Oxygen Evolution Electrocatalysts Research Articles

Designing 3d Transition Metal Cation-Doped MRuOx As Durable Acidic Oxygen Evolution Electrocatalysts for PEM Water Electrolyzers.

The continuous dissolution and oxidation of active sites in Ru-based electrocatalysts have greatly hindered their practical application in proton exchange membrane water electrolyzers (PEMWE). In this work, we first used density functional theory (DFT) to calculate the dissolution energy of Ru in the 3d transition metal-doped MRuOx (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) to evaluate their stability for acidic oxygen evolution reaction (OER) and screen out ZnRuOx as the best candidate. To confirm the theoretical predictions, we experimentally synthesized these MRuOx materials and found that ZnRuOx indeed displays robust acidic OER stability with a negligible decay of η10 after 15 000 CV cycles. Of importance, using ZnRuOx as the anode, the PEMWE can run stably for 120 h at 200 mA cm-2. We also further uncover the stability mechanism of ZnRuOx, i.e., Zn atoms doped in the outside of ZnRuOx nanocrystal would form a "Zn-rich" shell, which effectively shortened average Ru-O bond lengths in ZnRuOx to strengthen the Ru-O interaction and therefore boosted intrinsic stability of ZnRuOx in acidic OER. In short, this work not only provides a new study paradigm of using DFT calculations to guide the experimental synthesis but also offers a proof-of-concept with 3d metal dopants as RuO2 stabilizer as a universal principle to develop high-durability Ru-based catalysts for PEMWE.

Superior Oxygen Evolution Electrocatalyst based on Ni‐Ellagic Acid Coordination Polymer

AbstractThe oxygen evolution reaction (OER) is central to energy conversion technologies, but the high cost and scarcity of commercial noble metal catalysts limit their widespread application. Natural products exhibit great potential in preparing high‐performance electrocatalysts due to their cost‐effectiveness and sustainability. Here, a kind of 1D polymers [M‐EA (M═Co, Cu, Ni)] for oxygen evolution reaction via the complexation of ellagic acid (EA) with metal ions are reported. It is found that Ni‐EA displays a low overpotential (190 mV at 10 mA cm−2) and an ultralow Tafel slope (28 mV dec−1), with a production cost of only 3.6 × 10−2% of IrO2. Density functional theory investigations reveal the electrocatalytic mechanism of the OER. A rechargeable Zn‐Air battery using Ni‐EA+Pt/C as the air electrode shows a lower charging potential and better cycling stability than the IrO2+Pt/C‐based battery. This work provides a train for the development of state‐of‐the‐art OER catalysts.

The current state of transition metal-based electrocatalysts (oxides, alloys, POMs, and MOFs) for oxygen reduction, oxygen evolution, and hydrogen evolution reactions

Climate change is showing its impacts now more than ever. The intense use of fossil fuels and the resulting CO2 emissions are mainly to blame, accentuating the need to develop further the available energy conversion and storage technologies, which are regarded as effective solutions to maximize the use of intermittent renewable energy sources and reduce global CO2 emissions. This work comprehensively overviews the most recent progress and trends in the use of transition metal-based electrocatalysts for three crucial reactions in electrochemical energy conversion and storage, namely, the oxygen evolution (OER), oxygen reduction (ORR), and hydrogen evolution (HER) reactions. By analyzing the state-of-the-art polyoxometalates (POMs) and metal-organic frameworks (MOFs), the performance of these two promising types of materials for OER, ORR, and HER is compared to that of more traditional transition metal oxides and alloy-based electrocatalysts. Both catalytic activity and stability are highly influenced by the adsorption energies of the intermediate species formed in each reaction, which are very sensitive to changes in the microstructure and chemical microenvironment. POMs and MOFs allow these aspects to be easily modified to fine-tune the catalytic performances. Therefore, their chemical tunability and versatility make it possible to tailor such properties to obtain higher electrocatalytic activities, or even to obtain derived materials with more compelling properties towards these reactions.

CoFe(OH)x-Co3O4/NF as highly efficient electrocatalyst for oxygen evolution and urea oxidation reactions at high current densities

The advancement of an affordable and highly effective catalyst for the oxygen evolution reaction (OER) is essential to enhance the performance of overall water splitting (OWS). Here, we report a highly efficient nickel foam (NF)-supported CoFe(OH)x-Co3O4/NF heterostructure catalyst for OER. The CoFe(OH)x-Co3O4/NF heterostructure catalyst contain amorphous phase CoFe(OH)x and crystalline Co3O4, and the synergistic interaction between the two different phases reduces the charge transfer resistance, accelerates the kinetic processes of electrocatalysis and makes the catalysts exhibit excellent catalytic performance. In 1.0 M KOH solution, an overpotential (η) of merely 262 mV is needed to attain a current density of 100 mA cm−2. Even at high current densities demanded for commercial applications, the overpotentials remain very low (η500 = 291 mV, η1000 = 319 mV). The catalytic activity of CoFe(OH)x-Co3O4/NF has exceeded that of most non-noble metal OER catalysts documented in the literature. Furthermore, the CoFe(OH)x-Co3O4/NF catalyst demonstrates superior catalytic stability to OER, with only a 23 mV potential increase after 24 h of stability testing at a high current density of 500 mA cm−2. Owing to the heterostructure, the CoFe(OH)x-Co3O4/NF catalyst also exhibits excellent catalytic performance for the urea oxidation reaction (UOR), and the use of UOR instead of OER at the anode of OWS significantly reduces the cell voltage, thereby reducing the electrolytic energy consumption. The findings in this work offer precious insights into the design of OWS anode catalysts and their important applications in industrial water electrolysis. These insights are crucial for advancing the development of highly efficient and sustainable water electrolysis processes, which is essential for the production of green hydrogen and other valuable chemicals.

Fabrication of 0D/2D CoFe2O4/CoFe LDH composite intruded within CNTs network as a high-performance electrocatalyst for oxygen evolution and hydrogen evolution reactions

Designing highly efficient and durable multicomponent heterostructured composites as catalytic materials for concomitant hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is highly desirable. Researchers all over the world are continuously working to develop such materials. Herein, CNTs wrapped CoFe2O4/CoFe LDH (CoF/CoFe LDH@CNTs) ternary composite is synthesized by hydrothermal and ultra-sonication routes. Numerous methods, including X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammetry (CV), electrical Mott-Schottky, and electrochemical impedance spectroscopy (EIS) are employed to study structure, morphology, flat band potential, and electrochemical properties of prepared samples. In terms of water splitting performance, CoF/CoFe LDH@CNTs composite showed predominant performance for both HER and OER activities, as compared to its analogs (CoF and CoF/CoFe LDH). Faster electron transfer is also exhibited by CoF/CoFe LDH@CNTs, as it possesses a lower Tafel slope. For OER, CoF/CoFe, LDH@CNTs require a small overpotential of 170 mV to reach a current density of 10 mA cm−2 in 1 M KOH, with a Tafel slope of 42 mV dec-1. Similarly, for HER an overpotential of 218 mV is required to drive 10 mA cm−2 with a small Tafel slope of 31 mV dec-1. Impedance studies show a small value of charge transfer resistance (Rct = 1.11 Ω) for CoF/CoFe, LDH@CNTs. Significant electrochemical performance for CoF/CoFe, LDH@CNTs for both half-reactions (OER and HER) is ascribed to the synergy among electrochemically active CoF and CoFe LDH, and a highly conductive network of CNTs. The present strategy improves the electrochemical performance of electrochemical systems relevant to energy applications.

Synthesis of novel heteroatom-rich bis-Schiff base for enhancing performance of multi-walled carbon nanotube/polyaniline nanocatalyst in oxygen evolution reaction

Fabrication of oxygen evolution electrocatalysts with high performance and endurance is of interest for the electrolysis of water. To date, several compounds have been introduced to achieve it but the idea of using bis-Schiff base with conductive materials/noble metal may be a thoughtful strategy. Herein, bis-Schiff base of 6,6′ ((oxybis(4,1phenylene)) bis (azanylylidene)) bis (methanylylidene) bis (3-(2-(2- hydroxyethoxy) ethoxy) phenol) (HBIEP) was prepared and used as a modifier for the preparation of an electrocatalyst. A highly efficient electrocatalyst is reported based on HBIEP deposited on Au nanoparticles (NPs) and hollow hierarchical polyaniline (PANI) nanorod/multi-walled carbon nanotube (MWCNT) to accelerate the electron transfer rate and enhance the chemical stability for oxygen evolution reaction (OER). The MWCNT/PANI/HBIEP/Au exhibits high current density for OER at low overpotential and provides low Tafel slope of 35 mV dec−1 and remarkable stability during 50 h. Electrochemical impedance spectroscopy showed that in comparison to MWCNT/PANI, the presence of both AuNPs and HBIEP can further facilitate the charge transfer and improve the performance of the electrocatalyst for OER. Although MWCNT/PANI/Au presents proper performance, HBIEP enhances its efficiency and stability during OER. The suitable functionality of the electrocatalyst comes from its electronic structure and large active sites which improved in the presence of bis-Schiff base.

Performance of Co9S8/Cu2S@LDH nanowires prepared by dual sulfur sources to promote oxygen evolution performance

Hydrogen production through water electrolysis is an effective method for obtaining clean energy. The oxygen evolution reaction plays a key role in the process of water electrolysis, and the development of efficient and stable oxygen evolution electrocatalysts is crucial to improve the efficiency of hydrogen production. This paper presents the preparation of Co9S8/Cu2S@LDH nanowire catalysts on copper foam using thiourea and sodium sulfide as dual sulfur sources by a hydrothermal method combined with electrochemical deposition. The composition, structure, and performance of the catalysts were investigated using characterization methods of XRD, SEM, Raman, and electrochemical analyses. Also, the mechanism of thiourea's role in the process of sulfurization of dual sulfur sources was also revealed. The results indicate that the introduction of thiourea facilitates the generation of the active center CoOOH and improves the catalytic efficiency of oxygen precipitation with a low overpotential of 199 mV at 10 mA/cm2 in 1.0 M KOH electrolyte. Additionally, the LDH deposited in the outer layer effectively prevents the oxidation of Co9S8/Cu2S and improves the catalyst's stability. Therefore, the prepared Co9S8/Cu2S@LDH nanowire catalyst exhibits high oxygen evolution reaction (OER) catalytic activity and stability in alkaline electrolyte, making it a promising OER catalyst.

Stabilizing Lattice Oxygen through Mn Doping in NiCo2O4-δ Spinel Electrocatalysts for Efficient and Durable Acid Oxygen Evolution.

Design the electrocatalysts without noble metal is still a challenge for oxygen evolution reaction (OER) in acid media. Herein, we reported the manganese (Mn) doping method to decrease the concentration of oxygen vacancy (VO) and form the Mn-O structure adjacent octahedral sites in spinel NiCo2O4-δ (NiMn1.5Co3O4-δ), which highly enhanced the activity and stability of spinel NiCo2O4-δ with a low overpotential (η) of 280 mV at j=10 mA cm-2 and long-term stability of 80 h in acid media. The isotopic labelling experiment based on differential electrochemical mass spectrometry (DEMS) clearly demonstrated the lattice oxygen in NiMn1.5Co3O4-δ is more stable due to strong Mn-O bond and shows synergetic adsorbate evolution mechanism (SAEM) for acid OER. Density functional theory (DFT) calculations reveal highly increased oxygen vacancy formation energy (EVO) of NiCo2O4-δ after Mn doping. More importantly, the highly hydrogen bonding between Mn-O and *OOH adsorbed on adjacent Co octahedral sites promote the formation of *OO from *OOH due to the greatly enhanced charge density of O in Mn substituted sites.

Exploring Cu-Doped Co3O4 Bifunctional Oxygen Electrocatalysts for Aqueous Zn-Air Batteries.

The efficiency of oxygen electrocatalysis is a key factor in diverse energy domain applications, including the performance of metal-air batteries, such as aqueous Zinc (Zn)-air batteries. We demonstrate here that the doping of cobalt oxide with optimal amounts of copper (abbreviated as Cu-doped Co3O4) results in a stable and efficient bifunctional electrocatalyst for oxygen reduction (ORR) and evolution (OER) reactions in aqueous Zn-air batteries. At high Cu-doping concentrations (≥5%), phase segregation occurs with the simultaneous presence of Co3O4 and copper oxide (CuO). At Cu-doping concentrations ≤5%, the Cu ion resides in the octahedral (Oh) site of Co3O4, as revealed by X-ray diffraction (XRD)/Raman spectroscopy investigations and molecular dynamics (MD) calculations. The residence of Cu@Oh sites leads to an increased concentration of surface Co3+-ions (at catalytically active planes) and oxygen vacancies, which is beneficial for the OER. Temperature-dependent magnetization measurements reveal favorable d-orbital configuration (high eg occupancy ≈ 1) and a low → high spin-state transition of the Co3+-ions, which are beneficial for the ORR in the alkaline medium. The influence of Cu-doping on the ORR activity of Co3O4 is additionally accounted in DFT calculations via interactions between solvent water molecules and oxygen vacancies. The application of the bifunctional Cu-doped (≤5%) Co3O4 electrocatalyst resulted in an aqueous Zn-air battery with promising power density (=84 mW/cm2), stable cyclability (over 210 cycles), and low charge/discharge overpotential (=0.92 V).

Interface Engineering of Electrocatalysts for Efficient and Selective Oxygen Evolution in Alkaline/Seawater

Electrochemical water splitting is regarded as an effective technology for producing green hydrogen, which is crucial for addressing energy and environmental challenges. In particular, direct seawater splitting offers significant economic and environmental advantages. However, its efficiency is hindered by the high overpotential required for the oxygen evolution reaction (OER) and the competition from chloride oxidation. This review highlights the potential of interface engineering to overcome these limitations and develop efficient OER electrocatalysts. We comprehensively explore recent advancements in interface engineering for OER in both alkaline and seawater environments. We begin by introducing the mechanisms of freshwater and seawater electrolysis, emphasizing key considerations for OER catalyst design. Subsequently, we review the recent progress made in various interface engineering strategies, analyzing their impact on OER performance in both electrolytes. Finally, we outline promising future directions for developing efficient seawater oxidation catalysts through interface engineering.

Biochar from olive tree twigs and spent malt rootlets as electrodes in Zn-air batteries

Biochars, i.e. porous carbons obtained by pyrolysis of biomass, can act as electrocatalysts for oxygen evolution and oxygen reduction reaction. In the present work, two biochars have been prepared by using materials of completely different biomass origin: olive-tree twigs and spent malt rootlets (brewery wastes). Both biomass species were subjected to pyrolysis under limited oxygen supply and then they were activated by mixing with KOH and pyrolysis again. The obtained biochars were characterized by several techniques in order to determine their structural characteristics and the composition of their active components. Despite their different origin, the two biochars demonstrated similar structural and compositional characteristics thus highlighting the importance of the pyrolysis and activation procedure. Both biochars were used as electrocatalysts in the operation of rechargeable Zn-air batteries, where they also demonstrated similar electrocatalytic capacities with only a small advantage gained by olive-tree-twigs biochar. Compared to bare nanoparticulate carbon (carbon black), both biochars demonstrated a marked advantage towards oxygen evolution reaction.

Stabilizing Lattice Oxygen through Mn Doping in NiCo2O4−d Spinel Electrocatalysts for Efficient and Durable Acid Oxygen Evolution

Design the electrocatalysts without noble metal is still a challenge for oxygen evolution reaction (OER) in acid media. Herein, we reported the manganese doping method to decrease the concentration of oxygen vacancy (Vo) and form the Mn−O structure adjacent octahedral sites in spinel NiCo2O4−δ (NiMn1.5Co3O4−δ), which highly enhanced the activity and stability of spinel NiCo2O4−δ with a low overpotential (η) of 280 mV at j = 10 mA cm−2 and long‐term stability of 80 h in acid media. The isotopic labelling experiment based on differential electrochemical mass spectrometry (DEMS) clearly demonstrated the lattice oxygen in NiMn1.5Co3O4−δ is more stable due to strong Mn‐O bond and synergetic adsorbate evolution mechanism (SAEM) for acid OER. Density functional theory (DFT) calculations reveal highly increased oxygen vacancy formation energy (EVO) of NiCo2O4−δ after Mn doping. More importantly, the highly hydrogen bonding between Mn−O and *OOH adsorbed on adjacent Co octahedral sites promote the formation of *OO from *OOH due to the greatly enhanced charge density of O in Mn substituted sites.

Direct Synthesis of CuP2 and Cu3P and Their Performance as Electrocatalysts for Hydrogen Evolution, Oxygen Evolution, and Oxygen Reduction Reactions

Copper phosphides are promising materials for energy conversion applications because of their unique electronic structure and controllable composition. Two stoichiometric copper phosphides, CuP2 and Cu3P, were prepared by direct wet-chemical synthesis using red phosphorus. They were characterized by powder X-ray diffraction, scanning and transmission electron microscopy, and X-ray photoelectron spectroscopy. The precursor selection, reaction temperature, time and solvent composition were also studied. CuP2 is the thermodynamically more stable product, but Cu3P is more commonly obtained. This work demonstrated that higher temperature helps in CuP2 formation. More importantly, using more trioctylphosphine oxide helps control the morphology leading to crystal growth along the crystallographic a-axis. CuP2 and Cu3P were tested for hydrogen evolution, oxygen evolution, and oxygen reduction reactions. CuP2 works better for HER in acidic conditions and OER in general, and Cu3P showed better activity than CuP2 for HER and ORR in an alkaline medium. This study has led to a simple approach to the synthesis of CuP2 nanowires.

Cobalt molybdenum di-selenide surface modification: A path to improved trifunctional catalysis via partial oxygenation

Efficient, stable, and cost-effective electrocatalysts for hydrogen evolution, oxygen evolution, and oxygen reduction reactions have been in demand for decades. Recently, layered transition metals (Co, Mo, Ni, and Fe) and chalcogen compounds (S/Se/Te) gained prominence in catalysis and device studies. Density functional theory identified the covalency of Co and Mo, oxygenated bimetallic selenium bond, crystal structure distortions, and adsorption properties as crucial for enhanced electrocatalytic activity. Hybridizing the Co and Mo d-orbitals around the Fermi level of 0.463 eV improves bonding with metal surface-adsorbate intermediates validated by partial density of states. Oxygenated cobalt molybdenum selenide (O-CoMoSe2) (210) exhibited remarkable electrocatalytic properties at various active sites, with Gibbs free energy and theoretical overpotential at an active site of Co = 0.086 eV, 0.41 V, and Se = 0.50 V.

Nickel molybdenum selenide on carbon cloth as an efficient bifunctional electrocatalyst for alkaline seawater splitting

Exploring cost-effective and highly efficient electrocatalysts is desirable for the overall water-splitting challenge. In this work, a promising bifunctional electrocatalyst for oxygen evolution and hydrogen evolution reactions (OER/HER) in an alkaline medium (1 M KOH) and simulated alkaline seawater (1 M KOH + 0.5 M NaCl) was rationally developed by a simple, one-step, inexpensive, and eco-friendly method. Mo-doped nickel selenide supported on activated carbon cloth (NiMoSe@CC) was successfully synthesized via a hydrothermal method. NiMoSe nanoparticles were observed to be densely grown with better uniformity on the carbon fibers, as confirmed by different characterization techniques. The NiMoSe@CC showed an enhanced OER activity with a low overpotential of 320 mV (alkaline medium) and 360 mV (alkaline seawater) at 10 mA cm−2. The HER performance of the NiMoSe@CC was also the highest amongst NiMoSe, NiSe@CC, and MoSe@CC in both the alkaline and seawater environments. In addition, NiMoSe@CC bears a high electrochemically active surface area, low charge transfer resistance of 1.77 Ω, and high stability for both OER and HER. The NiMoSe@CC//NiMoSe@CC system was stable for 5000 LSV cycles with η10 values of 1.63 V (1st LSV cycle) and 1.71 V (5000th LSV cycle).

Self-etching assembly of designed NiFeMOF nanosheet arrays as high-efficient oxygen evolution electrocatalyst for water splitting.

2D metal-organic frameworks (MOFs) have emerged as potential candidates for electrocatalytic oxygen evolution reactions (OER) due to their inherent properties like abundant coordination unsaturated active sites and efficient charge transfer. Herein, a versatile and massively synthesizable self-etching assembly strategy wherein nickel-iron foam (NFF) acts as a substrate and a metal ion source. Specifically, by etching the nickel-iron foam (NFF) surface using ligands and solvents, Ni/Fe metal ions are activated and subsequently reacted under hydrothermal conditions, resulting in the formation of self-supporting nanosheet arrays, eliminating the need for external metal salts. The obtained 33 % NiFeMOF/NFF exhibits remarkable OER performance with ultra-low overpotentials of 188/231 mV at 10/100 mA cm-2 , respectively, outperforming most recently reported catalysts. Besides, the built 33 % NiFeMOF/NFF(+) ||Pt/C(-) electrolyzer presents low cell voltages of 1.55/1.83 V at 10/100 mA cm-2 , superior to the benchmark RuO2 (+) ||Pt/C(-) , implying good industrialization prospects. The excellent catalytic activity stems from the modulation of the electronic spin state of the Ni active site by the introduction of Fe, which facilitates the adsorption process of oxygen-containing intermediates and thus enhances the OER activity. This innovative approach offers a promising pathway for commercial-scale sustainable energy solutions.

P-doped RuPd nanoparticles anchored on Y2Ru2-xPdxO7 pyrochlore oxide surface as oxygen evolution and reduction electrocatalysts for Zn-air battery

Metal-air battery technology is the most promising green technology. However, the sluggish kinetics of the oxygen evolution/reduction reaction (OER and ORR), which are key reactions in air cathode, must be improved. In this study, Pd substitution was introduced into Y2Ru2O7 pyrochlore oxides and the ratio of Pd was varied (YRPO-x). Then, P-doped RuPd nanoparticles were synthesized on Pd-substituted YRPO pyrochlore (YRPO/RuPd-P) by an in situ exsolution process to create bifunctional electrocatalysts facilitating both reactions. The uniquely designed YRPO/RuPd-P catalyst exhibited the OER overpotential and Tafel slope (Ej10 = 232 mV; Tafel slope = 37.1 mV/dec). Furthermore, YRPO/RuPd-P shows an E1/2 of 0.82 V, indicating superior ORR activity. This was further investigated by applying in a unit-cell battery system, which showed an outstanding power density (163 mW/cm2) and robust charge–discharge stability. This study proposes a novel design strategy for bifunctional electrocatalysts.

Construction of nickel phosphide/iron oxyhydroxide heterostructure nanoparticles for oxygen evolution

Active and stable oxygen evolution electrocatalysts are essential in increasing the efficiency of water electrolyzers. The Ni2P/Fe(O)OH heterostructure nanoparticles are prepared via solvothermal phosphidization of Ni metal-organic frameworks (MOF) followed by immersing in Fe3+ aqueous solution. Characterizations reveal that the Ni2P/Fe(O)OH heterostructure nanoparticles are 12.83 nm in size averagely, and the heterointerface induces electron interactions between the Ni2P and Fe(O)OH phases. When used to catalyze OER in alkaline solutions, the Ni2P/Fe(O)OH-40/nickel foam (NF) is the most active and exhibits 240 mV overpotential to reach 10 mA cm−2 oxygen evolution (OER) current densities, which is significantly better than the Ni2P/NF. Lower apparent activation energy, charge transfer resistance, and Tafel slope, along with higher electron rate constant are observed at Ni2P/Fe(O)OH-40/NF, which suggests that the OER kinetics is more facile at the surface of heterostructure nanoparticles. The OER mechanistic pathways of both Ni2P/Fe(O)OH-40/NF and Ni2P/NF involve decoupled electron and proton transfer processes, and higher degree of lattice oxygen oxidation mechanism (LOM) participation is observed at Ni2P/Fe(O)OH-40/NF, which results from the increased acidity of the Ni sites. Density functional theory calculations prove that the formation of heterostructure with Fe(O)OH alters the band structure and the adsorption energies of OER intermediates, which leads to lower energy barrier in the rate-determining step. The Ni2P/Fe(O)OH-40/NF is also stable towards OER in alkaline solutions.

NiCo2O4/MXene Hybrid as an Efficient Bifunctional Electrocatalyst for Oxygen Evolution and Reduction Reaction

AbstractFor the advancement of electrochemical energy conversion and storage technologies, bifunctional electrocatalysts are crucial for efficiently driving both the oxygen evolution (OER) and reduction reactions (ORR). Cobalt‐based spinel oxides are a class of promising bifunctional electrocatalysts. However their low electrical conductivity and stability may hinder further improvement. A novel composite material composed of NiCo2O4 nanoparticles integrated with emerging two dimensional MXene nanosheets (NiCo2O4/MXene) was developed. The successful integration of NiCo2O4 with MXene brings about a number of attractive structural features. This includes synergistic effects between NiCo2O4 and MXene, highly accessible surface areas, complete exposure of numerous active sites, and excellent electronic conductivity, all of which collectively contribute to the desirability of composite material for OER and ORR. The synthesized NiCo2O4/MXene composite showed extraordinary OER electrocatalytic activity with a lower overpotential of 360 mV at a current density of 10 mA/cm2, and a small Tafel slope of 64 mV/dec compared to NiCo2O4, MXene and NiCo2O4+MXene (physically mixed). Additionally, NiCo2O4/MXene displays an ORR limiting current density of −4 mA/cm2 and exhibited highest onset potential and half wave potential of 0.92 V and 0.72 V vs. RHE, respectively, for the ORR in alkaline media compared to NiCo2O4, MXene and NiCo2O4+MXene (physically mixed).

Ionic liquid in-situ functionalized carbon nanotube film as self-supported metal-free electrocatalysts for oxygen evolution

The oxygen evolution reaction (OER) is a critical cathode reaction for hydrogen production from water splitting. However, due to the sluggish kinetics of OER, the water-splitting process is impeded. Thus, it is imperative to develop efficient and low-cost electrocatalysts that reduce the overpotential and improve the kinetics of OER. Herein, an in-situ synthesis strategy was applied to prepare the ionic liquid functionalized carbon nanotube (IL-CNT) that served as a metal-free electrocatalyst for OER. This powder material exhibited exceptional electrocatalytic activity for OER, with an overpotential of 335 mV at 10 mA cm−2 and a Tafel slope of 71 mV dec-1. Then, it was found that catalytic activity was influenced by the IL anion. Moreover, this IL-CNT powder could self-assemble to form carbon film during preparation, exhibiting outstanding catalytic activity for OER (a low overpotential of 153 mV at 10 mA cm−2), which was highly beneficial for practical application. Based on the theoretical calculations and experimental results, these in-situ functionalization sites on CNT surface played a significant role in regulating their electron structure. This, in turn, promoted electron transfer and hydroxyl adsorption, resulting in a substantial increase in catalytic activity for the OER.