Black phosphorous dots phosphatized bio-based carbon nanofibers/bimetallic organic framework as catalysts for oxygen evolution reaction

As a multi-step and more complex half-cell reaction than the hydrogen reverse evolution reaction (HER), the oxygen evolution reaction (OER) always requires a higher overpotential than HER. In order to minimize the associated energy loss as an overpotential, these electrochemical half-reactions of water splitting should be catalyzed by suitable materials. Due to the abundant exposed surface area and extensive active edge sites, black phosphorous quantum dots (BP QDs) have shown great potential in OER. Here, BP QDs was introduced to incorporate with bio-based carbon nanofibers (CNF) and Co–Ni bimetallic organic framework (CoNiMOF), preparing a novel catalyst for oxygen evolution reaction (OER) by a facile one-pot reaction (Scheme 1). The unique structures and greater BET surface areas of CoNiMOF-BP QDs/CNF could possibly supply a larger electrocatalytic surface, expose further active sites. The obtained CoNiMOF-BP QDs/CNF possesses excellent electrocatalytic activity in alkaline electrolyte (1 M KOH) with a low overpotential of 281 mV at 10 mA cm^?2 and a low Tafel slope of 111.9 mV dec^?1. The CoNiMOF-BP QDs/CNF can remain stable for 25,000 s under alkaline electrolyte, showing excellent stability. The increase of electrocatalyst activity is mainly attributed to the synergistic effect of excellent conductivity and enriched active sites arising from BP QDs. This work not only provides an effective strategy for the development of bimetallic MOFs derived electrocatalysts, but also puts forward a new insight for the application of BP QDs in water splitting.     

Tuning the d-band center enables nickel-iron phosphide nanoprisms as efficient electrocatalyst towards oxygen evolution

Highly active and low-cost catalytic electrodes for oxygen evolution reaction (OER) are always crucial for obtaining clean hydrogen energy via large-scale electrolytic water splitting. Herein, endowing the nickel-iron phosphide (NiFeP) nanoprisms with the tunable electronic structures have been carried out by tailoring the energy level of d-band in our study. The bimetallic synergistic effect efficiently accelerates the formation and cleavage rates of MO bonding, enabling the greatly improved OER catalytic performance after doping Fe into Ni₂P. The large surface area benefiting from the porous architecture also facilitates more contact between electrocatalyst and alkaline electrolytes, resulting in an advanced OER activity. Therefore, NiFeP can drive the OER process with a low potential of 258 mV at a current density of 10 mA cm⁻² and a Tafel slope of 46 mV dec⁻¹ in 1.0 M KOH solution. The present work provides the bimetallic phosphide nanoprism electrocatalyst with the tailored electronic structure for further application relevant to renewable energy exploration.     

Metal-organic framework derived iron-nickel sulfide nanorods for oxygen evolution reaction

Highly efficient oxygen evolution reaction (OER) on noble metal-free catalysts is a major challenge for green hydrogen production. We report herein a rational preparation strategy for MOF-derived chalcogenide electrocatalysts. The optimal sulfuration time is 12 h under the conditions of the theoretical Fe/Ni ratio of 1:1 and treatment temperature at 120 °C. In this case, the pyrite Fe_0.75Ni_0.25S₂ nanorods combining with amorphous FeNiOOH formed in situ exhibit a low overpotential of 247 mV with a small Tafel slope of 47.6 mV dec^?1 at a current density of 10 mA cm^?2 in alkaline media along with high electrochemical stability for OER. The enhanced performance is derived from the synergistic effect between FeNi sulfide with favorable electrical conductivity and generated (oxy)hydroxides with high intrinsic activity. More importantly, the more active sites and appropriate mesoporous structure further facilitate electrocatalytic activity due to improved mass transfer. This facile synthesis method is a potential pathway for MOF derived highly efficient electrocatalysis for sustainable hydrogen product.     

Adjusting electronic structure coupling of Fe–Ni2P (NiFeP-MOF) multilevel structure for ultra-activity and durable catalytic water oxidation

Efficient electrocatalyst for alkaline oxygen evolution reaction is the critical core to the wide application of metal-air energy storage and water electrolysis hydrogen energy. Therefore, appropriate design of highly active and stable non-noble metal oxygen evolution electrocatalyst with good electronic structure and multilevel structure is both a goal and a challenge. Here, we report a Fe–Ni₂P electrocatalyst (NiFeP-MOF) with multilevel structure, which was obtained by anion exchange on the basis of Fe–Ni(OH)₂ (NiFe-MOF) grown on nickel foam in situ by solvothermal method. As expected, Fe substitution regulates the Ni oxidation state in the NiFeP-MOF and realizes electronic structure coupling, showing a highly active and stable oxygen evolution reaction (OER) in alkaline electrolyte solution. Specifically, the NiFeP-MOF demonstrates an ultralow overpotentials (232 mV, 10 mA cm^?2; 267 mV 100 mA cm^?2), respectively, an extremely small Tafel slope (34 mV dec^?1). Separately, the electrocatalyst shows an excellent cycle stability at 10 mA cm^?2 for 12 h (43,200 s). More importantly, this work come up with an available policy for the preparation of excellent alkaline hydrolysis electrolysis catalysts and air cathodes with excellent performance.     

NiFe layered double hydroxide nanosheet arrays for efficient oxygen evolution reaction in alkaline media

Exploring efficient oxygen evolution reaction (OER) catalysts synthesized from low-cost and earth-abundant elements are crucial to the progression of water splitting. In this paper, NiFe layered double hydroxide (LDH) nanosheets were grown on Ni foam (NF) through a straightforward hydrothermal method. The Fe doping effects were systematically investigated by controlling Ni/Fe ratios and Fe valence states, and the in-depth influence mechanisms were discussed. The results indicate that, through controlling structure morphology and enhancing Ni²⁺ oxidation, NiFe_III(1:1)-LDH displays the best and outstanding OER performance, with a low over potential of 382 mV at 50 mA cm^?2, a low Tafel slope of 31.1 mVdec^?1 and only 20 mV increase after 10 h continuous test at 50 mA cm^?2. To our knowledge, this is one of the best OER electrocatalysts in alkaline media to date. This work provides a facile and novel strategy for the fabrication of bimetallic LDH catalysts with desired structures and compositions.     

Co–NiFe layered double hydroxide nanosheets as an efficient electrocatalyst for the electrochemical evolution of oxygen

The development of non-precious metal catalysts for the electrochemical oxygen evolution reaction (OER) is especially important for the water electrolysis process. Herein, a two-dimensional (2D) ultrathin hybrid Co–NiFe layered double hydroxide (LDH) is synthesized via a facile hydrothermal method. In 1.0 M KOH electrolyte, Co–NiFe LDH exhibits remarkable activities for OER. At the current density of 10 mA cm⁻², it only needs an overpotential of 278 mV, which is ca. 50 mV and 20 mV lower than those for NiFe LDH (328 mV) and RuO₂ catalysts (298 mV), respectively. In addition, Co–NiFe LDH also shows impressive long-term stability for OER. Besides the stable morphology and crystal structure, the potential is always kept at 1.50 V and shows almost no attenuation during the 20 h of durability test. Changes in the electronic structure of LDH due to introduction of Co ions, as well as the large specific surface area facilitate the mass/electron transfer and the oxygen bubbles release, and thus lead to the enhanced catalytic properties for OER. This work can be informative not only for understanding the role of physical and electronic structures on OER but also for designing high-performance non-precious metal OER electrocatalysts.     

Bimetallic-MOF derived nickel-iron phosphide nanosheets on carbon cloth for efficacious oxygen evolution reaction

It is of momentously realistic significance to exploit highly efficacious and cost-effective non-noble metal electrocatalysts for oxygen evolution reaction (OER), considering its promising renewable energy application. Herein, a self-supporting electrocatalyst composed of nickel-iron phosphide nanosheets on carbon cloth (NiFeP@CC) is proposed for OER, which are derived from the phosphating treatment of two-dimensional NiFe-MOF nanosheets. The NiFeP@CC composite possesses the synergistic effect of bimetallic NiFe phosphides in promoting the OER, the fully exposed active sites of the nano-sheet structure and the fast charge/mass transfer from the hierarchical porous structure. Owing to the above structural features, the optimized NiFeP@CC presents an impressive OER performance in alkaline solution. The overpotential and Tafel slope are as low as 229 mV and 36.4 mV dec^?1 under a current density of 10 mA cm^?2, respectively, much superior to those for the commercial IrO₂ catalyst. More excitingly, this self-supporting electrocatalyst also possesses an exceptionally high durability, showing no activity degradation for 25 h. This work offers a simple and feasible strategy for developing practically available OER catalysts with a high activity and stability.     

In situ grown Cu-Based metal-organic framework on copper foam as high-performance electrocatalysts for oxygen evolution reaction

It is of great significance to develop highly efficient and robust oxygen evolution reaction (OER) electrocatalysts derived from earth-abundant and inexpensive elements for future hydrogen economy via electrochemical water splitting. Herein, Cu-based metal-organic framework (MOF) is directly supported on conductive Cu foam (CF) by a simply chemical oxidation of Cu substrate to grow Cu(OH)₂ nanowire arrays, followed by solvothermal treatment to obtain in situ grown Cu-based MOF electrode (MOF [Cu(OH)₂]/CF). The as-prepared 3D electrode shows superior OER activity with a low potential of 330 mV to deliver a current density of 10 mA cm⁻², a Tafel slope of 108 mV dec⁻¹, and excellent durability in alkaline media (1.0 M KOH). After electrolysis, XRD confirms that the initial MOFs have been transformed into CuO species, which are essentially active components for OER performance. This demonstrates that the MOFs can serve as efficient precursors for formation of highly active Cu oxide catalysts towards OER. This work provides a new strategy to develop MOFs-derived electrocatalysts for future clean energy conversion and storage systems.     

Bimetal metal-organic framework hollow nanoprisms for enhanced electrochemical oxygen evolution

Carboxylate-based metal-organic frameworks (MOFs) have emerged as promising electrocatalyst candidates for the water splitting and metal-air batteries. Hierarchical porous structure and redox-active metal centers with unsaturated coordination sites in MOFs facilitate the enhanced catalytic activity of oxygen evolution reaction (OER). Herein, uniform hollow structured Fe-free bi-metal (Co, Ni) MOF-74 nanoprisms are successfully synthesized using a solvothermal method and (Co₁Ni₁)₃(OH)(CH₃COO)₅ as the sacrificial templates, where Co and Ni are the metal nodes and 2,5-dihydroxyterephthalic acid (H₄DOBDC) serves as the organic ligand. At an overpotential of 300 mV, CoNi MOF-74 shows a high electrocatalytic activity towards OER in 0.1 M KOH, where the current density is 10 mA cm^?2 and the Tafel slope is 65.6 mV dec^?1. Meanwhile, CoNi MOF-74 is durable that sustains in alkaline for 100 h with 83.25% retention of current density. The improved catalytic activity can be associated with the in-situ generated amorphous Ni–Co (oxy)hydroxide, as well as the electron transfer from Ni²⁺ to Co²⁺. This work elucidates the potential application of MOF materials as efficient electrocatalysts for OER.     

AC magnetic field enhancement oxygen evolution reaction of bimetallic metal-organic framework

Cost-effective oxygen evolution reaction (OER) electrocatalysts play a key role in electrocatalytic water splitting process. Here, a facile and scalable strategy was applied to synthesize the bimetallic metal-organic frameworks (MOFs) with high OER activity, and the effects of AC magnetic field on OER was also investigated. Results shows that the bimetallic MOFs (Co_0.4Ni_0.6-MOF-74) exhibited a three-dimensional flower-like morphology, and possessed a higher BET specific area of 905.39 m² g^?1 as well as a smaller median pore size of 0.49 nm as compared to single metal MOFs; It owned a lowest overpotential of 314 mV at 10 mA cm^?2 and Tafel slope of 79.39 mV dec^?1, both are much lower than these of single metal MOFs, being due to the high specific area and more active sites derived from the distorted crystal structure; When AC magnetic field strength equaled to 5.50 mT, overpotential at 10 mA cm^?2 for Co_0.4Ni_0.6-MOF-74 reached minimum value of 201 mV, reduced by about 36% as compared to that without magnetic field, indicated that AC magnetic field could greatly improve OER process. These improvements resulted from the spin polarization effect, magnetohydrodynamic (MHD) convection and improved active point temperature.     

Cobalt carbonate hydroxide assisted formation of self-supported CoNi-based Metal–Organic framework nanostrips as efficient electrocatalysts for oxygen evolution reaction

The development of efficient and low-cost electrocatalysts is crucial for improving the efficiency of electrochemical oxygen evolution reaction (OER). Herein, self-supported CoNi-based metal-organic framework (MOF) nanostrips grown on Ni foam (NF) were synthesized with cobalt carbonate hydroxide (CoCH) nanoneedles as a sacrificial template and demonstrated to be highly efficient electrocatalysts for OER. In this approach, the CoCH nanoneedles play a key role in modulating the morphology of CoNi-MOF with reduced thickness and sizes through affording Co source and slowing down the leaching of Ni ions from the NF substrate. The resultant CoNi-MOF/CoCH/NF electrode possesses higher catalytically active surface area and smaller electrochemical impedance than CoCH template-free electrodes, which enable rapid mass transport and charge transfer during OER, thus showing enhanced electrocatalytic activity for OER. In alkaline media (1.0 M KOH), it needs a low overpotential of 251 mV to deliver a current density of 10 mA cm⁻² and exhibits a small Tafel slope of 40.7 mV dec⁻¹ as well as excellent durability. The developed approach may inspire further capability on constructing more promising catalysts for energy related applications.     

Local electronic structure modulation of NiVP@NiFeV-LDH electrode for high-efficiency oxygen evolution reaction

The emergence of alternative sustainable energy technologies has stimulated the utilisation of high-efficiency, cost-effective electrodes for renewable energy conversion. The oxygen evolution reaction (OER) is critical for water splitting and rechargeable metal-air batteries. However, the identification of efficient and robust non-noble-metal-based OER electrocatalysts remains a major hurdle for large-scale hydrogen production. Herein, NiVP@NiFeV-LDH heterojunction catalysts were constructed by phosphidation and hydrothermal processing, because OER activity can be improved by coupling NiVP and NiFeV-LDH. NiVP@NiFeV-LDH/NF exhibited remarkable OER performance with an ultralow overpotential of 317 mV at a current density of 100 mA cm⁻² and a Tafel slope of 83.0 mV dec⁻¹ in an alkaline environment. The high efficiency of NiVP@NiFeV-LDH/NF is attributed to increased mass and electron transport because of array structure formation and interfacial electronic structure optimisation, respectively. This work provides a novel approach for augmenting the OER performance of non-noble-metal-based electrocatalysts for energy conversion applications.     

Structural and electronic engineering of zirconium-induced bimetallic phosphides supported by nitrogen-doped carbon fibers for highly efficient oxygen evolution reaction

The exploitation of non noble metal oxygen evolution reaction (OER) electrocatalysts with tuneable electronic structures and chemical compositions is an effective way to improve water splitting, which is of great significance to the development of clean energy. Here, we report a zirconium-induced transition metal phosphide supported by nitrogen-doped carbon fiber (P–CoFeZr/NCBC) as an efficient electrocatalyst for the OER. The electrocatalyst is produced in situ on the surface of nitrogen-doped carbon fibers to form an open structure, achieving a high concentration of active sites. Additionally, the electronic structure is modified through the introduction of zirconium to increase the intrinsic activity of the electrocatalyst. These phenomena greatly enhance the oxygen evolution activity of the electrocatalyst. In alkaline media, P–CoFeZr/NCBC exhibits excellent catalytic activity and fast kinetics, with overpotentials and Tafel slopes of 300 mV and 51 mV/dec at 10 mA/cm², and displays excellent long-term stability for more than 24 h at 50 mA/cm².     

Structure-design and synthesis of nickel-cobalt oxide/sulfide/phosphide composite nanowire arrays for efficient overall water splitting

The construction of cost-effective bifunctional electrocatalysts with the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is significant for efficient overall water splitting. Herein, this work demonstrates a novel strategy for the synthesis of nickel-cobalt oxides/sulfides/phosphides composite (denoted as NiCoO–2P/S) nanoarrays on Ni foam. In this method, Ni–Co bimetallic oxide nanowires on Ni foam were partially phosphorized and sulfurized simultaneously in situ to yield Ni–Co oxide/sulfide/phosphide composite. The NiCoO–2P/S arrays have good interfacial effects and display many holes in the nanowires, giving it the advantage of large accessible surfaces on the nanowires and a beneficial for the release of gas bubbles, resulting in an excellent OER performance with a low overpotential (η) of 254 mV at 100 mA cm^?2 and good HER activity (η₁₀ = 143 mV at 10 mA cm^?2). The electrocatalytic test results demonstrate small Tafel slopes (82 mV dec^?1 for HER, 88 mV dec^?1 for OER) and the satisfying durability in an alkaline electrolyte, indicating that the HER and OER activity was enhanced by the introduction of the Ni/Co sulfides and phosphides into Ni–Co oxides composite nanowires. Furthermore, the as-prepared NiCoO–2P/S catalyst can be used as both the anode and the cathode simultaneously to realize overall water splitting in the two-electrode electrolyzer. This system can be driven at low cell voltages of 1.50 and 1.68 V to achieve current densities of 10 and 100 mA cm^?2, respectively. This work provides an alternative strategy to prepare high-performance bifunctional electrochemical materials and demonstrates the advantages of Ni–Co oxide/sulfide/phosphide composites for water splitting.     

Flower-like HEA/MoS2/MoP heterostructure based on interface engineering for efficient overall water splitting

The development of cheap, efficient, and active non-noble metal electrocatalysts for total hydrolysis of water (oxygen evolution reaction (OER) and hydrogen evolution reaction (HER)) is of great significance to promote the application of water splitting. Herein, a heterogeneous structured electrode based on FeAlCrMoV high-entropy alloy (HEA) was synthesized as a cost-effective electrocatalyst for hydrogen and oxygen evolution reactions in alkaline media. In combination of the interfacial synergistic effect and the high-entropy coordination environment, flower-like HEA/MoS₂/MoP exhibited the excellent HER and OER electrocatalytic performance. It showed a low overpotential of 230 mV at the current density of 10 mA cm⁻² for OER and 148 mV for HER in alkaline electrolyte, respectively. Furthermore, HEA/MoS₂/MoP as both anode and cathode also exhibited an overpotential of 1.60 V for overall water splitting. This work provides a new strategy for heterogeneous structure construction and overall water splitting based on high-entropy alloys.     

Cu vacancy engineering on facet dependent CuO to enhance water oxidation efficiency

The performance of the electrocatalyst is strongly depended on its electronic structure. Herein, the cuprous oxide (Cu₂O) with three different morphology (facet) is successfully synthesized to reveal the correlated relationship between oxygen evolution reaction (OER) activity and electronic structure, where the Cu₂O cube enclosed by high electronic density facet (100) exhibits enhanced OER performance. Then, CuO samples with different surface oxidation degree are obtained for further investigating the structure-function relationship. Finally, the CuO Cube_3h with Cu vacancy (V_Cu–CuO Cube_3h) contains more electroactive species and shows high catalytic performance with an onset overpotential of 252 mV and a Tafel slope of 63.4 mV dec^?1, respectively. It only needs 330 mV overpotential to drive 10 mA cm^?2 current density and maintains its catalytic property for at least 48 h. The density functional theory (DFT) calculation reveals that the exist of V_Cu has a positive effect on neighboring atoms to generate new electronic states near the Fermi level at the intermediate-absorbed structure, which also optimizes the absorption energy of oxygen intermediates, leading to faster charge transport to participate in the OER. This work provides a guidance for improving the OER performance by accurately regulating the surface charge distribution of the catalyst.     

Bifunctional electrocatalysts of CoFeP/rGO heterostructure for water splitting

Bifunctional non-precious electrocatalysts with high performance are highly desired for renewable energy but remain challenging. Herein, a CoFeP/rGO heterostructure was rational developed based on the synergistic effect, including superior conductivity, increased catalytic active sites of rGO support and the regulated electron distribution of bimetallic phosphide. At a current of 10 mA cm^?2, the CoFeP/rGO-2 composite exhibits excellent HER activity with low overpotentials of 101 mV and 76 mV in 1.0 M KOH and 0.5 M H₂SO₄ electrolyte, respectively. And highly active alkaline OER performance was provided with an overpotential of only 275 mV to reach a current density of 10 mA cm^?2. By the way, the CoFeP/rGO-2 electrode showed a pleasured working voltage of 1.58 V for overall water splitting in alkaline environment. More importantly, the long term durability and higher stability of the catalysts demonstrated their feasibility of bimetallic phosphide/rGO system as bifunctional electrocatalysts.     

Ultrathin fan-like multimetallic oxide as a superior oxygen evolution electrocatalyst in alkaline water and seawater

Multimetallic systems exhibit high catalytic activity because of the flexibility to change the electronic and crystal structures of the materials. On the other hand, the preparation of homogeneous catalysts and the revelation of synergistic interactions in the catalytic process limit the further development of multimetallic catalysts due to the increase in chemical complexity. Here, atomically thin quinary CNWFVO_x (CoNiWFeVO_x) fan-like nanobelts are successfully synthesized as an OER electrocatalyst by a simple colloidal chemistry strategy. Compared with the ternary and quaternary systems, the quinary CNWFVO_x shows more excellent catalytic performance, requiring only low overpotentials of 245 mV and 272 mV to achieve a current density of 10 mA cm⁻² under alkaline conditions and simulated seawater, respectively, and a small Tafel slope of 47.17 mV dec⁻¹ under alkaline conditions. Moreover, the electrode activity remained almost constant after more than 83 h of stability testing. The OER activity of the catalyst was significantly enhanced and the kinetics were accelerated thanks to the synergistic effect of the multi-metals and the amorphous ultra-thin structure. This work may provide opportunities for the design and study of atomically thin multinary transition metal oxide nanomaterials.     

Quick-to-synthesize hybrid electrodes composed of activated carbon cloth with Co/Fe-based films as bifunctional electrocatalysts for water splitting

Hybrid electrodes have recently been investigated as attractive alternatives to noble-metal-based electrocatalysts for hydrogen production by water splitting. Herein, we propose an electrode composed of an oxidized carbon cloth with an electrodeposited bimetallic Co/Fe-based film. By optimizing the electrodeposition conditions and applying electrochemically activated carbon cloth as a substrate, one can prepare a free-standing noble-metal-free electrocatalytic electrode with high bifunctional electrocatalytic activity in hydrogen and oxygen evolution from alkaline solution. The developed Fe_0.25Co_0.75 electrode requires overpotentials of 245 mV for HER and 360 mV for OER at high current densities of −100 and 100 mA cm⁻², respectively. Furthermore, its overall synthesis time from commercially available raw materials is only approximately 20 min. The electrode material was used as both a cathode and an anode in the model electrolyzer, which can deliver 10 mA cm⁻² of current density at 1.66 V without loss of activity during 100 h of performance.     

Enhanced oxygen evolution reaction kinetics through biochar-based nickel-iron phosphides nanocages in water electrolysis for hydrogen production

Highly-efficient and stable non-noble metal electrocatalysts for overcoming the sluggish kinetics of oxygen evolution reaction (OER) is urgent for water electrolysis. Biomass-derived biochar has been considered as promising carbon material because of its advantages such as low-cost, renewable, simple preparation, rich structure, and easy to obtain heteroatom by in-situ doping. Herein, Ni₂P–Fe₂P bimetallic phosphide spherical nanocages encapsulated in N/P-doped pine needles biochar is prepared via a simple two-step pyrolysis method. Benefiting from the maximum synergistic effects of bimetallic phosphide and biochar, high conductivity of biochar encapsulation, highly exposed active sites of Ni₂P–Fe₂P spherical nanocages, rapid mass transfer in porous channels with large specific surface area, and the promotion in adsorption of reaction intermediates by high-level heteroatom doping, the (Ni_0.75Fe_0.25)₂P@NP/C demonstrates excellent OER activity with an overpotential of 250 mV and a Tafel slope of 48 mV/dec at 10 mA/cm² in 1 M KOH. Also it exhibits a long-term durability in 10 h electrolysis and its activity even improves during the electrocatalytic process. The present work provides a favorable strategy for the inexpensive synthesis of biochar-based transition metal electrocatalysts toward OER, and improves the water electrolysis for hydrogen production.