Electrokinetic-mechanism of water and furfural oxidation on pulsed laser-interlaced Cu_(2)O and CoO on nickel foam

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.

Achieving High Strength and Tensile Ductility in Pure Nickel by Cryorolling with Subsequent Low-Temperature Short-Time Annealing

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.

Enhancing hydrogen evolution and oxidation kinetics through oxygen insertion into nickel lattice

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.

Efficiency of high-loaded nickel catalysts modified by Mg in hydrogen storage/extraction using quinoline/decahydroquinoline pair as LOHC substrates

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.

Nickel catalysts with asymmetric steric hindrance for ethylene polymerization

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.

Probing nickelate superconductors at atomic scale:A STEM review

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.

Microscopic Magnetism of Nickel-Based Infinite-Layer Superconducting Parent Compounds RNiO_(2)(R=La,Nd):A μSR Study

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.

Accurate estimation of Li/Ni mixing degree of lithium nickel oxide cathode materials

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.

Engineering of Self-Supported Electrocatalysts on a Three-Dimensional Nickel Foam Platform for Efficient Water Electrolysis

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.

Solubility of iron(Ⅲ) and nickel(Ⅱ) acetylacetonates in supercritical carbon dioxide

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.

A universal multifunctional dual cation doping strategy towards stabilized ultra-high nickel cobalt-free lithium layered oxide cathode

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.

Indirect Electroanalysis of 3-Methyl-4-Nitrophenol in Water Using Carbon Fiber Microelectrode Modified with Nickel Tetrasulfonated Phthalocyanine Complex

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.

Research Progress of Nickel Iron Bimetallic Series Electrocatalytic Materials

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.

Nickel single atom overcoordinated active sites to accelerate the electrochemical reaction kinetics for Li-S cathode

Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their applications.Herein,single nickel(Ni)atoms on two-dimensional(2D)nitrogen(N)-doped carbon with Ni-N_(4)-O overcoordinated structure(SANi-N_(4)-O/NC)are prepared and firstly used as a sulfur host of Li-S batteries.Due to the efficient polysulfides traps and highly LiPSs conversion effect of SANi-N_(4)-O/NC,the electrochemical performance of Li-S batteries obviously improved.The batteries can well operate even under high sulfur loading(5.8 mg cm^(-2))and lean electrolyte(6.1μL mg^(-1))condition.Meanwhile,density functional theory(DFT)calculations demonstrate that Ni single atom’s active sites decrease the energy barriers of conversion reactions from Li_(2)S_(8)to Li2S due to the strong interaction between SANi-N_(4)-O/NC and LiPSs.Thus,the kinetic conversion of LiPSs was accelerated and the shuttle effect is suppressed on SANi-N_(4)-O/NC host.This study provides a new design strategy for a 2D structure with single-atom overcoordinated active sites to facilitate the fast kinetic conversion of LiPSs for Li-S cathode.

Comparative structural and electrochemical properties of mixed P2/O′3-layered sodium nickel manganese oxide prepared by sol-gel and electrospinning methods:Effect of Na-excess content

The effect of Na-excess content in the precursor on the structural and electrochemical performances of sodium nickel manganese oxide(NNMO)prepared by sol-gel and electrospinning methods is investigated in this paper.X-ray diffraction results of the prepared NNMO without adding Na-excess content indicate sodium loss,while the mixed phase of P2/O′3-type layered NNMO presented after adding Na-excess content.Compared with the sol-gel method,the secondary phase of NiO is more suppressed by using the electrospinning method,which is further confirmed by field emission scanning electron microscope images.N_(2) adsorption-desorption isotherms show no remarkably difference in specific surface areas between different preparation methods and Na-excess contents.The analysis of X-ray absorption near edge structure indicates that the oxidation states of Ni and Mn are+2 and+4,respectively.For the electrochemical properties,superior electrochemical performance is observed in the NNMO electrode with a low Na-excess content of 5wt%.The highest specific capacitance is 36.07 F·g^(-1)at0.1 A·g^(-1)in the NNMO electrode prepared by using the sol-gel method.By contrast,the NNMO electrode prepared using the electrospinning method with decreased Na-excess content shows excellent cycling stability of 100%after charge-discharge measurements for 300 cycles.Therefore,controlling the Na excess in the precursor together with the preparation method is important for improving the electrochemical performance of Na-based electrode materials in supercapacitors.

In situ formed ultrafine metallic Ni from nickel(Ⅱ) acetylacetonate precursor to realize an exceptional hydrogen storage performance of MgH_(2)-Ni-EG nanocomposite

It has been well known that doping nano-scale catalysts can significantly improve both the kinetics and reversible hydrogen storage capacity of MgH_(2) . However, so far it is still a challenge to directly synthesize ultrafine catalysts(e.g., < 5 nm), mainly because of the complicated chemical reaction processes. Here, a facile one-step high-energy ball milling process is developed to in situ form ultrafine Ni nanoparticles from the nickel acetylacetonate precursor in the MgH_(2) matrix. With the combined action of ultrafine metallic Ni and expanded graphite(EG), the formed MgH_(2)-Ni-EG nanocomposite with the optimized doping amounts of Ni and EG can still release 7.03 wt.% H_(2) within 8.5 min at 300 ℃ after 10 cycles. At a temperature close to room temperature(50 ℃), it can also absorb 2.42 wt.% H_(2) within 1 h. It can be confirmed from the microstructural characterization analysis that the in situ formed ultrafine metallic Ni is transformed into Mg_(2)Ni/Mg_(2)NiH_4 in the subsequent hydrogen absorption and desorption cycles. It is calculated that the dehydrogenation activation energy of the MgH_(2)-Ni-EG nanocomposite is also reduced obviously in comparison with the pure MgH_(2) . Our work provides a methodology to significantly improve the hydrogen storage performance of MgH_(2) by combining the in situ formed and uniformly dispersed ultrafine metallic catalyst from the precursor and EG.

Metal-organic decomposition growth of thin film metastable perovskite nickelates with kinetically improved quantum transitions

The multiple quantum transitions within d-band correlation oxides such as rare-earth nickelates(RENiO_(3))triggered by critical temperatures and/or hydrogenation opened up a new paradigm for correlated electronics applications,e.g.ocean electric field sensor,bio-sensor,and neuron synapse logical devices.Nevertheless,these applications are obstructed by the present ineffectiveness in the thin film growth of the metastable RENiO_(3)with flexibly adjustable rare-earth compositions and electronic structures.Herein,we demonstrate a metal-organic decompositions(MOD)approach that can effectively grow metastable RENiO_(3)covering a large variety of the rare-earth composition without introducing any vacuum process.Unlike the previous chemical growths for RENiO_(3)relying on strict interfacial coherency that limit the film thickness,the MOD growth using reactive isooctanoate percussors is tolerant to lattice defects and therefore achieves comparable film thickness to vacuum depositions.Further indicated by positron annihilation spectroscopy,the RENiO_(3)grown by MOD exhibit large amount of lattice defects that improves their hydrogen incorporation amount and electron transfers,as demonstrated by the resonant nuclear reaction analysis and near edge X-ray absorption fine structure analysis.This effectively enlarges the magnitude in the resistance regulations in particular for RENiO_(3)with lighter RE,shedding a light on the extrinsic regulation of the hydrogen induced quantum transitions for correlated oxides semiconductors kinetically via defect engineering.

Tuned d-band states over lanthanum doped nickel oxide for efficient oxygen evolution reaction

The d-band state of materials is an important descriptor for activity of oxygen evolution reaction(OER).For NiO materials,there is rarely concern about tuning their d-band states to tailor the OER behaviors.Herein,NiO nanocrystals with doping small amount of La^(3+)were used to regulate d-band states for promoting OER activity.Density of states calculations based on density functional theory revealed that La^(3+)doping produced upper shift of d-band center,which would induce stronger electronic interaction between surface Ni atoms and species of oxygen evolution reaction intermediates.Further density functional theory calculation illustrated that La^(3+)doped NiO possessed reduced Gibbs free energy in adsorbing species of OER intermediate.Predicted by theoretical calculations,trace La^(3+)was introduced into crystal lattice of NiO nanoparticles.The La^(3+)doped NiO nanocrystal showed much promoted OER activity than corresponding pristine NiO product.Further electrochemical analysis revealed that La^(3+)doping into NiO increased the intrinsic activity such as improved active sites and reduced charge transfer resistance.The in-situ Raman spectra suggested that NiO phase in La^(3+)doped NiO could be better maintained than pristine NiO during the OER.This work provides an effective strategy to tune the d-band center of NiO for efficient electrocatalytic OER.

Peripheral octamethyl-substituted nickel(Ⅱ)-phthalocyanine-decorated carbon-nanotube electrodes for high-performance all-solid-state flexible symmetric supercapacitors

Construction of advanced electrode materials with unique performance for supercapacitors(SCs)is essential to achieving high implementation in the commercial market.Here,we report a novel peripheral octamethyl-substituted nickel(Ⅱ)phthalocyanine(Ni Me_(2)Pc)-based nanocomposite as the electrode material of all-solid-state SCs.The highly redox-active NiMe_(2)Pc/carboxylated carbon nanotube(CNTCOOH)dendritic nanocomposite provides rapid electron/electrolyte ion-transport pathways and exhibits excellent structural stability,resulting in high-capacity activity and impressive cycling stability.The composite prepared with the optimized weight ratio of Ni Me_(2)Pc:CNT-COOH(6:10)showed the highest specific capacitance of 330.5 F g^(-1)at 0.25 A g^(-1).The constructed NiMe_(2)Pc/CNT-COOH-based all-solid-state symmetric SC device showed excellent performance with a maximum energy density of 22.8 Wh kg^(-1)and outstanding cycling stability(111.6%retained after 35,000 cycles).Moreover,flexible carbon cloth significantly enhanced the energy density of the NiMe_(2)Pc/CNT-COOH all-solid-state symmetric device to 52.1 Wh kg^(-1)with 95.4%capacitance retention after 35,000 cycles,and it could be applied to highperformance flexible electronics applications.These findings provide a novel strategy to design phthalocyanine-based electrode materials for next-generation flexible SC devices.

Concentration-Dependent Effect of Nickel Ions on Amyloid Fibril Formation Kinetics of Hen Egg White Lysozyme:a Raman Spectroscopy Study

Nickel,an important transi-tion metal element,is one of the trace elements for hu-man body and has a crucial impact on life and health.Some evidences show the excess exposure to metal ions might be associated with neurological diseases.Herein,we applied Raman spectroscopy to study the Ni(II)ion effect on kinetics of amyloid fibrillation of hen egg white lysozyme(HEWL)in thermal and acidic conditions.Using the well-known Raman indicators for protein tertiary and secondary structures,we monitored and analyzed the concentration effect of Ni(II)ions on the unfolding of tertiary structures and the transformation of sec-ondary structures.The experimental evidence validates the accelerator role of the metal ion in the kinetics.Notably,the additional analysis of the amide I band profile,combined with thioflavin-T fluorescence assays,clearly indicates the inhibitory effect of Ni(II)ions on the formation of amyloid fibrils with organizedβ-sheets structures.Instead,a more significant promotion influence is affirmed on the assembly into other aggregates with disordered struc-tures.The present results provide rich information about the specific metal-mediated protein fibrillation.