Multiple metallic dopants in nickel nanoparticles for electrocatalytic oxygen evolution

Developing efficient oxygen evolution reaction(OER) electrocatalysts is of great importance for sustainable energy conversion and storage. Ni-based catalysts have shown great potential as OER electrocatalysts, but their performance still needs to be improved. Herein, we report the multiple metal doped nickel nanoparticles synthesized via a simple oil phase strategy as efficient OER catalysts. The FeMnMoV–Ni exhibits superior OER performance with an overpotential of 220 mV at 10 mA cm^-2     

Effect of B sites on the catalytic activities for perovskite oxides La_(.6)Sr_(.4)Co_xFe_(1-x)O_(3-δ) as metal-air batteries catalysts

The effect of B sites on the catalytic activities of oxygen evolution reaction(OER)for perovskite oxides La_(0.6)Sr_(0.4)Co_xFe_(1-x)O_(3-δ)(x=0,0.2,0.4,0.6,0.8,1,denoted as LSF,LSCF-28,LSCF-46,LSCF-64,LSCF-82 and LSC,respectively)prepared by a convenient and simple method of electrospinning technique is reported.The prepared La_(0.6)Sr_(0.4)Co_xFe_(1-x)O_(3-δ)catalysts possess almost same crystal structures,similar morphologies(except for the LSC catalyst)and slightly different BET surface areas.Upon the optimization of the Co/Fe atomic ratio,the optimal LSCF-82 catalyst exhibits the OER performance with a low onset potential of 1.541 V,a small Tafel slope of 80.56 mV dec~(-1),a high charge-transfer rate and a large electrochemical surface area in 0.1 M KOH solution.LSCF-82 catalyst exhibits the long-term stability under the catalytic operation condition for 12 h.Such catalytic activity may mainly cause by the synergy of higher catalytic activity Co and lower catalytic activity Fe.Thus,the reasonable optimization of the transition metal composition in B sites for the perovskite oxides is in favor of the improvement of OER performance.     

Cu2O-templated fabrication of Ni(OH)2·0.75H2O hollow tubes for electrocatalytic oxygen evolution reaction

Cu₂O is an ideal template material for the preparation of transition metal hydroxide/oxyhydroxides with oxygen evolution reaction (OER) enhanced catalytic performance. Here, inspired by Pearson's principle, Cu₂O wires were prepared and used as a sacrificial template to prepare Ni(OH)₂·0.75H₂O hollow tubes (Ni(OH)₂ HTs) with highly improved surface roughness. Benefiting from unique structural advantages, the Ni(OH)₂ HTs showed excellent catalytic activity, rapid kinetics and a long-term stability as the OER catalyst, where an overpotential of only 207 ?mV was required to drive a current density of 10 ?mA ?cm^?2, an ideal kinetics with a Tafel slope as 79.8 ?mV dec^?1 was calculated, and no obvious attenuation in chronoamperometry was discovered after operation for 24 ?h. This paper provides a novel template-assisted strategy to prepare high-performance transition metal-based OER catalysts possessing hollow and tubular structures.     

二维NiFe-LDH/Mo(OS)x纳米片协同促进电催化析氧反应

过渡族金属基二维纳米材料作为电催化析氧反应（oxygen evolution reaction, OER）催化剂具有巨大的潜力。通过原位电沉积法,在泡沫镍基底表面制备了二维层状镍铁双氢氧化物（NiFe-LDH）和氧硫化钼Mo(OS)_x纳米片异质结构。NiFe LDH/Mo(OS)_x电极在1 M KOH溶液中表现出优异的OER性能和长效稳定性,在10 mA/cm²电流密度下过电势仅为220 mV。在100、500 mA/cm²的高电流密度下,也能达到253、304 mV的低过电势。研究结果表明,NiFe-LDH/Mo(OS)_x电极优异的OER性能归因于Mo(OS)_x和NiFe LDH的协同作用,极大地促进了Fe²⁺向Fe³⁺活性物质的转化,并促进了氧空位的形成。这种协同制备方法为合理构建和设计异质结构电催化剂,实现高效的水分解提供了帮助。     

Gas-Liquid Interfacial Plasma engineering under dilute nitric acid to improve hydrophilicity and OER performance of nickel foam

The world has been moving rapidly to find new eco-friendly energy sources. Water electrolysis consists of two reactions of Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER), whereas the OER is considered the rate-limiting step. The most commercialized electrode for OER in the alkaline electrolyte is Ni foam, but its original surface is hydrophobic. It is possible to accelerate the adsorption and desorption process of reactants and products during OER by adding hydrophilic functional groups such as –OH on the surface of Ni foam. In this study, a novel Gas-Liquid Interfacial Plasma (GLIP) engineering at room temperature was successfully applied to modify the Ni foam surface dilute (1 ?M) HNO₃ solution. At a current density of 400 ?mA ?cm^?2, GLIP-treated Ni foam electrodes at 1 ?M HNO₃ concentrations showed OER overpotentials of 458 ?mV. Among all, GLIP with 1 ?M HNO₃ treatment of 30 ?min showed 129 ?mV less overpotential than the nickel foam before treatment. In summary, GLIP can be justified as an environmentally friendly and efficient surface treatment to improve the wettability and OER performance of Ni-based electrodes in water electrolysis.     

Magnetic field induced synthesis of (Ni,Zn)Fe2O4 spinel nanorod for enhanced alkaline hydrogen evolution reaction

Recently, the introduction of external fields(light, thermal, magnetism, etc.) during electrocatalysis reactions gradually becomes a new strategy to modulate the catalytic activities. In this work, an external magnetic field was innovatively employed for the synthesis progress of(Ni, Zn)Fe₂O₄spinel oxide(M-(Ni, Zn)Fe₂O₄). Results indicated the magnetic field(≤250 m T) would affect the morphology of catalyst due to the existing Fe ions, inducing the M-(...     

Unveiling the role of Zn dopants in NiFe phosphide nanosheet for oxygen evolution reaction

Transition metal phosphides have been recognized as promising electrocatalysts for oxygen evolution reaction(OER) due to their low cost and high activity. However, the insufficient exposed active region limited the OER performance. Recently, the introduction of sacrificial dopants has been considered an effective strategy to enlarge the surface area. Herein, the Zn dopants are introduced in NiFe phosphide(NiFeZnP) nanosheet, which work as the sacrificial dopants to generate more exposed active N...     

Bimetal nickel–cobalt phosphide directly grown on commercial graphite substrate by the one-step electrodeposition as efficient electrocatalytic electrode

It is challenging to find a method to obtain a catalyst with low cost and efficient multifunctional performances. Herein, in order to obtain the electrode with high-performance water splitting and non-enzymatic glucose detection, the commercial graphite sheet (GS) with excellent durability and electroconductivity was used as substrate material, and the non-noble ternary component Ni–Co–P catalyst with hierarchical architecture was fabricated on GS via a co-electrodeposition. The catalyst only required low overpotentials of 44.6, 76.5 and 49 mV to drive the current density of 10 mA cm⁻² alongside with the smaller Tafel slopes of 39.2, 44.8 and 112 mV dec⁻¹ for hydrogen evolution reaction (HER) in 1.0 M KOH, 0.5 M H₂SO₄ and 1.0 M PBS solution, respectively. For oxygen evolution reaction (OER), the catalyst demonstrated a low overpotential of 304 mV to achieve the current density of 20 mA cm⁻² with excellent Tafel slope of 89.8 mV dec⁻¹ in alkaline solution. Furthermore, the Ni–Co–P/GS electrode serving as non-enzymatic glucose sensor exhibited the superior electrocatalytic activity with an ultrahigh sensitivity of 7400 μA mM⁻¹ cm⁻², low detection limit of 0.425 μM (S/N = 3), and wide linear range (1–1200 μM).     

Synthesis, conductivity and photosensitivity of 2-D conjugated polymers of metalporphyrazine with sulfur bridges

The title polymers PMS₈Pz, M=Mn^II, Fe^II, Co^II, Ni^II, Cu^II, Zn^II, were synthesized by reaction of 2, 3, 5, 6-tetracyano-1, 4-dithiin with corresponding metal salts, respectively. The structure and properties of these polymers were characterized by elemental analysis, transmission electron microscope, DTA, IR, UV-Vis, fluorescence and EPR spectra. It has been found that these conjugated polymers have the property of intrinsic semiconductor. The conductivity σ_298K of these polymers is in the range of 10⁻⁹≈10⁻³ S·cm⁻¹ under pressure 10.63 MPa and incrementals in the metal order Mn<Co<Fe<Zn<Cu<Ni. The photosensitivity of the MS₈Pz to the CdS-PVA films is incrementals in the metal order Zn<Mn<Co<Fe<Cu<Ni. Supported by the National Natural Science Foundation of China and by the Approach Fund of State Key Laboratory of Coordination Chemistry in Nanjing University Peng Zhenghe: born in Apr. 22, 1945, Professor     

Supramolecular self-assembly of nickel (Ⅱ)-substituted α-Keggin-type polyoxometalate and polyaniline coated Fe2O3 hollow nanospindle for microwave absorption application

A general strategy has been developed here to supramolecular self-assembly of nickel (Ⅱ)-substituted α-Keggin-type polyoxometalate and polyaniline coated Fe₂O₃ hollow nanospindle (Fe₂O₃ hollow nanospindle@PANI/α-SiW₁₁Ni composites) via electrostatic attraction and hydrothermal method. Fe³⁺ was first hydrolyzed and polymerized into Fe₂O₃, then dissolved into [Fe(H₂PO₄)_x]^3?x, resulting in hollow structure. The polyoxometalate existed in polyaniline as a proton-doped counter-ion form, rather than as a separate crystalline state. The protons and anions entered the PANI main chain and combined with N atoms of amines and imines on the PANI chain ((-NH^?+ ?= ?)/α-[SiW₁₁Ni(H₂O)O₃₉]^6-) to form poles and bipolar delocalization into π bonds of the whole polyaniline molecular chain, which leaded to conductance and polarization. The Fe₂O₃ hollow nanospindle@PANI/α-SiW₁₁Ni composites were proven to be excellent microwave absorber in terms of reflection loss (R_L) and bandwidth. The maximum R_L value was up to ?53.6 ?dB at 3.5 ?mm and 6.9 ?GHz. The broadest absorption bandwidth exceeding ?10 dB was 6.3 ?GHz at a thickness of only 1.9 ?mm. Moreover, the ternary composites presented obvious multi-band absorption with the matching thickness range of 1.5–5 ?mm. The absorption peaks bandwidth reached as wide as 14.3 ?GHz, which included all C-Ku bands. The hollow and core-shell structures could provide non-uniform interface for the induced polarization loss and space for the reflecting and scattering of microwave. The carrier, pair-ion carrier and hydrogen bond network could lead to conduction loss. The magnetic losses were caused by eddy current effect and natural resonance. This work can lay a theoretical foundation for the design and performance regulation of new absorbing materials.     

Effect of Ce addition on hot corrosion behaviours of a cast γ′-strengthened Co–Al–W–Mo–Ta–B alloy at 800 ​°C

Hot corrosion behaviours of a novel Co–9Al-4.5W-4.5Mo–2Ta-0.02B alloy doped with 0.01, 0.05, 0.1 and 0.2 ?at% Ce exposed at 800 ?°C in a solution of 75%Na₂SO₄/25%NaCl were investigated. The alloys comprised a coherent γ-Co_SS/γ′-Co₃(Al, W) microstructure (0.01Ce and 0.05Ce alloys) and κ-Co₃(W, Mo) precipitates (0.1Ce and 0.2Ce alloys) at grain boundaries. Hot corrosion kinetics curves demonstrated the parabolic time dependency profile with two stages: the first parabolic stage is within the beginning ～50 ?h corrosion and follows by the second parabolic stage. With an increasing nominal Ce content the weight gain of the alloy significantly decreased from approximately 70.1 ?mg ?cm^?2 (0.01Ce) to 40.8 ?mg ?cm^?2 (0.2Ce) when exposed for 100 ?h. A two-layer corrosion scale formed, and the scale was composed of an outer layer of Co₃O₄ oxide with spinel compounds of CoAl₂O₄, CoWO₄and CoSO₄, and an inner γ/needle-like Co₃W/sulphide layer adhered to the substrate. Heavy spallation of the corrosion scale occurred in the 0.01Ce～0.1Ce alloys, however, spallation was slight in the 0.2Ce alloy. The excellent corrosion resistance of the 0.2Ce alloy could be attributed mainly to the formation of continuous Al₂O₃ lines in the corrosion scale, as well as the prolongation of the incubation period of the corrosion product spallation.     

Cobalt coordination modified double-schiff-base with low solubility as a long-cycle life anode for sodium-ion batteries

Sodium-ion batteries (SIBs) have been recently considered as an intriguing candidate for next-generation battery systems with their advantages in large-scale energy storage applications. However, the design of electrode materials of SIBs still suffers from severe volume expansion and low capacity caused by the larger ion radius, high re-dox potential and heavy atom weight of Na. Organic electrode materials with structural flexibility have attracted great attention recently for their potential in alleviating volume expansion. However, most organic electrode materials suffer from dissolution in electrolytes and consequent capacity fading during the long-term cycling process. In this work, a method coordinating with Co²⁺ was applied to solve the shuttle effect of H₄salphdc (N, N’-phenylene-bis-(salicylideneimine) dicarboxylic acid). By virtue of the Co²⁺ coordination, the Co(H₂salphdc) electrode delivered a desirable discharge capacity of 123 mAh g^?1 after 1500 cycles at the current density of 200 ?mA ?g^?1, while the H₄salphdc electrode exhibited severe capacity fading. Such excellent electrochemical performance can be credited to the Co²⁺ coordination repressing the electrode dissolution and improving the structure stability.     

Effect of Zr addition on the stability of precipitated Laves phase and mechanical properties of Fe–Cr–Al-based alloys at high temperatures

The effect of a small amount of Zr addition on the temperature-dependent stability of Laves phase particles and mechanical properties of Fe-13.5Cr-4.73Al-2.07Mo-(0.34–0.5)Nb-(0.65–0.98)Ta-(0–0.33)Zr (wt. %) ferritic alloys was investigated in the present study. The designed alloy ingots were hot-rolled, aged at 1073 ?K for 24 ?h, and then re-treated at 1273 ?K, 1323 ?K, 1373 ?K, and 1473 ?K for 1 ?h, respectively. It was found that the Zr addition could not only stabilize the Fe₂M Laves phase (M ?= ?Mo,Nb,Ta,Zr) to a much higher temperature, but also induce the formation of stable Fe₂₃Zr₆ phase. The high-temperature (HT) microstructural stability of the alloys significantly was improved, as evidenced by the fact that a certain amount (0.66–1.19%) of precipitates (Fe₂M, Fe₂₃Zr₆, and core(Fe₂₃Zr₆)-shell(Fe₂M)-structured particles) with an appropriate size (～1.0 ?μm) uniformly distributed in the ferritic matrix even after being re-treated at 1473 ?K. Particularly, the formation of core-shell-structured particles at HTs was studied from the viewpoint of both solid solubility and diffusion coefficient of M in the matrix. All these aged alloys exhibited prominent mechanical properties at both room and elevated temperatures, showing high yield strength with σ_YS ?= ?490–560 ?MPa at room-temperature and σ_YS ?= ?80–85 ?MPa at 1073 ?K. The strengthening effect was further discussed in light of various strengthening mechanisms, and the calculated strength are in good agreement with the experimental results.     

Highly stable N-containing polymer-based Fe/Nx/C electrocatalyst for alkaline anion exchange membrane fuel cell applications

A cost-effective electrocatalyst with high activity and stability was developed. The Fe-Nx and pyridinic-N active sites were embedded in nitrogen-doped mesoporous carbon nanomaterial by carbonization at high temperature. The electrocatalyst exhibited excellent electrochemical performance for the oxygen reduction reaction, with high onset potential and half-wave potential values (E_onset = 1.10 ?V and E_1/2 ?= ?0.944 ?V) than 20 ?wt % Pt/C catalyst (1.04 and 0.910 ?V). The mass activity of the Schiff base network (SNW) based SNW-Fe/N/C@800° electrocatalyst (0.64 ?mA ?mg^?1 @ 1 ?V) reached about half of the commercial Pt/C electrocatalyst (1.35 ?mA ?mg^?1 @ 1 ?V). The electrocatalyst followed the 4-electron transfer mechanism due to very low hydrogen peroxide yield (H₂O₂ ?< ?1.5%) was obtained. In addition, this electrocatalyst with dual active sites showed high stability during cyclic voltammetry and chronoamperometry measurements. More importantly, the electrocatalyst also demonstrated the power density of 266 ?mW ?cm^?2 in the alkaline anions exchange membrane fuel cell (AEMFC) test, indicating its prospective application for fuel cells.     

A multi-component nanocrystalline FeCrV alloy with improved mechanical properties and excellent irradiation resistance

An equiatomic low-activated FeCrV ternary alloy was prepared by mechanical alloying and spark plasma sintering. The BCC solid solution alloy exhibited an excellent strength-ductility synergy properties, which was 1.85 ?GPa compressive yield strength, 3.04 ?GPa fracture strength and more than 28% plasticity at room temperature. Even at an elevated temperature of 600 ?°C, its yield strength was still more than 1 ?GPa, revealing a pronounced high temperature resistance. The FeCrV alloy had a homogeneous microstructure with high-density dislocations. A nanocrystalline characteristic was demonstrated and the average grain size was about 322 ?nm, leading to the improved mechanical properties. The strengthening mechanism was discussed in detail and the contributions of strengthening factors were calculated. The FeCrV alloy was irradiated up to 160 dpa with 2 ?MeV Au²⁺ ions at 573 ?K. The nanoindentation test was carried out to simply evaluate the hardening degree under such a high dose irradiation with heavy ions. The semi-quantitative analysis results show that FeCrV alloy has an excellent irradiation tolerance compared with pure Fe.     

热处理对Fe_(40)Co_(40)Zr_7V_2B_9Ta_2合金微观结构及磁性能的影响

采用单辊快淬法制备Fe40Co40Zr7V2B9Ta2非晶合金薄带,并对该合金在不同温度下进行热处理.利用差热分析(DTA)、X射线衍射(XRD)、扫描电镜(SEM)和振动样品磁强计(VSM)测量合金的热性能、微观结构及磁性能.结果表明:Fe40Co40Zr7V2B9Ta2合金的初始晶化产物为α-FeCo相,高温时析出ZrCo3B2,Co23Zr6和ZrB2相;薄带横断面的形貌在快淬态和300℃退火后,合金的自由面呈网状结构,贴辊面呈枝状结构;高于550℃退火,横断面呈颗粒状;550℃退火后合金的矫顽力(Hc)最小,高于550℃退火,Hc随退火温度的升高而增大.     

The inhibition of corrosion of aluminum in acid environment byin situ electrocoagulation of polybutadienoic acid

The dissolution rate of naked Al sheet in the acidic solutions containing polybutadienoic acid (PBA) with pH value of 0.3∼3.0 at 20∼60°C has been determined by electrometry and gravimetry methods. The form of electroactive Al(III) ions occurred on the anode and the behavior of electrocoagulation of PBA have been approached. The results indicate that the superior condition of electrocoagulation of water-soluble nonsaturable low polymer PBA is the adoption of the electroactive Al(III) ions occurred in electrolyte containing 1.0 g·L⁻¹ PBA+0.2 mol·L⁻¹C₆H₈O₇ citric acid with pH value of 3.0 at 30°C. The mechanism of corrosion-inhibited or electrocoagulation resulted from the electroactive Al(III) ions coordinate-COOH group of PBA and free ions of citric groups into the aluminum soaps with bicyclic structure are briefly discussed in this paper. Supported by the National Natural Science Foundation of China Tao Yingchu: born in 1943, Professor     

Enhancement of water absorption capacity and compressibility of hydrogel sponges prepared from gelatin/chitosan matrix with different polyols

The hydrogel sponges have prepared successfully from gelatin/chitosan (GEL/CTS) matrix with different polyols basing on scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR) analysis. The results indicate that the compressibility and thermal properties (thermal gravimetric analysis, TGA) were improved significantly with adding the different polyols [poly(vinyl alcohol) – PVA, and poly(ethylene glycol)-poly(propylene glycol)- poly(ethylene glycol) – PEPEG] into GEL/CTS matrix. Specially, the as-prepared hydrogel sponges with superabsorbent behavior were also investigated with the attained water absorption capacity to 605 ?g ?g^?1 and 585 ?g ?g^?1 for GCV_1/1/0.3 and GCE_1/1/0.3 sponges, respectively, as well as the excellent water absorption capacity in a wide range of pH and salt concentration. Hence, these studies demonstrated that the hydrogel sponges are concerned as potential and promising candidates to apply especially in the fields of biomedicine and hygiene.     

A ternary FeS_2/Fe_7S_8@nitrogen-sulfur co-doping reduced graphene oxide hybrid towards superior-performance lithium storage

Iron sulfides are promising anode materials for lithium ion batteries(LIBs) owe to their high theoretical capacity and low cost. However, unsatisfactory electronic conductivity, dissolution of polysulfides, and severe agglomeration during the cycling process limit their applications. To solve these issues, a ternary FeS_2/Fe_7S_8@nitrogensulfur co-doping reduced graphene oxide hybrid(FeS_2/Fe_7S_8@NSG) was designed and synthesized through a facile hydrolysis-sulfurization strategy, in which the FeS_2/Fe_7S_8 could be well distributed upon the NSG. The NSG was believed to buffer the volume change and augment the electronic conductivity of the electrode, and the nanodimensional FeS_2/Fe_7S_8 particles with a diameter of 50–100 nm could shorten the ion-diffusion paths during the lithiation/delithiation process. Benefiting from synergistic contributions from nano-dimensional FeS_2/Fe_7S_8 and flexible NSG, the FeS_2/Fe_7S_8@NSG hybrid displayed a high initial capacity of ～1068 m Ah g~(-1) at 200 mA g~(-1),good cycling stability(～898 mAh g~(-1) at 500 mA g~(-1) after 200 cycles) and high-rate performance. Further kinetic analysis corroborated that the introduction of NSG boosted the capacitive behavior. Above results indicate the potential applications of FeS_2/Fe_7S_8@NSG hybrid in LIBs with low-cost and high energy density.     

Determination of crystal structure of omphacite

The chemical formula of omphacite was expressed with (MⅡ MⅠ ) (Si, AI)2O6. Cations that occupied the MⅡ site were large cations such as Ca or Na, and (Na/(Na+Ca)) ratio ranged from 0.2 to 0.8; the 6-coordinated MⅠ site accommodated cations such as Mg, Fe2+, Al, Fe3+ ,and(AI/(AI+Fe3+)) ratio was more than 0.5. Omphacite space groups reported were C2/ c, P2, P2/n, P2/c, cell parameters are α0 = 0.9600-0.9630 nm,b0 = 0.8750-0.8830 nm,c0 = 0.5230-0.5290 nm,β = 106°40′-107°10'. The sample was picked up from the eclogites in Zhucheng County, Shangdong Province. The intensity data were collected with the RIGAKU RASA Ⅱ -S four-circle single crystal diffractometer.The correct structure model was obtained by using the Patterson method and Fourier synthesis, SHELX-76 program, structure refinement with 905 independent diffraction points (| F0 |> 3σ |F0 |). After the structure parameter refinement, the R-factor reduced to 0.0515. The crystal structure analysis indicates that omphacite has a new space group-Pn space group.