The 3D ultra-thin Cu1-xNixS/NF nanosheet as a highly efficient and stable electrocatalyst for overall water splitting

In recent years, the exploration of efficient and stable noble-metal-free electrocatalysts is becoming increasingly important, used mainly for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). In this work, a new ultrathin porous Cu_1-xNi_xS/NF nanosheets array was constructed on the 3D nickel skeleton by two-step method: hydrothermal method and vulcanization method. Through these two processes, Cu_1-xNi_xS/NF has a larger specific surface area than that of foamed nickel (NF) and Cu_1-xNi_xO/NF. The Cu_1-xNi_xS/NF materials show excellent catalytic activity by accelerating the electron transfer rate and increase the amount of H₂ and O₂ produced. The lower overpotential was obtained only 350 mV at 20 mA cm⁻² for OER, not only that, but also the same phenomenon is pointed out in HER, optimal Cu_1-xNi_xS/NF presents low overpotentials of 189 mV to reach a current density of 10 mA cm⁻² in 1.0 M KOH for HER. Both OER and HER shows a lower Tafel slope: 51.2 mV dec⁻¹ and 127.2 mV dec⁻¹, subsequently, the overall water splitting activity of Cu_1-xNi_xS/NF was investigated, and the low cell voltage was 1.64 V (current density 10 mA cm⁻²). It can be stable for 14 h during the overall water splitting reaction. These results fully demonstrate that Cu_1-xNi_xS/NF non-precious metal materials can be invoked become one of the effective catalysts for overall water splitting, providing a richer resource for energy storage.     

Ni3S2-MoSx nanorods grown on Ni foam as high-efficient electrocatalysts for overall water splitting

In order to solve the problem of large overpotential in water electrolysis for hydrogen production, transition metal sulfides are promising bifunctional electrocatalysts for hydrogen evolution reaction/oxygen evolution reaction that can significantly reduce overpotential. In this work, Ni₃S₂ and amorphous MoS_x nanorods directly grown on Ni foam (Ni₃S₂-MoS_x/NF) were prepared via one-step solvothermal process, which were used as a high-efficient electrocatalyst for overall water splitting. The Ni₃S₂-MoS_x/NF composite exhibits very low overpotentials of 65 and 312 mV to reach 10 mA cm⁻² and 50 mA cm⁻² in 1.0 M KOH for HER and OER, respectively. Besides, it exhibits a low Tafel slope (81 mV dec⁻¹ for HER, 103 mV dec⁻¹ for OER), high exchange current density (1.51 mA cm⁻² for HER, 0.26 mA cm⁻² for OER), and remarkable long-term cycle stability. This work provides new perspective for further the development of highly effective non-noble-metal materials in the energy field.     

Engineering multiphase for activating electroactive sites for highly efficient hydrogen evolution: Experimental and theoretical investigation

An ideal electrocatalyst for the hydrogen evolution reaction of water splitting requires substantial active sites with high catalytic activity, fast electron and mass transfer, low gas adsorption energy, and high stability. However, a single component catalyst usually has only one of the many properties of an ideal electrocatalyst. Herein, for the first time, we synthesize Co_xSe/MoSe₂ micro-prisms on foam via a hydrothermal and selenization strategy. After selenization, a crystallized CoMoO₄ smooth prismatic structure can be converted into a Co_xSe/MoSe₂ prismatic structure with lamellar morphology. Such synergistic effects lead to Co_xSe/MoSe₂ superior electrochemical catalytic activity with a 109 mV over-potential at 10 mA cm⁻² and 204 mV over-potential at 100 mA cm⁻², an appropriate Tafel slope of 90 mV dec⁻¹, and remarkable long-term stability during 20 h of testing for the hydrogen evolution reaction in an alkaline medium. Density-functional calculations reveal the absorption energy of water and Gibbs free-energy of intermediate adsorb hydrogen of Co_xSe/MoSe₂ is more favorable for hydrogen evolution reaction than single component catalyst. Both experimental and theoretical calculation results reveal that synergistic effect can efficiently reduce energy barrier of both the initial water adsorption step and subsequent H₂ generation on binary catalysts, and improve catalytic activity.     

Phytic acid-derived Co2-xNixP2O7-C/RGO and its superior OER electrocatalytic performance

A phytic acid-derived Co_2-xNi_xP₂O₇-C/RGO composite was designed and facilely synthesized, in which phytic acid acted as both a phosphoric source and carbon source. Both carbon derived from phytic acid and reduced graphene oxide (RGO) in composite, enhanced the conductivity and thus improve its electrocatalytical capability. As-synthesized Co_1.22Ni_0.78P₂O₇-C/RGO composite exhibited excellent oxygen evolution reaction (OER) catalytic performances: At the current density of 10 mA cm⁻², only a low overpotential of 283 mV and a small Tafel slope of 51 mV dec⁻¹ were observed. Good OER catalytic performance was retained even after 10 h continuously running at a constant voltage, which is even comparable to those of first-rate noble metal catalyst RuO₂. In addition, the performances of Co_2-xNi_xP₂O₇-C/RGO catalysts were also strongly dependent on Ni content.     

One-step electrodeposition of cauliflower-like CozNiySx@polypyrrole electrocatalysts on carbon fiber paper for hydrogen evolution reaction

Transition-metal chalcogenides as the promising alternatives to noble-metal-based electrocatalysts for hydrogen evolution reaction (HER) with high activity and durability in water splitting have attracted extensive attention in recent years. Herein, Co_zNi_yS_x@PPy composites with three-dimensional (3D) cauliflower-like were firstly prepared on carbon fiber paper (CFP) via a simple and efficient electrochemical reduction of elemental sulfur in the precursor of S@PPy composite coated on CFP to react with Co and Ni ions in the electrolyte. The optimum electrode, i.e., Co_zNi_yS_x@PPy/CFP-6 (A-6) prepared by using an electrolyte with a Co/Ni molar ratio of 0/6, showed excellent catalytic activity (with an overpotential of 185 mV@10 mA cm⁻² and a small Tafel slope of 78.13 mV dec⁻¹) as well as long-term stability (at least 100 h) in 1 M KOH solutions. This work provides a novel way to fabricate effective and non-noble-metal electrodes for HER in water splitting.     

Fabricating NixCo1−xO@C cocatalysts sensitized by CdS through electrostatic interaction for efficient photocatalytic H2 evolution

Exploiting efficient and stable noble metal-free hydrogen evolution catalysts for water splitting is of great importance. In this work, Ni_xCo_1-xO@C/CdS hybrid is successfully fabricated through an electrostatic interaction of oppositely charged nanoparticles on their surfaces. The resulting Ni_xCo_1-xO@C nanoboxes cocatalysts which were derived from NiCo-LDH@ZIF-67 with Ni–Co layered double hydroxides (LDH) decorated with ZIF-67 precursor exhibited improved hydrogen production rate compared with bare CdS semiconductor from 0.7 mmol g⁻¹ h⁻¹ to 56 mmol g⁻¹ h⁻¹. It is demonstrated that the electrostatic interaction between the two surface charged nanoparticles of Ni_xCo_1-xO@C and CdS play an important role in migrating and separating of photogenerated charge carriers. The synthesized Ni_xCo_1-xO@C as excellent candidates for cost-effective cocatalysts is aimed to substitute for noble metals in photocatalytic H₂ evolution.     

A nano-spherical structure Ni3S2/Ni(OH)2 electrocatalyst prepared by one-step fast electrodeposition for efficient and durable water splitting

Developing non-noble metal catalysts with excellent electrocatalytic performance and stability is of great significance to hydrogen production by water electrolysis, but there are still problems of low activity, complex preparation and high cost. Herein, we fabricated a novel Ni₃S₂/Ni(OH)₂ dual-functional electrocatalyst by a one-step fast electrodeposition on nickel foam (NF). While maintaining the electrocatalytic performance of Ni₃S₂, the existence of heterostructure and Ni(OH)₂ co-catalyst function greatly improves the overall water splitting performance of Ni₃S₂/Ni(OH)₂–NF. Hence, It shows a low overpotential of 66 mV at 10 mA cm^?2 for HER and 249 mV at 20 mA cm^?2 for OER. The dual-functional electrocatalyst needs only 1.58 V at 20 mA cm^?2 when assembled two-electrode electrolytic cell. Impressively, the electrocatalyst also shows outstanding catalytic stability for about 800 h when 20 and 50 mA cm^?2 constant current was applied, respectively which demonstrates a potential electrocatalyst for overall water splitting.     

Enhanced electrochemical and hydrogen storage properties of La–Mg–Ni-based alloy electrode using a Ni and N co-doped reduced graphene oxide nanocomposite as a catalyst

To enhance the electrochemical property of a La_0.7Mg_0.3(Ni_0.9Co_0.1)_3.5 alloy, a three-dimensional (3D) reduced graphene oxide (rGO)-supported nickel and nitrogen co-doped (Ni–N@rGO) nanocomposite is fabricated by an impregnation method and introduced into the La_0.7Mg_0.3(Ni_0.9Co_0.1)_3.5 alloy. The results show that the reversible hydrogen storage property and the comprehensive electrochemical performance of the La_0.7Mg_0.3(Ni_0.9Co_0.1)_3.5 alloy are enhanced effectively when it is modified by the Ni–N@rGO nanocomposite. The high-rate dischargeability values at a discharge current density of 1500 mA g⁻¹ for the La_0.7Mg_0.3(Ni_0.9Co_0.1)_3.5 alloy and Ni–N@rGO-modified samples are 0.0% and 70.5%, respectively. Additionally, the anodic peak currents for the unmodified alloy electrode is 892 mA g⁻¹. Under the catalytic action of the Ni–N@rGO nanocomposite, the value increases to 2307 mA g⁻¹, which is 2.59 times larger than that of unmodified samples. The results also indicate that the diffusion ability of the hydrogen atom in the alloy electrode body enhances significantly when modified by the Ni–N@rGO nanocomposite. The hydrogen diffusion coefficient for the La_0.7Mg_0.3(Ni_0.9Co_0.1)_3.5 alloy electrode increases from 3.93 × 10⁻¹⁰ cm² s⁻¹ to 6.15 × 10⁻¹⁰ cm² s⁻¹ when is modified by Ni–N@rGO nanocomposite. These improvements in the comprehensive electrochemical properties are mainly attributed to the excellent electrochemical activity and conductivity of the Ni–N@rGO nanocomposite.     

Ni3S2@Co(OH)2 heterostructures grown on Ni foam as an efficient electrocatalyst for water oxidation

It is of high significance to design robust, low-cost and stable electrocatalysts for the oxygen evolution reaction (OER) under alkaline medium. In this communication, we present the exploitation of Ni₃S₂@Co(OH)₂ which directly grown on nickel foam (Ni₃S₂@Co(OH)₂/NF) as a robust and stable electrocatalyst for OER. Such Ni₃S₂@Co(OH)₂/NF-5h demanding overpotential of only 290 mV is less than that of Ni₃S₂@Co(OH)₂/NF-10h (310 mV), Ni₃S₂@Co(OH)₂/NF-2h (320 mV) and Ni₃S₂/NF(350 mV), respectively, to drive a geometrical catalytic current density of 35 mA cm⁻², which is also better than that of noble metal catalyst IrO₂/NF (320 mV). In addition, the Ni₃S₂@Co(OH)₂/NF-5h presents a superior long-term electrocatalytic stability, keeping its activity at 26 mA cm⁻² for 40 h.     

One-step solution-induced impregnation synthesis of strongly coupled platinum–molybdenum/silicon carbide quantum dots heterostructures encapsulated on reduced graphene oxide sheet as electrocatalyst for hydrogen evolution reaction

Strongly coupled platinum-based transition-metal oxide/carbon hybrids and the development of quantum-dot structures of hybrid catalysts are cost-effective and maximize accessible active sites. However, a significant obstacle still exists for the rational proposal and simple synthesis of hybrid quantum-dot material catalysts. Herein, novel Pt_xMo_1-xSiC quantum dots encapsulated in reduced graphene oxide (rGO) (Pt_xMo_1-xSiC QDs @rGO) for catalyzing the hydrogen evolution reaction (HER) were fabricated through a simple solution-induced impregnation method. The optimized Pt₅Mo₉₅SiC QDs @rGO catalyst only require overpotentials of 18 mV and 25 mV to deliver current densities of 10 mA cm⁻² and 250 mA cm⁻² in acidic media, respectively. The synergistic effects of the inner Pt_xMo_1-xSiC QDs networks and outer conductive rGO sheets that promote electron transfer are responsible for the outstanding HER performance. This work presents a novel method for producing an extremely effective HER catalyst for applications on large-scale.     

Vermicular Ni3S2–Ni(OH)2 heterostructure supported on nickel foam as efficient electrocatalyst for hydrogen evolution reaction in alkaline solution

Alkaline solution is considered to be more suitable for industrial application of hydrogen production by water electrolysis. However, most of the low-cost electrocatalyts such as Ni₃S₂ has poor ability to dissociate HO–H, resulting in unsatisfied hydrogen evolution performance in alkaline media. In this paper, a novel vermicular structure of Ni₃S₂–Ni(OH)₂ hybrid have been successfully prepared on nickel foam substrate (v-Ni₃S₂–Ni(OH)₂/NF) through a facile two-step containing hydrothermal and electrodeposition processes. The heterostructure consists of rod-like Ni₃S₂ and Ni(OH)₂ nanosheets, in which Ni(OH)₂ is coated on the surface of Ni₃S₂. This structure not only constructs a fast electron transfer channel but also possesses rich heterointerface, thus accelerating the Volmer step and allowing more active sites of Ni₃S₂ to functioning well. As a result, v-Ni₃S₂–Ni(OH)₂/NF exhibited excellent electrocatalytic activity toward HER in 1.0 M KOH solution. It only needs 78 mV and 137 mV to drive current density of 10 mA cm⁻² and 100 mA cm⁻². Moreover, the catalytic stability of this electrocatalyst in alkaline solution is also satisfactory.     

High-efficiency Co6W6C catalyst with three-dimensional ginger-like morphology for promoting the hydrogen and oxygen evolution reactions

Development of electrocatalysts composed of low cost and abundant elements that exhibit catalytic activity comparable to noble metals is important for water splitting. As such, in this study, a catalyst material with a ginger-like morphology consisting of Co₆W₆C is synthesized via a hydrothermal reaction and pyrolysis treatment. The Co₆W₆C catalyst exhibits satisfactory electrochemical properties towards both hydrogen and oxygen evolution reactions in an alkaline electrolyte, with a low overpotential, low Tafel slope, and durable stability. Co₆W₆C possesses a high activity for the hydrogen evolution reaction in alkaline conditions, with an onset potential and overpotential of −0.024 V and 101 mV, respectively, and low Tafel slope of 80.5 mV dec⁻¹ at a current density of 10 mA cm⁻². In addition, Co₆W₆C achieves a current density of 10 mA cm⁻² for the oxygen evolution reaction at an overpotential of only 343 mV. Furthermore, electrochemical stability tests indicate that the Co₆W₆C catalyst maintains 91% of the original current after 60,000 s for the hydrogen evolution reaction and 95% of the original current after 45,000 s for the oxygen evolution reaction. Moreover, electrochemical splitting of water via a two-electrode system employing this catalyst can hold 89% of the initial current after 40,000 s in 1 M KOH.     

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.     

Boosting the oxygen evolution electrocatalysis of layered nickel hydroxidenitrate nanosheets by iron doping

Development of earth-abundant electrocatalysts with high activities and strong duribilities for oxygen evolution reaction (OER) has received the increased interests for various sustainable energy storage and conversion systems. Herein, we report a novel non-noble-metal electrocatalyst based on layered nickel hydroxidenitrate [Ni₃(NO₃)₂(OH)₄] nanosheets and demonstrate that iron doping strategy greatly boosts their OER performances._. The spectroscopic investigation and cyclic voltammetry analysis confirm the favorable electronic interaction between nickel and iron in Ni_3-xFe_x(NO₃)₂(OH)₄. The optimal Ni_2·85Fe_0·15(NO₃)₂(OH)₄ catalyst exhibits the earlier onset potential and smaller overpotential at 10 mA cm⁻² compared with those of the state-of-the-art IrO₂ in 1.0 M KOH solution.     

SrTi0.1CoxFe0.9-xO3-δ Perovskites for enhanced oxygen evolution reaction activity

We developed a series of Fe doping in Co-based perovskites SrTi_0.1Co_xFe_0.9-xO_3-δ (x = 0.5, 0.6, 0.7, 0.9) to investigate their OER activity and stability in alkaline media. Among all the samples, SrTi_0·1Co_0·5Fe_0·4O_3-δ (donated as STCF-154) shows wonderful OER activity with an overpotential of 0.37 V, a current density of 33.65 mA cm⁻² at 1.71 V, and a Tafel slope of 94.82 mV dec⁻¹. Besides, the potential of STCF-154 remained nearly unchanged for at least 8 h at a fixed current density of 10 mA cm⁻²_disk on GC electrode. The improved activity and stability are likely originating from the highly oxidative oxygen species O₂²⁻/O⁻ formed in STCf-154, which can easily migrate from bulk STCF-154 and “spillover” to the surface of the catalyst during OER process. The Fe doping in Co-based perovskites had synergetically enhanced activity and can be considered as a good candidate for the OER in alkaline solution.     

Construction of NiCo2S4/Ni3S2 nanoarrays on Ni foam substrate as an enhanced electrode for hydrogen evolution reaction and supercapacitors

Developing a multifunctional and sustainable electrode material for hydrogen evolution reaction and supercapacitors is a highly feasible avenue for producing the high energy density and renewable energies. In our study, nanostructured NiCo₂S₄/Ni₃S₂/NF nanoarrays are rational developed in experiments via a simple hydrothermal reaction. Ascribed to the 3D nanostructured NiCo₂S₄/Ni₃S₂ with numerous exposure active sites and large contact areas for the electrolyte, the binder-free feature of NiCo₂S₄/Ni₃S₂/NF facilitates a low charge transfer resistance, as well as the synergetic effect of NiCo₂S₄ and Ni₃S₂. The obtained electrocatalyst showed ultrahigh electrocatalytic activity with an overpotential of 111 mV at 10 mA cm⁻² and a Tafel slope of 57 mV dec⁻¹. In addition, the electrode showed an area specific capacity of 6.13 F cm⁻² at 10 mA cm⁻² and superior rate capability (2.72 F cm⁻² at 80 mA cm⁻²), accompanied by excellent cycling stability. This results presented in our work can provide an effective strategy for rational design of other hybrid materials with excellent electrochemical performance in the application of electrocatalysis and supercapacitors.     

Highly-stable,bifunctional, binder-free & stand-alone photoelectrode (FexNi1-xO@a-CC) for natural waters splitting into hydrogen

Photoelectrochemical (PEC) water splitting is a promising approach to boost green hydrogen production. Herein, we prepared novel binder-free photoelectrode by direct growth of iron doped nickel oxide catalyst over activated carbon cloth (Fe_xNi_1-xO@a-CC) having band gap energy of 2.2 eV for overall water splitting. Fe_xNi_1-xO@a-CC photoelectrode had shown remarkable lower potential of only 1.36 V for oxygen evolution reaction (OER) to reach 10 mA cm^?2 current density using very low photonic intensity of 8.36 × 10^?4 E/L.s. For the first time, we also reported electrical efficiency required for PEC water splitting for 1 m³ of water that is equal to 0.09 kWh/m³. Fe_xNi_1-xO@a-CC photoelectrode also exhibits low potentials of 1.44 V (OER) and ?0.210 V (HER) at 10 mA cm^?2 to split sea water. Our results confirmed that designing Fe_xNi_1-xO@a-CC photoelectrode would be an innovative step to widen green energy conversion applications using natural waters (both sea and fresh water).     

Composition-controlled chemical bath deposition of Fe-doped NiO microflowers for boosting oxygen evolution reaction

Water electrolysis for green hydrogen production is gaining tremendous attention in the quest towards sustainable energy sources. At the heart of water splitting technology are the electrocatalysts, which facilitate the two half-cell reactions, i.e., the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with the latter being the most thermodynamically uphill. Herein, we managed to fabricate Ni_1-xFe_xO microflowers (μFs) with varying % of Fe doping (0 < x < 0.36) via an easy chemical bath deposition (CBD) method. The as-synthesized μFs drop-casted on graphene paper (GP) are then applied as electrocatalysts for OER. Compared to contrast catalysts, the electrocatalyst with x_Fe = 0.1 exhibits a lower overpotential of 297 mV at a current density of 10 mA cm⁻², Tafel slope of 44 mV dec⁻¹ and unprecedented turnover frequency of 4.6 s⁻¹ at 300 mV. It is believed that this remarkable electrochemical performance mainly stems from the synergistic effects of Ni and Fe species, working in harmony to enhance charge transfer kinetics and intrinsic activity of the catalyst. This work provides a promising avenue for developing cost-effective and highly active electrocatalysts as advanced electrodes for energy related applications.     

Porous flower-like nickel nitride as highly efficient bifunctional electrocatalysts for less energy-intensive hydrogen evolution and urea oxidation

Finding a suitable replacement for the high potential of anodic water electrolysis (oxygen evolution reaction (OER)) is significant for hydrogen energy storage and conversion. In this work, a simple and scalable method synthesizes a structurally unique Ni₃N nanoarray on Ni foam, Ni₃N-350/NF, that provides efficient electrocatalysis for the urea oxidation reaction (UOR) that transports 10 mA cm⁻² at a low potential of 1.34 V. In addition, Ni₃N-350/NF exhibits electro-defense electrocatalytic performance for hydrogen evolution reaction, which provides a low overpotential of 128 mV at 10 mA cm⁻². As proof of concept, all-water-urea electrolysis measurement is carried out in 1 M KOH with 0.5 M Urea with Ni₃N-350/NF as cathode and anode respectively. Ni₃N-350/NF||Ni₃N-350/NF electrode can provide 100 mA cm⁻² at a voltage of only 1.51 V, 160 mV less than that of water electrolysis, which proves its commercial viability in energy-saving hydrogen production.     

Efficient overall water splitting using nickel boride-based electrocatalysts

Currently there is tremendous interest in the discovery of low cost and efficient electrocatalysts for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). In this work, iron-doped nickel boride (Fe_xNi_1-xB) and nickel boride (NiB) were successfully grown on 3D self-supporting graphene (SSG) electrodes via a one-step reduction approach. The Fe_0.2Ni_0.8B/SSG electrode required a very low overpotential of only 263 mV for OER (the best OER activity achieved to date for a metal boride). NiB/SSG showed modest OER performance but excellent HER activity. A water electrolyzer comprising Fe_0.2Ni_0.8B/SSG and NiB/SSG delivered a current density of 10 mA cm⁻² at a voltage of only 1.62 V. Further, the Fe_0.2Ni_0.8B/SSG and NiB/SSG catalysts showed excellent stability with no deactivation observed over 14 h of testing. Results demonstrate that nickel boride-based electrocatalysts are promising lost cost alternatives to precious metal-based electrocatalysts for OER, HER and overall water splitting.