Ultrathin WS2 nanosheets vertically aligned on TiO2 nanobelts as efficient alkaline hydrogen evolution electrocatalyst

Highly efficient and durable non-noble metal-based hydrogen evolution electrocatalysts are critical to advance the production of hydrogen energy via alkaline water electrolysis. Herein, we prepared a novel TiO₂@WS₂ hybrid via a facile and scalable two-step hydrothermal strategy combined with selective etching. Benefited from acid-etched TiO₂ nanobelts with rough surface as substrate, ultrathin WS₂ nanosheets nucleated and vertically grew into few layers in the confined configuration with more exposed active edges. Furthermore, the partial incorporation of oxygen in WS₂ inherited from the remaining O–W bonds of tungsten precursor enhanced the electrical conductivity of the hybrid. Therefore, TiO₂@WS₂ hybrid was proved to be efficient and durable electrocatalyst for hydrogen evolution in alkaline medium. Upon optimal conditions, the hybrid only required a small onset overpotential of 95 mV and a low overpotential of 142 mV at 10 mA cm⁻², superior to pristine WS₂ and TiO₂. In addition, better cycling stability during the alkaline HER process was also obtained, indicating its capability in future practical application. The synthesis strategy presents a cost-effective approach to produce efficient WS₂-based HER electrocatalyst for electrochemical water splitting.     

Tuning of electrocatalytic activity of mixed metal dichalcogenides supported NiMoP coatings for alkaline hydrogen evolution reaction

The mixed metal dichalcogenides combination of WS₂–MoS₂ was coated onto Cu substrate by electroless NiMoP plating technique and the electrocatalytic hydrogen evolution reaction (HER) performance was investigated. The enhanced structural, morphological parameters and boosted electrocatalytic performance of the various metal-metal molar ratio of WS₂–MoS₂ onto NiMoP plate were identified under variable operating conditions and it was successfully evaluated by various characterization techniques. The well-defined crystalline nature, phase, particle size, structure, elemental analysis and surface morphology of prepared coatings were analyzed by FESEM, XRD, AFM and EDS mapping. The electrochemical analysis was performed using open circuit potential (OCP) analysis, chronoamperometry (CA), electrochemical impedance spectroscopy (EIS), Tafel curves, linear sweep voltammetry (LSV), cyclic voltammetry (CV) and polarization studies to find the activity of prepared electrocatalyst towards electrochemical hydrogen evolution reactions. The performance of bare NiMoP and WS₂–MoS₂/NiMoP plates were compared and found that the HER activity of NiMoP can be reinforced by composite incorporation through the synergic effect arises with in the catalytic system, which improves surface roughness and enhances the magnitude of electrocatalyst toward HER. The achievement of enhanced catalytic performance of coatings was authenticate by the kinetic parameters such as decreases in Tafel slope (98 mV dec^?1), enhanced exchange current densities (9.32 × 10^?4 A cm^?2), and a lower overpotential. The consistent performance and durability of the catalyst were also investigated. The enhanced electrocatalytic activity of WS₂–MoS₂/NiMoP coatings increased with respect to the surface-active sites associated with combination of mixed dichalcogenides and the synergic effect arises in between different components present in the coating system. This work envisages the progressive strategies for the economical exploration of a novel WS₂–MoS₂/NiMoP water splitting catalyst used for large scale H₂ generation. The prepared WS₂–MoS₂/NiMoP embedded Cu substrate possess high catalytic activity due to its least overpotential of 101 mV at a benchmark current density of 10 mA cm^?2, which demonstrated the sustainable, efficient and promising electrocatalytic property of prepared catalyst towards HER under alkaline conditions.     

Ru–MoS2@PPy hollow nanowire as an ultra-stable catalyst for alkaline hydrogen evolution reaction

Electrocatalytic hydrogen evolution reaction (HER) is one of the green and effective method to produce clean hydrogen energy. However, the development of non-Pt HER catalysts with excellent catalytic activity and long-term stability still remains a great challenge. Herein, a vertically aligned core-shell structure material with hollow polypyrrole (PPy) nanowire as a core and Ru-doped MoS₂ (Ru–MoS₂) nanosheets as a shell is firstly reported as a highly efficient and ultra-stable catalyst for HER in alkaline solutions. Results indicate that Ru–MoS₂@PPy catalyst demands a low overpotential of 37 mV at 10 mA cm^?2. In addition, the overpotential at 100 mA cm^?2 is 157 mV and it is almost unchanged after 40,000 cyclic voltammetry cycles. The existence of PPy core not only ensures the vertical growth of MoS₂ nanosheets to expose more edge sites, but also promotes the rapid transfer of electrons, contributing to the improvement of catalytic activity. More importantly, the strong interface interaction between MoS₂ and PPy prevents the collapse of the vertical structure of MoS₂ sheets in the electrocatalytic process and greatly enhances the stability of catalysts, which offers an effective strategy to design and synthesize the HER catalysts with superior catalytic stability.     

Easily-prepared bimetallic metal phosphides as high-performance electrode materials for asymmetric supercapacitor and hydrogen evolution reaction

Transition metal phosphides are very attractive because of the remarkable performance in energy storage and conversion. Herein, a series of bimetallic phosphides are synthesized through a one-step solid-state reaction. The obtained bimetallic phosphides show outstanding properties as supercapacitor electrode materials. Results show that the incorporation of secondary metal into phosphides tunes composition, electronic structure and then the electrochemical performance. And electrochemical properties are closely associated with the secondary metal content. Notably, the obtained NiCoP shows the best performance with 2011 F g⁻¹ at 1 A g⁻¹. And an asymmetric supercapacitor (ASC) based on NiCoP shows energy density of 47.6 W h kg⁻¹, along with 90.5% of capacitance maintained after 10000 cycles. In addition, the NiCoP also possesses great performance toward hydrogen evolution reaction (HER), which displays the lowest potential of 0.221 V vs. RHE and 0.173 V vs. RHE at 10 mA cm⁻² in 0.5 M H₂SO₄ as well as 1.0 M KOH, respectively. The excellent properties may result from the enhanced electrical conductivity, synergistic effects among metal elements and the increased local electrical dipole. The regulation of electronic structure through introduction of secondary metal atom sheds considerable light on realization and preparation of the bimetallic transition metal compounds as electrode materials.     

Enhanced hydrogen evolution reaction of WS2–CoS2 heterostructure by synergistic effect

Transition metal dichalcogenides (TMDs) have attracted significant research interest due to its promising performance in hydrogen evolution reaction (HER). Synergistic effect between materials interface can improve the electrocatalytic properties. In this work, the WS₂–CoS₂ heterostructure supported on carbon paper (CP) was elaborately fabricated by a three-step method. Owing to the synergistic effect, WS₂–CoS₂ heterostructure exhibits an excellent electrocatalytic activity with a low overpotential of 245 mV at 100 mA/cm² and a small Tafel slope of 270 mV/dec toward HER. We demonstrate that the increased specific surface area and conductivity of the heterostructure play a key role in enhancing the overall catalytic efficiency. Moreover, the crystal lattice distortion in the heterostructure could induce charge redistribution and improve electron transfer efficiency, which may also benefit the whole HER activity.     

High-performance Ru-based electrocatalyst composed of Ru nanoparticles and Ru single atoms for hydrogen evolution reaction in alkaline solution

Hydrogen evolution reaction (HER) plays a critical role in electrocatalysis, and developing highly active, cheap and stable Pt-free catalysts for HER in alkaline media is imperative for conversion of renewable energy into hydrogen fuels via photo/electrochemical water splitting. Herein, we report a facile strategy to fabricate a high-performance Ru-NMCNs-T electrocatalyst (T is the annealing temperature) for HER, which consist of both Ru nanoparticles and single Ru atoms well dispersed on nitrogen-doped mesoporous carbon nanospheres (NMCNs). Ru-NMCNs-500 exhibited the best HER performance in the series. To achieve a current density of 10 mA cm⁻² in 1 M KOH, it only needs an overpotential of 28 mV with a small Tafel slope of 35.2 mA dec⁻¹, superior to the commercial Pt/C catalyst. It also exhibited exceedingly improved long-term stability than Pt/C. This study can open a new avenue for preparing Ru-based catalysts toward HER under extreme alkaline conditions.     

Nickel-doped MoSe2 nanosheets with Ni–Se bond for alkaline electrocatalytic hydrogen evolution

Molybdenum diselenide (MoSe₂) is a potential catalytic material for the electrocatalytic hydrogen evolution reaction (HER). However, due to the low density of its active sites, MoSe₂ nanosheets feature high overpotential in HER, which limits its practical application. This describes the method of doping the Ni in MoSe₂ nanosheets to increase active sites. The NiO₂ evenly dispersed on MoSe₂ by ethanol solution reduces to ~4 nm Ni nanoclusters under annealing process, which is firmly adhered to MoSe₂ nanosheets with Ni–Se bond. The electrochemical active surface area of Ni-doped MoSe₂ expands, proving that Ni dopants produce more activity sites in MoSe₂ nanosheets. The overpotential of MoSe₂ (at 10 mA cm⁻²) decreases from 335 mV to 181 mV with 4.5 at.% Ni doped in 1 M KOH. The Ni–MoSe₂ also characterizes excellent stability for 12 h with the formation of Ni–Se bond. The study of doping Ni in MoSe₂ nanosheets is of great guiding significance to the design and production of non-noble electrocatalysts for HER in alkaline media.     

Synthesis of Co2FeAl alloys as highly efficient electrocatalysts for alkaline hydrogen evolution reaction

The development of cost-effective non-precious metal electrocatalysts is a major challenge for water splitting applications, but it is important for the realization of renewable energy systems. Alloying has proved an effective way to design metal-based electrocatalysts, and by controlling the annealing temperature, the surface morphology and crystallinity of the alloy can be tuned to control the hydrogen evolution reaction (HER) performance. In this work, with a simple coprecipitation method, we have prepared Co₂FeAl alloys at different annealing temperatures (550 °C–670 °C), which exhibit excellent crystallinity and electrocatalytic performance for HER in alkaline solution. Among all conditions, the Co₂FeAl alloys prepared at 620 °C shows the better crystallinity and the higher purity, and it could achieve a low overpotential of 149 mV at 10 mA cm^?2 in alkaline solution. The overpotential demonstrates persistent stability with only 3 mV change after over 1000 cycles. Both density functional theory (DFT) calculations and experimental results revealed that alloying optimizes the electronic structure near the Fermi surface of the system, improving the electron transport efficiency and enhancing the catalytic activity. These Co₂FeAl alloys are appealing candidates for high-performance alkaline HER electrocatalytic electrodes in water electrolysis due to their outstanding electrocatalytic properties.     

Superior hydrogen evolution electrocatalysis enabled by CoP nanowire array on graphite felt

Renewable electricity-powered hydrogen production is an attractive alternative to unsustainable industrial processes, but the large-scale implantation of such sustainable technology still requires efficient and noble-metal-free electrocatalysts for driving cathodic hydrogen evolution reaction (HER), especially under alkaline conditions. In this paper, CoP nanowire array was in-situ developed on porous graphite felt (CoP/GF) as a new 3D electrocatalyst in facilitating hydrogen evolution electrocatalysis. This CoP/GF presents outstanding HER activity, requiring a low overpotential of 130 mV to deliver a current density of 20 mA cm^?2 as tested in 1.0 M KOH. Furthermore, this free-standing catalyst exhibits impressive long-term durability of up to 50 h under working conditions.     

WS2/NiSx heterojunction nanosheet clusters: A highly efficient electrocatalyst for hydrogen evolution reaction

The development of highly active and stable electrocatalysts is essential to solve energy and environmental problems and realize sustainable social and economic development. Herein, we synthesized a bimetallic sulfide material by a kinetically controlled low-temperature solid-phase reaction. The bimetallic sulfide improves the conductivity of the electrocatalysts by optimized electronic structure, and the coupling effect at the heterogeneous interface of WS₂ and NiS_x increases the charge density on the S site at W–S–Ni, making it easier for the electrocatalysts to trap the active material in solution. In addition, nanosheet clusters expose abundant catalytic sites, which together improve hydrogen evolution reaction (HER) for catalytic activity. Optimized WS₂/NiS_x composite show near-precious metal catalyst activity with an overpotential at 10 mA cm^?2 of only 72 mV in alkaline media, which exhibits excellent catalytic stability and outperforms most non-precious metal electrocatalysts.     

Hollow bimetallic M-Fe-P (M=Mn,Co, Cu) nanoparticles as efficient electrocatalysts for hydrogen evolution reaction

Searching for low-cost electrocatalysts with high activity towards the hydrogen evolution reaction (HER) is of great significance to enable large-scale hydrogen production via water electrolysis. In this study, by using inverse spinel MFe₂O₄(M = Mn, Fe, Co, Cu) nanoparticles (NPs) as the precursors, monodisperse bimetallic phosphide M-Fe-P NPs/C with hollow structures were readily obtained by a gas-solid annealing method. These hollow phosphide NPs displayed excellent HER activity in an acidic medium with a low loading amount of 0.2 mg cm⁻². In particular, the Co–Fe–P NPs/C shows highest HER activity that only requiring an overpotential of 97 mV to retain a current density of 10 mA cm⁻². A volcano relation between activity and incorporated elements was revealed. Incorporation of cation with high electronegativity stabilized the FeP active centres, while phase segregation resulted in the loss of activity for Cu–Fe–P NPs/C.     

Ni(OH)2/ NiSe2 hybrid nanosheet arrays for enhanced alkaline hydrogen evolution reaction

Developing efficient, non-noble electrocatalysts toward hydrogen evolution reaction (HER) in alkaline electrolytes is of important significance for future energy supplement but still a challenge. Recently, pyrite-type NiSe₂ nanomaterial has been considered as an idea HER electrocatalyst due to its high conductivity, strong corrosion resistance and low cost. However, the HER performance of NiSe₂ in alkaline electrolytes is still unsatisfactory, which is possibly limited to the activate water dissociation in alkaline media. Herein, a novel hybrid electrocatalyst of Ni(OH)₂/NiSe₂ nanosheet arrays on carbon cloth (Ni(OH)₂/NiSe₂/CC) is fabricated, exhibiting excellent HER catalytic activity with a low overpotential of 82 mV to drive a current density of 10 mAcm⁻² as well as maintaining a long-term durability for 12 h in 1.0 M KOH, which is 77 mV less than that of NiSe₂/CC and superior to most recently reported non-noble HER electrocatalysts. In addition, the Tafel slope of Ni(OH)₂/NiSe₂/CC (60 mV dec ⁻¹) is also much smaller than that of NiSe₂/CC (112 mV dec ⁻¹), suggesting a promotion kinetics of HER process for Ni(OH)₂/NiSe₂/CC. Our further experimental results show that the significantly improved activity of Ni(OH)₂/NiSe₂/CC electrode should ascribe to its enlarged active surface, good conductivity and interfacial synergy between Ni(OH)₂ and NiSe₂. The synergetic strategy may provide an efficient way to promote the HER activity of other non-noble transition metal selenides in alkaline electrolyte.     

Nickel hydroxide armour promoted CoP nanowires for alkaline hydrogen evolution at large current density

The development of hydrogen evolution activity (HER) electrocatalyst that can run durably and efficiently under the large current density is of special significance but still challengeable for the massive production of hydrogen. Herein, a CoP/Ni(OH)₂ nanowire catalysts grown on Co foam (CF) with a three-dimensional heterojunction structure has been successfully prepared by electrodepositing nickel hydroxide on the surface of cobalt phosphide. The prepared CoP/Ni(OH)₂–15 min sample reveals a superior HER activity and stability. It merely requires ultralow overpotentials of 108 and 175 mV to 100 and 500 mA cm^?2, respectively. In addition, the long-term stability test shows that the catalyst (CoP/Ni(OH)₂–15 min) can operate stably for at least 70 h at 400 mA cm^?2. Utilizing NiFe-LDH/IF with high OER activity, the NiFe-LDH/IF || CoP/Ni(OH)₂–15 min catalyst system possesses the same outstanding performance for overall water splitting (OWS), which can accomplish ≈ 500 mA cm^?2 at 1.74 V in 1 M KOH electrolyte. Moreover, the NiFe-LDH/IF || CoP/Ni(OH)₂–15 min couple can work for more than 80 h at 500 mA cm^?2, indicating its a great prospect in the area of electrolysis water. Such excellent catalytic performance is mainly attributed to the armor effect of Ni(OH)₂, which can not only promote the rapid decomposition of water molecules, but also prevent the loss of phosphorus and enhance the synergistic effect of CoP and Ni(OH)₂. This work can offer a significant reference for the design with high-performance and durable transition metal phosphide electrocatalysts.     

In situ synthesis by organometallic method of vulcan supported PdNi nanostructures for hydrogen evolution reaction in alkaline solution

Pd and Pd-based catalysts for hydrogen production remain the best alternative to Pt substitution because of similarities in their electronic structure and more abundant reserves. In this work, it was carried out the in-situ synthesis of Pd_xNi_1-x/C electrode materials (x = 0, 30, 50, 70 and 100 wt%) by the displacement of ligands from organometallic compounds followed by an annealing process at 300 °C in Ar atmosphere. The electrocatalytic performance of these materials was evaluated on the hydrogen evolution reaction in alkaline medium (1 M KOH). The results showed that annealing process, after the synthesis of stabilized nanostructures by organometallic method, did not affect the particle size (4.27 ± 1.14 to 4.62 ± 1.59 nm) and dispersion (25.75–27.07%) of the alloyed nanostructures. The modification of Pd electronic features with low Ni amount facilitates the adsorption of the hydrogen on the bimetallic active surface of the catalysts. The PdNi alloys, especially Pd₇₀Ni₃₀/C, tend to display the overpotential of HER to more positive values in comparison with Pd/C catalysts. This behavior is clearly correlated with an improvement by the synergistic effect between the components, which in turn enhance the electrochemical surface area (ECSA) and the real area. Either the hydrogen adsorption resistance and charge transfer resistance are dependent of the Ni amount, due to Ni influences ion/atom recombination or hydrogen desorption.     

Ultrashort pulse laser-structured nickel surfaces as hydrogen evolution electrodes for alkaline water electrolysis

In this study, we report on micro- and nanostructured Ni surfaces produced by an ultrashort pulse laser process as cathode materials for the alkaline electrolysis of water. We studied the influence of the laser-induced microstructure and surface morphology as well as a cyclic voltammetric activation process on the electrochemical activity of the hydrogen evolution reaction. Galvanostatic techniques, steady-state polarization curves to attain Tafel parameters and capacitance calculations via electrochemical impedance spectroscopy were used to analyze the electrodes. The analyses reveal that the ultrashort pulse laser process increases the specific surface on formerly flat Ni surfaces. Further, the cyclic voltammetric activation process gives rise to an increased intrinsic activity. Both effects lead to a strongly reduced overpotential value. This work demonstrates that different processes can be combined to dramatically boost the activity of Ni electrodes for the hydrogen evolution reaction.     

NiCo2O4 nanowire arrays rich in oxygen deficiencies for hydrogen evolution reaction

The rational design of highly efficient electrocatalysts to generate hydrogen by catalyzing hydrogen evolution reaction still remains a challenge. Herein, we report a simple strategy to significantly enhance the catalytic activities of NiCo₂O₄ nanowire arrays by simply tuning the amount of oxygen vacancies. Remarkably, the oxygen-deficient NiCo₂O₄ catalysts obtained in Ar environment show significantly improved catalytic activities toward hydrogen evolution reaction with the requirement of 104 mV overpotential to afford 10 mA cm⁻², 122 mV less than that for air-sintered NiCo₂O₄ (226 mV). Moreover, such catalysts also exhibit superior long-term durability for 24 h at 100 mA cm⁻². The present study further promotes the application of NiCo₂O₄ in other energy storage and conversion system.     

Enhanced alkaline/seawater hydrogen evolution reaction performance of NiSe2 by ruthenium and tungsten bimetal doping

The exploration of high-efficiency and stable electrocatalysts for alkaline and seawater hydrogen evolution reaction (HER) is the key to realize energy conversion, but there is still a significant challenge owing to the slow HER kinetics in alkaline and seawater systems. In this study, we prepared nickel foamed-supported Ru, W co-doped NiSe₂ (Ru, W–NiSe₂/NF) by a brief two-step hydrothermal strategy and the prepared Ru, W–NiSe₂/NF displays exceptional HER property, requiring only a low overpotential of 100 and 353 mV to reach 10 mA cm⁻² in 1 M KOH and natural seawater, respectively, far superior to Ru–NiSe₂/NF, W–NiSe₂/NF and NiSe₂/NF. Electrochemical surface area (ECSA) and operando electrochemical impedance spectroscopy (EIS) verify the abundant active sites and superior electron transfer rate of Ru, W–NiSe₂, which optimized the HER kinetics in alkaline solution and natural seawater. The ECSA normalization and TOF results indicated that Ru, W co-doping increased the intrinsic activity of NiSe₂. This study revealed the impact of bimetallic doping on the intrinsic activity of NiSe₂, and provided a practical strategy for designing and developing the HER electrocatalysts with excellent performance.     

Super-hydrophilic/super-aerophobic Ni2P/Co(PO3)2 heterostructure for high-efficiency and durable hydrogen evolution electrocatalysis at large current density in alkaline fresh water,alkaline seawater and industrial wastewater

Seawater electrolysis has become an efficient method which makes full use of natural resources to produce hydrogen. However, it suffers high energy cost and chloride corrosion. Herein, we first present a Ni₂P/Co(PO₃)₂/NF heterostructure in which Co(PO₃)₂ with the nano-rose morphology in-situ grown on the rough Ni₂P/NF. The unique 3D nano-rose structure and the optimized electronic structure of the heterostructure enable Ni₂P/Co(PO₃)₂/NF super-hydrophilic and super-aerophobic characteristics, and highly facilitate hydrogen evolution reaction (HER) kinetics in alkaline fresh water, alkaline seawater and even industrial wastewater at large current density, which is rarely reported. Significantly, at large current densities, Ni₂P/Co(PO₃)₂/NF only requires overpotentials of 217 and 307 mV for HER to achieve 1000 mA cm⁻² in alkaline fresh water and alkaline seawater, respectively, and requires an overpotential of 469 mV for HER to deliver 500 mA cm⁻² in industrial wastewater. Furthermore, the overall seawater splitting system in the two-electrode electrolyzer only requires voltage of 1.98 V to drive 1000 mA cm⁻², which also demonstrates significant durability to keep 600 mA cm⁻² for at least 60 h. This study opens a new avenue of designing high efficiency electrocatalysts for hydrogen production at large current densities in alkaline seawater and industrial wastewater.     

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.     

Monometallic,bimetallic, and trimetallic chalcogenide-based electrodes for electrocatalytic hydrogen evolution reaction

Cu₂CoSnS₄, Cu₂SnS₃, Cu₂CoS₄, Co₂SnS₃, Cu₂S, CoS₂, and SnS₂ were synthesized using a one-step solvent-free solid-phase approach. The surface structure, morphology, and composition were characterized using an X-ray diffractometer (XRD), Fourier-Transform Infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), and X-ray Photoelectron Spectroscopy (XPS). The characterizations reveal pure phase formation and porous morphology. Further, the Hydrogen evolution reaction was performed using Cu₂CoSnS₄, Cu₂SnS₃, Cu₂CoS₄, Co₂SnS₃, Cu₂S, CoS₂, and SnS₂-based electrodes. Amid all electrocatalysts, Cu₂CoSnS₄ shows an excellent hydrogen evolution reaction with a low overpotential of ?192.1 mV at ?10 mA/cm² in 0.5 M H₂SO₄. And higher current density. Cu₂CoSnS₄ also shows a lower Tafel slope of 98.6 mV/dec and charge transfer resistance than mono and bimetallic chalcogenide-based electrodes. The Cu₂CoSnS₄ exhibit very good stability for ～22 h at ?10 mA/cm² current density in 0.5 M H₂SO₄.