CoP-anchored high N-doped carbon@graphene sheet as bifunctional electrocatalyst for efficient overall water splitting

Electrocatalytic water splitting, as an ideal technology in renewable energy applications, suffers from high electrical energy consumption due to the slow kinetics of HER and OER reactions. Therefore, it is urgent to design efficient bifunctional catalysts to improve the reaction kinetics. Herein, a self-supported electrode, anchoring CoP nanoparticles on N-doped carbon/graphene (NC-G) and chemically growing on Ni foam as a whole electrode (denoted as NC-G-CoP/NF) displays promising electrocatalytic performance in 1.0 M KOH electrolyte, with a low overpotentials of 68 mV at 10 mA cm^?2 for HER and 255 mV at 50 mA cm^?2 for OER. This bifunctional electrocatalyst only needs 1.435 V to generate 10 mA cm^?2 for overall water splitting. The outstanding electrocatalytic performance is ascribed to the following factors: i) inherent nature of transition metal phosphides, ii) abundant and high dispersion N active sites in NC-G, iii) strong interaction between the NC-G and CoP nanoparticles, and iv) rapid electron transfer between the catalytic centers and Nickle foam. This provides a new perspective to design efficient electrocatalysts for electrocatalytic water splitting.     

Surface-assembled Fe-Oxide colloidal nanoparticles for high performance electrocatalytic water oxidation

Nanoscale electrocatalytic materials having enhanced electroactive sites has been considered trendier and can drive kinetically uphill OER at much lower energy cost with high efficiency. However, very complex synthetic strategies, extensive functionalization processes, and less stability have stimulated quest for economically viable, straightforward and facile preparative methods for designing stable, robust and active nanoscale electrocatalysts engaging geologically abundant materials to ensure their industrial implications. Here we present surface-assembled Fe(OH)_x/FeO_x type colloidal catalytic thin-films, with or without post annealing, derived from Fe-colloidal NPs in simple carbonate system for efficient water oxidation. Comprehensive electrochemical studies including cyclic voltammetry, chronoamperometry, chronopotentiometry, impedance spectroscopy, Tafel slope analysis, mass activity, electrochemically active surface area measurements are conducted to comparatively evaluate the performance of simple (FeO_x/HCO₃^?@FTO and annealed (FeO_x/HCO₃^?@FTO₂₅₀, FeO_x/HCO₃^?@FTO₅₀₀) catalysts for oxygen evolution reaction (OER) under employed conditions. The FeO_x/HCO₃^?@FTO₂₅₀ annealed at 250 °C initiates water oxidation at much lower overpotential of 1.52 V vs. RHE with remarkable stability during long-term electrochemical experimentations. In addition to enhanced OER activity as evidence by better onset potential (<1.55 V vs. RHE), lower Tafel slope value (36 mV dec^1?) and negligible charge transfer resistance, the Fe(OH)_x/HCO₃^?@FTO type catalyst presented excellent electroactive nature during long term controlled potential electrolysis experiments where more and more electroactive sites were getting exposed during continuous hours of electrolysis. The catalysts behave as a potential enduring, inexpensive and competent candidate for catalyzing water oxidation reaction when tested under begin conditions.     

NiSe2@NixSy nanorod on nickel foam as efficient bifunctional electrocatalyst for overall water splitting

Electrocatalytic water splitting technology has become one of the most promising methods to solve the energy crisis, which can produce a large amount of high purity H₂ and O₂. It is necessary to develop efficient and stable water splitting catalyst for reducing the overpotential of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) and accelerating their reaction kinetics. A series of NiSe₂@Ni_xS_y nanoarrays was firstly in situ grown on the nickel foam through the typical hydrothermal, selenylation and sulfuration pathways. The Na₂SeO₃ homogeneous solution is formed by hydrothermal and the selenization process is done at the temperature of 180^。C. Then the nickel foam (NF) is put into the Na₂SeO₃ solution to form NiSe₂ material at the temperature of 120^。C. After that, the NiSe₂ materials were sulfuretted with different amounts of sulfur to form NiSe₂@Ni_xS_y hybrid materials. The experimental results demonstrate that the NiSe₂@Ni_xS_y material as a 3D electrode can maximize the synergistic reaction between NiSe₂ and Ni_xS_y, thus exhibiting an efficient and comprehensive water splitting performance. The NiSe₂@Ni_xS_y-1 material presents a superior OER performance with requiring the overpotential of only 206 mV at 100 mA cm⁻². Moreover, the NiSe₂@Ni_xS_y-0.3 material presents a superior HER performance with requiring the overpotential of only 148 mV at 100 mA cm⁻². It is worth noting that when NiSe₂@Ni_xS_y-1 material and the NiSe₂@Ni_xS_y-0.3 material was used as cathode and anode, only 1.53 V cell voltage is needed to produce a current density of 10 mA cm⁻² throughout the water splitting process, which is one of the smallest values reported so far. Density functional theory calculations results show that the Ni₃S₂ has the best water adsorption energy, so it is an active species in the process of catalysis. However, NiSe₂ has more density distribution around the Fermi level, indicating that it exhibits better metallic properties, which makes the NiSe₂@Ni_xS_y-1 hybrid material exhibit better electronic conductivity.     

Hierarchical flower-like CoS2-MoS2 heterostructure spheres as efficient bifunctional electrocatalyst for overall water splitting

Electrochemical water splitting technique requires high-efficient bifunctional electrocatalysts to obtain large-scale hydrogen production for resolving the impending energy and environmental crisis. Herein, hierarchical flower-like CoS₂-MoS₂ heterostructure hybrid spheres grown on carbon cloth (CoS₂-MoS₂/CC) were prepared by sulfuring wheel-shaped polyoxometalate {Co₂₀Mo₁₆}. The as-prepared CoS₂-MoS₂/CC as bifunctional electrocatalyst manifests excellent alkaline oxygen evolution and hydrogen evolution activities with low overpotentials of 240 mV for OER and 60 mV for HER at 10 mA cm^?2, respectively. When assembled as two-electrode cell, CoS₂-MoS₂/CC delivers an extremely low cell-voltage of 1.52 V at 10 mA cm^?2 accompanied with remarkable long-term durability. Additionally, CoS₂-MoS₂/CC exhibits favorable overall-water-splitting performance in simulated seawater. The superior performance of CoS₂-MoS₂/CC should be ascribed to the optimized intrinsic electron structure via electron transfer from MoS₂ to CoS₂ along with the synergistic effect of well-exposed heterostructure interfaces and favorable diffusion channels. This work offers a practical strategy for exploring high-efficient bifunctional electrocatalysts for overall water splitting.     

High active and ultra-stable bifunctional FeNi/CNT electrocatalyst for overall water splitting

Efficient non-noble metal catalysts are desirable to greatly improve the efficiency of anodic oxygen evolution and cathodic hydrogen evolution reactions. Herein, iron-nickel/carbon nanotube composites are synthesized as efficient bifunctional electrocatalysts for water splitting. The catalyst is homogeneously distributed, while the formation of iron-nickel alloy is confirmed. Because of the synergism of iron and copper and the contribution of carbon nanotubes, the Fe–Ni/CNT electrocatalyst shows excellent oxygen evolution reaction performance with the overpotential of 221 mV at 10 mA cm^?2 and maintains stable at 0.48 V for 150 h. It expedites overall water splitting at 10 mA cm^?2 with 1.50 V and show excellent stability at 20 mA cm^?2 for 65 h, providing great potential for large-scale applications.     

Combustion-derived BaNiO3 nanoparticles as a potential bifunctional electrocatalyst for overall water splitting

Electrochemical water electrolyser though an assuring solution for clean hydrogen production, the sluggish kinetics and high cost of existing precious metal electrocatalyst remains a barrier to its effective utilization. Herein, solution combustion route derived perovskite type barium nickelate (BaNiO₃) nanoparticles were developed and studied for their bifunctional electrocatalytic properties towards overall water splitting. The unannealed BaNiO₃ nanoparticles exhibited the highest OER and HER activity with overpotentials 253 mV and 427 mV respectively to attain 10 mAcm⁻² in 1.0 M KOH. Using unannealed BaNiO₃ as a bifunctional electrocatalyst in a two-electrode alkaline electrolyser, the cell was able to achieve the benchmark current density at a low cell voltage of 1.82 V. Impressively the setup's electrocatalytic performance improved 4.9% after continuous overall water splitting for 24 h at 30 mAcm⁻². Therefore, BaNiO₃ nanoparticles can be a low-cost and efficient alternative for noble metal electrocatalysts for clean H₂ production.     

Growth of nickel vacancy NiFe-LDHs on Ni(OH)2 nanosheets as highly efficient bifunctional electrocatalyst for overall water splitting

A bifunctional electrocatalyst was fabricated by in-situ vertical growth of Ni(OH)₂ nanosheets on nickel foam (NF), with subsequent accretion of nickel vacancy NiFe-LDHs (Ni^vacFe-LDHs) by two step hydrothermal method. It was exhibited to be a high-efficiency overall water splitting performance with good stability. The low over-potentials of 292, 330, and 376 mV were acquired when the current density was selected as 50, 100, and 200 mA/cm² for oxygen evolution reaction (OER) with a relatively low Tafel slope. It also achieved low over-potentials of 116 and 247 mV when the current densities were 10 and 200 mA/cm² for hydrogen evolution reaction (HER), and Tafel slope was estimated to be 95.87 mV/dec. For the overall water splitting, NF–Ni(OH)₂-Ni^vacFe-LDHs needed only a low overpotential (291 mV) to achieve 25 mA/cm² in 1 mol/L potassium hydroxide. The long-term testing of this electrode for 24 h chronopotentiometric test at 25 mA/cm² demonstrated very eminent stability.     

Electrodeposited nickel–iron–carbon–molybdenum film as efficient bifunctional electrocatalyst for overall water splitting in alkaline solution

Designing and synthesizing of efficient and inexpensive bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is one of the current research topics. In this study, NiFeCMo film in nickel mesh substrate is prepared by one-step direct-current electrodeposition method. The obtained NiFeCMo film shows the excellent electrocatalytic activity, which only requires overpotentials of 254 mV for HER and 256 mV for OER to drive current density of 10 mA cm⁻², with corresponding Tafel slopes of 163.9 and 60.3 mV·dec⁻¹ in 30% KOH medium, respectively. Moreover, NiFeCMo film only needs a low cell voltage of 1.61 V to drive current density of 10 mA cm⁻² in an alkaline electrolyzer. Such remarkably HER and OER properties of NiFeCMo alloy is attributed to the increased effective electrochemically active surface area and the synergy effect among Ni, Fe, C and Mo.     

Multi-active site CoNi-MOFs as non-noble bifunctional electrocatalysts for highly efficient overall water splitting

The high-efficiency non-precious metal catalysts for oxygen evolution (OER) and hydrogen evolution (HER) are of great significance to the development of renewable energy technologies. Herein, a multiple active sites CoNi-MOFs-DBD electrocatalyst modified by low temperature plasma (DBD) was successfully synthesized by converting metal hydroxyfluoride on nickel foam into a well-arranged MOFs array using vapor deposition. The as-prepared CoNi-MOFs-DBD electrode showed better HER and OER catalytic activity, super hydrophilicity, and excellent stability. In an alkaline medium, the overpotential of HER is 203 mV at 10 mA cm^?2 and that of OER is 168 mV at 40 mA cm^?2. When CoNi-MOFs-DBD was used as a bifunctional electrocatalyst for overall water splitting in a two-electrode system, a current density of 10 mA cm^?2 can be achieved at a low voltage of 1.42 V, which shows great potential in electrocatalytic water splitting.     

CoSe2@NiSe2 nanoarray as better and efficient electrocatalyst for overall water splitting

Electrocatalytic water splitting is identified as one of the most promising solutions to energy crisis. The CoSe₂@NiSe₂ materials were first prepared and in situ grown on nickel foam by typical hydrothermal and selenification process at 120 °C. The results show that the CoSe₂@NiSe₂ material used as the 3D substrates electrode can maximize the synergy between the CoSe₂ and NiSe₂, and also exhibits high efficiency of water splitting reaction. The lower overpotential of only 235 mV is presented to attain 20 mA cm⁻² compared to the benchmark of RuO₂ electrodes (270 mV @ 20 mA cm⁻²). Besides, the CoSe₂@NiSe₂ material also shows a remarkable improved hydrogen evolution reaction activity compared to NiSe₂ (192 mV@10 mA cm⁻²) and Co precursor catalysts (208 mV@10 mA cm⁻²) individually, which a low overpotential of only 162 mV is achieved at 10 mA cm⁻². The CoSe₂@NiSe₂ catalysts exhibit excellent water splitting performance (cell voltage of 1.50 V@ 10 mA cm⁻²) under alkaline conditions. It was proved that the high water splitting performance of the catalyst is attributed to high electrochemical activity area and synergistic effect. The work offers new ideas for the exploitation of synergistic catalysis of composite catalysts and adds new examples for the exploitation of efficient, better and relatively non-toxic electrocatalysts.     

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.     

Effects of the cation and anion co-doping in perovskite as bifunctional electrocatalyst for water splitting

Element doping is a very important way to modify perovskite oxide (ABO₃) electrocatalyst. Herein, the O, B and A-site of BaCoO_3-δ are doped with F, Fe and Sr elements, respectively, which are used to investigate the effect of different doping sites on water splitting performance. The results show that doping F can generate more oxygen vacancies and increase the Co valence state. On the basis of anionic doping, when Co is partially substitute by Fe, the Fe⁴⁺ formed makes the O 2P orbital close to E_F, and the bandwidth is narrower, enhancing the conductivity. Subsequently, doping Sr in A-site can change the crystal structure from P63/mmc to pm-3m, and exhibit metallic properties. This work can contribute to an effective approach for the design of perovskite oxide materials for efficient electrocatalytic water splitting.     

Controlled synthesis of NixP-Co2P hybrid materials as robust overall water splitting electrocatalyst

Environmentally friendly overall water splitting electrocatalysts can be exploited through construction of efficient heterogeneous interfaces. Flexible preparation of lattice-matching Ni₂P–Co₂P heterointerfaces is exploited to promote electrochemical activity for overall water splitting because of the outstanding electrical conductivity of Co₂P and admirable durability of Ni₂P. Density functional theory calculations demonstrate that construction of lattice-matching Ni₂P–Co₂P heterogeneous interfaces and the regulation of density of states between the heterogeneous interfaces can effectively optimize the water adsorption energy. Hence, a series of Ni_xP-Co₂P hybrid materials were in site grown on nickel foam through hydrothermal synthesis and phosphorization approach. What is noteworthy is that the Ni₂P–Co₂P-0.5//Ni₂P–Co₂P-1 electrode couple presents superior electrochemical performance with only 1.60 V cell voltage to obtain a current density of 10 mA cm^?2 under alkaline condition. In addition, the Ni₂P–Co₂P-0.5//Ni₂P–Co₂P-1 electrode couple display superior durability over 15 h at large current densities of 30 mA cm^?2 during water electrolysis process. The construction of heterostructures is conducive to the regulation of state density and the maximization of synergistic catalytic effect. The work provides a novel idea for the exploitation of highly efficient and robust water electrolysis catalysts and this work might be a new breakthrough for the construction of lattice-matching hybrid structures.     

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.     

Crystalline nickel sulfide integrated with amorphous cobalt sulfide as an efficient bifunctional electrocatalyst for water splitting

The development of highly efficient and low-cost electrocatalysts is critical to the mass production of hydrogen from water splitting. Herein, a facile yet effective method was developed to synthesize bimetallic sulfides Ni₃S₂/CoS_x, which were aimed for use as the electrocatalysts in both HER and OER. Encouragingly, the Ni₃S₂/CoS_x demonstrated a low overpotential of 110 mV for HER at a current density of 10 mA·cm^?2. It was discovered that the surface of Ni₃S₂/CoS_x during OER process would undergo an in-situ oxidation to form MOOH (M = Co, Ni), that is, MOOH/Ni₃S₂/CoS_x were the real functioning species in catalysis, which had an excellent OER activity and a low overpotential of 226 mV. Additionally, the assembled electrolyzer required only a low cell voltage of 1.53 V to achieve a current density of 10 mA·cm^?2 in a 1 M KOH solution, and its performance was stable. Overall, this work provided a promising strategy for the facile fabrication of low-cost amorphous electrocatalysts, which is expected to promote the progress of overall water splitting.     

Highly active Ni/Co-metal organic framework bifunctional electrocatalyst for water splitting reaction

Rational design of electrocatalycally active materials with excellent performance for renewable energy conversion is of great interest. We have developed a nanosheet array of Ni/Co metal-organic framework (MOF) grown on CoO modified Ni foam (CoO/NF) substrate via the solvothermal process. The high surface area and low resistance of Ni/Co-MOF@CoO/NF (NC@CoO/NF) catalyst contribute to efficient water splitting. We have prepared a series of NC-n/CoO/NF (n = 1–4) catalysts to optimize the molar ratio of the Co atom in Ni MOF-74. Among them, NC-2@CoO/NF shows an excellent electrochemical performance in alkaline medium, i.e., low overpotential of 290 and 139 mV for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. For a two-electrode system with NC-2@CoO/NF, a low cell voltage of 1.54 V at 10 mA cm^?2 has been obtained for overall water splitting which is much smaller than that with commercial Ir/C– Pt/C pair. This excellent performance can be attributed to the synergistic effects of Ni/Co-MOF and CoO/NF. In addition, the as-prepared NC-2@CoO/NF exhibits excellent long-term stability. The computational simulation also supports experimental results.     

Embedding Co2P nanoparticles into co-doped carbon hollow polyhedron as a bifunctional electrocatalyst for efficient overall water splitting

The reasonable design and construction of non-precious metal electrocatalysts with low cost and high performance is critical for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, a facile polymerization-pyrolysis method is proposed to encapsulate Co₂P nanoparticles in co-doped hollow carbon shell by using ZIF-67 and P-containing polymers as precursor. The unique construction not only effectively prevents nanoparticles from detaching, showing good stability after long-term testing, but also provides abundant active sites, large surface areas and large pore volumes, enabling the electrolyte and electrode material to full contact. As expected, the Co₂P/NPSC-800 performs superior HER performance with low overpotential of 173 mV at 10 mA cm⁻² and excellent stability of 88% retention for 35 h and OER performance with low overpotential of 320 mV at 10 mA cm⁻², which endows Co₂P/NPSC-800 with good catalytic activity in overall water splitting. Furthermore, density functional theory (DFT) calculations reveal that the metallic property and the decreased reaction barriers of Co₂P can promote the catalytic reactions. This work offers an effective route in synthesizing other transition metal phosphides with high catalytic properties.     

Crossed FeCo2S4 nanosheet arrays grown on 3D nickel foam as high-efficient electrocatalyst for overall water splitting

Great efforts in developing low-cost, highly efficient and stable electrocatalysts are to tune the chemical compositions and morphological characteristics for enhancing efficiency of water splitting. In this communication, FeCo₂S₄ nanosheet was grown in situ on nickel foam (FeCo₂S₄/NF) via a facile hydrothermal sulfidization method and served as a high-efficient bifunctional electrocatalyst for overall water splitting. As-synthesized FeCo₂S₄/NF self-supported electrode delivers 20 mA cm^?2 at an overpotential of 259 mV toward OER and 10 mA cm^?2 at an overpotential of 131 mV toward HER in alkaline media. Moreover, when used as both anode and cathode in a two-electrode electrolyzer, only a small cell voltage of 1.541 V is needed to afford a current density of 10 mA cm^?2 for overall water splitting. Bifunctional electrode FeCo₂S₄/NF also revealed a distinguished electrochemical durability during a 12 h stability test at 1.63 V, which would provide a promising water splitting installation for commercial hydrogen production.     

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.     

Effective surface roughening of three-dimensional copper foam via sulfurization treatment as a bifunctional electrocatalyst for water splitting

Cost effective electrocatalysts in water splitting reaction are critically important for the practical application of hydrogen fuel. The surface of three-dimensional copper foam is successfully roughened via one-step sulfurization reaction, and cuprous sulfide is formed on copper foam accordingly, which is denoted as Cu₂S@Cu. The as-prepared Cu₂S@Cu electrocatalyst exhibits remarkable performance on oxygen evolution reaction in basic solution, with a low overpotential of 345 mV to achieve 20 mA cm⁻². Cu₂S@Cu also shows enhanced performance on hydrogen production, compared to the original copper foam. Furthermore, Cu₂S@Cu can work as both cathode and anode in full water splitting, with superior activity to the noble metal-based electrocatalysts under large current densities. This study demonstrates that surface roughening technique on copper foam by sulfurization reaction can be valuable for developing novel copper-based electrocatalysts for water splitting.