Because of their low electrical conductivity,sluggish ion diffusion,and poor stability,conventional electrode materials are not able to meet the growing demands of energy storage and portable devices.Graphene assemble...Because of their low electrical conductivity,sluggish ion diffusion,and poor stability,conventional electrode materials are not able to meet the growing demands of energy storage and portable devices.Graphene assembled films(GAFs)formed from graphene nanosheets have an ultrahigh conductivity,a unique 2D network structure,and exceptional mechanical strength,which give them the potential to solve these problems.However,a systematic understanding of GAFs as an advanced electrode material is lacking.This review focuses on the use of GAFs in electrochemistry,providing a comprehensive analysis of their synthesis methods,surface/structural characteristics,and physical properties,and thus understand their structure-property relationships.Their advantages in batteries,supercapacitors,and electrochemical sensors are systematically evaluated,with an emphasis on their excellent electrical conductivity,ion transport kinetics,and interfacial stability.The existing problems in these devices,such as chemical inertness and mechanical brittleness,are discussed and potential solutions are proposed,including defect engineering and hybrid structures.This review should deepen our mechanistic understanding of the use of GAFs in electrochemical systems and provide actionable strategies for developing stable,high-performance electrode materials.展开更多
Detection of target analytes at low concentrations is significant in various fields,including pharmaceuticals,healthcare,and environmental protection.Theophylline(TP),a natural alkaloid used as a bronchodilator to tre...Detection of target analytes at low concentrations is significant in various fields,including pharmaceuticals,healthcare,and environmental protection.Theophylline(TP),a natural alkaloid used as a bronchodilator to treat respiratory disorders such as asthma,bronchitis,and emphysema,has a narrow therapeutic window with a safe plasma concentration ranging from 55.5-111.0μmol·L^(-1)in adults.Accurate monitoring of TP levels is essential because too low or too high can cause se-rious side effects.In this regard,non-enzymatic electrochemical sensors offer a practical solution with rapidity,portability,and high sensitivity.This article aims to provide a comprehensive review of the recent developments of non-enzymatic electrochemical sensors for TP detection,highlighting the basic principles,electro-oxidation mechanisms,catalytic effects,and the role of modifying materials on electrode performance.Carbon-based electrodes such as glassy carbon electrodes(GCEs),carbon paste electrodes(CPEs),and carbon screen-printed electrodes(SPCEs)have become the primary choices for non-enzymatic sensors due to their chemical stability,low cost,and flexibility in modification.This article identifies the sig-nificant contribution of various modifying materials,including nanomaterials such as carbon nanotubes(CNTs),graphene,metal oxides,and multi-element nanocomposites.These modifications enhance sensors’electron transfer,sensitivity,and selectivity in detecting TP at low concentrations in complex media such as blood plasma and pharmaceutical samples.The electro-oxidation mechanism of TP is also discussed in depth,emphasizing the hydroxyl and carbonyl reaction pathways strongly influenced by pH and electrode materials.These mechanisms guide the selection of the appropriate electrode ma-terial for a particular application.The main contribution of this article is to identify superior modifying materials that can improve the performance of non-enzymatic electrochemical sensors.In a recent study,the combination of multi-element nanocomposites based on titanium dioxide(TiO_(2)),CNTs,and gold nanoparticles(AuNPs)resulted in the lowest detection limit of 3×10^(-5)μmol·L^(-1),reflecting the great potential of these materials for developing high-performance electrochemical sensors.The main conclusion of this article is the importance of a multidisciplinary approach in electrode material design to support the sensitivity and selectivity of TP detection.In addition,there is still a research gap in understanding TP’s more detailed oxidation mechanism,especially under pH variations and complex environments.Therefore,further research on electrode modification and analysis of the TP oxidation mechanism are urgently needed to improve the accuracy and sta-bility of the sensor while expanding its applications in pharmaceutical monitoring and medical diagnostics.By integrating various innovative materials and technical approaches,this review is expected to be an essential reference for developing efficient and affordable non-enzymatic electrochemical sensors.展开更多
Pitch is a complex mixture of polycyclic aromatic hydrocarbons and their non-metal derivatives that has a high carbon content.Using pitch as a precursor for carbon materials in alkali metal ion(Li^(+)/Na^(+)/K^(+))bat...Pitch is a complex mixture of polycyclic aromatic hydrocarbons and their non-metal derivatives that has a high carbon content.Using pitch as a precursor for carbon materials in alkali metal ion(Li^(+)/Na^(+)/K^(+))batteries has become of great interest.However,its direct pyrolysis often leads to microstructures with a high orientation and small interlayer spacing due to uncontrolled liquid-phase carbonization,resulting in subpar electrochemical performance.It is therefore important to control the microstructures of pitch-derived carbon materials in order to improve their electrochemical properties.We evaluate the latest progress in the development of these materials using various microstructural engineering approaches,highlighting their use in metal-ion batteries and supercapacitors.The advantages and limitations of pitch molecules and their carbon derivatives are outlined,together with strategies for their modification in order to improve their properties for specific applications.Future research possibilities for structure optimization,scalable production,and waste pitch recycling are also considered.展开更多
Under the condition of solvothermal synthesis,the viologen ligand 1,1′-bis(3-carboxyphenyl)-(4,4′-bipyri-dine)dichloride(H_(2)bcbpy·2Cl)and KI are coordinated with the metal cadmium ions.A case of thermochromic...Under the condition of solvothermal synthesis,the viologen ligand 1,1′-bis(3-carboxyphenyl)-(4,4′-bipyri-dine)dichloride(H_(2)bcbpy·2Cl)and KI are coordinated with the metal cadmium ions.A case of thermochromic coor-dination polymer[Cd(bcbpy)I_(2)]·2H_(2)O(1)was constructed.Complex 1 displays a 1D chain structure and exhibits thermochromic behavior.Under different temperature stimulation,the complex(ground)slowly changed from green to yellow-green,and with the increase of temperature,the color of complex 1 gradually deepened,and finally became orange-yellow.Therefore,complex 1 was prepared as a thermochromic film.In addition,we also performed electrochemical tests on complex 1,which showed that the complex is a semiconductor material.CCDC:2391802.展开更多
Hanyu Xu 1,Xuedan Song 1,*,Qing Zhang 1,Chang Yu 1,Jieshan Qiu 1,2,*1 Liaoning Key Lab for Energy Materials and Chemical Engineering,State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian Univers...Hanyu Xu 1,Xuedan Song 1,*,Qing Zhang 1,Chang Yu 1,Jieshan Qiu 1,2,*1 Liaoning Key Lab for Energy Materials and Chemical Engineering,State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,Liaoning Province,China.展开更多
Dopamine(DA)is a vital neurotransmitter,and accurate detection of its concentration is critical for both clinical diagnos-tics and neuroscience research.Due to its electrochemical activity,DA is commonly detected usin...Dopamine(DA)is a vital neurotransmitter,and accurate detection of its concentration is critical for both clinical diagnos-tics and neuroscience research.Due to its electrochemical activity,DA is commonly detected using electrochemical methods,which are favored for their simplicity,fast response time,and suitability for in vivo analysis.In this work,a highly sensitive DA electrochemical sensor was developed using an Au@MoS_(2)composite,created by modifying molybdenum disulfide(MoS_(2))nanosheets with gold nanoparticles through HAuCl_(4) reduction,and it was aimed at enhancing DA adsorption and improving detection performance.Scanning Electron Microscopy(SEM),transmission electron microscopy(TEM),Energy Dispersive Spectroscopy(EDS),X-ray photoelectron spectroscopy(XPS)and X-ray Diffraction(XRD)confirmed the suc-cessful synthesis of Au@MoS_(2)and the uniform distribution of gold nanoparticles across the MoS_(2)nanosheets.Then,the electrochemical characterization demonstrated that the Au@MoS_(2)/GCE exhibited distinct oxidation peaks in a 10μmol·L^(-1)DA solution,with significantly enhanced electrochemical activity compared to both unmodified GCE and pristine MoS_(2).Furthermore,differential pulse voltammetry(DPV)further revealed a strong linear relationship between DA concentration and the current response in the range of 800 nmol·L^(-1)to 10μmol·L^(-1),with a low detection limit(LOD)of 78.9 nmol·L^(-1)(S/N=3).Additionally,the sensor showed excellent selectivity against other interfering substances.Moreover,the laser-induced Au@MoS_(2)(LIAu@MoS_(2)),with its abundance of negatively charged surface defects,enabled the ultra-sensitive detection of the ultra-low concentrations of DA.In conclusion,the successfully fabricated Au@MoS_(2)based sensor offers advantages such as low cost,ease of operation,and scalability,making it a promising candidate for biosensing applications due to its enhanced DA detection capabilities.展开更多
In recent years,chiral inorganic nanomaterials have become promising candidates for applications in sensing,catalysis,biomedicine,and photonics.Plasmonic nanomaterials with an intrinsic chiral structure exhibit intrig...In recent years,chiral inorganic nanomaterials have become promising candidates for applications in sensing,catalysis,biomedicine,and photonics.Plasmonic nanomaterials with an intrinsic chiral structure exhibit intriguing geometry‑dependent optical chirality,which benefits the combination of plasmonic characteristics with chirality.Recent advances in the biomolecule‑directed geometric control of intrinsically chiral plasmonic nanomaterials have further provided great opportunities for their widespread applications in many emerging technological areas.In this review,we present the recent progress in biosensing using chiral inorganic nanomaterials,with a particular focus on electrochemical and enzyme‑mimicking catalytic approaches.This paper commences with a review of the basic tenets underlying chiral nanocatalysts,incorporating the chiral ligand‑induced mechanism and the architectures of intrinsically chiral nanostructures.Additionally,it methodically expounds upon the applications of chiral nanocatalysts in the realms of electrochemical biosensing and enzyme‑mimicking catalytic biosensing respectively.Conclusively,it proffers a prospective view of the hurdles and prospects that accompany the deployment of chiral nanoprobes for nascent biosensing applications.By rational design of the chiral nanoprobes,it is envisioned that biosensing with increasing sensitivity and resolution toward the single‑molecule level can be achieved,which will substantially promote sensing applications in many emerging interdisciplinary areas.展开更多
With the acceleration of advanced industrialization and urbanization,the environment is deteriorating rapidly,and non-renewable energy resources are depleted.The gradual advent of potential clean energy storage techno...With the acceleration of advanced industrialization and urbanization,the environment is deteriorating rapidly,and non-renewable energy resources are depleted.The gradual advent of potential clean energy storage technologies is particularly urgent.Electrochemical energy storage technologies have been widely used in multiple fields,especially supercapacitors and rechargeable batteries,as vital elements of storing renewable energy.In recent years,two-dimensional material MXene has shown great potential in energy and multiple application fields thanks to its excellent electrical properties,large specific surface area,and tunability.Based on the layered materials of MXene,researchers have successfully achieved the dual functions of energy storage and conversion by adjusting the surface terminals at the Fermi level.It is worth noting that compared with other two-dimensional materials,MXene has more active sites on the basal plane,showing excellent catalytic performance.In contrast,other two-dimensional materials have catalytic activity only at the edge sites.This article comprehensively overviews the synthesis process,structural characteristics,modification methods for MXene-based polymer materials,and their applications in electrochemical energy storage.It also briefly discusses the potential of MXene-polymer materials in electromagnetic shielding technology and sensors and looks forward to future research directions.展开更多
A cobalt-based metal-organic framework[Co_(3)(L)_(2)(1,4-bib)_(4)]·4H_(2)O(Co-MOF)was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid(H_(3)L)and 1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib)as ligands.The...A cobalt-based metal-organic framework[Co_(3)(L)_(2)(1,4-bib)_(4)]·4H_(2)O(Co-MOF)was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid(H_(3)L)and 1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib)as ligands.Then,an electrochemical sensor modified with Co-MOF on a glassy carbon electrode(Co-MOF@GCE)was constructed for detecting Cd^(2+)and Pb^(2+)in aqueous solutions.The sensor exhibited a linear range of 1.0-16.0µmol·L^(-1)with a detection limit(LOD)of 4.609 nmol·L^(-1)for Cd^(2+),and 0.5-10.0µmol·L^(-1)with an LOD of 1.307 nmol·L^(-1)for Pb^(2+).Simultaneous detection of both ions within 0.5-7.0µmol·L^(-1)achieved LOD values of 0.47 nmol·L^(-1)(Cd^(2+))and 0.008 nmol·L^(-1)(Pb^(2+)),respectively.Analysis of real water samples(tap water,mineral water,and river water)yielded recoveries of 95%-105%,validating practical applicability.Density functional theory(DFT)calculations reveal that synergistic interactions between cobalt centers and N/O atoms enhance adsorption and electron-transfer efficiency.CCDC:2160744.展开更多
In the process of protecting ferrous materials,aluminum coating usually forms a dense oxide film on the surface of the iron-based alloy.However,the capacity of the sacrificial anode is rather insufficient.In order to ...In the process of protecting ferrous materials,aluminum coating usually forms a dense oxide film on the surface of the iron-based alloy.However,the capacity of the sacrificial anode is rather insufficient.In order to solve this problem,the microstructure and electrochemical corrosion properties of Al-8Si-3Fe-xIn alloy under low chlorine conditions were studied.The results show that indium(In)dissolves to form In^(3+)and In^(+)reverse plating on the surface of the bare substrate to form a passivation film defect.When the In content is high,the segregated In forms an activation point in the form of a cathode phase.In activatesτ_(6)phase to form a micro-couple,which improves the non-uniform corrosion.The In-containing corrosion products at the phase boundary hinder the diffusion of Cl−.With an increase of In content,the self-corrosion potential(Ecorr)of the alloy shifts negatively,and the self-corrosion current density(Jcorr)decreases from 6.477μA/cm^(2)to 1.352μA/cm^(2),and then increases gradually.However,when the In content is 0.1%,the Ecorr of the alloy changes from−0.824 V to−0.932 V,and the Jcorr decreases from 6.477μA/cm^(2)to 4.699μA/cm^(2),suggesting that the use of sacrificial anode will give the best effect.展开更多
Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as ...Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.展开更多
Based on three different kinds of conductive paths in microstructure of soil and theory of electrochemical impedance spectroscopy(EIS), an integrated equivalent circuit model and impedance formula for soils were propo...Based on three different kinds of conductive paths in microstructure of soil and theory of electrochemical impedance spectroscopy(EIS), an integrated equivalent circuit model and impedance formula for soils were proposed, which contain 6 meaningful resistance and reactance parameters. Considering the conductive properties of soils and dispersion effects, mathematical equations for impedance under various circuit models were deduced and studied. The mathematical expression presents two semicircles for theoretical EIS Nyquist spectrum, in which the center of one semicircle is degraded to simply the equivalent model. Based on the measured parameters of EIS Nyquist spectrum, meaningful soil parameters can easily be determined. Additionally, EIS was used to investigate the soil properties with different water contents along with the mathematical relationships and mechanism between the physical parameters and water content. Magnitude of the impedance decreases with the increase of testing frequency and water content for Bode graphs. The proposed model would help us to better understand the soil microstructure and properties and offer more reasonable explanations for EIS spectra.展开更多
The fatigue pre-cracking 304 stainless steel （SS） specimens with lengths of 1.002 mm （L-crack） and 0.575 mm （S-crack） were prepared. Their corrosion behavior was studied by electrochemical noise （EN） in 4 mol/...The fatigue pre-cracking 304 stainless steel （SS） specimens with lengths of 1.002 mm （L-crack） and 0.575 mm （S-crack） were prepared. Their corrosion behavior was studied by electrochemical noise （EN） in 4 mol/L NaC1 ＋ 0.01 mol/L Na2S203 solution under slow-strain-rate-testing （SSRT） conditions. Moreover, the characteristics of L-crack＇s surface morphology and potential distribution with scanning Kelvin probe （SKP） before and after SSRT were also discussed. Compared with S-crack, L-crack is propagated and the features of crack propagation can be obtained. After propagation, the noise amplitudes increase with increasing stress and accelerating corrosion, the white noises at low and high frequencies （WE and WH） of the later stage are one order of magnitude larger than that at early stage in the current power spectral densities （PSDs）. The potential PSDs also increase, but WH disappears. In addition, the crack propagation can be demonstrated according to variation of probability distribution, surface morphology and potential distribution.展开更多
The effect of electrochemical chloride extraction （ECE） on bond strength between steel bar and freeze-thaw concrete contaminated by chloride was experimentally investigated for beam specimens with dimensions of 100 ...The effect of electrochemical chloride extraction （ECE） on bond strength between steel bar and freeze-thaw concrete contaminated by chloride was experimentally investigated for beam specimens with dimensions of 100 mm × 100 mm × 400 ram. During the experiment, 3% NaC1 （vs mass of cement, mass fraction） was mixed into concrete to simulate chloride contamination, and the specimens experienced 0, 25, 50, 75 freeze-thaw cycles before ECE. In the process of ECE, different current densities and durations were adopted. It is indicated that the bond strength between reinforcement and concrete decreases with the increase of freeze-thaw cycles; the more the current and the electric quantity of ECE are, the more the loss of bond strength is; and the largest loss is up to 58.7%. So, it is important to choose proper parameters of ECE for the reinforced concrete structures contaminated by chloride and subjected to freeze-thaw cycles.展开更多
Electrochemical machining (ECM) is one of the best al ternatives for producing complex shapes in advanced materials used in aircraft a nd aerospace industries. However, the reduction of the stray material removal co n...Electrochemical machining (ECM) is one of the best al ternatives for producing complex shapes in advanced materials used in aircraft a nd aerospace industries. However, the reduction of the stray material removal co ntinues to be major challenges for industries in addressing accuracy improvement . This study presents a method of improving machining accuracy in ECM by using a dual pole tool with a metallic bush outside the insulated coating of a cathode tool. The bush is connected with anode and so the electric field at the side gap area is substantially weakened. The modeling and simulation indicate that the p ositive bush brings down the current density at the side gap area of the machine d hole and hence reduces the stray material removal there. It has been experimen tally observed that the machining accuracy and the process stability are signifi cantly improved.展开更多
In this study,the electrochemical oxidation of reactive brilliant orange X-GN dye with a boron-doped diamond(BDD)anode was investigated.The BDD electrodes were deposited on the niobium(Nb)substrates by the hot filamen...In this study,the electrochemical oxidation of reactive brilliant orange X-GN dye with a boron-doped diamond(BDD)anode was investigated.The BDD electrodes were deposited on the niobium(Nb)substrates by the hot filament chemical vapor deposition method.The effects of processing parameters,such as film thickness,current density,supporting electrolyte concentration,initial solution pH,solution temperature,and initial dye concentration,were evaluated following the variation in the degradation efficiency.The microstructure and the electrochemical property of BDD were characterized by scanning electron microscopy,Raman spectroscopy,and electrochemical workstation;and the degradation of X-GN was estimated using UV-Vis spectrophotometry.Further,the results indicated that the film thickness of BDD had a significant impact on the electrolysis of X-GN.After 3 h of treatment,100%color and 63.2%total organic carbon removal was achieved under optimized experimental conditions:current density of 100 mA/cm2,supporting electrolyte concentration of 0.05 mol/L,initial solution pH 3.08,and solution temperature of 60°C.展开更多
The influences of the mask wall angle on the current density distribution,shape of the evolving cavity and machining accuracy were investigated in electrochemical machining(ECM) by mask.A mathematical model was develo...The influences of the mask wall angle on the current density distribution,shape of the evolving cavity and machining accuracy were investigated in electrochemical machining(ECM) by mask.A mathematical model was developed to predict the shape evolution during the ECM by mask.The current density distribution is sensitive to mask wall angle.The evolution of cavity is determined by the current density distribution of evolving workpiece surface.The maximum depth is away from the center of holes machined,which leads to the island appearing at the center of cavity for mask wall angles greater than or equal to 90°(β≥90°).The experimental system was established and the simulation results were experimentally verified.The results indicate that the simulation results of cavity shape are consistent with the actual ones.The experiments also show that the repetition accuracy of matrix-hole for β≥90° is higher than that for β<90°.A hole taper is diminished,and the machining accuracy is improved with the mask wall angle increasing.展开更多
Electrochemical behaviors of Zn-Fe alloy and Zn-Fe-TiO2 composite electrodeposition in alkaline zincatesolutions were studied respectively by the methods of linear potential sweep and cyclic voltammetry. From the re-s...Electrochemical behaviors of Zn-Fe alloy and Zn-Fe-TiO2 composite electrodeposition in alkaline zincatesolutions were studied respectively by the methods of linear potential sweep and cyclic voltammetry. From the re-sults it can be concluded that Zn shows under potential deposition, Zn-Fe alloy codeposition is anomalous codeposi-tion and Zn-Fe alloy cathode polarization is increased with the introduction of additive. From the view point of elec-trochemistry, the reasons that the content of Fe in the Zn-Fe coating changes with the composition of the electrolyteand the process conditions altering and the relationship between the content of Fe and the appearance of the coatingare interpreted. The cathode polarization of Zn-Fe alloy codeposition is enhanced obviously with addition of additive.In the course of composite electrodeposition, TiO2 has less promotion to electrodeposition of zinc ions than to iron i-ons, while the electrodeposition of iron ions improves the content of TiO2 in composite coating, which is inagreement with the results of process experiments.展开更多
Al7075 alloy is a typical aviation aluminum with good mechanical properties and anodic oxidation effect.Laser engineered net shaping technology has unique advantages in the integrated forming of high-performance large...Al7075 alloy is a typical aviation aluminum with good mechanical properties and anodic oxidation effect.Laser engineered net shaping technology has unique advantages in the integrated forming of high-performance large aircraft structural parts.The manufacturing of 7075 aluminum alloy structural parts by laser engineered net shaping technology has become an important development direction in the future aerospace field.Electrochemical corrosion resistance of aluminum alloys is of vital importance to improve reliability and life-span of lightweight components.A comparative study on microstructure and anti-corrosion performance of Al7075 alloy prepared by laser additive manufacturing and forging technology was conducted.There are hole defects in LENS-fabricated Al7075 alloy with uniformly distributedηphase.No defects are observed in Al7075 forgings.The large S phase particles and small ellipsoidalηphase particles are found in Al matrix.The corrosion mechanisms were revealed according to the analysis of polarization curves and corrosion morphology.It was found that compared with that prepared by forgings,the additive manufactured samples have lower corrosion tendency and higher corrosion rate.Corrosion occurred preferentially at the hole defects.The incomplete passivation film at the defects leads to the formation of a local cell composed of the internal Al,corrosion solution and the surrounding passive film,which further aggravates the corrosion.展开更多
Lithium difluoro(axalato)borate (LiODFB) was synthesized in dimethyl carbonate (DMC) solvent and purified by the method of solventing-out crystallization. The structure characterization of the purified LiODFB was perf...Lithium difluoro(axalato)borate (LiODFB) was synthesized in dimethyl carbonate (DMC) solvent and purified by the method of solventing-out crystallization. The structure characterization of the purified LiODFB was performed by Fourier transform infrared (FTIR) spectrometry and nuclear magnetic resonance (NMR) spectrometry. The electrochemical properties of the cells using 1 mol/L LiPF6 and 1 mol/L LiODFB in ethylene carbonate (EC)/DMC were investigated, respectively. The results indicate that LiODFB can be reduced at about 1.5 V and form a robust protective solid electrolyte interface (SEI) film on the graphite surface in the first cycle. The graphite/LiNi1/3Mn1/3Co1/3O2 cells with LiODFB-based electrolyte have very good capacity retention at 55 ℃, and show very good rate capability at 0.5C and 1C charge/discharge rate. Therefore, as a new salt, LiODFB is a most promising alternative lithium salt to replace LiPF6 for lithium ion battery electrolytes in the future.展开更多
基金the National Natural Science Foundation of China(22279097)the Key R&D Program of Hubei Province(2023BAB103)the PhD Scientific Research and Innovation Foundation of The Education Department of Hainan Province Joint Project of Sanya Yazhou Bay Science and Technology City(HSPHDSRF-2024-03-022)。
文摘Because of their low electrical conductivity,sluggish ion diffusion,and poor stability,conventional electrode materials are not able to meet the growing demands of energy storage and portable devices.Graphene assembled films(GAFs)formed from graphene nanosheets have an ultrahigh conductivity,a unique 2D network structure,and exceptional mechanical strength,which give them the potential to solve these problems.However,a systematic understanding of GAFs as an advanced electrode material is lacking.This review focuses on the use of GAFs in electrochemistry,providing a comprehensive analysis of their synthesis methods,surface/structural characteristics,and physical properties,and thus understand their structure-property relationships.Their advantages in batteries,supercapacitors,and electrochemical sensors are systematically evaluated,with an emphasis on their excellent electrical conductivity,ion transport kinetics,and interfacial stability.The existing problems in these devices,such as chemical inertness and mechanical brittleness,are discussed and potential solutions are proposed,including defect engineering and hybrid structures.This review should deepen our mechanistic understanding of the use of GAFs in electrochemical systems and provide actionable strategies for developing stable,high-performance electrode materials.
基金the funding from Lembaga Penelitian dan Pengabdian Masyarakat(LPPM)Universitas Indonesia,by Riset Kolaborasi Indonesia(RKI)-World Class University(WCU)Program with grant number NKB-1067/UN2-RST/HKP.05.00/2023 and NKB-781/UN2.RST/HKP.05.00/2024.
文摘Detection of target analytes at low concentrations is significant in various fields,including pharmaceuticals,healthcare,and environmental protection.Theophylline(TP),a natural alkaloid used as a bronchodilator to treat respiratory disorders such as asthma,bronchitis,and emphysema,has a narrow therapeutic window with a safe plasma concentration ranging from 55.5-111.0μmol·L^(-1)in adults.Accurate monitoring of TP levels is essential because too low or too high can cause se-rious side effects.In this regard,non-enzymatic electrochemical sensors offer a practical solution with rapidity,portability,and high sensitivity.This article aims to provide a comprehensive review of the recent developments of non-enzymatic electrochemical sensors for TP detection,highlighting the basic principles,electro-oxidation mechanisms,catalytic effects,and the role of modifying materials on electrode performance.Carbon-based electrodes such as glassy carbon electrodes(GCEs),carbon paste electrodes(CPEs),and carbon screen-printed electrodes(SPCEs)have become the primary choices for non-enzymatic sensors due to their chemical stability,low cost,and flexibility in modification.This article identifies the sig-nificant contribution of various modifying materials,including nanomaterials such as carbon nanotubes(CNTs),graphene,metal oxides,and multi-element nanocomposites.These modifications enhance sensors’electron transfer,sensitivity,and selectivity in detecting TP at low concentrations in complex media such as blood plasma and pharmaceutical samples.The electro-oxidation mechanism of TP is also discussed in depth,emphasizing the hydroxyl and carbonyl reaction pathways strongly influenced by pH and electrode materials.These mechanisms guide the selection of the appropriate electrode ma-terial for a particular application.The main contribution of this article is to identify superior modifying materials that can improve the performance of non-enzymatic electrochemical sensors.In a recent study,the combination of multi-element nanocomposites based on titanium dioxide(TiO_(2)),CNTs,and gold nanoparticles(AuNPs)resulted in the lowest detection limit of 3×10^(-5)μmol·L^(-1),reflecting the great potential of these materials for developing high-performance electrochemical sensors.The main conclusion of this article is the importance of a multidisciplinary approach in electrode material design to support the sensitivity and selectivity of TP detection.In addition,there is still a research gap in understanding TP’s more detailed oxidation mechanism,especially under pH variations and complex environments.Therefore,further research on electrode modification and analysis of the TP oxidation mechanism are urgently needed to improve the accuracy and sta-bility of the sensor while expanding its applications in pharmaceutical monitoring and medical diagnostics.By integrating various innovative materials and technical approaches,this review is expected to be an essential reference for developing efficient and affordable non-enzymatic electrochemical sensors.
文摘Pitch is a complex mixture of polycyclic aromatic hydrocarbons and their non-metal derivatives that has a high carbon content.Using pitch as a precursor for carbon materials in alkali metal ion(Li^(+)/Na^(+)/K^(+))batteries has become of great interest.However,its direct pyrolysis often leads to microstructures with a high orientation and small interlayer spacing due to uncontrolled liquid-phase carbonization,resulting in subpar electrochemical performance.It is therefore important to control the microstructures of pitch-derived carbon materials in order to improve their electrochemical properties.We evaluate the latest progress in the development of these materials using various microstructural engineering approaches,highlighting their use in metal-ion batteries and supercapacitors.The advantages and limitations of pitch molecules and their carbon derivatives are outlined,together with strategies for their modification in order to improve their properties for specific applications.Future research possibilities for structure optimization,scalable production,and waste pitch recycling are also considered.
文摘Under the condition of solvothermal synthesis,the viologen ligand 1,1′-bis(3-carboxyphenyl)-(4,4′-bipyri-dine)dichloride(H_(2)bcbpy·2Cl)and KI are coordinated with the metal cadmium ions.A case of thermochromic coor-dination polymer[Cd(bcbpy)I_(2)]·2H_(2)O(1)was constructed.Complex 1 displays a 1D chain structure and exhibits thermochromic behavior.Under different temperature stimulation,the complex(ground)slowly changed from green to yellow-green,and with the increase of temperature,the color of complex 1 gradually deepened,and finally became orange-yellow.Therefore,complex 1 was prepared as a thermochromic film.In addition,we also performed electrochemical tests on complex 1,which showed that the complex is a semiconductor material.CCDC:2391802.
文摘Hanyu Xu 1,Xuedan Song 1,*,Qing Zhang 1,Chang Yu 1,Jieshan Qiu 1,2,*1 Liaoning Key Lab for Energy Materials and Chemical Engineering,State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,Liaoning Province,China.
基金supported by the Young Talent Innovation Team Support Project from Zhengzhou University(No.32213280)the scientific research program of innovation platform in State Tobacco Monopoly Administrationthe State Key Program of National Natural Science Foundation of China(Grant No.32130083).
文摘Dopamine(DA)is a vital neurotransmitter,and accurate detection of its concentration is critical for both clinical diagnos-tics and neuroscience research.Due to its electrochemical activity,DA is commonly detected using electrochemical methods,which are favored for their simplicity,fast response time,and suitability for in vivo analysis.In this work,a highly sensitive DA electrochemical sensor was developed using an Au@MoS_(2)composite,created by modifying molybdenum disulfide(MoS_(2))nanosheets with gold nanoparticles through HAuCl_(4) reduction,and it was aimed at enhancing DA adsorption and improving detection performance.Scanning Electron Microscopy(SEM),transmission electron microscopy(TEM),Energy Dispersive Spectroscopy(EDS),X-ray photoelectron spectroscopy(XPS)and X-ray Diffraction(XRD)confirmed the suc-cessful synthesis of Au@MoS_(2)and the uniform distribution of gold nanoparticles across the MoS_(2)nanosheets.Then,the electrochemical characterization demonstrated that the Au@MoS_(2)/GCE exhibited distinct oxidation peaks in a 10μmol·L^(-1)DA solution,with significantly enhanced electrochemical activity compared to both unmodified GCE and pristine MoS_(2).Furthermore,differential pulse voltammetry(DPV)further revealed a strong linear relationship between DA concentration and the current response in the range of 800 nmol·L^(-1)to 10μmol·L^(-1),with a low detection limit(LOD)of 78.9 nmol·L^(-1)(S/N=3).Additionally,the sensor showed excellent selectivity against other interfering substances.Moreover,the laser-induced Au@MoS_(2)(LIAu@MoS_(2)),with its abundance of negatively charged surface defects,enabled the ultra-sensitive detection of the ultra-low concentrations of DA.In conclusion,the successfully fabricated Au@MoS_(2)based sensor offers advantages such as low cost,ease of operation,and scalability,making it a promising candidate for biosensing applications due to its enhanced DA detection capabilities.
文摘In recent years,chiral inorganic nanomaterials have become promising candidates for applications in sensing,catalysis,biomedicine,and photonics.Plasmonic nanomaterials with an intrinsic chiral structure exhibit intriguing geometry‑dependent optical chirality,which benefits the combination of plasmonic characteristics with chirality.Recent advances in the biomolecule‑directed geometric control of intrinsically chiral plasmonic nanomaterials have further provided great opportunities for their widespread applications in many emerging technological areas.In this review,we present the recent progress in biosensing using chiral inorganic nanomaterials,with a particular focus on electrochemical and enzyme‑mimicking catalytic approaches.This paper commences with a review of the basic tenets underlying chiral nanocatalysts,incorporating the chiral ligand‑induced mechanism and the architectures of intrinsically chiral nanostructures.Additionally,it methodically expounds upon the applications of chiral nanocatalysts in the realms of electrochemical biosensing and enzyme‑mimicking catalytic biosensing respectively.Conclusively,it proffers a prospective view of the hurdles and prospects that accompany the deployment of chiral nanoprobes for nascent biosensing applications.By rational design of the chiral nanoprobes,it is envisioned that biosensing with increasing sensitivity and resolution toward the single‑molecule level can be achieved,which will substantially promote sensing applications in many emerging interdisciplinary areas.
基金supported by the Natural Science Basic Research Plan in the Shaanxi Province of China(No.2023-JC-ZD-25)Shaanxi Province(Qin ChuangYuan)“Scientist+Engineer”Team Building(No.2022KXJ-040)+1 种基金Shaanxi Provincial Department of Education Key Scientific Research Project(No.22JY024)Science and Technology Guidance Project Plan of China National Textile and Apparel Council(No.2022038,2023018).
文摘With the acceleration of advanced industrialization and urbanization,the environment is deteriorating rapidly,and non-renewable energy resources are depleted.The gradual advent of potential clean energy storage technologies is particularly urgent.Electrochemical energy storage technologies have been widely used in multiple fields,especially supercapacitors and rechargeable batteries,as vital elements of storing renewable energy.In recent years,two-dimensional material MXene has shown great potential in energy and multiple application fields thanks to its excellent electrical properties,large specific surface area,and tunability.Based on the layered materials of MXene,researchers have successfully achieved the dual functions of energy storage and conversion by adjusting the surface terminals at the Fermi level.It is worth noting that compared with other two-dimensional materials,MXene has more active sites on the basal plane,showing excellent catalytic performance.In contrast,other two-dimensional materials have catalytic activity only at the edge sites.This article comprehensively overviews the synthesis process,structural characteristics,modification methods for MXene-based polymer materials,and their applications in electrochemical energy storage.It also briefly discusses the potential of MXene-polymer materials in electromagnetic shielding technology and sensors and looks forward to future research directions.
文摘A cobalt-based metal-organic framework[Co_(3)(L)_(2)(1,4-bib)_(4)]·4H_(2)O(Co-MOF)was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid(H_(3)L)and 1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib)as ligands.Then,an electrochemical sensor modified with Co-MOF on a glassy carbon electrode(Co-MOF@GCE)was constructed for detecting Cd^(2+)and Pb^(2+)in aqueous solutions.The sensor exhibited a linear range of 1.0-16.0µmol·L^(-1)with a detection limit(LOD)of 4.609 nmol·L^(-1)for Cd^(2+),and 0.5-10.0µmol·L^(-1)with an LOD of 1.307 nmol·L^(-1)for Pb^(2+).Simultaneous detection of both ions within 0.5-7.0µmol·L^(-1)achieved LOD values of 0.47 nmol·L^(-1)(Cd^(2+))and 0.008 nmol·L^(-1)(Pb^(2+)),respectively.Analysis of real water samples(tap water,mineral water,and river water)yielded recoveries of 95%-105%,validating practical applicability.Density functional theory(DFT)calculations reveal that synergistic interactions between cobalt centers and N/O atoms enhance adsorption and electron-transfer efficiency.CCDC:2160744.
基金Projects(52171003,52271005)supported by the National Science and Technology Major Project of ChinaProject(KYCX23_3032)supported by the Postgraduate Research&Practice Innovation Program of Jiangsu Province,China。
文摘In the process of protecting ferrous materials,aluminum coating usually forms a dense oxide film on the surface of the iron-based alloy.However,the capacity of the sacrificial anode is rather insufficient.In order to solve this problem,the microstructure and electrochemical corrosion properties of Al-8Si-3Fe-xIn alloy under low chlorine conditions were studied.The results show that indium(In)dissolves to form In^(3+)and In^(+)reverse plating on the surface of the bare substrate to form a passivation film defect.When the In content is high,the segregated In forms an activation point in the form of a cathode phase.In activatesτ_(6)phase to form a micro-couple,which improves the non-uniform corrosion.The In-containing corrosion products at the phase boundary hinder the diffusion of Cl−.With an increase of In content,the self-corrosion potential(Ecorr)of the alloy shifts negatively,and the self-corrosion current density(Jcorr)decreases from 6.477μA/cm^(2)to 1.352μA/cm^(2),and then increases gradually.However,when the In content is 0.1%,the Ecorr of the alloy changes from−0.824 V to−0.932 V,and the Jcorr decreases from 6.477μA/cm^(2)to 4.699μA/cm^(2),suggesting that the use of sacrificial anode will give the best effect.
基金the National Basic Research Development of China(2011CB936003)the National Natural Science Foundation of China(50971116)。
文摘Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.
基金Projects(5120833351078253)supported by the National Natural Science Foundation of China+4 种基金Projects(2014011036-12014131019TYUT2014YQ017OIT2015)supported by the Natural Science Foundation of Shanxi ProvinceChina
文摘Based on three different kinds of conductive paths in microstructure of soil and theory of electrochemical impedance spectroscopy(EIS), an integrated equivalent circuit model and impedance formula for soils were proposed, which contain 6 meaningful resistance and reactance parameters. Considering the conductive properties of soils and dispersion effects, mathematical equations for impedance under various circuit models were deduced and studied. The mathematical expression presents two semicircles for theoretical EIS Nyquist spectrum, in which the center of one semicircle is degraded to simply the equivalent model. Based on the measured parameters of EIS Nyquist spectrum, meaningful soil parameters can easily be determined. Additionally, EIS was used to investigate the soil properties with different water contents along with the mathematical relationships and mechanism between the physical parameters and water content. Magnitude of the impedance decreases with the increase of testing frequency and water content for Bode graphs. The proposed model would help us to better understand the soil microstructure and properties and offer more reasonable explanations for EIS spectra.
基金Project(2006CB605004) supported by the National Basic Research Program of China
文摘The fatigue pre-cracking 304 stainless steel （SS） specimens with lengths of 1.002 mm （L-crack） and 0.575 mm （S-crack） were prepared. Their corrosion behavior was studied by electrochemical noise （EN） in 4 mol/L NaC1 ＋ 0.01 mol/L Na2S203 solution under slow-strain-rate-testing （SSRT） conditions. Moreover, the characteristics of L-crack＇s surface morphology and potential distribution with scanning Kelvin probe （SKP） before and after SSRT were also discussed. Compared with S-crack, L-crack is propagated and the features of crack propagation can be obtained. After propagation, the noise amplitudes increase with increasing stress and accelerating corrosion, the white noises at low and high frequencies （WE and WH） of the later stage are one order of magnitude larger than that at early stage in the current power spectral densities （PSDs）. The potential PSDs also increase, but WH disappears. In addition, the crack propagation can be demonstrated according to variation of probability distribution, surface morphology and potential distribution.
基金Project(IRT0518) supported by the Program of Innovative Team of the Ministry of Education of China
文摘The effect of electrochemical chloride extraction （ECE） on bond strength between steel bar and freeze-thaw concrete contaminated by chloride was experimentally investigated for beam specimens with dimensions of 100 mm × 100 mm × 400 ram. During the experiment, 3% NaC1 （vs mass of cement, mass fraction） was mixed into concrete to simulate chloride contamination, and the specimens experienced 0, 25, 50, 75 freeze-thaw cycles before ECE. In the process of ECE, different current densities and durations were adopted. It is indicated that the bond strength between reinforcement and concrete decreases with the increase of freeze-thaw cycles; the more the current and the electric quantity of ECE are, the more the loss of bond strength is; and the largest loss is up to 58.7%. So, it is important to choose proper parameters of ECE for the reinforced concrete structures contaminated by chloride and subjected to freeze-thaw cycles.
文摘Electrochemical machining (ECM) is one of the best al ternatives for producing complex shapes in advanced materials used in aircraft a nd aerospace industries. However, the reduction of the stray material removal co ntinues to be major challenges for industries in addressing accuracy improvement . This study presents a method of improving machining accuracy in ECM by using a dual pole tool with a metallic bush outside the insulated coating of a cathode tool. The bush is connected with anode and so the electric field at the side gap area is substantially weakened. The modeling and simulation indicate that the p ositive bush brings down the current density at the side gap area of the machine d hole and hence reduces the stray material removal there. It has been experimen tally observed that the machining accuracy and the process stability are signifi cantly improved.
基金Project(2016YEB0301402) supported by the National Key Research and Development Program of ChinaProject(51601226) supported by the National Natural Science Foundation of China+1 种基金Project supported by the Open-End Fund for the Valuable and Precision Instruments of Central South University,ChinaProject supported by State Key Laboratory of Powder Metallurgy,China
文摘In this study,the electrochemical oxidation of reactive brilliant orange X-GN dye with a boron-doped diamond(BDD)anode was investigated.The BDD electrodes were deposited on the niobium(Nb)substrates by the hot filament chemical vapor deposition method.The effects of processing parameters,such as film thickness,current density,supporting electrolyte concentration,initial solution pH,solution temperature,and initial dye concentration,were evaluated following the variation in the degradation efficiency.The microstructure and the electrochemical property of BDD were characterized by scanning electron microscopy,Raman spectroscopy,and electrochemical workstation;and the degradation of X-GN was estimated using UV-Vis spectrophotometry.Further,the results indicated that the film thickness of BDD had a significant impact on the electrolysis of X-GN.After 3 h of treatment,100%color and 63.2%total organic carbon removal was achieved under optimized experimental conditions:current density of 100 mA/cm2,supporting electrolyte concentration of 0.05 mol/L,initial solution pH 3.08,and solution temperature of 60°C.
基金Project(50635040) supported by the National Natural Science Foundation of ChinaProject(2009AA044205) supported by the National High Technology Research and Development ProgramProject(BK2008043) supported by the Jiangsu Provincial Natural Science Foundation,China
文摘The influences of the mask wall angle on the current density distribution,shape of the evolving cavity and machining accuracy were investigated in electrochemical machining(ECM) by mask.A mathematical model was developed to predict the shape evolution during the ECM by mask.The current density distribution is sensitive to mask wall angle.The evolution of cavity is determined by the current density distribution of evolving workpiece surface.The maximum depth is away from the center of holes machined,which leads to the island appearing at the center of cavity for mask wall angles greater than or equal to 90°(β≥90°).The experimental system was established and the simulation results were experimentally verified.The results indicate that the simulation results of cavity shape are consistent with the actual ones.The experiments also show that the repetition accuracy of matrix-hole for β≥90° is higher than that for β<90°.A hole taper is diminished,and the machining accuracy is improved with the mask wall angle increasing.
文摘Electrochemical behaviors of Zn-Fe alloy and Zn-Fe-TiO2 composite electrodeposition in alkaline zincatesolutions were studied respectively by the methods of linear potential sweep and cyclic voltammetry. From the re-sults it can be concluded that Zn shows under potential deposition, Zn-Fe alloy codeposition is anomalous codeposi-tion and Zn-Fe alloy cathode polarization is increased with the introduction of additive. From the view point of elec-trochemistry, the reasons that the content of Fe in the Zn-Fe coating changes with the composition of the electrolyteand the process conditions altering and the relationship between the content of Fe and the appearance of the coatingare interpreted. The cathode polarization of Zn-Fe alloy codeposition is enhanced obviously with addition of additive.In the course of composite electrodeposition, TiO2 has less promotion to electrodeposition of zinc ions than to iron i-ons, while the electrodeposition of iron ions improves the content of TiO2 in composite coating, which is inagreement with the results of process experiments.
基金Project(2016YFB1100101)supported by the National Key Research and Development Program of China。
文摘Al7075 alloy is a typical aviation aluminum with good mechanical properties and anodic oxidation effect.Laser engineered net shaping technology has unique advantages in the integrated forming of high-performance large aircraft structural parts.The manufacturing of 7075 aluminum alloy structural parts by laser engineered net shaping technology has become an important development direction in the future aerospace field.Electrochemical corrosion resistance of aluminum alloys is of vital importance to improve reliability and life-span of lightweight components.A comparative study on microstructure and anti-corrosion performance of Al7075 alloy prepared by laser additive manufacturing and forging technology was conducted.There are hole defects in LENS-fabricated Al7075 alloy with uniformly distributedηphase.No defects are observed in Al7075 forgings.The large S phase particles and small ellipsoidalηphase particles are found in Al matrix.The corrosion mechanisms were revealed according to the analysis of polarization curves and corrosion morphology.It was found that compared with that prepared by forgings,the additive manufactured samples have lower corrosion tendency and higher corrosion rate.Corrosion occurred preferentially at the hole defects.The incomplete passivation film at the defects leads to the formation of a local cell composed of the internal Al,corrosion solution and the surrounding passive film,which further aggravates the corrosion.
基金Project(2007BAE12B01) supported by the National Key Technology Research and Development Program of ChinaProject(20803095) supported by the National Natural Science Foundation of China
文摘Lithium difluoro(axalato)borate (LiODFB) was synthesized in dimethyl carbonate (DMC) solvent and purified by the method of solventing-out crystallization. The structure characterization of the purified LiODFB was performed by Fourier transform infrared (FTIR) spectrometry and nuclear magnetic resonance (NMR) spectrometry. The electrochemical properties of the cells using 1 mol/L LiPF6 and 1 mol/L LiODFB in ethylene carbonate (EC)/DMC were investigated, respectively. The results indicate that LiODFB can be reduced at about 1.5 V and form a robust protective solid electrolyte interface (SEI) film on the graphite surface in the first cycle. The graphite/LiNi1/3Mn1/3Co1/3O2 cells with LiODFB-based electrolyte have very good capacity retention at 55 ℃, and show very good rate capability at 0.5C and 1C charge/discharge rate. Therefore, as a new salt, LiODFB is a most promising alternative lithium salt to replace LiPF6 for lithium ion battery electrolytes in the future.
