One-pot solvothermal synthesis of Co2P nanoparticles: An efficient HER and OER electrocatalysts

Development of an inexpensive electrocatalyst for hydrogen evolution (HER) and oxygen evolution reactions (OER) receives much traction recently. Herein, we report a facile one-pot ethyleneglycol (EG) mediated solvothermal synthesis of orthorhombic Co₂P with particle size ~20–30 nm as an efficient HER and OER catalysts. Synthesis parameters like various solvents, temperatures, precursors ratios, and reaction time influences the formation of phase pure Co₂P. Investigation of Co₂P as an electrocatalyst for HER in acidic (0.5 M H₂SO₄) and alkaline medium (1.0 M KOH), furnishes low overpotential of 178 mV and 190 mV, respectively to achieve a 10 mA cm^?2 current density with a long term stability and durability. As an OER catalyst in 1.0 M KOH, Co₂P shows an overpotential of 364 mV at 10 mA cm^?2 current density. Investigation of Co₂P NP by XPS analysis after OER stability test under alkaline medium confirms the formation of amorphous cobalt oxyhydroxide (CoOOH) as an intermediate during OER process.     

High throughput preparation of Ni–Mo alloy thin films as efficient bifunctional electrocatalysts for water splitting

The synthesis of cost-effective and high-performance electrocatalysts for water splitting is the main challenge in electrochemical hydrogen production. In this study, we adopted a high throughput method to prepare bi-metallic catalysts for oxygen/hydrogen evolution reactions (OER/HER). A series of Ni–Mo alloy electrocatalysts with tunable compositions were prepared by a simple co-sputtering method. Due to the synergistic effect between Ni and Mo, the intrinsic electrocatalytic activity of the Ni–Mo alloy electrocatalysts is improved, resulting in excellent HER and OER performances. The Ni₉₀Mo₁₀ electrocatalyst shows the best HER performance, with an extremely low overpotential of 58 mV at 10 mA cm^?2, while the Ni₄₀Mo₆₀ electrocatalyst shows an overpotential of 258 mV at 10 mA cm^?2 in OER. More significantly, the assembled Ni₄₀Mo₆₀//Ni₉₀Mo₁₀ electrolyzer only needs a cell voltage of 1.57 V to reach 10 mA cm^?2 for overall water splitting.     

Se-doped cobalt oxide nanoparticle as highly-efficient electrocatalyst for oxygen evolution reaction

Electrolysis of water has been one of the most promising approaches for renewable energy resources while the efficient oxygen evolution reaction (OER) remains challenging. Herein, a series of different ratio of Se doped Co₃O₄ nanoparticles XSe-Co₃O₄ are prepared by hydrothermal method and applied as OER electrocatalysts. Se^2? is doped into the Co₃O₄ crystal lattice by substituting of O^2? and a large number of oxygen vacancies are generated, which provides more available activity sites for OER. Se doping increases the surface ratio of Co²⁺/Co³⁺ and accelerates the electron transport that favors OER activity promotion. The optimized doping ratio of 6%Se–Co₃O₄ presents low overpotential of 281 mV at 10 mA cm^?2, as well as a low Tafel slope of 70 mV dec^?1 in 1 M KOH solution, which has great advantages compared to the recently reported Co₃O₄-based OER electrocatalysts. This work provides new ideas for the development of efficient Co₃O₄-based OER electrocatalysts.     

A novel in-situ strategy develops for Mo2C nanoparticles incorporated on N,P co-doped stereotaxically carbon as efficient electrocatalyst for overall water splitting

Developing cost-effective and remarkable electrocatalysts toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performs excelling role in boosting the hydrogen energy application. Herein, a novel in-situ one-pot strategy is developed for the first time to synthesize molybdenum carbide nanoparticles (Mo₂C NPs) incorporated on nitrogen (N) and phosphorous (P) co-doped stereotaxically carbon (SC). The optimized Mo₂C NPs/N, P–SC–800 electrocatalyst exhibits lower overpotentials of 131 and 287 mV for HER and OER to deliver a current density of 10 mA cm^?2 in 1.0 M KOH medium with smaller Tafel slopes of 58.9 and 74.4 mV/dec, respectively. In addition, an electrolyzer using Mo₂C NPs/N, P–SC–800 electrode as cathode and anode delivers a current density of 10 mA cm^?2 at a small voltage of 1.64 V for overall water splitting. The excellent water splitting performance could be ascribed to optimum Mo₂C NPs for more accessible active sites, highly active N, P-SC networks for accelerated electron transfers, and synergetic effect between Mo₂C NPs and N, P-SC networks. The N, P-SC network not only enhances the overall dispersion of Mo₂C NPs but also contributes numerous electroactive edges to enhance the performance of HER, OER, and overall water splitting activity. This research work explores the in-situ one-step strategies of advanced, cost-effective, and non-precious metal electrocatalysts for efficient water splitting and motivates the consideration of a novel class of heteroatom doped stereotaxically carbon nanocomposites for sustainable energy production.     

Functionalized Co3O4 graphitic nanoparticles: A high performance electrocatalyst for the oxygen evolution reaction

We describe a novel synthesis technique for the production of graphitic carbon functionalized Co₃O₄ (G/Co₃O₄), which involves the rapid decomposition of cobalt nitrate in the presence of citric acid. Upon immobilization of the G/Co₃O₄ upon Screen-Printed macroElectrodes (G/Co₃O₄-SPEs) the G/Co₃O₄-SPEs were found to exhibit remarkable electrocatalytic properties towards the Oxygen Reduction Reaction (OER). A detailed investigation has been carried out on the influence that the graphitization of the citric acid has, during the course of preparation of Co₃O_4, upon the ability of the G/Co₃O₄ to catalyse the OER within alkaline conditions (1.0 M KOH). The graphitization of citric acid ensures the uniform distribution of Co₃O₄ and enhanced conductivity with maximal exposure of active sites, which are the key parameters to delivering enhanced electrochemical activity. The G/Co₃O₄-SPEs exhibits an overpotential of 304 mV (recorded at 10 mA cm⁻²), a Tafel slope of 110 mV dec⁻¹ and remain stable in its signal output (achievable current density) at varying temperatures (5–50 °C), and after 10 h of chronoamperometry in 1.0 M KOH. The G/Co₃O₄-SPE's OER activity was found to be superior to that of bulk and nano Co₃O₄. The results exhibited within this study will enable production of high-performance and environmentally benign electrocatalysts towards the OER for use within water splitting devices.     

First insight on Mo(II) as electrocatalytically active species for oxygen evolution reaction

The replacement of noble metals with earth-abundant metals is still a big challenge for the practical application of electrocatalysis. In this work, we have developed the Mo_xC-modified alloy@nitrogen-doped carbon hybrid electrocatalysts (Mo_xC-alloy@NC, alloy: FeCo, NiCo) for oxygen evolution reaction (OER) by a simple thermolysis method. Compared with FeCo@NC and NiCo@NC, the OER performances of Mo_xC-FeCo@NC and MoC-NiCo@NC are greatly enhanced, mainly due to the improved electrical conductivity by the introduce of Mo_xC. Moreover, Mo_xC-FeCo@NC exhibits a smaller Tafel slope (80 mV/dec) and a lower overpotential (318 mV) at 10 mA cm⁻² in 1 M KOH solution, compared with MoC-NiCo@NC (186 mV/dec, 352 mV). In consideration of a lower BET area (6.6 m² g⁻¹) of Mo_xC-FeCo@NC than those of MoC-NiCo@NC (25.4 m² g⁻²), the remarkable electrocatalytic activity of Mo_xC-FeCo@NC is mainly attributed to the presence of Mo(II) acting as the OER active species. Although Mo as hydrogen evolution reaction (HER) active species is well known, Mo(II) as the OER active species has not been reported before.     

Electrodeposition of Mo-doped NiFex nanospheres on 3D graphene fibers for efficient overall alkaline water splitting

Developing efficient bifunctional catalysts for hydrogen and oxygen evolution reactions (HER/OER) has attracted great interest in hydrogen production from water splitting. In this work, a novel material of Mo-doped NiFe_x nanospheres on 3D graphene fibers (Mo-NiFe_x/3DGFs) has been successfully fabricated through a simple and cheap one-step electrodeposition method. The Mo-NiFe_x/3DGFs possessed ultra-high conductivity and specific surface area, greatly benefiting to electrocatalytic hydrolysis activity. And it was found that Fe element could obviously promote OER process, while Mo doping facilitated both OER and HER reactions. We proved that there existed synergetic roles between Fe and Mo element, which could realize the control of the electronic structure and optimize the adsorption/desorption of intermediates. And electrochemical tests showed that the Mo–Ni/3DGFs exhibited a relatively smaller overpotential of 109.9 mV for HER, while the Mo-NiFe_x/3DGFs presented better OER performance with an overpotential of 240.8 mV at the current density of 100 mA cm^-2 in 1.0 M KOH. Finally, a system for overall water splitting constructed by Mo–Ni/3DGFs||Mo–NiFe_0.68/3DGFs electrodes has a low cell voltage of 1.52 V at 10 mA cm^?2 and long-term stability, exceeding most of literature results. Our findings provide insight into possibilities for the simple synthesis of high-performance and cheap catalysts, and laid the foundation for the practical application of transition metal catalysts.     

Co–Co3O4 nanostructure with nitrogen-doped carbon as bifunctional catalyst for oxygen electrocatalysis

In view of the development of advanced bi-functional oxygen electrodes for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), herein, we report the synthesis of Co–Co₃O₄ nanostructure encased in N-doped carbon (Co–Co₃O₄/NC) by carbothermal reduction followed by controlled oxidative treatment. The formation of a protective-active oxide layer on the metallic-Co not only facilitated the effective charge separation and transport but also displayed improved stability of Co–Co₃O₄/NC in an alkaline operating condition. The Co–Co₃O₄/NC catalyst afforded 0.810 V overvoltage between ORR and OER in 0.1 M KOH solution, consequently, this lower reversible overvoltage would result in energy saving of around 0.246 V if Co–Co₃O₄/NC is used as an oxygen electrode instead of commercially available 40 wt % Pt/C. Furthermore, in comparison with the use of Pt/C + IrO₂ as an ORR and OER catalyst, respectively the single bi-functional electrocatalyst i.e., Co–Co₃O₄/NC would result in energy saving of around 0.13 V.     

Co3O4 nanoparticles decorated Polypyrrole/carbon nanocomposite as efficient bi-functional electrocatalyst for electrochemical water splitting

An effective bi-functional electrocatalyst of Co₃O₄/Polypyrrole/Carbon (Co₃O₄/Ppy/C) nanocomposite was prepared through a simple dry chemical method and used to catalyze the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Three types of carbon support as Vulcan carbon, reduced graphite oxide (RGO) and multi-walled carbon nanotubes (MCNTs) were used to study the influence on electrochemical reactions. Spherical shaped Co₃O₄ nanoparticles with 8–10 nm was found uniformly distributed on Ppy/C composite, which were analyzed by X-ray diffraction and transmission electron microscopy techniques. Amongst, Co₃O₄/Ppy/MWCNT shows improved bifunctional electrocatalytic activity towards both OER and HER with relatively low over potential (340 mV vs. 490 mV at 10 mA cm⁻²) and Tafel slope (87 vs. 110 mV dec⁻¹). In addition to that, MWCNT supported Co₃O₄/Ppy nanocomposite exhibits good electronic conductivity and electrochemical stability up to 2000 potential cycles. The results clearly indicate that the Co₃O₄/Ppy/MWCNT nanocomposite could be the promising bi-functional electrocatalyst for efficient water electrolysis.     

Iron-doped cobalt nitride nanoparticles (Fe–Co3N): An efficient electrocatalyst for water oxidation

The exploration of efficient, low-cost and earth-abundant oxygen-evolution reaction (OER) electrocatalysts and the understanding of the intrinsic mechanism are important to advance the clean energy conversion technique based on electrochemical water oxidation. In this work, Fe-doping Co₃N catalysts were successfully synthesized by a simple nitridation reaction of the Co_3-xFe_xO₄ precursor. This material exhibited a low overpotential of 294 mV at a current density of 10 mA cm^?2, and a small Tafel slope of 49 mV dec^?1 in 1 M KOH solution, superior to the performance of Co₃N and IrO₂. As revealed by the spectroscopic and electrochemical analyses, the enhanced OER performance mainly originates from the electronic modulation induced by the incorporation of Fe into Co₃N, benefitting the formation of CoOOH as active surface species and thus facilitating the OER process. These findings also demonstrate the introduction of heterogeneous element is a simple and effective strategy to regulate the OER property of the cobalt nitrides (Co₃N) catalysts.     

Cobalt phosphide nanoparticles embedded in 3D N-doped porous carbon for efficient hydrogen and oxygen evolution reactions

An electrocatalyst based on a unique three-dimensional (3D) N-doped porous carbon sheet networks embedded with CoP₂ nanoparticles (CoP₂@3D-NPC) was synthesized by a facile pyrolysis process as well as an in-situ phosphatization method. The improved CoP₂@3D-NPC hybrid materials show excellent electrocatalytic activity toward HER and OER. This material provides a low overpotential of 126 mV at 10 mA cm⁻² in 0.5 M H₂SO₄ and 167 mV at 20 mA cm⁻² in 1.0 M KOH for HER with a small Tafel slope value of 59 mV dec⁻¹, respectively. Besides, it is also active for the OER under alkaline conditions. Such a prominent property of the CoP₂@3D-NPC electrocatalyst could be attributed to its excellent electrical conductivity of 3D carbon substrate, strong synergistic effect between CoP₂ nanoparticles and carbon nanosheet as well as extra active sites created by the N-doped structure.     

Evidencing enhanced oxygen and hydrogen evolution reactions using In–Zn–Co ternary transition metal oxide nanostructures: A novel bifunctional electrocatalyst

Ternary transition metal oxides are gaining popularity for cost effective bifunctional electrocatalytic activities and to realization of novel water splitting devices. In this regard, In₂O₃/ZnO/Co₃O₄ based ternary oxide nanostructures were investigated in detail for their oxygen/hydrogen evolution reaction (OER/HER) in alkaline environment. The ternary oxides were at first processed through a simple chemical route involving hydrothermal treatment. The prepared nanostructures were then investigated by using high-resolution transmission electron microscopy (TEM/HRTEM) to ascertain their morphological traits. X-ray diffraction, Raman signals and photoluminescence data demonstrated the In₂O₃ phase to be prevalent in the ternary mixture on par with that of ZnO and Co₃O₄. The valence state of various metal ions and the In–O, Zn–O and Co–O bonding was verified using XPS. The ternary oxide coated electrodes exhibited excellent overall water splitting activity. Overpotential values of 398 and 510 mV were registered for OER and HER experiments under a current density of ±10 mA cm⁻², demonstrating the material to be an ideal OER/HER electrocatalyst at room temperature. The exceptional long-term stability in ternary oxides and their Tafel slope (88 mV/dec for OER and 60 mV/dec for HER) further affirmed their unique anodic/cathodic characteristics for water splitting applications.     

3D flower-like polypyrrole-derived N-doped porous carbon coupled cobalt oxide as efficient oxygen evolution electrocatalyst

For electrochemical splitting of water, highly active and non-precious metal electrocatalysts towards the oxygen evolution reaction (OER) are direly needed to address the cost and stability issues. Herein, polypyrrole (PPy) with 3D flower-like structure has been prepared to obtain N-doped porous carbon sheets (N–C) and to implant with cobalt oxides (Co₃O₄) via simple and cost-effective hydrothermal reaction. Benefitting from the 3D flower-like porous carbon structure, Co₃O₄/N–C demonstrates enlarged surface area replenished with more electrocatalytic active sites. What's more, Co₃O₄ nanoparticles are evenly dispersed onto the N-doped carbon surface which effectively prevents their aggregation and detachment. These exclusive structural features render amazing catalytic activity for Co₃O₄/N–C towards OER with an onset potential of ~1.31 V (vs RHE), low overpotential of 120 mV at 10 mA cm⁻² and a Tafel slope of only 33 mV dec⁻¹ in basic media. This work presents a simple approach to meet an ideal catalytic material with better morphology and advantageous properties for the possible energy and environmental applications.     

Advanced Co3O4–CuO nano-composite based electrocatalyst for efficient hydrogen evolution reaction in alkaline media

In this study, we incorporate a copper impurity into (Co₃O₄) nanowires precursor that turn them into an active catalyst for the hydrogen evolution reaction in 1M KOH. The XRD and XPS results are in good agreement and confirmed the formation of Co₃O₄–CuO nano-composite by wet chemical method. To date, the performance of hydrogen evolution reaction in alkaline for the composite catalyst is comparable or superior to cobalt oxide based HER electro-catalysts. The HER catalyst exhibits the lowest Tafel slope of 65 mVdec⁻¹ for the cobalt-based catalysts in alkaline media. A current density of 10 mA/cm² is achieved at a potential of 0.288 V vs reversible hydrogen electrode (RHE). The mixed transition metal oxide Co₃O₄–CuO based HER electro-catalyst is highly stable and durable. The EIS results demonstrates that HER is highly favorable on the Co₃O₄–CuO due to the relatively small charge transfer resistance (173.20 Ohm) and higher capacitance values (1.97 mF).     

Ir-doped Co3O4 as efficient electrocatalyst for acidic oxygen evolution reaction

Oxygen evolution reaction (OER) is an important bottleneck for large-scale acidic water splitting applications due to its sluggish reaction kinetics. Therefore, the development of highly active, stable, and inexpensive electrocatalysts for OER remains a challenge. Herein, we develop the iridium doped Co₃O₄ (Ir–Co₃O₄) with low Ir content of 2.88 wt% for efficient acidic OER. Considering systemic characterizations, it is probably concluded that Ir can be uniformly doped into the lattice of Co₃O₄ and induce a certain distortion. The electrochemical results reveal that Ir–Co₃O₄ nanoparticles demonstrate significantly enhanced electrocatalytic OER activity and stability in 0.5 M H₂SO₄ solution compared with pure Co₃O₄, in which the overpotential at the current density of 10 mA cm⁻² decreases from 382 mV to 225 mV and the value of Tafel slope decreases from 101.7 mV dec⁻¹ to 64.1 mV dec⁻¹. Besides, Ir–Co₃O₄ exhibits excellent electrocatalytic durability for continuous 130 h's test without any activity attenuation. Moreover, this work provides a kind of high-performance acidic OER electrocatalyst for the development of hydrogen energy.     

Effect of copper addition on cobalt-molybdenum electrodeposited coatings for the hydrogen evolution reaction in alkaline medium

Co–Mo materials have been reported as electrocatalysts that present good performance in alkaline electrolytes. In this paper, the addition of copper into Co–Mo catalysts was evaluated for the hydrogen evolution reaction (HER). It was observed that the electrochemical activity of the Co–Mo for the HER benefited from the addition of copper. The overpotentials required to reach a current density of −10 mA cm⁻² were of −156 mV and −119 mV for Co₆₇Mo₃₃ and Co₅₆Mo₂₁Cu₂₃, respectively. Besides the increased surface area resulting from the addition of copper, it was observed that the improved intrinsic activity for Co₆₁Mo₃₂Cu₇, compared to Co₆₇Mo₃₃, is related to a thermodynamic favoring of the hydrogen adsorption and desorption stages. Large quantities of copper do not favor the HER; therefore, the increased catalytic activity depends on a balance between the intrinsic catalytic activity and the increase of the electroactive area.     

High electrochemical stability and low-agglomeration of defective Co3O4 nanoparticles supported on N-doped graphitic carbon nano-spheres for oxygen evolution reaction

The design of hybrid electrocatalysts with abundant active sites and long term stability is crucial for efficient oxygen evolution reaction (OER) application. Cobalt oxide is considered as one of the most promising electrocatalysts to replace noble metal due to its low cost, availability, and electrocatalytic activity towards the oxygen evolution reaction in alkaline media. However, nano-scale cobalt oxide suffers from severe surface self-agglomeration during the OER process, so that leading to poor activity and durability. Herein, ultra-small cobalt oxide nanoparticles are anchored on the surface of nitrogen doped porous 3D graphitic carbon nano-spheres (N-ACS@Co₃O₄) to increase the amount of exposed active site and avoid the self-agglomeration. The obtained electrocatalyst (N-ACS@Co₃O₄) is enriched with abundant oxygen vacancies and exhibits a superior OER activity (Overpotential of 237 mV at 10 mA.cm⁻²) and exceptional stability for at least 30 h in alkaline electrolyte (1 M KOH). The DFT calculations demonstrate that the strong adsorption of Co₃O₄ on N-doped graphene can prevent its agglomeration, and therefore improves the stability of Co₃O₄ nanoparticles during OER process in line with the experimental results.     

Multi-shelled CoS2–MoS2 hollow spheres as efficient bifunctional electrocatalysts for overall water splitting

The exploration of highly efficient non-precious electrocatalysts is essential for water splitting devices. Herein, we synthesized CoS₂–MoS₂ multi-shelled hollow spheres (MSHSs) as efficient electrocatalysts both for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) using a Schiff base coordination polymer (CP). Co-CP solid spheres were converted to Co₃O₄ MSHSs by sintering in air. CoS₂–MoS₂ MSHSs were obtained by a solvothermal reaction of Co₃O₄ MSHSs and MoS₄²⁻ anions. CoS₂–MoS₂ MSHSs have a high specific surface area of 73.5 m²g^-1. Due to the synergistic effect between the CoS₂ and MoS₂, the electrode of CoS₂–MoS₂ MSHSs shows low overpotential of 109 mV with Tafel slope of 52.0 mV dec⁻¹ for HER, as well as a low overpotential of 288 mV with Tafel slope of 62.1 mV dec⁻¹ for OER at a current density of 10 mA cm⁻² in alkaline solution. The corresponding two-electrode system needs a potential of 1.61 V (vs. RHE) to obtain anodic current density of 10 mA cm⁻² for OER and maintains excellent stability for 10 h.     

Ni3Mo3N coupled with nitrogen-rich carbon microspheres as an efficient hydrogen evolution reaction catalyst and electrochemical sensor for H2O2 detection

Hydrogen evolution reaction (HER) and electrochemical analysis are two important fields of electrochemical research at present. We found that both HER and some electrochemical analytical reactions relied on the concentration of hydrogen ions (H⁺) in solution, so we intended to develop an electrode material that is sensitive to H⁺ and can be used for both HER and some electrochemical analyses. In this work, we synthesized Ni₃Mo₃N coupled with nitrogen-rich carbon microspheres (Ni₃Mo₃N@NC MSs) as highly efficient electrode material for HER and detection of Hydrogen peroxide (H₂O₂), which plays an important role in physiological processes. Here the aniline was used as the nitrogen and carbon sources to synthesize Ni₃Mo₃N@NC. The Ni₃Mo₃N@NC MSs showed high performance for HER in 1 M KOH solution with a small overpotential of 51 mV at 10 mA cm^?2 and superior stability. For H₂O₂ detection, a detection limit of 1 μM (S/N = 3), sensitivity of 120.3 μA·mM^?1 cm^?2 and linear range of 5 μM–40 mM can be achieved, respectively. This work will open up a low-cost and easy avenue to synthesize transition metal nitrides coupled with N-doped carbon as bifunctional electrode material for HER and electrochemical detection.     

Okra-like hollow Cu0.15-CoP/Co3O4@CC nanotube arrays catalyst for overall water splitting

The manufacture of hydrogen energy by overall water splitting (OWS) has been broadly considered as a promising candidate for constant energy systems. Herein, we report an okra-like hollow Cu_0.15-CoP/Co₃O₄@CC nanotube arrays catalyst through a simple hydrothermal-phosphating method. As a noble-metal-free catalyst, it exhibits outstanding HER (hydrogen evolution reaction) catalytic activity with an overpotential of 13 mV to achieve 10 mA cm^?2 in 1 M KOH electrolyte. For OER (oxygen evolution reaction), it demands 225 mV to achieve 10 mA cm^?2. When okra-like hollow Cu_0.15-CoP/Co₃O₄@CC is used as both cathode and anode electrode materials, 1.487 V is required to reach 10 mA cm^?2 for OWS, better than numerous electrocatalysts that have been reported. Moreover, it displays excellent stability in a continuously 60 h i-t test, proving an enormous potential for large-scale applications. The theoretical calculation of density functional theory (DFT) further reveals that Cu doping can bring localized structure polarization and reduce the hydrogen adsorption free energy (ΔG_H1) on the interstitial sites, thus leading to a significant increase in catalytic activity.