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1.
Herein, the authors demonstrate a heterostructured NiFe LDH‐NS@DG10 hybrid catalyst by coupling of exfoliated Ni–Fe layered double hydroxide (LDH) nanosheet (NS) and defective graphene (DG). The catalyst has exhibited extremely high electrocatalytic activity for oxygen evolution reaction (OER) in an alkaline solution with an overpotential of 0.21 V at a current density of 10 mA cm?2, which is comparable to the current record (≈0.20 V in Fe–Co–Ni metal‐oxide‐film system) and superior to all other non‐noble metal catalysts. Also, it possesses outstanding kinetics (Tafel slope of 52 mV dec?1) for the reaction. Interestingly, the NiFe LDH‐NS@DG10 hybrid has also exhibited the high hydrogen evolution reaction (HER) performance in an alkaline solution (with an overpotential of 115 mV by 2 mg cm?2 loading at a current density of 20 mA cm?2) in contrast to barely HER activity for NiFe LDH‐NS itself. As a result, the bifunctional catalyst the authors developed can achieve a current density of 20 mA cm?2 by a voltage of only 1.5 V, which is also a record for the overall water splitting. Density functional theory calculation reveals that the synergetic effects of highly exposed 3d transition metal atoms and carbon defects are essential for the bifunctional activity for OER and HER.  相似文献   

2.
The development of cost‐efficient, active, and stable electrode materials as bifunctional catalysts for electrochemical water splitting is crucial to high‐performance renewable energy storage and conversion devices. In this work, the synthesis of Co‐based multi‐metal borides nanochains with amorphous structure is reported for boosting the oxygen evolution (OER) and hydrogen evolution reactions (HER) by one‐pot NaBH4 reduction of Co2+, Ni2+, and Fe2+ under ambient temperature. In all the investigated Co‐based metal borides, NiCoFeB nanochains show the excellent OER performance with a low overpotential of 284 mV at 10 mA cm‐2 and Tafel slope of 46 mV dec‐1, respectively, together with excellent catalytic stability, and robust HER performance with an overpotential of 345 mV at 10 mA cm‐2. The density functional theory (DFT) calculations reveal that the excellent electrocatalytic performance is mainly attributed to optimal electronic structure by tuning the Co‐3d band activities by the incorporation of Ni and Fe for enhanced water splitting via the potentially existed Co0 state. Moreover, the electrolyzer using NiCoFeB nanochains as anode and cathode offers 10 mA cm‐2 at a cell voltage of 1.81 V, comparable to commercial Pt/C // Ir/C, providing a simple method to design and explore highly efficient and cheap bifunctional electrocatalysts for overall water splitting.  相似文献   

3.
Among the bifunctional catalysts for water splitting, recently emerged transition‐metal single‐atom catalysts are theoretically considered to possess high potential, while the experimental activity is not satisfactory yet. Herein, an exceptionally efficient trifunctional metal–nitrogen–carbon (M–N–C) catalyst electrode, composed of a hierarchical carbon matrix embedding isolated nickel atoms with nickel–iron (NiFe) clusters, is presented. 1D microfibers and nanotubes grow sequentially from 2D nanosheets as sacrificial templates via two stages of solution‐ and solid‐phase reactions to form a 1D hierarchy. Exceptionally efficient bifunctional activity with an overpotential of only 13 mV at 10 mA cm?2 toward hydrogen evolution reaction (HER) and an overpotential of 210 mV at 30 mA cm?2 toward oxygen evolution reaction (OER) is obtained, surpassing each monofunctional activity ever reported. More importantly, an overpotential of only 126 and 326 mV is required to drive 500 mA cm?2 toward the HER and OER, respectively. For the first time, industrial‐scale water splitting with two bifunctional catalyst electrodes with a current density of 500 mA cm?2 at a potential of 1.71 V is demonstrated. Lastly, trifunctional catalytic activity including oxygen reduction reaction is also proven with a half‐wave potential at 0.848 V.  相似文献   

4.
Facile design of low‐cost and high‐efficiency catalysts with earth‐abundant and cheap materials is desirable to replace platinum (Pt) for the hydrogen evolution reaction (HER) in water splitting, but the development of such HER catalysts with Pt‐like activity using simple strategies remains challenging. A mesoporous hybrid catalyst of nickel phosphides nanoparticles and cobalt phosphosulfide/phosphide (CoS|Ni|P) nanosheet arrays for HER is reported here, which is developed by a facile three‐step approach consisting of electrodeposition, thermal sulfurization, and phosphorization. This hybrid catalyst is highly robust and stable in acid for HER, and is distinguished by very low overpotentials of 41, 88, and 150 mV to achieve 10, 100, and 1000 mA cm?2, respectively, as well as a small Tafel slope (45.2 mV dec?1), and a large exchange current density (964 µA cm?2). It is among the most efficient earth‐abundant catalysts reported thus far for HER. More importantly, this electrocatalyst has electrochemical durability over 20 h under a wide range of current densities (up to 1 A cm?2) in acidic conditions, as well as very high turnover frequencies of 0.40 and 1.26 H2 s?1 at overpotentials of 75 and 100 mV, respectively, showing that it has great potential for practical applications in large‐scale water electrolysis.  相似文献   

5.
To generate hydrogen, which is a clean energy carrier, a combination of electrolysis and renewable energy sources is desirable. In particular, for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in electrolysis, it is necessary to develop nonprecious, efficient, and durable catalysts. A robust nonprecious copper–iron (CuFe) bimetallic composite is reported that can be used as a highly efficient bifunctional catalyst for overall water splitting in an alkaline medium. The catalyst exhibits outstanding OER and HER activity, and very low OER and HER overpotentials (218 and 158 mV, respectively) are necessary to attain a current density of 10 mA cm?2. When used in a two‐electrode water electrolyzer system for overall water splitting, it not only achieves high durability (even at a very high current density of 100 mA cm?2) but also reduces the potential required to split water into oxygen and hydrogen at 10 mA cm?2 to 1.64 V for 100 h of continuous operation.  相似文献   

6.
Carbides are commonly regarded as efficient hydrogen evolution reaction (HER) catalysts, but their poor oxygen evolution reaction (OER) catalytic activities seriously limit their practical application in overall water splitting. Here, vertically aligned porous cobalt tungsten carbide nanosheet embedded in N‐doped carbon matrix (Co6W6C@NC) is successfully constructed on flexible carbon cloth (CC) as an efficient bifunctional electrocatalyst for overall water splitting via a facile metal–organic framework (MOF) derived method. The synergistic effect of Co and W atoms effectively tailors the electron state of carbide, optimizing the hydrogen‐binding energy. Thus Co6W6C@NC shows an enhanced HER performance with an overpotential of 59 mV at a current density of ?10 mA cm?2. Besides, Co6W6C@NC easily in situ transforms into tungsten actived cobalt oxide/hydroxide during the OER process, serving as OER active species, which provides an excellent OER activity with an overpotential of 286 mV at a current density of ?10 mA cm?2. The water splitting device, by applying Co6W6C@NC as both the cathode and anode, requires a low cell voltage of 1.585 V at 10 mA cm?2 with the great stability in alkaline solution. This work provides a feasible strategy to fabricate bimetallic carbides and explores their possibility as bifunctional catalysts toward overall water splitting.  相似文献   

7.
The development of efficient bifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of extreme importance for future renewable energy systems. This Communication reports the recent finding that room‐temperature treatment of CoO nanowire array on Ti mesh by NaBH4 in alkaline media leads to in situ development of Co? B nanoparticles on nanowire surface. The resulting self‐supported Co? B@CoO nanoarray behaves as a 3D bifunctional electrocatalyst with high activity and durability for both HER (<17% current density degradation after 20 h electrolysis) and OER (<14% current density degradation after 20 h electrolysis) with the need of the overpotentials of 102 and 290 mV to drive 50 mA cm?2 in 1.0 m KOH, respectively. Moreover, its two‐electrode alkaline water electrolyzer also shows remarkably high durability and only demands a cell voltage of 1.67 V to deliver 50 mA cm?2 water‐splitting current with a current density retention of 81% after 20 h electrolysis. This work provides a promising methodology for the designing and fabricating of metal‐boride based nanoarray as a high‐active water‐splitting catalyst electrode for applications.  相似文献   

8.
The development of efficient bifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of extreme importance for future renewable energy systems. This Communication reports the recent finding that room‐temperature treatment of CoO nanowire array on Ti mesh by NaBH4 in alkaline media leads to in situ development of Co?B nanoparticles on nanowire surface. The resulting self‐supported Co?B@CoO nanoarray behaves as a 3D bifunctional electrocatalyst with high activity and durability for both HER (<17% current density degradation after 20 h electrolysis) and OER (<14% current density degradation after 20 h electrolysis) with the need of the overpotentials of 102 and 290 mV to drive 50 mA cm?2 in 1.0 m KOH, respectively. Moreover, its two‐electrode alkaline water electrolyzer also shows remarkably high durability and only demands a cell voltage of 1.67 V to deliver 50 mA cm?2 water‐splitting current with a current density retention of 81% after 20 h electrolysis. This work provides a promising methodology for the designing and fabricating of metal‐boride based nanoarray as a high‐active water‐splitting catalyst electrode for applications.  相似文献   

9.
Developing highly efficient earth‐abundant nickel‐based compounds is an important step to realize hydrogen generation from water. Herein, the electronic modulation of the semiconducting NiS2 by cation doping for advanced water electrolysis is reported. Both theoretical calculations and temperature‐dependent resistivity measurements indicate the semiconductor‐to‐conductor transition of NiS2 after Cu incorporation. Further calculations also suggest the advantages of Cu dopant to cathodic water electrolysis by bringing Gibbs free energy of H adsorption at both Ni sites and S sites much closer to zero. It is noteworthy that water dissociation on Cu‐doped NiS2 (Cu‐NiS2) surface is even more favorable than those on NiS2 and Pt(111). Thus, the prepared Cu‐NiS2 shows noticeably improved performance toward alkaline hydrogen and oxygen evolution reactions (HER and OER). Specifically, it requires merely 232 mV OER overpotential to drive 10 mA cm?2; in parallel with Tafel slopes of 46 mV dec?1. Regarding HER, an onset overpotential of only 68 mV is achieved. When integrated as both electrodes for water electrolysis, Cu‐NiS2 needs only 1.64 V to drive 10 mA cm?2, surpassing the state‐of‐the‐art Ir/C–Pt/C couple (1.71 V). This work opens up an avenue to engineer low‐cost and earth‐abundant catalysts performing on par with the noble‐metal‐based one for water splitting.  相似文献   

10.
Designing elaborate nanostructures and engineering defects have been promising approaches to fabricate cost‐efficient electrocatalysts toward overall water splitting. In this work, a controllable Prussian‐blue‐analogue‐sacrificed strategy followed by an annealing process to harvest defect‐rich Ni‐Fe‐doped K0.23MnO2 cubic nanoflowers (Ni‐Fe‐K0.23MnO2 CNFs‐300) as highly active bifunctional catalysts for oxygen and hydrogen evolution reactions (OER and HER) is reported. Benefiting from many merits, including unique morphology, abundant defects, and doping effect, Ni‐Fe‐K0.23MnO2 CNFs‐300 shows the best electrocatalytic performances among currently reported Mn oxide‐based electrocatalysts. This catalyst affords low overpotentials of 270 (320) mV at 10 (100) mA cm?2 for OER with a small Tafel slope of 42.3 mV dec?1, while requiring overpotentials of 116 and 243 mV to attain 10 and 100 mA cm?2 for HER respectively. Moreover, Ni‐Fe‐K0.23MnO2 CNFs‐300 applied to overall water splitting exhibits a low cell voltage of 1.62 V at 10 mA cm?2 and excellent durability, even superior to the Pt/C||IrO2 cell at large current density. Density functional theory calculations further confirm that doping Ni and Fe into the crystal lattice of δ‐MnO2 can not only reinforce the conductivity but also reduces the adsorption free‐energy barriers on the active sites during OER and HER.  相似文献   

11.
The development of earth‐abundant, low cost, and versatile electrocatalysts for producing hydrogen from water electrolysis is still challenging. Herein, based on high hydrogen evolution reaction (HER) activity of transition metal phosphides, a CoP3 nanowire decorated with copper phosphides (denoted as CuPx) nanodots structures synthesized through a simple and easily scalable precursor‐transformation strategy is reported as a highly efficient HER catalyst. By decorating with CuPx nanodots, the optimized CoP3 nanowires electrode exhibits excellent catalytic activity and long‐term durability for HER in alkaline conditions, achieving a low overpotential of 49.5 mV at a geometrical catalytic current density of 10 mA cm?2 with a small Tafel slope of 58.0 mV dec?1, while also performing quite well in neutral and acidic media. Moreover, its overall performance exceeds most of the reported state‐of‐the‐art catalysts, especially under high current density of 100 mA cm?2, demonstrating its potential as a promising versatile pH universal electrocatalyst for efficient water electrolysis. These results indicate that the incorporation of earth‐abundant stable element copper can significantly enhance catalytic activity, which widens the application range of copper and provides a new path for design and selection of HER catalysts.  相似文献   

12.
The design of cost‐efficient earth‐abundant catalysts with superior performance for the electrochemical water splitting is highly desirable. Herein, a general strategy for fabricating superior bifunctional water splitting electrodes is reported, where cost‐efficient earth‐abundant ultrathin Ni‐based nanosheets arrays are directly grown on nickel foam (NF). The newly created Ni‐based nanosheets@NF exhibit unique features of ultrathin building block, 3D hierarchical structure, and alloy effect with the optimized Ni5Fe layered double hydroxide@NF (Ni5Fe LDH@NF) exhibiting low overpotentials of 210 and 133 mV toward both oxygen evolution reaction and hydrogen evolution reaction at 10 mA cm?2 in alkaline condition, respectively. More significantly, when applying as the bifunctional overall water splitting electrocatalyst, the Ni5Fe LDH@NF shows an appealing potential of 1.59 V at 10 mA cm?2 and also superior durability at the very high current density of 50 mA cm?2.  相似文献   

13.
Exploring high‐efficiency, stable, and cost‐effective bifunctional electrocatalysts for overall water splitting is greatly desirable and challenging. Herein, a newly designed hybrid catalyst with Cr‐doped FeNi–P nanoparticles encapsulated into N‐doped carbon nanotubes (Cr‐doped FeNi–P/NCN) with unprecedented electrocatalytic activity is developed by a simple one‐step heating treatment. The as‐synthesized Cr‐doped FeNi–P/NCN with moderate Cr doping exhibits admirable oxygen evolution reaction and hydrogen evolution reaction activities with overpotentials of 240 and 190 mV to reach a current density of 10 mA cm?2 in 1 m KOH solution. When used in overall water splitting as a bifunctional catalyst, it needs only 1.50 V to give a current density of 10 mA cm?2, which is superior to its typically integrated Pt/C and RuO2 counterparts (1.54 V @ 10 mA cm?2). Density functional theory calculation confirms that Cr doping into a FeNi‐host can effectively alter the relative Gibbs adsorption energy and reduces the theoretical overpotential. Additionally, the synergetic effects between Cr‐doped FeNi–P nanoparticles and NCNs are regarded as significant contributors to accelerate charge transfer and promote electrocatalytic activity in hybrid catalysts.  相似文献   

14.
Atom‐scale modulation of electronic regulation in nonprecious‐based electrocatalysts is promising for efficient catalytic activities. Here, hierarchically hollow VOOH nanostructures are rationally constructed by partial iron substitution and systematically investigated for electrocatalytic water splitting. Benefiting from the hierarchically stable scaffold configuration, highly electrochemically active surface area, the synergistic effect of the active metal atoms, and optimal adsorption energies, the 3% Fe (mole ratio) substituted electrocatalyst (VOOH‐3Fe) exhibits a low overpotential of 90 and 195 mV at 10 mA cm?2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media, respectively, superior than the other samples with a different substituted ratio. To the best of current knowledge, 195 mV overpotential at 10 mA cm?2 is the best value reported for V or Fe (oxy)hydroxide‐based OER catalysts. Moreover, the electrolytic cell employing the VOOH‐3Fe electrode as both the cathode and anode exhibits a cell voltage of 0.30 V at 10 mA cm?2 with a remarkable stability over 60 h. This work heralds a new pathway to design efficient bifunctional catalysts toward overall water splitting.  相似文献   

15.
Hydrogen evolution reaction (HER) from water electrolysis is an attractive technique developed in recent years for cost‐effective clean energy. Although considerable efforts have been paid to create efficient catalysts for HER, the development of an affordable HER catalyst with superior performance under mild conditions is still highly desired. In this work, metal–organic frameworks (MOFs)‐templated strategy is proposed for in situ coupling of cobalt phosphide (CoP) polyhedrons nanoparticles and carbon nanotubes (CNTs). Due to the synergistic catalytic effect between CoP polyhedrons and CNTs, the as‐prepared CoP–CNTs hybrids show excellent HER performance. The resultant CoP–CNTs demonstrate excellent HER activity in 0.5 m H2SO4 with Tafel slope of 52 mV dec?1, small onset overpotential of ≈64 mV, and a low overpotential of ≈139 mV at 10 mA cm?2. Additionally, the catalyst also manifests superior durability in acid media. Considering the structure diversity of MOFs, the strategy presented here can be extended for synthesizing other well‐defined metal phosphides–CNTs hybrids, which may be used in the fields of catalysis, energy conversion and storage.  相似文献   

16.
Exploring effective electrocatalysts is a crucial requirement for boosting the efficiency of water splitting to obtain clean fuels. Here, a self‐templating strategy is reported to synthesize Ni–Fe mixed diselenide cubic nanocages for the electrocatalytic oxygen evolution reaction (OER). The diselenide nanocages are derived from corresponding Prussian‐blue analog nanocages, which are first obtained by treating the nanocube precursor with a site‐selective ammonia etchant. The resulting Ni–Fe mixed diselenide nanocages perform as a superior OER electrocatalyst, which affords a current density of 10 mA cm?2 at a small overpotential of 240 mV; a high current density, mass activity, and turnover frequency of 100 mA cm?2, 1000 A g?1, and 0.58 s?1, respectively, at the overpotential of 270 mV; a Tafel slope as small as 24 mV dec?1; and excellent stability in alkaline medium.  相似文献   

17.
Exploring earth‐abundant bifunctional electrocatalysts with high efficiency for water electrolysis is extremely demanding and challenging. Herein, density functional theory (DFT) predictions reveal that coupling Ni with Ni3C can not only facilitate the oxygen evolution reaction (OER) kinetics, but also optimize the hydrogen adsorption and water adsorption energies. Experimentally, a facile strategy is designed to in situ fabricate Ni3C nanosheets on carbon cloth (CC), and simultaneously couple with Ni nanoparticles, resulting in the formation of an integrated heterostructure catalyst (Ni–Ni3C/CC). Benefiting from the superior intrinsic activity as well as the abundant active sites, the Ni–Ni3C/CC electrode demonstrates excellent bifunctional electrocatalytic activities toward the OER and hydrogen evolution reaction (HER), which are superior to all the documented Ni3C‐based electrocatalysts in alkaline electrolytes. Specifically, the Ni–Ni3C/CC catalyst exhibits the low overpotentials of only 299 mV at the current density of 20 mA cm?2 for the OER and 98 mV at 10 mA cm?2 for the HER in 1 m KOH. Furthermore, the bifunctional Ni–Ni3C/CC catalyst can propel water electrolysis with excellent activity and nearly 100% faradic efficiency. This work highlights an easy approach for designing and constructing advanced nickel carbide‐based catalysts with high activity based on the theoretical predictions.  相似文献   

18.
Searching for highly efficient and stable bifunctional electrocatalysts toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is highly desirable for the practical application of water electrolysis under alkaline electrolyte. Although electrocatalysts based on transition metal sulfides (TMSs) are widely studied as efficient (pre)catalysts toward OER under alkaline media, their HER performances are far less than the state‐of‐the‐art Pt catalyst. Herein, the synthesis of nitrogen doped 3D dandelion‐flower‐like CoS2 architecture directly grown on Ni foam (N‐CoS2/NF) is reported that possesses outstanding HER activity and durability, with an overpotential of 28 mV to obtain the current density of 10 mA cm?2, exceeding almost all the documented TMS‐based electrocatalysts. Density functional theory calculations and experimental results reveal that the d‐band center of CoS2 could be efficiently tailored by N doping, resulting in optimized adsorption free energies of hydrogen (ΔG*H) and water , which can accelerate the HER process in alkaline electrolyte. Besides, the resulting N‐CoS2/NF also displays excellent performance for OER, making it a high‐performance bifunctional electrocatalyst toward overall water splitting, with a cell voltage of 1.50 V to achieve 10 mA cm?2.  相似文献   

19.
The development of active bifunctional electrocatalysts with low cost and earth‐abundance toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) remains a great challenge for overall water splitting. Herein, metallic Ni4Mo nanoalloys are firstly implanted on the surface of NiMoOx nanowires array (NiMo/NiMoOx ) as metal/metal oxides hybrid. Inspired by the superiority of carbon conductivity, an ultrathin nitrogen‐doped carbon sheath intercalated NiMo/NiMoOx (NC/NiMo/NiMoOx ) nanowires as integrated core–shell architecture are constructed. The integrated NC/NiMo/NiMoOx array exhibits an overpotential of 29 mV at 10 mA cm?2 and a low Tafel slope of 46 mV dec?1 for HER due to the abundant active sites, fast electron transport, low charge‐transfer resistance, unique architectural structure and synergistic effect of carbon sheath, nanoalloys, and oxides. Moreover, as OER catalysts, the NC/NiMo/NiMoOx hybrids require an overpotential of 284 mV at 10 mA cm?2. More importantly, the NC/NiMo/NiMoOx array as a highly active and stable electrocatalyst approaches ≈10 mA cm?2 at a voltage of 1.57 V, opening an avenue to the rational design and fabrication of the promising electrode materials with architecture structures toward the electrochemical energy storage and conversion.  相似文献   

20.
The development of efficient water‐oxidation electrocatalysts based on inexpensive and earth‐abundant materials is significant to enable water splitting as a future renewable energy source. Herein, the synthesis of novel FeNiP solid‐solution nanoplate (FeNiP‐NP) arrays and their use as an active catalyst for high‐performance water‐oxidation catalysis are reported. The as‐prepared FeNiP‐NP catalyst on a 3D nickel foam substrate exhibits excellent electrochemical performance with a very low overpotential of only 180 mV to reach a current density of 10 mA cm?2 and an onset overpotential of 120 mV in 1.0 m KOH for the oxygen evolution reaction (OER). The slope of the Tafel plot is as low as 76.0 mV dec?1. Furthermore, the long‐term electrochemical stability of the FeNiP‐NP electrode is investigated by cyclic voltammetry (CV) at 1.10–1.55 V versus reversible hydrogen electrode (RHE), demonstrating very stable performance with negligible loss in activity after 1000 CV cycles. This present FeNiP‐NP solid solution is thought to represent the best OER catalytic activity among the non‐noble metal catalysts reported so far.  相似文献   

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