reaction (OER) is critical for large-scale hydrogen production. In this study, tri-metallic Prussian blue analogue (PBA) of FeCoNi-PBA was synthesized using a facile and low-energy consumption co-precipitation method. The FeCoNi-PBA was found to be etched by the high-pH 1 M KOH electrolyte such that under anodic applied potential during electrolysis the formation of metal (oxy)hydroxide is accelerated. Operando Raman and post-mortem characterizations reveal that the applied anodic potential promotes the phase transformation so that the PBA undergoes self-reconstruction to form metal (oxy)hydroxide embedded in a carbon matrix with fully exposed active sites. The metal (oxy)hydroxide serves as the real active sites while the carbon matrix is believed to enhance the conductivity and hydrophilicity, which facilitates the electron transfer and electrolyte diffusion to improve the OER performance. In alkaline media, FeCoNi-PBA demonstrates excellent OER performance with a low overpotential of 236 mV at 10 mA cm−2, small Tafel slope of 43.8 mV dec-1, and long-term durability.

Revealing the characteristics of oxygen evolution reaction performance of NiZn ferrites

Magnetic field-assisted method has been proved as an effective method to improve oxygen evolution reaction performance (OER) of water splitting, however, the essential reason for the improvement of OER performance still remains unclear. Herein, Ni1-xZnxFe2O4 ferrites were prepared by the combination of hydrothermal and calcination method, the magnetic properties, oxygen evolution reaction performance and the effect of applied magnetic field on OER performance were studied and discussed according to the magnetic properties and ion site situation. The magnetic field effect depended on the applied magnetic field strength and the magnetic magnetization density of catalysts, it was attributed to changes of electron state and redistribution of ions in the spinel structure. The overpotential decreased by approximately 50 mV and its double layer capacitance increased about 60 % at 125 mT applied magnetic field. The results provided a newness research view for the domain of electrochemistry.

Ce-4f as an electron-modulation reservoir weakening Fe-O bond to induce iron vacancies in CeFevNi hydroxide for enhancing oxygen evolution reaction

Designing novel rare-earth-transition metal composites is at the forefront of electrocatalyst research. However, the modulation of transition metal electronic structures by rare earths to induce vacancy defects and enhance electrochemical performance has rarely been reported. In this study, we systematically investigate the mechanism by which Ce-4f electron modulation weakens the Fe-O bond, thereby altering the electronic structure in CeFevNi hydroxide to improve oxygen evolution reaction (OER) performance. Theoretical calculations and experimental characterizations reveal that Ce-4f orbitals function as electron-modulation reservoirs, capable not only of retaining or donating electrons but also of influencing the material's electronic structure. Moreover, Ce-4f bands optimize the Fe lower Hubbard bands (LHB) and O-2p bands, leading to weakened Fe-O bonds and the formation of cationic vacancies. This change results in the upshift of the d-band center at the active sites, favoring the reaction energy barrier for oxygen intermediates in the OER process. The synthesized catalyst demonstrated an overpotential of 201 mV at 10 mA cm−2 and a lifetime exceeding 200 h at 100 mA cm−2 under alkaline conditions. This work offers a proof-of-concept for the application of the mechanism of rare earth-induced transition metal vacancy defects, providing a general guideline for the design and development of novel highly efficient catalysts.

Large-area ultrathin 2D Co(OH)2 nanosheets: a bifunctional electrode material for supercapacitor and water oxidation

Ultrathin film of active materials having thickness <5 nm emerged as a promising candidate for miniaturized energy storage and conversion devices. However, the small lateral size restricts its real device applications. Herein, we report large area, 2D, ultrathin (thickness: 4.3 ± 0.3 nm) Co(OH)2 nanosheets as bifunctional electrode material for supercapacitor and oxygen evolution reaction developed by ionic layer epitaxy method at the water-air interface. The symmetric supercapacitor device exhibited excellent volumetric capacitance of 2313 F/cm3 at 0.4 mA/cm2 current density. Additionally, it exhibited a remarkable volumetric energy density of 0.205 Wh/cm3 at a power density of 0.145 W/cm3, which is better than reported 2D electrode materials. Furthermore, the cobalt hydroxide (Co(OH)2) ultrathin-film electrodes showed improved oxygen evolution reaction electrocatalytic activity with low overpotential (ƞ10, 330 mV) and Tafel slope (47 mV/dec). The structural and morphological investigations after long-term operations show substantial stability of the electrode material. The theoretical investigations of electronic structures, quantum capacitance, and free energy profiles for the oxygen evolution reaction mechanism corroborate the experimental results.

Hierarchically Structured Graphene Aerogel Supported Nickel-Cobalt Oxide Nanowires as an Efficient Electrocatalyst for Oxygen Evolution Reaction.

The rational design of a heterostructure electrocatalyst is an attractive strategy to produce hydrogen energy by electrochemical water splitting. Herein, we have constructed hierarchically structured architectures by immobilizing nickel-cobalt oxide nanowires on/beneath the surface of reduced graphene aerogels (NiCoO2/rGAs) through solvent-thermal and activation treatments. The morphological structure of NiCoO2/rGAs was characterized by microscopic analysis, and the porous structure not only accelerates the electrolyte ion diffusion but also prevents the agglomeration of NiCoO2 nanowires, which is favorable to expose the large surface area and active sites. As further confirmed by the spectroscopic analysis, the tuned surface chemical state can boost the catalytic active sites to show the improved oxygen evolution reaction performance in alkaline electrolytes. Due to the synergistic effect of morphology and composition effect, NiCoO2/rGAs show the overpotential of 258 mV at the current density of 10 mA cm-2. Meanwhile, the small values of the Tafel slope and charge transfer resistance imply that NiCoO2/rGAs own fast kinetic behavior during the OER test. The overlap of CV curves at the initial and 1001st cycles and almost no change in current density after the chronoamperometric (CA) test for 10 h confirm that NiCoO2/rGAs own exceptional catalytic stability in a 1 M KOH electrolyte. This work provides a promising way to fabricate the hierarchically structured nanomaterials as efficient electrocatalysts for hydrogen production.

Cr dopant regulating d-orbital electronic configuration of NiFe spinel oxide to improve oxygen evolution reaction in Zn-air battery

Significant advancements towards enhancing the catalytic activity of spinel ferrites in oxygen evolution reaction (OER) have been achieved, however, further studies are required on this regard. In this study, Cr-doped spinel ferrite (NiFe2O4) embedded in N-doped C (Cr-NiFe2O4@NC) was synthesized via a high-temperature treatment using an NiFe Prussian blue analog as a precursor and K2Cr2O7 as a Cr source. Owing to the strong octahedral site preference energy, Cr3+ ions were successfully doped into octahedral sites and tailored the electronic configuration of NiFe2O4, as confirmed by XPS. The Cr-substituted Cr-NiFe2O4@NC exhibited the overpotential of 241 mV at 10 mA cm−2, which was smaller than that of NiFe2O4@NC (266 mV) at the same current density. Meanwhile, the Tafel slope of Cr-NiFe2O4@NC (65.32 mV dec−1) was also lower than that of NiFe2O4@NC (86.96 mV dec−1). Therefore, the Cr substitution can improve the electrocatalytic OER performance of NiFe2O4@NC. In particular, an assembled rechargeable Zn-air battery using Cr-NiFe2O4@NC as the cathode catalyst afforded a high power density (61.1 mA cm−2) together with a high specific capacity (740 mA g−1). Amazingly, it could power light-emitting diodes, demonstrating its real-world application. Density functional theory calculations revealed that Cr ion doping led to electron transfer in NiFe2O4, resulting in a density of electronic states close to the Fermi level, which probably regulated the adsorption/desorption behaviors of oxygenate intermediates (*O and *OOH), thus promoting the reaction kinetics of the OER. This study provides a helpful basis for the development of spinel oxides with high electrocatalytic OER activity and durability via cation doping.

Elucidating the green energy production potential of biomimetically fashioned [OFR-MnO/ZrO2]-MMO electrocatalyst

A new hybrid metal oxide (MnO/ZrO2) has been synthesized by an environmentally benign material from the Olea ferruginea royle (OFR)plant leaf extract as a green precursor. The hybrid material has improved oxygen evolution reaction (OER) electrochemical performance. The existence of [OFR-MnO/ZrO2] particles is confirmed by spectroscopic techniques, X-ray photoelectron spectroscopy (XPS), and elemental diffraction spectroscopic (EDS) investigations, emphasizing the role of organic species (N, O and C) during synthesis. To assess the electrode’s electrochemical performance, linear sweep voltametric and impedance measurements were performed. The electrode showed a lower linear sweep measurement of 382 mV and a Tafel value of 79 mV dec−1, suggesting MnO/ZrO2 as an efficient electrocatalytic material. These results demonstrate the potential of MnO/ZrO2 as an excellent, long-term and economical solution for a variety of applications, particularly in the area of water splitting research.

Improved Oxygen Evolution Reaction Kinetics with Titanium Incorporated Nickel Ferrite for Efficient Anion Exchange Membrane Electrolysis

Improved Oxygen Evolution Reaction Kinetics with Titanium Incorporated Nickel Ferrite for Efficient Anion Exchange Membrane Electrolysis

Cobalt‐based Co3Mo3N/Co4N/Co Metallic Heterostructure as a Highly Active Electrocatalyst for Alkaline Overall Water Splitting

AbstractAlkaline water electrolysis holds promise for large‐scale hydrogen production, yet it encounters challenges like high voltage and limited stability at higher current densities, primarily due to inefficient electron transport kinetics. Herein, a novel cobalt‐based metallic heterostructure (Co3Mo3N/Co4N/Co) is designed for excellent water electrolysis. In operando Raman experiments reveal that the formation of the Co3Mo3N/Co4N heterointerface boosts the free water adsorption and dissociation, increasing the available protons for subsequent hydrogen production. Furthermore, the altered electronic structure of the Co3Mo3N/Co4N heterointerface optimizes ΔGH of the nitrogen atoms at the interface. This synergistic effect between interfacial nitrogen atoms and metal phase cobalt creates highly efficient active sites for the hydrogen evolution reaction (HER), thereby enhancing the overall HER performance. Additionally, the heterostructure exhibits a rapid OH− adsorption rate, coupled with great adsorption strength, leading to improved oxygen evolution reaction (OER) performance. Crucially, the metallic heterojunction accelerates electron transport, expediting the afore‐mentioned reaction steps and enhancing water splitting efficiency. The Co3Mo3N/Co4N/Co electrocatalyst in the water electrolyzer delivers excellent performance, with a low 1.58 V cell voltage at 10 mA cm−2, and maintains 100 % retention over 100 hours at 200 mA cm−2, surpassing the Pt/C||RuO2 electrolyzer.

Cobalt-based Co3Mo3N/Co4N/Co Metallic Heterostructure as a Highly Active Electrocatalyst for Alkaline Overall Water Splitting.

Alkaline water electrolysis holds promise for large-scale hydrogen production, yet it encounters challenges like high voltage and limited stability at higher current densities, primarily due to inefficient electron transport kinetics. Herein, a novel cobalt-based metallic heterostructure (Co3Mo3N/Co4N/Co) is designed for excellent water electrolysis. In operando Raman experiments reveal that the formation of the Co3Mo3N/Co4N heterointerface boosts the free water adsorption and dissociation, increasing the available protons for subsequent hydrogen production. Furthermore, the altered electronic structure of the Co3Mo3N/Co4N heterointerface optimizes ΔGH of the nitrogen atoms at the interface. This synergistic effect between interfacial nitrogen atoms and metal phase cobalt creates highly efficient active sites for the hydrogen evolution reaction (HER), thereby enhancing the overall HER performance. Additionally, the heterostructure exhibits a rapid OH- adsorption rate, coupled with great adsorption strength, leading to improved oxygen evolution reaction (OER) performance. Crucially, the metallic heterojunction accelerates electron transport, expediting the afore-mentioned reaction steps and enhancing water splitting efficiency. The Co3Mo3N/Co4N/Co electrocatalyst in the water electrolyzer delivers excellent performance, with a low 1.58 V cell voltage at 10 mA cm-2, and maintains 100 % retention over 100 hours at 200 mA cm-2, surpassing the Pt/C||RuO2 electrolyzer.

Ligand-regulated Ni-based coordination compounds to promote self-reconstruction for improved oxygen evolution reaction

The Ni-based coordination compounds, during oxygen evolution reaction (OER), self-reconstruct to produce NiOOH, which are the real active sites. Thus, encouraging the self-reconstruction of pre-catalysts to generate more NiOOH species...

Ternary NiFeCo-glycerolate catalysts: rational design for improved oxygen evolution reaction efficiency

This work reports a ternary Ni0.4Fe0.3Co0.3-glycerolate as an OER electrocatalyst using a one-step solvothermal strategy. This optimized composition achieved an overpotential of 277 mV at a current density of 10 mA cm−2 in 1 M KOH.

Ni-Rh-based bimetallic conductive MOF as a high-performance electrocatalyst for the oxygen evolution reaction.

Metal-organic frameworks (MOFs) have recently been considered the promising catalysts due to their merits of abundant metal sites, versatile coordination groups, and tunable porous structure. However, low electronic conductivity of most MOFs obstructs their direct application in electrocatalysis. In this work, we fabricate an Ni-Rh bimetallic conductive MOF ([Ni2.85Rh0.15(HHTP)2]n/CC) grown in situ on carbon cloth. Abundant nanopores in the conductive MOFs expose additional catalytic active sites, and the advantageous 2D π-conjugated structure helps accelerate charge transfer. Owing to the introduction of Rh, [Ni2.85Rh0.15(HHTP)2]n/CC exhibited substantially improved oxygen evolution reaction (OER) activity and exhibited only an overpotential of 320mV to achieve the current density of 20mAcm-2. The remarkable OER performance confirmed by the electrochemical tests could be ascribed to the synergistic effect caused by the doped Rh together with Ni in [Ni2.85Rh0.15(HHTP)2]n/CC, thereby exhibiting outstanding electrocatalytic performance.

The role of nonmetallic ion substitution in perovskite LaCoO3 for improved oxygen evolution reaction activity

Transition metal perovskite (ABO3) is an emerging type of oxygen evolution reaction (OER) electrocatalyst that shows reasonably good activity and moderate stability. Although efforts have been made to improve perovskite’ OER performance by various element substitution at A/B-site, the influence of ion, particularly non-metallic ion, substitutions on the OER mechanism are rarely studied. More and more evidence has shown that the metal-center theory has failed to explain lots of OER-related phenomena. Therefore, it is urgent to understand how the cation and anion sites in perovskite determine OER performance. Here, we used a Fe and P co-doped LaCoO3 as a model system to explore the influence of substitution in perovskite by combinng operando/ex-situ X-ray characterization and density functional theroy (DFT). We observed enhanced OER catalytic activities in co-doped materials, which are attributed to the stronger transition-metal-oxygen-bonding-covalency (TMOBC). The detailed analyses by O K-edge XAS, electrochemical performance, and DFT suggest that the hybridization between O 2p and transition metal 3d eg orbitals could be a more credible descriptor of perovskite for OER, which is the combination of eg orbital theory and TMOBC theory. The finding in our work provides insights into the OER catalysis mechanism on metal oxides, which could guide new design of cost-effective oxide electrocatalysts.

Coordination Tuning of Metal Porphyrins for Improved Oxygen Evolution Reaction.

The nucleophilic attack of water or hydroxide on metal-oxo units forms an O-O bond in the oxygen evolution reaction (OER). Coordination tuning to improve this attack is intriguing but has been rarely realized. We herein report on improved OER catalysis by metal porphyrin 1-M (M=Co, Fe) with a coordinatively unsaturated metal ion. We designed and synthesized 1-M by sterically blocking one porphyrin side with a tethered tetraazacyclododecane unit. With this protection, the metal-oxo species generated in OER can maintain an unoccupied trans axial site. Importantly, 1-M displays a higher OER activity in alkaline solutions than analogues lacking such an axial protection by decreasing up to 150-mV overpotential to achieve 10 mA/cm2 current density. Theoretical studies suggest that with an unoccupied trans axial site, the metal-oxo unit becomes more positively charged and thus is more favoured for the hydroxide nucleophilic attack as compared to metal-oxo units bearing trans axial ligands.

One-step preparation of anti-ferromagnetic single-atom nickel to improve oxygen evolution reaction of photoelectrochemical water splitting

Noble metal single-atom catalysts (SACs) have been extensively investigated due to their unique electronic structure and high-efficiency catalytic performance. However, there are relatively few studies on the preparation of non-noble metal single atoms and their application in oxygen evolution reaction (OER). In this paper, nickel single-atom catalyst was prepared using a facile one pot method. Ni-SAC-2.5% showed uniform SACs distribution and anti-ferromagnetic property as evidenced by the aberration-corrected high resolution electron microscopy and the first-principle calculations, achieving the lowest overpotential of 220 mV (10 mA/cm2) and stable performance in 1 M KOH solution. Meanwhile, it exhibited the largest specific capacitance value of 1.77 mF/cm2 and the lowest charge transfer resistance value of 40.75 Ω due to the accelerated kinetic process. First-principle calculations further confirmed the lowest computed overpotential of 0.54 eV for Ni-SAC-2.5%. However, Ni small clusters and nanoclusters with superparamagnetic performance were observed when the Ni content was further increased to 3.5% and 4.5%, resulting in higher overpotentials of 0.85 eV and 2.01 eV for OER process as indicated by the theoretical simulation. This paper provides a facile method to prepare non-noble metal SACs and useful guidance for designing high performance OER catalysts.

Hexagonal Boron Nitride/Reduced Graphene Oxide Heterostructures as Promising Metal‐Free Electrocatalysts for Oxygen Evolution Reaction Driven by Boron Radicals

Developing highly efficient earth‐abundant alternatives to traditional noble metal catalysts is essential for clean and sustainable energy‐conversion and energy‐storage technologies, yet still challenging in limited active sites and weak resistance to electrochemical corrosion. Herein, density‐functional theory calculations demonstrate that hexagonal boron nitride (h‐BN), albeit often being considered inert, can generate boron‐active radicals at defective sites by forming heterogeneous structures with graphene‐containing point vacancies, leading to a substantial electron delocalization and charge transfer, indicating a superior catalytic activity. Experimentally, the van der Waals heterostructure is rationally designed with h‐BN nanosheets (BNNs) anchored on reduced graphene oxide (rGO) as strongly coupled composite catalysts. Despite the poor conductivity in BN and lower catalytic activity in rGO, the created heterostructures demonstrate unexpected, improved oxygen evolution reaction (OER) activity with excellent stability in alkaline electrolyte. Qualitative analysis of the valence band offset and theoretical calculation reveal that the formation of heterostructures can significantly drive the electron transfer between C and B atoms near the vacancies across the interface and cause a half‐metallic property of BN, decreasing the free energy barrier of four‐electron OER kinetics. Herein, the synthetic schemes of h‐BNNs are guided as highly active metal‐free OER electrocatalysts.