The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and...The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and Cu_(2)O/Ni O/NF electrodes via in situ pulsed laser irradiation in liquids(PLIL)for the bifunctional electrocatalysis of oxygen evolution reaction(OER)and furfural oxidation reaction(FOR),respectively.Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu_(2)O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR.CoO/NiO/NF electrocatalyst provides a consistently low overpotential of~359 m V(OER)at 10 m A/cm^(2),achieving the maximum FA yield(~16.37 m M)with 61.5%selectivity,79.5%carbon balance,and a remarkable Faradaic efficiency of~90.1%during 2 h of FOR at 1.43 V(vs.reversible hydrogen electrode).Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates(NiOOH and CoOOH)as surface-active centers during electrochemical oxidation.The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products.This method holds promise for large-scale applications,enabling simultaneous production of renewable building materials and fuel.展开更多
Li/Ni mixing negatively influences the discharge capacity of lithium nickel oxide and high-nickel ternary cathode materials.However,accurately measuring the Li/Ni mixing degree is difficult due to the preferred orient...Li/Ni mixing negatively influences the discharge capacity of lithium nickel oxide and high-nickel ternary cathode materials.However,accurately measuring the Li/Ni mixing degree is difficult due to the preferred orientation of labbased XRD measurements using Bragg–Brentano geometry.Here,we find that employing spherical harmonics in Rietveld refinement to eliminate the preferred orientation can significantly decrease the measurement error of the Li/Ni mixing ratio.The Li/Ni mixing ratio obtained from Rietveld refinement with spherical harmonics shows a strong correlation with discharge capacity,which means the electrochemical capacity of lithium nickel oxide and high-nickel ternary cathode can be estimated by the Li/Ni mixing degree.Our findings provide a simple and accurate method to estimate the Li/Ni mixing degree,which is valuable to the structural analysis and screening of the synthesis conditions of lithium nickel oxide and high-nickel ternary cathode materials.展开更多
Economical water electrolysis requires highly active non-noble electrocatalysts to overcome the sluggish kinetics of the two half-cell reactions,oxygen evolution reaction,and hydrogen evolution reaction.Although inten...Economical water electrolysis requires highly active non-noble electrocatalysts to overcome the sluggish kinetics of the two half-cell reactions,oxygen evolution reaction,and hydrogen evolution reaction.Although intensive efforts have been committed to achieve a hydrogen economy,the expensive noble metal-based catalysts remain under consideration.Therefore,the engineering of self-supported electrocatalysts prepared using a direct growth strategy on three-dimensional(3D)nickel foam(NF)as a conductive substrate has garnered significant interest.This is due to the large active surface area and 3D porous network offered by these electrocatalysts,which can enhance the synergistic eff ect between the catalyst and the substrate,as well as improve electrocatalytic performance.Hydrothermal-assisted growth,microwave heating,electrodeposition,and other physical methods(i.e.,chemical vapor deposition and plasma treatment)have been applied to NF to fabricate competitive electrocatalysts with low overpotential and high stability.In this review,recent advancements in the development of self-supported electrocatalysts on 3D NF are described.Finally,we provide future perspectives of self-supported electrode platforms in electrochemical water splitting.展开更多
Ultra fine-grained pure metals and their alloys have high strength and low ductility.In this study,cryorolling under different strains followed by low-temperature short-time annealing was used to fabricate pure nickel...Ultra fine-grained pure metals and their alloys have high strength and low ductility.In this study,cryorolling under different strains followed by low-temperature short-time annealing was used to fabricate pure nickel sheets combining high strength with good ductility.The results show that,for different cryorolling strains,the uniform elongation was greatly increased without sacrificing the strength after annealing.A yield strength of 607 MPa and a uniform elongation of 11.7%were obtained after annealing at a small cryorolling strain(ε=0.22),while annealing at a large cryorolling strain(ε=1.6)resulted in a yield strength of 990 MPa and a uniform elongation of 6.4%.X-ray diffraction(XRD),transmission electron microscopy(TEM),scanning electron microscopy(SEM),and electron backscattered diffraction(EBSD)were used to characterize the microstructure of the specimens and showed that the high strength could be attributed to strain hardening during cryorolling,with an additional contribution from grain refinement and the formation of dislocation walls.The high ductility could be attributed to annealing twins and micro-shear bands during stretching,which improved the strain hardening capacity.The results show that the synergistic effect of strength and ductility can be regulated through low-temperature short-time annealing with different cryorolling strains,which provides a new reference for the design of future thermo-mechanical processes.展开更多
Nickel-based materials,including metallic Ni and Ni oxide,have been widely studied in the exploration of non-precious-metal hydrogen electrocatalysts,but neither pure Ni nor NiO is ideal for the hydrogen evolution rea...Nickel-based materials,including metallic Ni and Ni oxide,have been widely studied in the exploration of non-precious-metal hydrogen electrocatalysts,but neither pure Ni nor NiO is ideal for the hydrogen evolution reaction(HER)and hydrogen oxidation reaction(HOR).In this paper,an oxygen insertion strategy was applied on nickel to regulate its hydrogen electrocatalytic performance,and the oxygen-inserted nickel catalyst was successfully obtained with the assistance of tungsten dioxide support(denoted as O-Ni/WO_(2)).The partial insertion of oxygen in Ni maintains the face-centered cubic arrangement of Ni atoms,simultaneously expanding the lattice and increasing the lattice spacing.Consequently,the adsorption strength of^(*)H and^(*)OH on Ni is optimized,thus resulting in superior electrocatalytic performance of0-Ni/WO_(2)in alkaline HER/HOR.The Tafel slope of O-Ni/WO_(2)@NF for HER is 56 mV dec^(-1),and the kinetic current density of O-Ni/WO_(2)for HOR reaches 4.85 mA cm^(-2),which is ahead of most currently reported catalysts.Our proposed strategy of inserting an appropriate amount of anions into the metal lattice could provide more possibilities for the design of high-performance catalysts.展开更多
By using muon spin relaxation(μSR)measurements,we perform a comparative study of the microscopic magnetism in the parent compounds of infinite-layer nickelate superconductors RNiO_(2)(R=La,Nd).In either compound,the ...By using muon spin relaxation(μSR)measurements,we perform a comparative study of the microscopic magnetism in the parent compounds of infinite-layer nickelate superconductors RNiO_(2)(R=La,Nd).In either compound,the zero-fieldμSR spectra down to the lowest measured temperature reveal no long-range magnetic order.In LaNiO_(2),short-range spin correlations appear below T=150 K,and spins fully freeze below T∼10 K.NdNiO_(2)exhibits a more complex spin dynamics driven by the Nd 4f and Ni3d electron spin fluctuations.Further,it shows features suggesting the proximity to a spin-glass state occurring below T=5 K.In both compounds,the spin behavior with temperature is further confirmed by longitudinal-field μSR measurements.These results provide new insight into the magnetism of the parent compounds of the superconducting nickelates,crucial to understanding the microscopic origin of their superconductivity.展开更多
α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were ...α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.展开更多
An effect of Mg introduction on efficiency of high-loaded nickel catalysts in dehydrogenation of decahydroquinoline(10HQ)was inves-tigated.10HQ dehydrogenation is key process for the liquid organic hydrogen carrier(LO...An effect of Mg introduction on efficiency of high-loaded nickel catalysts in dehydrogenation of decahydroquinoline(10HQ)was inves-tigated.10HQ dehydrogenation is key process for the liquid organic hydrogen carrier(LOHC)storage technology using the quinoline/10HQ pair as H_(2)-lean/H_(2)-rich substrates.An influence of synthesis technique of Ni/Mg/Al catalysts on their properties has been demonstrated.The catalysts were synthesized through coprecipitation of Ni,Mg,Al precursors to obtain layered double hydroxides(LDH)or via syn-thesis of(∼72 wt%)Ni-Al_(2)O_(3) system-also through coprecipitation,followed by modifying with a magnesium-containing precursor.For the catalysts of the first series,the inclusion of magnesium into LDH lattice led to a significant increase in catalytic activity in hydrogen extraction(10HQ dehydrogenation reaction).Despite the decrease in the content of catalytically active nickel,a significant increase in the yield of the dehydrogenation product was observed.This regularity is presumably associated with appearance of basic sites,that accelerates the dehydrogenation reaction.In the case of the second series,activity of pre-reduced(600°C,H_(2))catalysts in dehydrogenation of 10HQ also significantly depends on a MgO content and is maximal at Mg:Ni weight ratio 0.056.Using an in-depth study of structure of the original and reduced catalyst samples(Ni-Al_(2)O_(3) and Ni-MgNiOx-Al_(2)O_(3)),it was shown that this regularity is associated with the increased resistance of catalytically active Ni particles to agglomeration during the reductive activation.Also,using the Ni-MgNiOx-Al_(2)O_(3)catalyst for hydrogen storage process(hydrogenation reaction),the possibility of deep quinoline hydrogenation(up to 10HQ)in a flow-type reactor was demonstrated for the first time.展开更多
The discovery of nickelate superconductors,including doped infinite-layer(IL)nickelates RNiO2(R=La,Pr,Nd),layered square-planar nickelate Nd6Ni5O12,and the Ruddlesden–Popper(RP)phase La3Ni2O7,has spurred immense inte...The discovery of nickelate superconductors,including doped infinite-layer(IL)nickelates RNiO2(R=La,Pr,Nd),layered square-planar nickelate Nd6Ni5O12,and the Ruddlesden–Popper(RP)phase La3Ni2O7,has spurred immense interest in fundamental research and potential applications.Scanning transmission electron microscopy(STEM)has proven crucial for understanding structure–property correlations in these diverse nickelate superconducting systems.In this review,we summarize the key findings from various modes of STEM,elucidating the mechanism of different nickelate superconductors.We also discuss future perspectives on emerging STEM techniques for unraveling the pairing mechanism in the“nickel age”of superconductivity.展开更多
As a common precursor for supercritical CO_(2)(scCO_(2))deposition techniques,solubility data of organometallic complexes in scCO_(2)is crucial for the preparation of nanocomposites.Recently,metal acetylacetonates hav...As a common precursor for supercritical CO_(2)(scCO_(2))deposition techniques,solubility data of organometallic complexes in scCO_(2)is crucial for the preparation of nanocomposites.Recently,metal acetylacetonates have shown great potential for the preparation of single-atom catalytic materials.In this study,the solubilities of iron(Ⅲ)acetylacetonate(Fe(acac)3)and nickel(Ⅱ)acetylacetonate(Ni(acac)2)were measured at the temperature from 313.15 to 333.15 K and in the pressure range of 9.5–25.2 MPa to accumulate new solubility data.Solubility was measured using a static weight loss method.The semi-empirical models proposed by Chrastil and Sung et al.were used to correlate the solubility data of Fe(acac)3 and Ni(acac)2.The equations obtained can be used to predict the solubility of the same system in the experimental range.展开更多
Ultra-high nickel cobalt-free lithium layered oxides are promising cathode material for lithium-ion batteries(LIBs)because of their relatively high capacity and low cost.Nevertheless,the high nickel content would indu...Ultra-high nickel cobalt-free lithium layered oxides are promising cathode material for lithium-ion batteries(LIBs)because of their relatively high capacity and low cost.Nevertheless,the high nickel content would induce bulk structure degradation and interfacial environment deterioration,and the absence of Co element reduces the lithium diffusion kinetics,severely limiting the performance liberation of this kind of cathodes.Herein,a multifunctional Ti/Zr dual cation co-doping strategy has been employed to improve the lithium storage performance of LiNi_(0.9)Mn_(0.1)O_(2)(NM91)cathode.On the one hand,the Ti/Zr co-doping weakens the Li^(+)/Ni^(2+)mixing through magnetic interactions due to the inexistence of unpaired electrons for Ti^(4+)and Zr^(4+),increasing the lithium diffusion rate and suppressing the harmful coexistence of H1 and H2 phases.On the other hand,they enhance the lattice oxygen stability because of the strong Ti-O and Zr-O bonds,inhibiting the undesired H3 phase transition and lattice oxygen loss,improving the bulk structure and cathode-electrolyte interface stability.As a result,the Ti/Zr co-doped NM91(NMTZ)exhibits a 91.2%capacity retention rate after 100 cycles,while that of NM91 is only82.9%.Also,the NMTZ displays better rate performance than NM91 with output capacities of 115 and93 mA h g^(-1)at a high current density of 5 C,respectively.Moreover,the designed NMTZ could enable the full battery to deliver an energy density up to 263 W h kg^(-1),making the ultra-high nickel cobaltfree lithium layered oxide cathode closer to practical applications.展开更多
A direct hydrometallurgical route for nickel and molybdenum extraction from a nickel-molybdenum (Ni-Mo) ore using pressure acid leaching was studied. The nickel and molybdenum were extracted by acid leaching under o...A direct hydrometallurgical route for nickel and molybdenum extraction from a nickel-molybdenum (Ni-Mo) ore using pressure acid leaching was studied. The nickel and molybdenum were extracted by acid leaching under oxygen pressure. Compared with traditional roasting methods, this hydrometallurgical method eliminates SO2 and As203 emission (the Ni-Mo ore containing 15%-25% S). Compared with existing alkali leaching recovery of molybdenum process, almost all the nickel and considerable molybdenum were extracted in the acid leaching process. Under oxygen pressure conditions, almost all the nickel and a substantial part of the molybdenum were dissolved into the acid leaching liquor and the other part of the molybdenum was left in the acid leach residue. The acid leach residue was further leached under alkaline (NaOH) conditions. Under optimal experimental conditions, the extraction rates nickel and molybdenum reached 97% and 96%, respectively.展开更多
To acquire understanding of Ni enrichment from laterite ore,the mineralogy and crystal chemistry of a low grade limonite type nickel laterite ore sample assaying 0.97% Ni from Indonesia were studied using optical micr...To acquire understanding of Ni enrichment from laterite ore,the mineralogy and crystal chemistry of a low grade limonite type nickel laterite ore sample assaying 0.97% Ni from Indonesia were studied using optical microscopy,X-ray diffraction(XRD),scanning electron microscopy(SEM) and electron probe microanalysis(EPMA).According to EPMA results,the mineral includes 80% goethite((Fe,Ni,Al)O(OH)) with 0.87% Ni,15% silicate minerals with lizardite((Mg,Fe,Ni)3Si2O5(OH)) and olivine((Mg,Fe,Ni)2SiO4),and 1.19% Ni,and other minor phases,such as hematite,maghemite,chromite and quartz,and no Ni was detected.The mineralogy of the laterite ore indicates that due to the complicated association of the various phases and the variable distribution of Ni,this refractory laterite ore can not be upgraded by traditional physical beneficiation processes.展开更多
Fine nickel ferrite precursors NiFe2(C204)3·6H2O were obtained via co-precipitation method with low grade nickel matte as the raw material. Thermodynamic analysis of NiClz-FeC12-(NH4)2C204-H20 system for prec...Fine nickel ferrite precursors NiFe2(C204)3·6H2O were obtained via co-precipitation method with low grade nickel matte as the raw material. Thermodynamic analysis of NiClz-FeC12-(NH4)2C204-H20 system for precipitation identified that the theoretical optimum co-precipitation pH value is 2, and C2O2 has strong complexation with Ni2+ and Fe2+ ions. Based on these theoretical considerations, the effects of parameters on the precipitation rates and precursors size were investigated systematically. The results show that the optimum co-precipitation conditions are pH=2, temperature 45 ℃, 1.2 times theoretical amount of (NH4)2C204 dosage and 3% PEG400 addition. Under these conditions, the precipitation rates of Ni2+ and Fe2+ are both over 99.8%, with the precursors size of 1-2 urn. Furthermore, X-ray diffraction (XRD) and thermogravimetry-differential thermal analysis (TG-DTA) demonstrate that the precursors are single-phase solid solution, wherein the nickel/iron atoms are replaced by the iron/nickel atoms reciprocally.展开更多
Electrochemical detection of 3-methyl-4-nitrophenol (MNP) in direct phenol oxidation occurs at high potentials and generally leads to progressive passivation of the electrochemical sensor. This study describes the use...Electrochemical detection of 3-methyl-4-nitrophenol (MNP) in direct phenol oxidation occurs at high potentials and generally leads to progressive passivation of the electrochemical sensor. This study describes the use of a carbon fiber microelectrode modified with a tetrasulfonated nickel phthalocyanine complex for the detection of MNP at a lower potential than that of direct phenol oxidation. The MNP voltammogram showed the presence of an anodic peak at -0.11 V vs SCE, corresponding to the oxidation of the hydroxylamine group generated after the reduction of the nitro group. The effect of buffer pH on the peak current and SWV parameters such as frequency, scan increment, and pulse amplitude were studied and optimized to have better electrochemical response of the proposed sensor. With these optimal parameters, the calibration curve shows that the peak current varied linearly as a function of MNP concentration, leading to a limit of detection (LoD) of 1.1 μg/L. These results show an appreciable sensitivity of the sensor for detecting the MNP at relatively low potentials, making it possible to avoid passivation phenomena.展开更多
Hydrogen energy has become one of the recognized clean energy sources worldwide due to its advantages such as low cost,renewable energy,and green environmental protec-tion.Electrolytic water is currently one of the mo...Hydrogen energy has become one of the recognized clean energy sources worldwide due to its advantages such as low cost,renewable energy,and green environmental protec-tion.Electrolytic water is currently one of the most promising solutions for providing hydrogen fuel.Nickel iron bimetallic electrocatalysts have abundant sources,low cost,clean and pollution-free properties,and strong catalytic performance,This article mainly reviews the development and research of bimetallic nickel iron oxides and nickel iron alloys in recent years,and explores their synthesis methods,properties,and stability in depth.展开更多
The arsenic extraction from the arsenic-containing cobalt and nickel slag,which came from the purification process of zinc sulfate solution in a zinc smelting factory,was investigated.The alkaline leaching method was ...The arsenic extraction from the arsenic-containing cobalt and nickel slag,which came from the purification process of zinc sulfate solution in a zinc smelting factory,was investigated.The alkaline leaching method was proposed according to the mode of occurrence of arsenic in the slag and its amphoteric characteristic.The leaching experiments were conducted in the alkaline aqueous medium,with bubbling of oxygen into the solution,and the optimal conditions for leaching arsenic were determined.The results showed that the extraction rate of arsenic was maximized at 99.10%under the optimal conditions of temperature 140 ℃,NaOH concentration 150 g/L,oxygen partial pressure 0.5 MPa,and a liquid-to-solid ratio 5:1.Based on the solubilities of As2O5,ZnO and PbO in NaOH solution at 25 ℃,a method for the separation of As in the form of sodium arsenate salt from the arsenic-rich leachate via cooling crystallization was established,and the reaction medium could be fully recycled.The crystallization rate was confirmed to reach 88.9%(calculated on the basis of Na3AsO4) upon a direct cooling of the hot leachate down to room temperature.On the basis of redox potentials,the sodium arsenate solution could be further reduced by sulfur dioxide(SO2) gas to arsenite,at a reduction yield of 92%under the suitable conditions.Arsenic trioxide with regular octahedron shape could be prepared successfully from the reduced solution,and further recycled to the purification process to purify the zinc sulfate solution.Also,sodium arsenite solution obtained after the reduction of arsenate could be directly used to purify the zinc sulfate solution.Therefore,the technical scheme of alkaline leaching with pressured oxygen,cooling crystallization,arsenate reduction by SO2 gas,and arsenic trioxide preparation,provides an attractive approach to realize the resource utilization of arsenic-containing cobalt and nickel slag.展开更多
In order to utilize slag discarded by nickel plants, the selective recovery of nickel and copper versus iron was investigated by selective reduction, which was achieved by controlling the reduction parameters and magn...In order to utilize slag discarded by nickel plants, the selective recovery of nickel and copper versus iron was investigated by selective reduction, which was achieved by controlling the reduction parameters and magnetic separation process on bench scale. The results show that increasing the basicity (mass ratio of CaO to SIO2) of nickel slag facilitates the enrichment of nickel and copper The process parameters for selective reduction were optimized as follows: basicity of 0.15, reducing at 1200 ~C for 20 min, 5% coal on a dried slag mass base. The grinding-magnetic separation results of reduced briquettes show that concentrate containing 3.25%Ni, 1.20%Cu and 75.26%Fe is obtained and selective enrichment is achieved with a recovery of 82.20%, 80.00% for nickel and copper respectively, while the recovery of iron is only 42.17%. The S and P contents are not reduced obviously and further research may be needed to examine the behaviors of S and P in the process.展开更多
The influence of Zr and Y on the cast microstructure of a nickel-based superalloy was investigated by optical microscopy (OM),scanning electron microscopy(SEM),electron probe micro-analysis(EPMA)and X-ray diffra...The influence of Zr and Y on the cast microstructure of a nickel-based superalloy was investigated by optical microscopy (OM),scanning electron microscopy(SEM),electron probe micro-analysis(EPMA)and X-ray diffraction(XRD).Theγ+γ′eutectic volume in the superalloy rises notably with the increase of Zr or Y content.Meanwhile,the morphologies of primary MC carbides change from needle and platelet-like to blocky shape with increasing Zr and Y doped.The XRD results show that the primary MC carbide lattice constant increases with Zr and Y additions,and EPMA investigation shows that the platelet-like MC carbides contain primarily Nb and C,while those carbides in blocky shape have 39.2%Zr and 39.6%Nb in average,.These influences on the cast microstructure can be attributed to the atomic size effects of Zr and Y.展开更多
The electrodeposition behaviors of nickel on glassy carbon(GC) and carbon steel(CS) electrodes were investigated in the14.3%-85.7%(mole fraction) betaine.HCl ethylene glycol(EG) ionic liquid using cyclic volta...The electrodeposition behaviors of nickel on glassy carbon(GC) and carbon steel(CS) electrodes were investigated in the14.3%-85.7%(mole fraction) betaine.HCl ethylene glycol(EG) ionic liquid using cyclic voltammetry and chronoamperometry.The results indicated that the reduction of Ni(Ⅱ) on CS electrode via a diffusion-controlled quasi-reversible process was much more facile and easier than that occurred on GC electrode,which followed a diffusion-controlled three-dimensional instantaneous nucleation and growth.Scanning electron microscopy was used to observe that the deposit was dense and contained fine crystallites with average size of(80±4) nm.Energy dispersive spectrometer analysis showed that the obtained deposit was metallic nickel.X-ray diffraction spectroscopy indicated that(111) plane was the most preferred crystal orientation.The nickel deposit was luminous and bright,and had good adhesion with the CS substrate.展开更多
基金supported by the Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Ministry of Education(2019R1A6C1010042,2021R1A6C103A427)the financial support from the National Research Foundation of Korea(NRF)(2022R1A2C2010686,2022R1A4A3033528,2021R1I1A1A01060380,2021R1C1C2010726,2019H1D3A1A01071209)。
文摘The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and Cu_(2)O/Ni O/NF electrodes via in situ pulsed laser irradiation in liquids(PLIL)for the bifunctional electrocatalysis of oxygen evolution reaction(OER)and furfural oxidation reaction(FOR),respectively.Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu_(2)O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR.CoO/NiO/NF electrocatalyst provides a consistently low overpotential of~359 m V(OER)at 10 m A/cm^(2),achieving the maximum FA yield(~16.37 m M)with 61.5%selectivity,79.5%carbon balance,and a remarkable Faradaic efficiency of~90.1%during 2 h of FOR at 1.43 V(vs.reversible hydrogen electrode).Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates(NiOOH and CoOOH)as surface-active centers during electrochemical oxidation.The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products.This method holds promise for large-scale applications,enabling simultaneous production of renewable building materials and fuel.
基金Project supported by the Natural Science Foundation of Beijing(Grant No.Z200013)the Beijing Municipal Science&Technology(Grant No.Z191100004719001)the National Natural Science Foundation of China(Grant Nos.52325207 and 22005333)。
文摘Li/Ni mixing negatively influences the discharge capacity of lithium nickel oxide and high-nickel ternary cathode materials.However,accurately measuring the Li/Ni mixing degree is difficult due to the preferred orientation of labbased XRD measurements using Bragg–Brentano geometry.Here,we find that employing spherical harmonics in Rietveld refinement to eliminate the preferred orientation can significantly decrease the measurement error of the Li/Ni mixing ratio.The Li/Ni mixing ratio obtained from Rietveld refinement with spherical harmonics shows a strong correlation with discharge capacity,which means the electrochemical capacity of lithium nickel oxide and high-nickel ternary cathode can be estimated by the Li/Ni mixing degree.Our findings provide a simple and accurate method to estimate the Li/Ni mixing degree,which is valuable to the structural analysis and screening of the synthesis conditions of lithium nickel oxide and high-nickel ternary cathode materials.
基金supported by The Chinese Academy of Sciences (CAS) President’s International Fellowship Initiative (No. 2023VCB0014)The National Natural Science Foundation of China (No. 52203284)Shenzhen Science and Technology Program (Nos. GJHZ20220913143801003 and RCBS20221008093057026)
文摘Economical water electrolysis requires highly active non-noble electrocatalysts to overcome the sluggish kinetics of the two half-cell reactions,oxygen evolution reaction,and hydrogen evolution reaction.Although intensive efforts have been committed to achieve a hydrogen economy,the expensive noble metal-based catalysts remain under consideration.Therefore,the engineering of self-supported electrocatalysts prepared using a direct growth strategy on three-dimensional(3D)nickel foam(NF)as a conductive substrate has garnered significant interest.This is due to the large active surface area and 3D porous network offered by these electrocatalysts,which can enhance the synergistic eff ect between the catalyst and the substrate,as well as improve electrocatalytic performance.Hydrothermal-assisted growth,microwave heating,electrodeposition,and other physical methods(i.e.,chemical vapor deposition and plasma treatment)have been applied to NF to fabricate competitive electrocatalysts with low overpotential and high stability.In this review,recent advancements in the development of self-supported electrocatalysts on 3D NF are described.Finally,we provide future perspectives of self-supported electrode platforms in electrochemical water splitting.
基金the financial support from the High-Tech Industry Technology Innovation Leading Plan of Hunan Province,China(2020GK2032)the Innovation Driven Program of Central South University(CSU)(2019CX006)the Research Fund of the Key Laboratory of High Performance Complex Manufacturing at CSU。
文摘Ultra fine-grained pure metals and their alloys have high strength and low ductility.In this study,cryorolling under different strains followed by low-temperature short-time annealing was used to fabricate pure nickel sheets combining high strength with good ductility.The results show that,for different cryorolling strains,the uniform elongation was greatly increased without sacrificing the strength after annealing.A yield strength of 607 MPa and a uniform elongation of 11.7%were obtained after annealing at a small cryorolling strain(ε=0.22),while annealing at a large cryorolling strain(ε=1.6)resulted in a yield strength of 990 MPa and a uniform elongation of 6.4%.X-ray diffraction(XRD),transmission electron microscopy(TEM),scanning electron microscopy(SEM),and electron backscattered diffraction(EBSD)were used to characterize the microstructure of the specimens and showed that the high strength could be attributed to strain hardening during cryorolling,with an additional contribution from grain refinement and the formation of dislocation walls.The high ductility could be attributed to annealing twins and micro-shear bands during stretching,which improved the strain hardening capacity.The results show that the synergistic effect of strength and ductility can be regulated through low-temperature short-time annealing with different cryorolling strains,which provides a new reference for the design of future thermo-mechanical processes.
基金financially supported by National Natural Science Foundation of China(No.22209049,22075102,22005120)Natural Science Foundation of Guangdong Province(No.2023A1515012804)Fundamental Research Funds for the Central Universities(No.2022ZYGXZR048)。
文摘Nickel-based materials,including metallic Ni and Ni oxide,have been widely studied in the exploration of non-precious-metal hydrogen electrocatalysts,but neither pure Ni nor NiO is ideal for the hydrogen evolution reaction(HER)and hydrogen oxidation reaction(HOR).In this paper,an oxygen insertion strategy was applied on nickel to regulate its hydrogen electrocatalytic performance,and the oxygen-inserted nickel catalyst was successfully obtained with the assistance of tungsten dioxide support(denoted as O-Ni/WO_(2)).The partial insertion of oxygen in Ni maintains the face-centered cubic arrangement of Ni atoms,simultaneously expanding the lattice and increasing the lattice spacing.Consequently,the adsorption strength of^(*)H and^(*)OH on Ni is optimized,thus resulting in superior electrocatalytic performance of0-Ni/WO_(2)in alkaline HER/HOR.The Tafel slope of O-Ni/WO_(2)@NF for HER is 56 mV dec^(-1),and the kinetic current density of O-Ni/WO_(2)for HOR reaches 4.85 mA cm^(-2),which is ahead of most currently reported catalysts.Our proposed strategy of inserting an appropriate amount of anions into the metal lattice could provide more possibilities for the design of high-performance catalysts.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFA1402203)the National Natural Science Foundation of China(Grant No.12174065)supported by the Shenzhen Fundamental Research Program(Grant Nos.JCYJ20220818100405013 and JCYJ20230807093204010)。
文摘By using muon spin relaxation(μSR)measurements,we perform a comparative study of the microscopic magnetism in the parent compounds of infinite-layer nickelate superconductors RNiO_(2)(R=La,Nd).In either compound,the zero-fieldμSR spectra down to the lowest measured temperature reveal no long-range magnetic order.In LaNiO_(2),short-range spin correlations appear below T=150 K,and spins fully freeze below T∼10 K.NdNiO_(2)exhibits a more complex spin dynamics driven by the Nd 4f and Ni3d electron spin fluctuations.Further,it shows features suggesting the proximity to a spin-glass state occurring below T=5 K.In both compounds,the spin behavior with temperature is further confirmed by longitudinal-field μSR measurements.These results provide new insight into the magnetism of the parent compounds of the superconducting nickelates,crucial to understanding the microscopic origin of their superconductivity.
基金supported by the National Natural Science Foundation of China(52203016)the USTC Research Funds of the Double First-Class Initiative(YD9990002018)+3 种基金the Overseas Students Innovation and Entrepreneurship Support Program Project of Anhui Province(2021LCX022)the Key R&D Projects in Anhui Province(2022i01020012)the Natural Science Foundation of Hefei(2022039)the Excellent Research and Innovation Team Project of Anhui Province(2022AH010001).
文摘α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.
基金supported by the Ministry of Science and Higher Education of the Russian Federation within governmental order for Boreskov Institute of Catalysis SB RAS (projects FWUR-2024–0038, FWUR-2024–0032 and FWUR2024–0039)
文摘An effect of Mg introduction on efficiency of high-loaded nickel catalysts in dehydrogenation of decahydroquinoline(10HQ)was inves-tigated.10HQ dehydrogenation is key process for the liquid organic hydrogen carrier(LOHC)storage technology using the quinoline/10HQ pair as H_(2)-lean/H_(2)-rich substrates.An influence of synthesis technique of Ni/Mg/Al catalysts on their properties has been demonstrated.The catalysts were synthesized through coprecipitation of Ni,Mg,Al precursors to obtain layered double hydroxides(LDH)or via syn-thesis of(∼72 wt%)Ni-Al_(2)O_(3) system-also through coprecipitation,followed by modifying with a magnesium-containing precursor.For the catalysts of the first series,the inclusion of magnesium into LDH lattice led to a significant increase in catalytic activity in hydrogen extraction(10HQ dehydrogenation reaction).Despite the decrease in the content of catalytically active nickel,a significant increase in the yield of the dehydrogenation product was observed.This regularity is presumably associated with appearance of basic sites,that accelerates the dehydrogenation reaction.In the case of the second series,activity of pre-reduced(600°C,H_(2))catalysts in dehydrogenation of 10HQ also significantly depends on a MgO content and is maximal at Mg:Ni weight ratio 0.056.Using an in-depth study of structure of the original and reduced catalyst samples(Ni-Al_(2)O_(3) and Ni-MgNiOx-Al_(2)O_(3)),it was shown that this regularity is associated with the increased resistance of catalytically active Ni particles to agglomeration during the reductive activation.Also,using the Ni-MgNiOx-Al_(2)O_(3)catalyst for hydrogen storage process(hydrogenation reaction),the possibility of deep quinoline hydrogenation(up to 10HQ)in a flow-type reactor was demonstrated for the first time.
基金the insightful discussions with Prof.Dongsheng Song.Project supported by the National Natural Science Foundation of China(Grant No.52172115)the Guangdong Provincial Key Laboratory Program from the Department of Science and Technology of Guangdong Province(Grant No.2021B1212040001)+2 种基金Guangdong Basic and Applied Basic Research Foundation(Grant No.2022A1515012434)Shenzhen Science and Technology Program(Grant No.20231121093057002)Natural Science Foundation of Guangdong Province,China(Grant No.2022A1515010762).
文摘The discovery of nickelate superconductors,including doped infinite-layer(IL)nickelates RNiO2(R=La,Pr,Nd),layered square-planar nickelate Nd6Ni5O12,and the Ruddlesden–Popper(RP)phase La3Ni2O7,has spurred immense interest in fundamental research and potential applications.Scanning transmission electron microscopy(STEM)has proven crucial for understanding structure–property correlations in these diverse nickelate superconducting systems.In this review,we summarize the key findings from various modes of STEM,elucidating the mechanism of different nickelate superconductors.We also discuss future perspectives on emerging STEM techniques for unraveling the pairing mechanism in the“nickel age”of superconductivity.
基金financial support from the National Key Research and Development Program of China(2020YFA0710202)the National Natural Science Foundation of China(21978043,U1662130)+1 种基金Inner Mongolia University of Technology Scientific Research Initial Funding(DC2300001240)Talent Introduction Support Project of Inner Mongolia(DC2300001426).
文摘As a common precursor for supercritical CO_(2)(scCO_(2))deposition techniques,solubility data of organometallic complexes in scCO_(2)is crucial for the preparation of nanocomposites.Recently,metal acetylacetonates have shown great potential for the preparation of single-atom catalytic materials.In this study,the solubilities of iron(Ⅲ)acetylacetonate(Fe(acac)3)and nickel(Ⅱ)acetylacetonate(Ni(acac)2)were measured at the temperature from 313.15 to 333.15 K and in the pressure range of 9.5–25.2 MPa to accumulate new solubility data.Solubility was measured using a static weight loss method.The semi-empirical models proposed by Chrastil and Sung et al.were used to correlate the solubility data of Fe(acac)3 and Ni(acac)2.The equations obtained can be used to predict the solubility of the same system in the experimental range.
基金funded by the Key R&D Program of Jilin Province(20220201132GX)the Key R&D Program of Hubei Province(2022BAA084)the Open Funds of the State Key Laboratory of Rare Earth Resource Utilization(RERU2023008)。
文摘Ultra-high nickel cobalt-free lithium layered oxides are promising cathode material for lithium-ion batteries(LIBs)because of their relatively high capacity and low cost.Nevertheless,the high nickel content would induce bulk structure degradation and interfacial environment deterioration,and the absence of Co element reduces the lithium diffusion kinetics,severely limiting the performance liberation of this kind of cathodes.Herein,a multifunctional Ti/Zr dual cation co-doping strategy has been employed to improve the lithium storage performance of LiNi_(0.9)Mn_(0.1)O_(2)(NM91)cathode.On the one hand,the Ti/Zr co-doping weakens the Li^(+)/Ni^(2+)mixing through magnetic interactions due to the inexistence of unpaired electrons for Ti^(4+)and Zr^(4+),increasing the lithium diffusion rate and suppressing the harmful coexistence of H1 and H2 phases.On the other hand,they enhance the lattice oxygen stability because of the strong Ti-O and Zr-O bonds,inhibiting the undesired H3 phase transition and lattice oxygen loss,improving the bulk structure and cathode-electrolyte interface stability.As a result,the Ti/Zr co-doped NM91(NMTZ)exhibits a 91.2%capacity retention rate after 100 cycles,while that of NM91 is only82.9%.Also,the NMTZ displays better rate performance than NM91 with output capacities of 115 and93 mA h g^(-1)at a high current density of 5 C,respectively.Moreover,the designed NMTZ could enable the full battery to deliver an energy density up to 263 W h kg^(-1),making the ultra-high nickel cobaltfree lithium layered oxide cathode closer to practical applications.
基金Projects(51174104,50874053)supported by the National Natural Science Foundation of ChinaProject(2009AA06Z106)supported by Hi-Tech Research and Development Program of ChinaProject(20115314110001)supported by Doctoral Fund of Ministry of Education of China
文摘A direct hydrometallurgical route for nickel and molybdenum extraction from a nickel-molybdenum (Ni-Mo) ore using pressure acid leaching was studied. The nickel and molybdenum were extracted by acid leaching under oxygen pressure. Compared with traditional roasting methods, this hydrometallurgical method eliminates SO2 and As203 emission (the Ni-Mo ore containing 15%-25% S). Compared with existing alkali leaching recovery of molybdenum process, almost all the nickel and considerable molybdenum were extracted in the acid leaching process. Under oxygen pressure conditions, almost all the nickel and a substantial part of the molybdenum were dissolved into the acid leaching liquor and the other part of the molybdenum was left in the acid leach residue. The acid leach residue was further leached under alkaline (NaOH) conditions. Under optimal experimental conditions, the extraction rates nickel and molybdenum reached 97% and 96%, respectively.
基金Project (50974135) supported by the National Natural Science Foundation of China
文摘To acquire understanding of Ni enrichment from laterite ore,the mineralogy and crystal chemistry of a low grade limonite type nickel laterite ore sample assaying 0.97% Ni from Indonesia were studied using optical microscopy,X-ray diffraction(XRD),scanning electron microscopy(SEM) and electron probe microanalysis(EPMA).According to EPMA results,the mineral includes 80% goethite((Fe,Ni,Al)O(OH)) with 0.87% Ni,15% silicate minerals with lizardite((Mg,Fe,Ni)3Si2O5(OH)) and olivine((Mg,Fe,Ni)2SiO4),and 1.19% Ni,and other minor phases,such as hematite,maghemite,chromite and quartz,and no Ni was detected.The mineralogy of the laterite ore indicates that due to the complicated association of the various phases and the variable distribution of Ni,this refractory laterite ore can not be upgraded by traditional physical beneficiation processes.
基金Project(2012BAB10B04) supported by National Key Technology R&D Program of ChinaProject supported by Hunan Provincial Innovation Foundation for Postgraduate,China
文摘Fine nickel ferrite precursors NiFe2(C204)3·6H2O were obtained via co-precipitation method with low grade nickel matte as the raw material. Thermodynamic analysis of NiClz-FeC12-(NH4)2C204-H20 system for precipitation identified that the theoretical optimum co-precipitation pH value is 2, and C2O2 has strong complexation with Ni2+ and Fe2+ ions. Based on these theoretical considerations, the effects of parameters on the precipitation rates and precursors size were investigated systematically. The results show that the optimum co-precipitation conditions are pH=2, temperature 45 ℃, 1.2 times theoretical amount of (NH4)2C204 dosage and 3% PEG400 addition. Under these conditions, the precipitation rates of Ni2+ and Fe2+ are both over 99.8%, with the precursors size of 1-2 urn. Furthermore, X-ray diffraction (XRD) and thermogravimetry-differential thermal analysis (TG-DTA) demonstrate that the precursors are single-phase solid solution, wherein the nickel/iron atoms are replaced by the iron/nickel atoms reciprocally.
文摘Electrochemical detection of 3-methyl-4-nitrophenol (MNP) in direct phenol oxidation occurs at high potentials and generally leads to progressive passivation of the electrochemical sensor. This study describes the use of a carbon fiber microelectrode modified with a tetrasulfonated nickel phthalocyanine complex for the detection of MNP at a lower potential than that of direct phenol oxidation. The MNP voltammogram showed the presence of an anodic peak at -0.11 V vs SCE, corresponding to the oxidation of the hydroxylamine group generated after the reduction of the nitro group. The effect of buffer pH on the peak current and SWV parameters such as frequency, scan increment, and pulse amplitude were studied and optimized to have better electrochemical response of the proposed sensor. With these optimal parameters, the calibration curve shows that the peak current varied linearly as a function of MNP concentration, leading to a limit of detection (LoD) of 1.1 μg/L. These results show an appreciable sensitivity of the sensor for detecting the MNP at relatively low potentials, making it possible to avoid passivation phenomena.
文摘Hydrogen energy has become one of the recognized clean energy sources worldwide due to its advantages such as low cost,renewable energy,and green environmental protec-tion.Electrolytic water is currently one of the most promising solutions for providing hydrogen fuel.Nickel iron bimetallic electrocatalysts have abundant sources,low cost,clean and pollution-free properties,and strong catalytic performance,This article mainly reviews the development and research of bimetallic nickel iron oxides and nickel iron alloys in recent years,and explores their synthesis methods,properties,and stability in depth.
基金Project (2012BAC12B01) supported by the National Key Technologies R&D Program of ChinaProject (2012FJ1010) supported by Science and Technology Major Project of Hunan Province,China
文摘The arsenic extraction from the arsenic-containing cobalt and nickel slag,which came from the purification process of zinc sulfate solution in a zinc smelting factory,was investigated.The alkaline leaching method was proposed according to the mode of occurrence of arsenic in the slag and its amphoteric characteristic.The leaching experiments were conducted in the alkaline aqueous medium,with bubbling of oxygen into the solution,and the optimal conditions for leaching arsenic were determined.The results showed that the extraction rate of arsenic was maximized at 99.10%under the optimal conditions of temperature 140 ℃,NaOH concentration 150 g/L,oxygen partial pressure 0.5 MPa,and a liquid-to-solid ratio 5:1.Based on the solubilities of As2O5,ZnO and PbO in NaOH solution at 25 ℃,a method for the separation of As in the form of sodium arsenate salt from the arsenic-rich leachate via cooling crystallization was established,and the reaction medium could be fully recycled.The crystallization rate was confirmed to reach 88.9%(calculated on the basis of Na3AsO4) upon a direct cooling of the hot leachate down to room temperature.On the basis of redox potentials,the sodium arsenate solution could be further reduced by sulfur dioxide(SO2) gas to arsenite,at a reduction yield of 92%under the suitable conditions.Arsenic trioxide with regular octahedron shape could be prepared successfully from the reduced solution,and further recycled to the purification process to purify the zinc sulfate solution.Also,sodium arsenite solution obtained after the reduction of arsenate could be directly used to purify the zinc sulfate solution.Therefore,the technical scheme of alkaline leaching with pressured oxygen,cooling crystallization,arsenate reduction by SO2 gas,and arsenic trioxide preparation,provides an attractive approach to realize the resource utilization of arsenic-containing cobalt and nickel slag.
基金Project([2009]606)supported by the National Development and Reform Commission of ChinaProject(50974135)supported by the National Natural Science Foundation of China
文摘In order to utilize slag discarded by nickel plants, the selective recovery of nickel and copper versus iron was investigated by selective reduction, which was achieved by controlling the reduction parameters and magnetic separation process on bench scale. The results show that increasing the basicity (mass ratio of CaO to SIO2) of nickel slag facilitates the enrichment of nickel and copper The process parameters for selective reduction were optimized as follows: basicity of 0.15, reducing at 1200 ~C for 20 min, 5% coal on a dried slag mass base. The grinding-magnetic separation results of reduced briquettes show that concentrate containing 3.25%Ni, 1.20%Cu and 75.26%Fe is obtained and selective enrichment is achieved with a recovery of 82.20%, 80.00% for nickel and copper respectively, while the recovery of iron is only 42.17%. The S and P contents are not reduced obviously and further research may be needed to examine the behaviors of S and P in the process.
基金Project supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions,China
文摘The influence of Zr and Y on the cast microstructure of a nickel-based superalloy was investigated by optical microscopy (OM),scanning electron microscopy(SEM),electron probe micro-analysis(EPMA)and X-ray diffraction(XRD).Theγ+γ′eutectic volume in the superalloy rises notably with the increase of Zr or Y content.Meanwhile,the morphologies of primary MC carbides change from needle and platelet-like to blocky shape with increasing Zr and Y doped.The XRD results show that the primary MC carbide lattice constant increases with Zr and Y additions,and EPMA investigation shows that the platelet-like MC carbides contain primarily Nb and C,while those carbides in blocky shape have 39.2%Zr and 39.6%Nb in average,.These influences on the cast microstructure can be attributed to the atomic size effects of Zr and Y.
基金Projects(51274108,21263007,51204080)supported by the National Natural Science Foundation of ChinaProject(2011FA009)supported by the Applied Research Foundation of Yunnan Province,ChinaProject(14118441)supported by the Talents Cultivation Foundation of Kunming University of Science and Technology,China
文摘The electrodeposition behaviors of nickel on glassy carbon(GC) and carbon steel(CS) electrodes were investigated in the14.3%-85.7%(mole fraction) betaine.HCl ethylene glycol(EG) ionic liquid using cyclic voltammetry and chronoamperometry.The results indicated that the reduction of Ni(Ⅱ) on CS electrode via a diffusion-controlled quasi-reversible process was much more facile and easier than that occurred on GC electrode,which followed a diffusion-controlled three-dimensional instantaneous nucleation and growth.Scanning electron microscopy was used to observe that the deposit was dense and contained fine crystallites with average size of(80±4) nm.Energy dispersive spectrometer analysis showed that the obtained deposit was metallic nickel.X-ray diffraction spectroscopy indicated that(111) plane was the most preferred crystal orientation.The nickel deposit was luminous and bright,and had good adhesion with the CS substrate.