Electrochemically engineering defect-rich nickel-iron layered double hydroxides as a whole water splitting electrocatalyst

It is well proved that fabricating more defects on basal plane of layered double hydroxides (LDHs) is one of effective ways to boost the electrocatalytic performance for oxygen evolution reaction (OER). For the first time, the nickel iron LDHs (NiFe LDHs) with hierarchical morphology and abundant defects are simultaneously constructed by one-step electrodeposition (ED) strategy with easy operation, time-saving and green chemistry. Remarkably, the morphology is elaborately tailored by changing the species of doped anions which is unique. Also, the X-ray photoelectron spectroscopy (XPS) results elucidate that the Fe sites are in electron-rich state in LDHs which is revealed to enhance the catalytic activity strongly arising from the generation of oxygen vacancy. To deliver the current density of 10 mA cm⁻², the optimal NiFe LDHs require the overpotential of 128, 106 mV for OER and hydrogen evolution reaction (HER), and achieve 100 mA cm⁻² at the overpotential of 237, 242 mV, respectively. As a bifunctional electrocatalyst, the NiFe LDHs exhibit the current density of 10 mA cm⁻² at a cell voltage of 1.55 V and 100 mA cm⁻² at 1.76 V, which are lower than that of most of benchmarking materials reported previously.     

The construction of defective FeCo-LDHs by in-situ polyaniline curved strategy as a desirable bifunctional electrocatalyst for OER and HER

Here, Fe, Co-layered double hydroxide and polyaniline composites onto nickel foam (NF) (FeCo-LDH/PANI) were fabricated via one-step co-electrodeposition method. The test results indicate the co-existence of the amorphous structure and the smaller size of crystal district with more defects in optimal FeCo-LDH/PANI. Importantly, it is found that there are more defects in FeCo-LDH/PANI compared to that of FeCo-LDH possibly attributed to the local etching of H⁺ released from the polymerization of aniline. Benefitting from the numerous defects, higher electrochemical surface area (ECSA), lower charge-transfer resistance and electron interaction, the optimized FeCo-LDH/PANI needs the overpotentials of 104, 246, 285 and 323 mV vs RHE for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) to achieve 10 and 100 mA cm⁻², and shows desirable stability. Noticeably, the optimal FeCo-LDH/PANI requires a cell voltage of 1.53 V to drive 10 mA cm⁻² for the whole water splitting.     

Enhanced oxygen evolution reaction activity of NiFe layered double hydroxide on nickel foam- reduced graphene oxide interfaces

Herein, we prepared a novel nickel iron-layered double hydroxide/reduced graphene oxide/nickel foam (NiFe-LDH/RGO/NF) electrodes by two step electrodeposition processes for oxygen evolution reaction (OER). The modification of NF by RGO increased the interface conductivity and electrochemical active surface areas (ECSA) of the electrode. The NiFe-LDH/RGO/NF electrode has shown higher catalytic activity with a lower overpotential of 150 mV at the current density of 10 mA cm⁻². The NiFe-LDH/RGO/NF electrode has also shown a small Tafel slope of 35 mV per decade due to the synergy effect between the larger ECSA and the conductive RGO interface. Furthermore, the electrodes exhibits almost 10 h stability under a general current density of 10 mA cm⁻².     

Vertical Nickel–Iron layered double hydroxide nanosheets grown on hills-like nickel framework for efficient water oxidation and splitting

Herein, the vertical thin nickel–iron layered double hydroxide nanosheets grown on the hills-like nickel framework (NiFe LDH/Ni@NF) are employed for the oxygen evolution reaction (OER), securing at the low overpotentials of 197 and 270 mV to obtain the current densities of 20 and 100 mA cm⁻², respectively, with a Tafel slope of 73.34 mV dec⁻¹. The electrodeposited nickel film induces the NiFe LDH nanosheets grow vertically and thinly. As well, the nickel abundant interfaces and inner space makes this catalyst effective for OER. It was further served as the OER electrode in a water splitting system coupled the Pt/C cathode, and a cell voltage was at 1.52 and 1.67 V to achieve the current density of 10 mA cm⁻² and 50 mA cm⁻². In addition, the water electrolyzer can suffer a long time of 24 h at 50 mA cm⁻², showing the feasibility in a practical unbiased alkaline water splitting system.     

CoO/NF nanowires promote hydrogen and oxygen production for overall water splitting in alkaline media

The exploration of catalysts with high activity and low cost for water splitting is still necessary. Herein, a nanowire-like morphology CoO/NF electrode is synthesized using facile hydrothermal reaction and calcination treatment. The urea can regulate its morphology during the synthetic process of CoO/NF. Electrochemical studies reveal that the as-obtained CoO/NF exhibits excellent electrocatalytic performance with overpotential of 307 mV at current density of 10 mA cm⁻² and Tafel slope of 72 mV dec⁻¹ for oxygen evolution reaction, and CoO/NF delivers current density of 10 mA cm⁻² at overpotential of 224 mV for hydrogen evolution reaction. The results of the oxygen evolution reaction stability show that the overpotential of CoO/NF electrode is only increased by 4 mV at current density of 10 mA cm⁻². The two-electrode water splitting with CoO/NF electrodes as both anode and cathode needs a cell potential of 1.76 V to reach 10 mA cm⁻². Therefore, this simple method to prepare CoO/NF electrode can enhance the properties of electrocatalysts, which makes CoO/NF a promising material to replace noble metal-based catalysts.     

Improved electrochemical performance of nickel-cobalt hydroxides by electrodeposition of interlayered reduced graphene oxide

Efficient, economical, and eco-friendly water splitting catalysts are in priority to replace the fossil fuels. In the presented work, reduced graphene oxide is formed through electrochemical reduction and applied as an effective interlayer between nickel foam substrate and nickel-cobalt hydroxide catalyst to augment its activity toward hydrogen evolution reaction. Through subsequent cyclic voltammetry deposition of nickel-cobalt hydroxide over the surface of supported interlayer, the prepared electrocatalyst exhibited remarkable performance by reaching a current density of 10 mA cm⁻² at a small overpotential of 60 mV in 1.0 M KOH electrolyte, much lower than that of the same electrocatalyst without interlayer (78 mV). The proposed strategy made the active metallic catalyst phase acquiring a small Tafel slope and superior durability for hydrogen production in alkaline medium. By utilizing the reduce graphene oxide interlayer, the electrical conductivity of the final nickel-cobalt hydroxide electrode was boosted. Furthermore, a clear transition from ordered reticulated arrays of nanosheets to roughened and disordered nanosheet-comprised nanospheres is demonstrated for surface morphology of nickel-cobalt electrocatalyst that indeed prompts the increase in its electrochemically active surface area.     

NiCo/Ni/CuO nanosheets/nanowires on copper foam as an efficient and durable electrocatalyst for oxygen evolution reaction

Electrochemical water splitting for hydrogen production is a promising solution for the production of renewable and environmentally friendly energy sources, but it is hindered by the sluggish kinetic process of oxygen evolution reaction (OER). Here, a novel hierarchical core-shell nanoarray NiCo/Ni/CuO/CF was synthesized by assembling Ni–Co hydroxide nanosheets directly on the metallic nickel coated CuO nanowires, as a highly efficient electrocatalyst for alkaline OER. This NiCo/Ni/CuO/CF anode exhibited low overpotentials of 246 mV and 286 mV at current densities of 10 mA cm⁻² and 100 mA cm⁻², respectively, and a small Tafel slope of 37.9 mV dec⁻¹. Moreover, NiCo/Ni/CuO/CF showed robust durability at least 60 h at a current density of 100 mA cm⁻². Detailed investigations verified that the unique nanosheets/nanowires architecture with high conductivity metallic nickel layer can expand the exposure of active sites and accelerate the transport of electrons.     

Ni–Zn nanosheet anchored on rGO as bifunctional electrocatalyst for efficient alkaline water-to-hydrogen conversion via hydrazine electrolysis

Bifunctional Ni-15 at.% Zn/rGO catalyst was fabricated by a two-step electrodeposition to be used for efficient alkaline water-to-hydrogen conversion via hydrazine electrolysis. Experiments show that the as-deposited Ni-15 at.% Zn/rGO nanosheet arrays with porous structure possesses excellent catalytic activity and stability towards both hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR). A small overpotential of 49 mV at 10 mA cm⁻² with a low Tafel slope of 26.3 mV dec⁻¹, and a retention rate of 91.4% after 12 h at 10 mA cm⁻² are observed for Ni-15 at.% Zn/rGO towards HER. Moreover, Ni-15 at.% Zn/rGO also shows an extra-high current density of 1097 mA cm⁻² at 0.6 V vs RHE with a low Tafel slope of 33.5 mV dec⁻¹, and a high durability of 90.5% after 5000 s towards HzOR. Moreover, two-electrode cell was constructed using Ni-15 at.% Zn/rGO as both cathode and anode for HER and HzOR, achieving 100 mA cm⁻² at an ultralow cell voltage of 0.418 V. The above outstanding bifunctional catalytic performance should be attributed to its large ECSA, high electrical conductivity and most importantly, its superaerophobic surface induced by the porous structure with nanosheet arrays.     

A hierarchical and branch-like NiCoS/NF material prepared by gradient electrodeposition method for oxygen evolution reaction

Rational fabrication of high performance electrocatalysts materials is of great significance to efficiently accomplish energy conversion. In this work, taking the advantage of the remarkable features of nickel foam, a holey branch-like structure of NiCoS deposition supported on nickel foam (NF) was obtained via altering the current density in the whole electrolytic process for gradient electrodeposition. Benefiting from the three-dimension porous structure of nickel foam skeleton connected by spherical particles of irregular size and the strong synergistic effect among Ni, Co and S elements, NiCoS/NF only needed overpotential of 287 mV, Tafel slope of 64.74 mV dec⁻¹ and an excellent stability of 25 h in 1.0 M KOH at the current density of 10 mA cm⁻² and 100 mA cm⁻². Importantly, originated from the interconnected nanoparticles, this branchlike structure and the Co-doping-optimized electronic structure are responsible for the rapidly enlarged ECSA value 19,650 cm⁻² of deposition and the TOF value 2.2704 s⁻¹. This work will provide a constructive idea for enhancing the efficiency of hydrogen production through water splitting.     

Mesoporous nickel-sulfide/nickel/N-doped carbon as HER and OER bifunctional electrocatalyst for water electrolysis

The development of non-precious metal-based highly active bi-functional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is critical factor for making water electrolysis a viable process for large-scale industrial applications. In this study, bi-functional water splitting electrocatalysts in the form of nickel-sulfide/nickel nanoparticles integrated into a three-dimensional N-doped porous carbon matrix, are prepared using NaCl as a porous structure-forming template. Microstructures of the catalytic materials are characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and N₂ adsorption-desorption analysis. The most active catalyst synthesized in this study exhibits a low HER overpotential of 70 mV at 10 mA cm⁻² and a low Tafel slope of 45 mV dec⁻¹. In OER, the optimized sample performs better than a state-of-the-art RuO₂ catalyst and produces an overpotential of 337 mV at 10 mA cm⁻², lower than that of RuO₂. The newly obtained materials are also used as HER/OER electrocatalysts in a specially assembled two-electrode water splitting cell. The cell demonstrates high activity and good stability in overall water splitting.     

Ni/NiO@rGO as an efficient bifunctional electrocatalyst for enhanced overall water splitting reactions

Herein, we fabricated bifunctional, noble metal-free, highly efficient nickel/nickel oxide on reduced graphene oxide (Ni/NiO@rGO) by chemical synthesis approach for electrochemical water splitting reaction. Its structural and morphological characterization using thermogravimetric analysis (TGA), transmission electron microscopy (TEM), field emission scanning electron microscope (FESEM), energy dispersive analysis of X-ray (EDAX) and X-ray diffraction (XRD) represents, Ni/NiO@rGO is having Ni/NiO NPs ∼10 nm (±2 nm) on graphene oxide with face-centered cubic (FCC) crystal structure. Moreover, the presence of Ni/NiO (2.26%), O (6.56%), N (0.74%) and C (90.44%) from EDAX analysis further confirms the formation of Ni/NiO@rGO and it also supported by FTIR studies. This nanocatalyst is examined further for electrocatalytic water splitting reactions (HER and OER). It demonstrated low overpotential 582 mV to achieve current density at 10 mA cm⁻² and smaller Tafel slope of 63 mV dec⁻¹ obtained in 0.5 M H₂SO₄ towards HER. Also, at the other end at onset potential of 1.6 V vs. RHE towards OER. It demonstrated low overpotential 480 mV to achieve current density at 10 mA cm⁻² and smaller Tafel slope of 41 mV dec⁻¹ in 0.5 M KOH towards OER observed. Hydrogen fuel is eco-friendly to the environment and noteworthy performance of earth-saving reactions.     

Interfacial coupling effect of CoO/CoMoO4 promotes alkaline hydrogen electrode for hydrogen energy storage system

Herein, CoO and CoMoO₄ heterostructure supported on nickel foam (CoO/CoMoO₄@NF) are proposed as an effective bifunctional hydrogen evolution reaction (HER) and hydroxide reaction (HOR) electrocatalyst. The electron density distribution at the interface can be optimized by coupling CoO and CoMoO₄, thereby improving conductivity and regulating the hydrogen binding energy (HBE) and hydroxyl binding energy (OHBE). CoO/CoMoO₄@NF exhibits high stability and activity with an exchange current density of ∼3.67 mA cm⁻². Co/CoMoO₄@NF reaches the current density of −10 mA cm⁻² at only −29 mV and the corresponding Tafel slope of 40.2 mV dec⁻¹. This work provides a promising solution for non-precious metal catalyst for hydrogen reaction in energy storage.     

The P/NiFe doped NiMoO4 micro-pillars arrays for highly active and durable hydrogen/oxygen evolution reaction towards overall water splitting

Water splitting is an efficient strategy to produce purity hydrogen and convert intermittent electricity from renewable wind and solar sources. In this work, dense NiMoO₄ micro-pillars arrays (MPAs) were in-situ grown on nickel foam (NF) through facile hydrothermal method, then the NiMoO₄/NF were converted into NiMoO₄–P/NF and NiFe/NiMoO₄/NF via phosphating and electrodeposition method, respectively. The NiMoO₄–P/NF electrode required small overpotentials of 34 mV@10 mA cm⁻² and 130 mV@100 mA cm⁻² for hydrogen evolution reaction (HER). The NiFe/NiMoO₄/NF electrode exhibited excellent oxygen evolution reaction (OER) activity with overpotentials of 210 mV@10 mA cm⁻² and 300 mV@100 mA cm⁻². The overall water splitting using the anode-cathode couple of NiFe/NiMoO₄/NF||NiMoO₄–P/NF only consumes low voltages of 1.47 V@10 mA cm⁻² for 100 h and 1.66 V@100 mA cm⁻² for 50 h in 1 M KOH. The electronic modification and the well-designed hierarchical structure contribute the high energy-efficient and stabile overall water splitting.     

P-doped 3D graphene network supporting uniformly vertical MoS2 nanosheets for enhanced hydrogen evolution reaction

In order to optimize the conductivity of molybdenum disulfide (MoS₂) and promote its large-scale application as a catalyst for hydrogen evolution, MoS₂ is usually used to form composites with conductive materials, but these hybrid materials suffer from scare active sites, overlapping and complicate process. In this work, phosphoric acid is used as a builder of stereoscopic structures, which can not only twist graphene sheets into a P-doped three-dimensional (3D) graphene network but also promote surface electron transport between graphene sheets. Without adding additional framework materials such as carbon nanotubes or nickel foam, stereoscopic MoS₂/graphene structures are formed with a large number of twisted graphene sheets to support the vertical growth of MoS₂ and expose the edge sites of MoS₂, showing a low Tafel slope about 35 mV dec⁻¹, a high current density of 900 mA cm⁻² at about 300 mV and a robust stability over 2000 cycles. Thus, this work shows a possibility to synthesize an efficient catalyst on a large-scale for hydrogen evolution reaction, which can promote the realization of hydrogen economy.     

One-step synthesis of oxygen incorporated V–MoS2 supported on partially sulfurized nickel foam as a highly active catalyst for hydrogen evolution

Highly active noble-metal-free catalysts for hydrogen evolution reaction (HER) are essential for the sustainable production of hydrogen. MoS₂ based HER catalysts are potentially competitive to noble metals but facing the challenges of low conductivity, density of active sites and intrinsic activity in basal planes. Herein, oxygen incorporated V–MoS₂ supported on partially sulfurized nickel foam (V–Mo(x)S/NF) are synthesized as binder-free HER catalysts via a one-step in-situ hydrothermal method. By controlling the fed atomic ratios of V/Mo, the optimal V–Mo(0.05)S/NF shows the low HER overpotential of ~31 and ~115 at 10 mA cm⁻² and 100 mA cm⁻², respectively in alkaline electrolyte, which is among the most active noble-metal and noble-metal-free HER catalysts reported. In V–Mo(0.05)S/NF, the introduced V and partially sulfurized nickel foam increases the conductivity. The hedgehog-like morphology ensures the exposure of high-density active sites. More importantly, the incorporated surface oxygen can be readily tuned by the fed atomic ratios of V/Mo, which plays the primary role in promoting the intrinsic HER activity for V–Mo(x)S/NF. This work demonstrates the feasibility of boosting HER through the precise control of incorporated surface oxygen in MoS₂ based catalysts.     

Solvothermal synthesis of Pd10–Ni45–Co45/rGO composites as novel electrocatalysts for enhancement of the performance of DBFC

In this research, three Pd decorated Ni and Co catalyst nanoparticle were synthesized on reduced graphene oxide (rGO) supports are synthesized through a facile solvothermal procedure. Borohydride oxidation reaction (BOR) activity and performance of prepared electrocatalysts respect to NaBH₄ oxidation is evaluated by various electrochemical techniques in the three-electrode and the fuel cell configuration. Among the prepared catalysts, Pd₁₀–Ni₄₅–Co₄₅/rGO exhibits the highest BOR activity. The cyclic voltammograms showed that the measured current at 0.5 V for the electrode of Pd₁₀–Ni₄₅–Co₄₅/rGO is as much as 108 mA cm⁻² higher than Pd₁₀–Ni₉₀/rGO and 185 mA cm⁻² higher than Pd₁₀Co₉₀/rGO. X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectra were employed to study the morphology and crystal structure of the prepared catalyst. The results of DBFC test show that the Pd₁₀–Ni₄₅–Co₄₅/rGO nanoparticles as anodic catalyst, enhanced power density to 50.4 mW cm⁻² which is 10.5% and 45.2% higher than power density of DBFCs with Pd₁₀–Ni₉₀/rGO (45.6 mW cm⁻²) and Pd₁₀Co₉₀/rGO (34.7 mW cm⁻²) anode catalysts, respectively. These results indicate that the competency of operating procedure for assembling nickel alloys electrodes can improve the activity of the prepared catalysts for BOR considerably.     

Preparation of ultrathin molybdenum disulfide dispersed on graphene via cobalt doping: A bifunctional catalyst for hydrogen and oxygen evolution reaction

The development of highly active and low-cost catalysts for hydrogen evolution reaction (HER) is significant for the development of clean and renewable energy research. Owing to the low H adsorption free energy, molybdenum disulfide (MoS₂) is regarded as a promising candidate for HER, but it shows low activity for oxygen evolution reaction (OER). Herein, graphene-supported cobalt-doped ultrathin molybdenum disulfide (Co–MoS₂/rGO) was synthesized via a one-pot hydrothermal method. The obtained hybrids modified electrode exhibits a high HER catalytic activity with a low overpotential of 147 mV at the current density of 10 mA cm⁻², a small Tafel slope of 49.5 mV dec⁻¹, as well as good electrochemical stability in acidic electrolyte. Meanwhile, the catalyst shows remarkable OER activity with a low overpotential of 347 mV at 10 mA cm⁻². The superior activity is ascribed not only to the high conductivity originated from the reduced graphene, but also to the synergistic effect between MoS₂ and cobalt.     

Novel 3-D urchin-like Ni– Co–W porous nanostructure as efficient bifunctional superhydrophilic electrocatalyst for both hydrogen and oxygen evolution reactions

Fabrication of an electrocatalyst with remarkable electrocatalytic activity for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is important for the production of hydrogen energy. In this study, Ni–Co–W alloy urchin-like nanostructures were fabricated by binder-free and cost-effective electrochemical deposition method at different applied current densities and HER and OER electrocatalytic activity was studied. The results of this study showed that the microstructure and morphology are strongly influenced by the electrochemical deposition parameters and the best electrocatalytic properties are obtained at the electrode created at the 20 mA.cm⁻²applied current density. The optimum electrode requires −66 mV and 264 mV, respectively, for OER and HER reactions for delivering the 10 mA cm⁻² current density. The optimum electrode also showed negligible potential change after 10 h electrolysis at 100 mA cm⁻², which means remarkable electrocatalytic stability. In addition, when this electrode used as a for full water splitting, it required only 1.58 V to create a current density of 10 mA cm⁻². Such excellent electrocatalytic activity and stability can be related to the high electrochemical active surface area, being binder-free, high intrinsic electrocatalytic activity and hydrophilicity. This study introduces a simple and cost-effective method for fabricating of effective electrodes with high electrocatalytic activity.     

Self-supported cobalt–molybdenum oxide nanosheet clusters as efficient electrocatalysts for hydrogen evolution reaction

In this paper, we report the three-dimensional self-supported CoMoO₄ nanosheet clusters on the nickel foam (denoted as CoMoO₄/NF) by a facile hydrothermal-calcination method for efficient hydrogen generation. As a result, the freestanding CoMoO₄ electrode exhibits an efficient electrochemical activity towards hydrogen evolution reaction, showing overpotentials as low as 68 and 178 mV at current densities of 10 and 100 mA cm⁻² in the alkaline condition (1 M KOH), respectively, a Tafel slope value of 82 mV per decade. Moreover, the electrode exhibits remarkable electrochemical durability for 1000 cycles. Significantly, the water splitting electrolyzer assembled with CoMoO₄/NF || NiFe LDH/NF (the nickel iron layered double hydroxide supported on the nickel foam) system achieved 20 mA cm⁻² at 1.63 V, showing the CoMoO₄/NF is promising for practical water splitting applications.     

Multilevel N-doped carbon nanotube/graphene supported cobalt phosphide nanoparticles for electrocatalytic hydrogen evolution reaction

Electrochemical water splitting plays an important role in alternative energy studies, since it is highly efficient and environment-friendly. Accordingly, it is an ideal way of providing alternative to meet the urgent need of finding sustainable and clean energy. This study presents the fabrication of CoP attached on multilevel N-doped CNT/graphene (CoP–CNT/NG) hybrids. The multilevel carbon structure can enhance electrical conductivity efficiently and increase the reaction active area immensely. The obtained electrocatalyst exhibits great electronic conductivity (17.8 s cm⁻¹) and HER activity with low overpotential (155 mV at 10 mA cm⁻²), low Tafel slope (69.1 mV dec⁻¹) in 0.5 M H₂SO₄. In addition, the CoP–CNT/NG displays prominent electrochemical durability after 18 h.