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1.
Electrochemical water splitting is a promising approach for producing sustainable and clean hydrogen. Typically, high valence state sites are favorable for oxidation evolution reaction (OER), while low valence states can facilitate hydrogen evolution reaction (HER). However, here we proposed a high valence state of Co3+ in Ni9.5Co0.5−S−FeOx hybrid as the favorable center for efficient and stable HER, while structural analogues with low chemical states showed much worse performance. As a result, the Ni9.5Co0.5−S−FeOx catalyst could drive alkaline HER with an ultra-low overpotential of 22 mV for 10 mA cm−2, and 175 mV for 1000 mA cm−2 at the industrial temperature of 60 °C, with an excellent stability over 300 h. Moreover, this material could work for both OER and HER, with a low cell voltage being 1.730 V to achieve 1000 mA cm−2 for overall water splitting at 60 °C. X-ray absorption spectroscopy (XAS) clearly identified the high valence Co3+ sites, while in situ XAS during HER and theoretical calculations revealed the favorable electron capture at Co3+ and suitable H adsorption/desorption energy around Co3+, which could accelerate the HER. The understanding of high valence states to drive reductive reactions may pave the way for the rational design of energy-related catalysts.  相似文献   

2.
Nickel nanoparticle and graphene interfaces of various stoichiometries were created through electrodeposition techniques. The catalytic behavior of the electrodeposited films was investigated through spectro-electrochemical methodologies. UV-vis absorbance spectra of the electrodeposited films are significantly different in the air and alkaline medium. Furthermore, UV-vis and Raman spectroscopy confirmed the coupling of Ni nanoparticles (Ni-NP) with the graphene framework, along with NiO and Ni(OH)2. A combination of Raman and impedance spectroscopy revealed that the surface adsorption and charge transfer properties of the electrodeposited films are entirely dependent on the defects on graphene structure as well as distribution of Ni-NP on graphene. The electrodeposited films possess heterogeneous catalytic properties with a low overpotential of 50 mV (10 mA/cm−2) for hydrogen evolution reaction, as well as 601 mV and 391 mV (at 50 mA/cm−2) for the oxygen evolution reaction and urea oxidation reaction, respectively. In addition, eelectrodeposited samples show extraordinary overall water splitting performance by achieving a current density of 10 mA/cm2 at a very low applied potential of 1.38 V. This synergistic coupling of Ni and graphene renders the electrodeposited samples promising candidates as electrodes for overall water splitting in alkaline and urea-supplemented solutions.  相似文献   

3.
Metal-organic frameworks (MOFs) have been considered as potential oxygen evolution reaction (OER) electrocatalysts owning to their ultra-thin structure, adjustable composition, high surface area, and high porosity. Here, we designed and fabricated a vanadium-doped nickel organic framework (V1−x−NixMOF) system by using a facile two-step solvothermal method on nickel foam (NF). The doping of vanadium remarkably elevates the OER activity of V1−x−NixMOF, thus demonstrating better performance than the corresponding single metallic Ni-MOF, NiV-MOF and RuO2 catalysts at high current density (>400 mA cm−2). V0.09−Ni0.91MOF/NF provides a low overpotential of 235 mV and a small Tafel slope of 30.3 mV dec−1 at a current density of 10 mA cm−2. More importantly, a water-splitting device assembled with Pt/C/NF and V0.09−Ni0.91MOF/NF as cathode and anode yielded a cell voltage of 1.96 V@1000 mA cm−2, thereby outperforming the-state-of-the-art RuO2(+)||Pt/C(−). Our work sheds new insight on preparing stable, efficient OER electrocatalysts and a promising method for designing various MOF-based materials.  相似文献   

4.
Optimizing the electronic and synergistic effect of hybrid electrocatalysts based on Pt and Pt-based nanocatalysts is of tremendous importance towards a superior hydrogen evolution performance under both acidic and alkaline conditions. However, developing an ideal Pt-based hydrogen evolution reaction (HER) electrocatalyst with moderated electronic structure as well as strong synergistic effect is still a challenge. Herein, we fabricated boron (B)-doped PtNi nanobundles by a two-step method using NaBH4 as the boron source to obtain PtNi/Ni4B3 heterostructures with well-defined nanointerfaces between PtNi and Ni4B3, achieving an enhanced catalytic HER performance. Especially, the PtNi/Ni4B3 nanobundles (PtNi/Ni4B3 NBs) can deliver a current density of 10 mA cm−2 at the overpotential of 14.6 and 26.5 mV under alkaline and acidic media, respectively, as well as outstanding electrochemical stability over 40 h at the current density of 10 mA cm−2. Remarkably, this approach is also universal for the syntheses of PtCo/Co3B and PtFe/Fe49B with outstanding electrocatalytic HER performance.  相似文献   

5.
Hydrogen energy is considered as one of the ideal clean energies for solving the energy shortage and environmental issues, and developing highly efficient electrocatalysts for overall water splitting to produce hydrogen is still a huge challenge. Herein, for the first time, Ru-doped Cu2+1O vertically arranged nanotube arrays in situ grown on Cu foam (Ru/Cu2+1O NT/CuF) are reported and further investigated for their catalytic properties for overall water splitting. The Ru/Cu2+1O NT/CuF presents ultrahigh catalytic activities for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline conditions, and it exhibits a small overpotential of 32 mV at 10 mA cm−2 in the HER, and only needs 210 mV overpotential to achieve a current density of 10 mA cm−2 in the OER. Importantly, the alkaline electrolyzer using Ru/Cu2+1O NT/CuF as a bifunctional electrocatalyst only needs 1.53 V voltage to deliver a current density of 10 mA cm−2, which is much lower than the benchmark of IrO2(+)/Pt(−) counterpart (1.64 V at 10 mA cm−2). The excellent performance of the Ru/Cu2+1O NT/CuF catalyst is attributed to its high conductive substrate and special Ru-doped nanotube structure, which provides a high electrochemical active surface area and 3D gas diffusion channel.  相似文献   

6.
Identifying electrocatalysts with functions of easy dissociation of water, rapid transformation of hydroxyl and facile hydrogen-hydrogen bond formation are indispensable while challenge for realizing efficient alkaline hydrogen evolution reaction (HER). Herein, we presented the design of Ni3Sn2-NiSnOx nanocomposites towards addressing this challenge. We showed that Ni3Sn2 possessed ideal hydrogen adsorption and low hydroxyl adsorption abilities and NiSnOx facilitated water dissociation and hydroxyl transfer process, respectively. Consequently, the fine-tuned interplay of the two functional parts realized the mutual coordination among the multiple functions and led to significantly boosted HER kinetics. Current densities of 10 and 1000 mA cm−2 were obtained at overpotentials of 14 and 165 mV on the optimized catalyst. This work highlights the significance of considering intrinsic interactions between active sites and all pertinent intermediates on obtaining promising electrocatalysts.  相似文献   

7.
《化学:亚洲杂志》2017,12(22):2956-2961
Developing efficient non‐noble metal and earth‐abundant electrocatalysts with tunable microstructures for overall water splitting is critical to promote clean energy technologies for a hydrogen economy. Herein, novel three‐dimensional (3D) flower‐like Ni2P composed of mesoporous nanoplates with controllable morphology and high surface area was prepared by a hydrothermal method and low‐temperature phosphidation as efficient electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Compared with the urchin‐like Nix Py , the 3D flower‐like Ni2P with a diameter of 5 μm presented an efficient and stable catalytic performance in 0.5 m H2SO4, with a small Tafel slope of 79 mV dec−1 and an overpotential of about 240 mV at a current density of 10 mA cm−2 with a mass loading density of 0.283 mg cm−2. In addition, the catalyst also exhibited a remarkable performance for the OER in 1.0 m KOH electrolyte, with an overpotential of 320 mV to reach a current density of 10 mA cm−2 and a small Tafel slope of 72 mV dec−1. The excellent catalytic performance of the as‐prepared Ni2P may be ascribed to its novel 3D morphology with unique mesoporous structure.  相似文献   

8.
Electrocatalysis is the most promising strategy to generate clean energy H2, and the development of catalysts with excellent hydrogen evolution reaction (HER) performance at high current density that can resist strong alkaline and acidic electrolyte environment is of great significance for practical industrial application. Therefore, a P doped MoS2@Ni3S2 nanorods array (named P-NiMoS) was successfully synthesized through successive sulfuration and phosphorization. P-NiMoS presents a core/shell structure with a heterojunction between MoS2 (shell) and Ni3S2 (core). Furthermore, the doping of P modulates the electronic structure of the P-NiMoS; the electrons transfer from the t2g orbital of Ni element to the eg empty orbital of Mo element through the Ni−S−Mo bond at the Ni3S2 and MoS2 heterojunction, facilitating the hydrogen evolution reaction. As a result, P-NiMoS exhibits excellent HER activity; the overpotential is 290 mV at high current density of 250 mA cm−2 in alkaline electrolyte, which is close to Pt/C (282 mV@250 mA cm−2), and P-NiMoS can stably evolve hydrogen for 48 h.  相似文献   

9.
In the pursuit of long-term stability for oxygen evolution reaction (OER) in seawater, retaining the intrinsic catalytic activity is essential but has remained challenging. Herein, we developed a NixCryO electrocatalyst that manifested exceptional OER stability in alkaline condition while improving the activity over time by dynamic self-restructuring. In 1 M KOH, NixCryO required overpotentials of only 270 and 320 mV to achieve current densities of 100 and 500 mA cm−2, respectively, with excellent long-term stability exceeding 475 h at 100 mA cm−2 and 280 h at 500 mA cm−2. The combination of electrochemical measurements and in situ studies revealed that leaching and redistribution of Cr during the prolonged electrolysis resulted in increased electrochemically active surface area. This eventually enhanced the catalyst porosity and improved OER activity. NixCryO was further applied in real seawater from the Red Sea (without purification, 1 M KOH added), envisaging that the dynamically evolving porosity can offset the adverse active site-blocking effect posed by the seawater impurities. Remarkably, NixCryO exhibited stable operation for 2000, 275 and 100 h in seawater at 10, 100 and 500 mA cm−2, respectively. The proposed catalyst and the mechanistic insights represented a step towards realization of non-noble metal-based direct seawater splitting.  相似文献   

10.
The design and exploration of highly efficient and economical electrocatalysts for large-scale hydrogen generation from electrochemical water splitting is of great importance towards hydrogen economy. Herein, we have synthesized heterogeneous Cu1.92S@Cu3P/Ni2P nanospheres on nickel foam, which exhibits excellent OER activity in alkaline solution. When used as an anode, the overpotential of Cu1.92S@Cu3P/Ni2P at the current density of 10 mA cm−2 is only 211 mV, with a good stability (24 h). The heterogeneous Cu1.92S@Cu3P/Ni2P nanospheres has synergistic modulation of electronic structure, abundant active sites and fast electron transfer rate, which contributes to its high OER activity.  相似文献   

11.
The development of transition-metal-oxides (TMOs)-based bifunctional catalysts toward efficient overall water splitting through delicate control of composition and structure is a challenging task. Herein, the rational design and controllable fabrication of unique heterostructured inter-doped ruthenium–cobalt oxide [(Ru–Co)Ox] hollow nanosheet arrays on carbon cloth is reported. Benefiting from the desirable compositional and structural advantages of more exposed active sites, optimized electronic structure, and interfacial synergy effect, the (Ru–Co)Ox nanoarrays exhibited outstanding performance as a bifunctional catalyst. Particularly, the catalyst showed a remarkable hydrogen evolution reaction (HER) activity with an overpotential of 44.1 mV at 10 mA cm−2 and a small Tafel slope of 23.5 mV dec−1, as well as an excellent oxygen evolution reaction (OER) activity with an overpotential of 171.2 mV at 10 mA cm−2. As a result, a very low cell voltage of 1.488 V was needed at 10 mA cm−2 for alkaline overall water splitting.  相似文献   

12.
Cost-effective, highly efficient and stable non-noble metal-based catalysts for the oxygen evolution reaction (OER) are very crucial for energy storage and conversion. Here, an amorphous cobalt nickel phosphate (CoNiPO4), containing a considerable amount of high-valence Ni3+ species as an efficient electrocatalyst for OER in alkaline solution, is reported. The catalyst was converted from Co-doped Ni2P through pulsed laser ablation in liquid (PLAL) and exhibits a large specific surface area of 162.5 m2 g−1 and a low overpotential of 238 mV at 10 mA cm−2 with a Tafel slope of 46 mV dec−1, which is much lower than those of commercial RuO2 and IrO2. This work demonstrates that PLAL is a powerful technology for generating amorphous CoNiPO4 with high-valence Ni3+, thus paving a new way towards highly effective OER catalysts.  相似文献   

13.
Metal-organic coordination polymers (CP) have attracted the scientific attention for electrochemical water oxidation as it has the similar coordination structure like natural photosynthetic coordinated complex. However, the harsh synthesis conditions and bulky nature pose a major challenge in the field of catalysis. Herein, 3–5 nm CP particles synthesized at room temperature using aqueous solutions of Ni2+/Cu2+ and 2,5-dihydroxyterepthalic acid as precursor were applied for alkaline water and urea electrolysis. The overpotential required is only 300 mV at 10 mA cm−2 by Nano-Ni CP for water oxidation, with turnover frequency (TOF) of 21.4 s−1 which is around 8 times higher than its bulk-counterpart. Overall water and urea splitting were achieved with Nano-Cu (−) ∥ Nano-Ni (+) couple on Ni foam at 1.69 and 1.52 V to achieve 10 mA cm−2, respectively. High electrochemical surface area (ECSA), high TOF, and enhanced mass diffusion are found to be the key parameters responsible for the state-of-the-art water and urea splitting performances of nano-CPs as compared to their bulk counterparts.  相似文献   

14.
Herein, the synthesis of three nickel(II) dithiophosphonate complexes of the type [Ni{S2P(OR)(4-C6H4OMe)}2] [R=H ( 1 ), C3H7 ( 2 )] and [Ni{S2P(OR)(4-C6H4OEt}2] [R=(C6H5)2CH ( 3 )] is described; their structures were confirmed by single-crystal X-ray studies. These complexes were subjected to surfactant/solvent reactions at 300 °C for one hour as flexible molecular precursors to prepare either nickel sulfide or nickel phosphide particles. The decomposition of complex 2 in tri-octylphosphine oxide/1-octadecene (TOPO/ODE), TOPO/tri-n-octylphosphine (TOP), hexadecylamine (HDA)/TOP, and HDA/ODE yielded hexagonal NiS, Ni2P, Ni5P4, and rhombohedral NiS, respectively. Similarly, the decomposition of complex 1 in TOPO/TOP and HDA/TOP yielded hexagonal Ni2P and Ni5P4, respectively, and that of complex 3 in similar solvents led to hexagonal Ni5P4, with TOP as the likely phosphorus provider. Hexagonal NiS was prepared from the solvent-less decomposition of complexes 1 and 2 at 400 °C. NiS (rhom) had the best specific supercapacitance of 2304 F g−1 at a scan rate of 2 mV s−1 followed by 1672 F g−1 of Ni2P (hex). Similarly, NiS (rhom) and Ni2P (hex) showed the highest power and energy densities of 7.4 kW kg−1 and 54.16 W kg−1 as well as 6.3 kW kg−1 and 44.7 W kg−1, respectively. Ni5P4 (hex) had the lowest recorded overpotential of 350 mV at a current density of 50 mA cm−2 among the samples tested for the oxygen evolution reaction (OER). NiS (hex) and Ni5P4 (hex) had the lowest overpotentials of 231 and 235 mV to achieve a current density of 50 mA cm−2, respectively, in hydrogen evolution reaction (HER) examinations.  相似文献   

15.
The oxygen evolution reaction (OER) is key to renewable energy technologies such as water electrolysis and metal–air batteries. However, the multiple steps associated with proton-coupled electron transfer result in sluggish OER kinetics and catalysts are required. Here we demonstrate that a novel nitride, Ni2Mo3N, is a highly active OER catalyst that outperforms the benchmark material RuO2. Ni2Mo3N exhibits a current density of 10 mA cm−2 at a nominal overpotential of 270 mV in 0.1 m KOH with outstanding catalytic cyclability and durability. Structural characterization and computational studies reveal that the excellent activity stems from the formation of a surface-oxide-rich activation layer (SOAL). Secondary Mo atoms on the surface act as electron pumps that stabilize oxygen-containing species and facilitate the continuity of the reactions. This discovery will stimulate the further development of ternary nitrides with oxide surface layers as efficient OER catalysts for electrochemical energy devices.  相似文献   

16.
The development of high-efficiency, low-cost, and earth-abundant electrocatalysts for overall water splitting remains a challenge. In this work, Ni-modified MoS2 hybrid catalysts are grown on carbon cloth (Ni-Mo-S@CC) through a one-step hydrothermal treatment. The optimized Ni-Mo-S@CC catalyst shows excellent hydrogen evolution reaction (HER) activity with a low overpotential of 168 mV at a current density of 10 mA cm−2 in 1.0 m KOH, which is lower than those of Ni-Mo-S@CC (1:1), Ni-Mo-S@CC (3:1), and pure MoS2. Significantly, the Ni-Mo-S@CC hybrid catalyst also displays outstanding oxygen evolution reaction (OER) activity with a low overpotential of 320 mV at a current density of 10 mA cm−2, and remarkable long-term stability for 30 h at a constant current density of 10 mA cm−2. Experimental results and theoretical analysis based on density functional theory demonstrate that the excellent electrocatalytic performance can be attributed mainly to the remarkable conductivity, abundant active sites, and synergistic effect of the Ni-doped MoS2. This work sheds light on a unique strategy for the design of high-performance and stable electrocatalysts for water-splitting electrolyzers.  相似文献   

17.
To endow all-solid-state asymmetric supercapacitors with high energy density, cycling stability, and flexibility, we design a binder-free supercapacitor electrode by in situ growth of well-distributed broccoli-like Ni0.75Mn0.25O/C solid solution arrays on a flexible and three-dimensional Ni current collector (3D-Ni). The electrode consists of a bottom layer of compressed but still porous Ni foam with excellent flexibility and high electrical conductivity, an intermediate layer of interconnected Ni nanoparticles providing a large specific surface area for loading of active substances, and a top layer of vertically aligned mesoporous nanosheets of a Ni0.75Mn0.25O/C solid solution. The resultant 3D-Ni/Ni0.75Mn0.25O/C cathode exhibits a specific capacitance of 1657.6 mF cm−2 at 1 mA cm−2 and shows no degradation of the capacitance after 10 000 cycles at 3 mA cm−2. The assembled 3D-Ni/Ni0.75Mn0.25O/C//activated carbon asymmetric supercapacitor has a high specific capacitance of 797.7 mF cm−2 at 2 mA cm−2 and an excellent cycling stability with 85.3 % of capacitance retention after 10 000 cycles at a current density of 3 mA cm−2. The energy density and power density of the asymmetric supercapacitor are up to 6.6 mW h cm−3 and 40.8 mW cm−3, respectively, indicating a fairly promising future of the flexible 3D-Ni/Ni0.75Mn0.25O/C electrode for efficient energy storage applications.  相似文献   

18.
Hydrothermally synthesized NiMoO4 nanorods exhibit considerable electrocatalytic properties for the oxygen evolution in alkaline condition. The performance enhancement of ternary NiMoO4 over binary oxide NiO and MoO3 is attributed to the inclusion of Mo that promotes the pre-redox reaction of Ni to form active Ni species.  相似文献   

19.
Combining the self-sacrifice of a highly crystalline substance to design a multistep chain reaction towards ultrathin active-layer construction for high-performance water splitting with atmospheric-temperature conditions and an environmentally benign aqueous environment is extremely intriguing and full of challenges. Here, taking cobalt carbonate hydroxides (CCHs) as the initial crystalline material, we choose the Lewis acid metal salt of Fe(NO3)3 to induce an aqueous-phase chain reaction generating free CO32− ions with subsequent instant FeCO3 hydrolysis. The resultant ultrathin (∼5 nm) amorphous Fe-based hydroxide layer on CCH results in considerable activity in catalyzing the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), yielding 10/50 mA ⋅ cm−2 at overpotentials of 230/266.5 mV for OER and 72.5/197.5 mV for HER. The catalysts can operate constantly in 1.0 M KOH over 48 and 45 h for the OER and HER, respectively. For bifunctional catalysis for alkaline electrolyzer assembly, a cell voltage as low as 1.53 V was necessary to yield 10 mA cm−2 (1.7 V at 50 mA cm−2). This work rationally builds high-efficiency electrochemical bifunctional water-splitting catalysts and offers a trial in establishing a controllable nanolevel ultrathin lattice disorder layer through an atmospheric-temperature chemical route.  相似文献   

20.
A series of porphyrin‐based imine gels have been synthesized via dynamic covalent gelation between 5,10,15,20‐tetra(4‐aminophenyl)‐21H,23H‐porphyrin (H2TAPP) derivatives and various aldehyde compounds. The porphyrin‐ferrocene imine gels based on MTAPP (M=H2, Ni2+, Co2+, Pd2+ and Zn2+) and ferrocene‐1,1′‐dicarbaldehyde (NA) display efficient HER, OER and ORR activities in alkaline media. Among the gels, CoTAPP‐NA shows an HER current density of 10 mA cm?2 at low overpotential of 470 mV and small Tafel slope of 110 mV decade?1 in alkaline media. CoTAPP‐NA also exhibits OER catalytic activity with low overpotential (416 mV for 10 mA cm?2). CoTAPP‐NA shows ability in overall water splitting in alkaline media. In addition, CoTAPP‐NA exhibits onset potential (Ep) of 0.95 V and half‐wave potential (E1/2) of 0.84 V in 1.0 mol L?1 KOH solution for oxygen reduction. Moreover, the gel catalyst shows good stability.  相似文献   

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