Fabrication,characterization and application of three-dimensional copper nanodomes as efficient cathodes for hydrogen production

In this study, three-dimensional (3D) copper nanodomes (Cu-NDs) were fabricated by a combined method of nanosphere-soft lithography, electrochemical and physical vapor deposition (PVD) methods. The 3D Cu-NDs were characterized using surface characterization techniques. The hydrogen production performance and time-stability of the electrodes were examined in a concentrated alkaline solution (6 M KOH) using various electrochemical techniques. The experimental results showed that very uniformly and closely packed Cu-NDs were prepared by the combined methods. The hydrogen generation activity of the 3D Cu-NDs was significantly improved with respect to bulk Cu. Fabricating Cu-NDs does not effect of the hydrogen evolution mechanism and the reaction is activation controlled. The water splitting reaction starts at lower potentials and larger current densities at a fixed potential were appeared at the Cu-NDs electrode. The average reduction in the charge transfer resistance related to the reaction of hydrogen gas evolution is 91.9% at the Cu-NDs electrode with respect to the bulk Cu. The enhanced activity of the nanostructures was related to enlarging real surface area and available more active centers at the Cu-NDs surface. The Cu-NDs electrode has excellent time stability in alkaline solution.     

The effect of 3D silver nanodome size on hydrogen evolution activity in alkaline solution

Three-dimensional (3D) Ag nanodomes (AgNDs) having different sizes (400, 800, 1200 and 1600 nm) were fabricated using combination of nanosphere lithography and soft lithography. The surface structures of 3D assembled latex particles, nanovoids and metal nanodomes (ND) were examined using scanning electron microscopy (SEM). Their heights and widths analyses were performed with the help of atomic force microscopy (AFM). The effect of diameter of the NDs on their hydrogen evolution activity was examined in 6 M KOH solution at 298 K using electrochemical techniques. Their activities were compared with the activity of bulk Ag electrode. The preparation of 3D-AgNDs having various diameters and examination of their size effects on the water splitting activity have not been studied yet and are being reported firstly. It was found that very well-structured and very uniformly distributed NDs can be fabricated using this procedure. AgNDs exhibit higher hydrogen evolution activity with respect to bulk Ag. Their hydrogen evolution activity depends on their diameters; 1200 nm NDs were the best among them. The current density at ?1.40 V(Ag/AgCl) which is proportional to the rate of hydrogen releasing reaction increases from 0.70 mA cm^?2 to 44.13 mA cm^?2 at this ND electrode with respect to the bulk Ag electrode. At the same 3D-AgNDs electrode and potential, the resistance against the HER reduces from 148.7 Ω cm² to 1.12 Ω cm² (99.6%) by comparing with the bulk Ag electrode. The average surface roughness factors of bulk Ag, 400 nm, 800 nm, 1200 nm and 1600 nm AgNDs are 8, 123, 100, 291 and 176, respectively. The superior hydrogen evolution performance of this electrode is related to its well-structured surface and large real surface area.     

Electrodeposition of self-supported transition metal phosphides nanosheets as efficient hydrazine-assisted electrolytic hydrogen production catalyst

The synthesis of electrocatalysts which used simultaneously as electrodes for the hydrazine oxidation reaction (HzOR), and hydrogen evolution reaction (HER) can significantly improve the efficiency of hydrogen production in the water splitting process. Here, Ni–Co–Fe–P binder-free nanosheets were fabricated using the electrochemical deposition method and used as an effective, stable, and cost-effective electrode for hydrazine-assisted electrochemical hydrogen production. Taking advantage of high surface area, being binder-free, and synergistic effect between the elements in the electrode composition, this electrode showed unique electrocatalytic activity and stability. When this electrode was used as a bifunctional electrode for HzOR-HER, a cell voltage of 94 mV was required to reach a current density of 10 mA cm^?2. The results of this study indicated that the Ni–Co–Fe–P electrode is an excellent candidate for the hydrogen production industry.     

Free-standing carbon nanotubes as non-metal electrocatalyst for oxygen evolution reaction in water splitting

Oxygen evolution reaction (OER) has significant impact on the overall electrochemical water splitting. We introduce, for the first time, a facile approach towards the fabrication of versatile electrode composed of free-standing multiwalled carbon nanotubes (MWCNTs) as electrocatalyst for the water splitting reaction. Directly extracted MWCNTs as sheets from vertically grown arrays transferred over the glass substrate, are used without any post treatment as a working electrode for OER. Onset potential of 1.60 V was achieved for MWCNTs which is significantly reduced as compared to platinum based metal electrode (1.72 V) with excellent current density. No surface modification, metal-free nature, flexibility and low cost with excellent catalytic activity proved this material as a promising candidate for the replacement of metal based electrodes in electrochemical water splitting.     

Pulse-reverse electrodeposition of Ni–Mo–S nanosheets for energy saving electrochemical hydrogen production assisted by urea oxidation

Electrochemical hydrogen production from water splitting is one of the effective methods for hydrogen production that has recently attracted particular attention. One of the limitations of the electrochemical water splitting method is the slow oxygen evolution reaction (OER), which leads to an increase in overpotential and a decrease in hydrogen production efficiency. Here, Ni–Mo–S ultra-thin nanosheets were synthesized using the pulse reverse electrochemical deposition technique, and then this electrode was used as an electrode material for accelerating hydrogen evolution reaction (HER) and urea oxidation reaction (UOR). Remarkably, the optimized electrode needs only 74 mV to attain the 10 mA cm⁻² current density in HER and require only 1.3 V vs RHE potential in the UOR process. Also, results showed that the replacement of the UOR with the OER process resulted in a significant improvement in the electrochemical production of hydrogen in which for delivering the current density of 10 mA cm⁻² in overall urea electrolysis, only 1.384 V is needed. In addition, outstanding catalytic stability was obtained, after 50 h electrolysis, the voltage variation was negligible. Such outstanding catalytic activity and stability was due to 3-D ultrathin nanosheets, the synergistic effect between elements, and the superhydrophilic/superaerophobic nature of fabricated electrode.     

Double-template fabrication of three-dimensional porous nickel electrodes for hydrogen evolution reaction

Three-dimensional (3D) porous nickel structures were fabricated via a double-template electrochemical deposition process. The construction of the foam structures was achieved by means of a hydrogen bubble dynamic template, prepared from Cu electrodeposition at high current densities. Subsequently, a Ni layer was electrodeposited on the Cu 3D template. During the nickel coating, the typical finger-like microstructure of the Cu foam becomes denser and changes to a cauliflower microstructure. The hydrogen evolution reaction (HER) on these macroporous Ni electrodes was evaluated in 30 wt.% KOH solution by means of polarization curves and electrochemical impedance spectroscopy (EIS). Results demonstrate greater apparent activity of the developed electrodes towards HER in comparison with commercial smooth Ni electrode. The 3D porous Ni electrocatalyst obtained from Cu templates synthesized at the lowest current density and the highest electrodeposition time yielded the best electrochemical activity for HER.     

Morphological variation of electrodeposited nanostructured Ni-Co alloy electrodes and their property for hydrogen evolution reaction

Nanostructured nickel-cobalt alloys of the content of Co varying from 0% to 75% for hydrogen evolution reaction were fabricated by galvanostatic electrochemical deposition processes. With the incorporation of Co into Ni matrix, the morphologies of Ni-Co alloys are changed from nanocones to lamellar structure and finally evolved to a mixed shape of nanocone structure and lamellar structure. Among these Ni-Co alloys, the optimal Ni-60%Co alloy exhibits outstanding electrocatalytic activity with a small hydrogen overpotential of ?180 mV and follows Volmer-Tafel mechanism. Better performance of Ni-60%Co can be attributed to the synergetic combination of Ni and Co and unique complex mesh structure which provides the enlarged exposure of catalytically active sites. In addition, Ni-60%Co alloy also displays good electrochemical stability under 10 h galvanostatic test. With prominent electrochemical properties, Ni-60%Co alloy has a certain advantage in the catalytic hydrogen evolution material.     

Preparation of carbon dots/TiO2 electrodes and their photoelectrochemical activities for water splitting

Carbon dots with various functional groups can be employed as the potential sensitizer. In this study, carbon dots are obtained by electrochemical ablation of graphite rods in alkaline electrolyte. The better preparation condition is the applied potential of 40 V and the ablation time of 5 h. TiO₂ nanotube arrays and TiO₂ nanoparticles photoelectrodes are sensitized by the as-prepared carbon dots through using impregnation method. Carbon dots/TiO₂ nanotube arrays electrodes exhibit greater photoelectrochemical hydrogen production activities than carbon dots/TiO₂ nanoparticles electrodes. It is because more carbon dots can be well combined with TiO₂ nanotube arrays. Based on the IPCE values in visible light region, the role of carbon dots on TiO₂ nanotube arrays electrode depends on the up-converted PL behaviors from their surface states and the alkaline electrolyte. The results provide insight into carbon dots that serve as sensitizer of TiO₂ photoelectrode in water splitting system of alkaline solution.     

Ultrafine Mn3O4 nanoparticles supported on functionalized-graphite towards efficient photochemical and electrochemical water oxidation catalysis

Water oxidation is the key step for water splitting to produce hydrogen. Synthesis of earth-abundant, efficient, and robust water oxidation catalysts is vital for photocatalytic and electrocatalytic water splitting. Herein, inspired from natural oxygen evolving site Mn₄CaO₅ cluster, we fabricated very small Mn₃O₄ nanoparticles onto the surface of sulfonated-graphite (denoted as “Mn₃O₄@G-Ph-SN”) for photochemical and electrochemical water oxidation through a facile hydrothermal process. The supported Mn₃O₄ nanoparticles are homogeneously dispersed and the mean particle size is as small as 3.2 nm. The obtained hybrid exhibits efficient water oxidation activity with turnover frequency (TOF) of 0.1 s^?1, several orders of magnitude higher than commercial manganese-based oxide water oxidation catalysts. In addition, Mn₃O₄@G-Ph-SN shows electrochemical water oxidation performance with an overpotential of 473 mV in 1.0 M KOH solution and with good stability.     

Electrochemically active and robust cobalt doped copper phosphosulfide electro-catalysts for hydrogen evolution reaction in electrolytic and photoelectrochemical water splitting

The area of non-noble metals based electro-catalysts with electrochemical activity and stability similar or superior to that of noble metal electro-catalyst for efficient hydrogen production from electrolytic and photoelectrochemical (PEC) water splitting is a subject of intense research. In the current study, exploiting theoretical first principles study involving determination of hydrogen binding energy to the surface of the electro-catalyst, we have identified the (Cu_0.83Co_0.17)₃P: x at. % S system displaying excellent electrochemical activity for hydrogen evolution reaction (HER). Accordingly, we have experimentally synthesized (Cu_0.83Co_0.17)₃P: x at. % S (x = 10, 20, 30) demonstrating excellent electrochemical activity with an onset overpotential for HER similar to Pt/C in acidic, neutral as well as basic media. The highest electrochemical activity is exhibited by (Cu_0.83Co_0.17)₃P:30 at. % S nanoparticles (NPs) displaying overpotential to reach 100 mA cm^?2 in acidic, neutral and basic media similar to Pt/C. The (Cu_0.83Co_0.17)₃P:30 at. % S NPs also display excellent electrochemical stability in acidic media for long term electrolytic and PEC water splitting process [using our previously reported (Sn_0.95Nb_0.05) O₂: N-600 nanotubes (NTs) as the photoanode]. The applied bias photon-to-current efficiency obtained using (Cu_0.83Co_0.17)₃P:30 at. % S NPs as the cathode electro-catalyst for HER in an H-type PEC water splitting cell (～4%) is similar to that obtained using Pt/C (～4.1%) attesting to the promise of this exciting non-noble metal containing system.     

Nanoporous CoCu layered double hydroxide nanoplates as bifunctional electrocatalyst for high performance overall water splitting

The electrochemical water splitting into hydrogen and oxygen is the promising way for renewable hydrogen production as a carbon-neutral fuel, along with oxygen as a by-product. Herein, a novel nanoporous CoCu-layered double hydroxide (LDH) bifunctional electrocatalyst is fabricated by the hydrothermal method. The outstanding activity is mainly attributed to the incorporation of Cu²⁺ that promotes conductivity and enhances the electrochemical properties. As-prepared CoCu-LDH nanostructure works as efficient and stable water-splitting-electrolyzer and produces the voltage of 1.60 V at the current density of 10 mA cm^?2, which is better than catalyst based on the combination of commercial IrO₂ and Pt/C. Due to high electrocatalytic performance, together with its low cost and natural abundance of LDHs, it is expected that CoCu LDH can act as a candidate catalyst in the commercial alkaline overall water splitting.     

Hydrogenation and electrochemical studies of La–Mg–Ni alloys

La–Mg–Ni alloys are potential candidates for hydrogen storage materials. In this study, mechanical alloying with subsequent annealing under an argon atmosphere at 973 K for 0.5 h, were used to produce La_2-xMg_xNi₇ alloys (x = 0, 0.25, 0.5, 0.75, 1). Shaker type ball mill was used. An objective of the present study was to investigate an influence of amount of Mg in alloy on electrochemical, hydrogenation and dehydrogenation properties of La–Mg–Ni materials. X-ray diffraction analyses revealed formation of material with multi-phase structure. Obtained materials were studied by a conventional Sievert's type device at 303 K. It was observed that electrochemical discharge capacity and gaseous hydrogen storage capacity of La–Mg–Ni alloys increases with Mg content to reach maximum for La_1.5Mg_0.5Ni₇ alloy. Moreover, all of La–Mg–Ni alloys were characterized by improved hydrogen sorption kinetics in comparison to La–Ni alloy.     

One-step synthesis of amorphous Ni–Fe–P alloy as bifunctional electrocatalyst for overall water splitting in alkaline medium

Design of inexpensive and highly efficient bifunctional electrocatalyst is paramount for overall water splitting. In this study, amorphous Ni–Fe–P alloy was successfully synthesized by one-step direct-current electrodeposition method. The performance of Ni–Fe–P alloy as a bifunctional electrocatalyst toward both hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) was evaluated in 30 wt% KOH solution. It was found that Ni–Fe–P alloy exhibits excellent HER and OER performances, which delivers a current density of 10 mA cm^?2 at overpotential of ～335 mV for HER and ～309 mV for OER with Tafel slopes of 63.7 and 79.4 mV dec^?1, respectively. Moreover, the electrolyzer only needs a cell voltage of ～1.62 V to achieve 10 mA cm^?2 for overall water splitting. The excellent electrocatalytic performance of Ni–Fe–P alloy is attributed to its electrochemically active constituents, amorphous structure, and the conductive Cu Foil.     

Chiral CuO@Ni with continuous macroporous framework and its high catalytic activity for electrochemical water oxidation

Electrochemical water splitting is considered as a promising approach to storing renewable electricity in the form of hydrogen fuel. In this work, we report the design and electrocatalytic properties of chiral CuO@Ni with three dimensional (3D) continuous macroporous framework. With the chiral CuO@Ni as anode, the OER overpotential required to achieve the current density of 10 mA/cm² was as low as 110 mV in 0.1 M KOH electrolyte, and the hydrogen production rate of water splitting reaction could reach 1070 nL/s. Moreover, the OER overpotential could be regulated easily by controlling the deposition time of chiral CuO layer on Ni. The high catalytic activity of chiral CuO@Ni for water splitting is closely associated with the Chiral-induced spin selectivity (CISS) effect, the large reactive area provided by its 3D macroporous structure, and the effective cooperation between chiral CuO and Ni foam that facilitated the transportation of spin aligned electrons from chiral CuO layer to Ni. The results shown in this work indicate a simple and promising strategy to improve the electrocatalytic activity of other chiral earth-abundant catalysts for water splitting.     

An aluminum/cobalt/iron/nickel alloy as a precatalyst for water oxidation

Among different strategies, water splitting toward hydrogen production is a promising process to store energy from intermittent sources. However, the anodic water oxidation is a bottleneck for water splitting. In this paper, we report an aluminum/cobalt/iron/nickel alloy as a precatalyst for the electrochemical water oxidation. The alloy electrode contains different metal ions including cobalt, iron, and nickel which all are efficient for water oxidation is tested. We characterized this electrode using scanning electron microscopy, transmission electron microscopy, diffuse reflectance infrared Fourier transform spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical methods. After stabilization, the electrode shows an onset overpotential of 200.0 mV and affords a current density of 3.5 mA cm^?2 at an overpotential of 600.0 mV in KOH solution at pH 13.     

A novel nickel electrode with gradient porosity distribution for alkaline water splitting

Electrodes with porous structures are widely used in commercial alkaline water splitting devices. By optimizing the porous structure, the efficiency of alkaline water splitting devices could be evidently promoted. In this work, nickel electrodes with gradient porosity distribution were designed and fabricated through selective laser melting. The effect of gradient porous distribution structure on electrochemical performance of Ni electrode was evaluated. The results showed that with small pores towards counter electrode the prepared Ni electrodes exhibits better anodic performance, and a better cathodic performance is observed with big pores towards the counter electrode. It was considered as joint effect of active specific area and mass transfer. Finally, by applying an electrolysis cell with optimized arrangement, an improvement of 14% electrolysis efficiency is achieved, which shows the potential of Ni electrodes with gradient porosity distribution to be applied in commercial application of hydrogen generation.     

Pulsed current water splitting electrochemical cycle for hydrogen production

A pulsed current 3 D MnO₂ electrode water splitting electrochemical cycle is being proposed for hydrogen production. In 3D MnO₂ electrochemical cycle, the reactions take place at the solid/liquid and solid/gas two phase boundaries. Also, this electrochemical cycle should be able to generate hydrogen and oxygen gas separately at different periods of time. Here, we applied an interrupted pulsed current to reduce the overpotential caused by diffusion layers in conventional direct current electrolysis. The pulsed current, which disturbs the formation of the ion diffusion layer in the vicinity of the electrodes, is observed to be effective above 50 Hz. The best electrolysis performance was recorded at a current density of 0.2 A cm^?2, and the observed cell voltage was 1.69 V at 25 °C for a pulse frequency of 500 Hz, which is less than the corresponding conventional alkaline electrolysis.     

Electrodeposition of Ni–Fe–Mn ternary nanosheets as affordable and efficient electrocatalyst for both hydrogen and oxygen evolution reactions

The synthesis of high performance and economical electrocatalysts in the process of overall water splitting is very important for the production of hydrogen energy and has become one of the most important challenges. Here, various Ni, Ni–Fe, Ni–Mn nanosheets and Ni–Fe–Mn ternary nanosheets were created using cost-effective, versatile and binder-free electrochemical deposition methods, and the electrocatalytic activity of various electrodes for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) were investigated in an alkaline environment. Due to the high electrochemical active surface area due to the fabrication of nanosheets, the synergistic effect between different elements on the electronic structure, the high wettability due to the formation of nanosheets and the quick detachment of formed gasses from the electrode, the Ni–Fe–Mn nanosheets electrode showed excellent electrocatalytic activity. In order to deliver the 10 mA cm⁻² current density in HER and OER processes, this electrode required values of 64 mV and 230 mV overpotential, respectively. Also, the stability test showed that after 10 h of electrolysis at a current density of 100 mA cm⁻², the overpotential changes was very small (less than 4%), indicating that the electrode was excellent electrostatic stability. Also, when using as a bi-functional electrode in the full water splitting system, it only needed a cell voltage of 1528 V to deliver a current of 10 mA cm⁻². The results of this study indicate a new strategy for the synthesis of active and stable electrocatalysts.     

Tuning quaternary hybride Co–Ni–S–Se composition as a bifunctional electrocatalyst for hydrogen and oxygen evolution reactions

Developing high-efficiency and earth-abundant electrocatalysts for electrochemical water splitting is of paramount importance for energy conversion. Although tremendous effort has been paid to transition metal (TM) material-based electrocatalysts, rational design and controllable synthesis of fine structures to fully utilize the latent potential of TM materials remain great challenges. We herein report a composition-tuning strategy to achieve rational structure control of quaternary Co–Ni–S–Se materials through a facile one-pot hydrothermal method, in which earth-abundant Ni is introduced into a CoS_xSe_2-x matrix to optimize the morphology and electronic structure of the quaternary electrocatalyst. Because of the introduction of Ni, this novel Co–Ni–S–Se quaternary system shows better catalytic activity for water splitting with Tafel slopes of 42.1 mV dec⁻¹ for hydrogen evolution reaction (HER) and 65.5 mV dec⁻¹ for oxygen evolution reaction (OER), respectively, compared with its precursor Co–S–Se ternary system. For stability, there is negligible fading after long-term electrochemical test. Our work not only provides a novel thinking to introduce nickel into Co–S–Se ternary system by a facile hydrothermal synthesis for electrochemical water splitting, but also this quaternary system realizes bifunctional catalysis and better electrochemical performance relative to the ternary counterpart.     

Controlled synthesis of MnO2@TiO2 hybrid nanotube arrays with enhanced oxygen evolution reaction performance

A novel tube-in-tube nanostructure of MnO₂@ TiO₂ hybrid arrays has been obtained by a facile and controllable chemical bath deposition method. Scrutiny on the hybrid arrays indicates that the chemical bath deposition method favors the growth of the MnO₂ nanotubes with different diameter which can modulate the oxygen evolution reaction (OER) activity as well as bandgap width of the hybrid. In terms of OER activity, onset potential (E_s) shifts negatively from 0.698 V (vs.Ag/AgCl) of pristine titania nanotube arrays (TNAs) to 0.501 V of the hybrid loaded with 26.6%wt MnO₂, and the current density on the hybrid electrode can be significantly enhanced up to 20.87 mA/cm², almost 97 times higher than that on TNAs electrode (0.214 mA/cm²). Optical absorption measurement suggests that the bandgap width (E_g) can be tuned by loading MnO₂ onto the TNAs implying interaction between the MnO₂ and TNAs. The MnO₂@TiO₂ hybrid nanotube arrays may find promising potential in electrochemical water splitting, photocatalysis, thermocatalysis and other sustainable energy applications.