Metal-organic framework(MOF)nanostructures have emerged as a prominent class of materials in the advancement of electrochemical sensors.The rational design of bimetallic MOF-functionalized microelectrode is of importa...Metal-organic framework(MOF)nanostructures have emerged as a prominent class of materials in the advancement of electrochemical sensors.The rational design of bimetallic MOF-functionalized microelectrode is of importance for improv-ing the electrochemical performance but still in great challenge.In this work,the bimetallic FeCo-MOF nanostructures were assembled onto a gold disk ultramicroelectrode(Au UME,5.2μm in diameter)via an in-situ electrodeposition method,which enhanced the sensitive detection of epinephrine(EP).The in-situ electrodeposited FeCo-MOF exhibited a character-istic nanoflower-like morphology and was uniformly dispersed on the Au UME.The FeCo-MOF/Au UME demonstrated excellent electrochemical performance on the detection of EP with a high sensitivity of 36.93μA·μmol^(-1)·L·cm^(-2)and a low detection limit of 1.28μmol·L^(-1).It can be attributed to the nonlinear diffusion of EP onto the ultra-micro working substrate,coupled with synergistical catalytic activity of the bimetallic Fe,Co within MOF structure.Furthermore,the FeCo-MOF/Au UME has been successful applied to the analysis of EP in human serum samples,yielding high recovery rates.These results not only contribute to the expansion of the research area of electrochemical sensors,but also provide novel insights and directions into the development of high-performance MOF-based electrochemical sensors.展开更多
Electrochromic(EC)smart windows utilizing a reversible metal electrodeposition device(RMED)offer a compelling alternative for dynamically regulating transmissions of optical and thermal energy.An EC device(ECD)is cons...Electrochromic(EC)smart windows utilizing a reversible metal electrodeposition device(RMED)offer a compelling alternative for dynamically regulating transmissions of optical and thermal energy.An EC device(ECD)is constructed by reversible metal electrodeposition(RME)of Bi/Cu on WO_(3)·xH_(2)O film electrodeposited onto fluorine-doped tin oxide(FTO)transparent conductive glass.The electrolyte consists of CuCl_(2),BiCl_(3),KCl and HCl aqueous solution,supplying necessary components for both electrochemical and electrodeposition processes.The ECD shows ability to rapidly transition between colorless and black states,which achieves a large optical modulation of 77.0%at 570 nm.In the black state,the ECD exhibits a near-zero transmittance in the wavelength range of 400-1100 nm while maintaining 96.6%of its initial optical modulation after coloration/bleaching cycling of 60000 s,exhibiting good cyclic stability.This RMED has relatively high stability under open-circuit voltage and also possesses excellent heat insulation performance.The results offer a solution to overcome the poor cyclic stability of RMEDs and improve the optical modulation of ECDs.展开更多
pH-dependent multiple equilibria in cobalt sulfate-gluconate baths were calculated using stability constants adopted from literature.Changes of the bath speciation were then discussed in terms of spectrophotometric ex...pH-dependent multiple equilibria in cobalt sulfate-gluconate baths were calculated using stability constants adopted from literature.Changes of the bath speciation were then discussed in terms of spectrophotometric experiments and buffering properties of the solutions(pH 3-10).Cyclic voltammetry indicated changes in electrochemical behavior of cobalt species caused by different ionic compositions of the electrolytes.Tafel slopes were calculated and discussed in relation to electroreduction of cobalt species.Chronoamperometric studies showed 3D instantaneous nucleation of cobalt followed by diffusion-controlled growth,but it was disturbed at higher pH due to the release of cation from gluconate complexes as a limiting step.Diffusion coefficients of cobalt species were found.Changes in the pH were also reflected by modifications of morphology(SEM),development of preferred orientation planes(XRD,texture coefficients)and current efficiency,but not the thickness of the coatings deposited at constant potential of-1.0 V(vs Ag/AgCl).Anodic stripping analysis showed changes in anodic responses originated from the existence of preferentially oriented planes in cobalt layers.展开更多
Aqueous zinc-ion batteries(AZIBs)are attractive for large-scale energy storage due to their safety and low cost,but practical use is limited by dendrite growth,hydrogen evolution,and passivation.Traditional solutions ...Aqueous zinc-ion batteries(AZIBs)are attractive for large-scale energy storage due to their safety and low cost,but practical use is limited by dendrite growth,hydrogen evolution,and passivation.Traditional solutions often introduce additional complexity without addressing the root cause:unstable zinc deposition.Recent advancements now focus on controlling zinc crystallographic orientation to fundamentally suppress inhomogeneous nucleation and growth.The(002)basal plane supports smooth,reversible growth and can be promoted via heteroepitaxy or homoepitaxy,enabling long cycle life even at high rates.However,emerging studies show that Zn(100)and Zn(101)orientations may offer comparable benefits through faster kinetics and reduced parasitic reactions.Scalable,non-epitaxial methods,such as electrolyte tuning and pressure control also show promise.Despite these advances,balancing thermodynamic stability with kinetic performance remains a major challenge.Future research should integrate orientation control with strategies against corrosion and calendar aging to enable practical,highperformance AZIBs.展开更多
Zinc(Zn)-based materials show broad application prospects for bone repair due to their biodegradability and good biocompatibility.In particular,Zn metal foam has unique interconnected pore structure that facilitates i...Zinc(Zn)-based materials show broad application prospects for bone repair due to their biodegradability and good biocompatibility.In particular,Zn metal foam has unique interconnected pore structure that facilitates inward growth of new bone tissue,making it ideal candidates for orthopedic implants.However,pure Zn metal foam shows poor mechanical property,high degradation rate,and unsatisfactory osteogenic activity.Herein,Zinc-manganese(Zn-Mn)alloy foams were electrodeposited in Zn and Mn-containing electrolytes to overcome the concerns.The results showed that Mn could be incorporated into the foams in the form of MnZn_(13).Zn-Mn alloy foams showed better mechanical property and osteogenic activity as well as moderate degradation rate when compared with pure Zn metal foam.In addition,these properties could also be regulated by preparation process.The peak stress and osteogenic activity increased with deposition current(0.3‒0.5 A)and electrolyte pH(3‒5),but decreased with electrolyte temperature(20‒40℃),while the degradation rate exhibited opposite tendency,which suggests high deposition current and electrolyte pH and low electrolyte temperature can fabricate Zn-Mn alloy foam with favorable mechanical property,moderate degradation rate,and osteogenic activity.These findings provide a valuable reference for the design and fabrication of novel Zn-based biodegradable materials.展开更多
The development of low-energy consumption and environmentally friendly electrodeposition of metal/alloy films or coatings is presently one of the primary topics for the research community.For this purpose,deep eutecti...The development of low-energy consumption and environmentally friendly electrodeposition of metal/alloy films or coatings is presently one of the primary topics for the research community.For this purpose,deep eutectic solvents(DESs)are valued as electrolytes for their advantages of low operating temperature and wide electrochemical windows.At present,there is large amount of literature on this emerging field,but there are no specialized reviews of these studies.Here,after a brief introduction of DESs’concept and history,we comprehensively reviewed the lastest progress on the metal/alloy electrodeposition in DESs.Additionally,we discussed the key influence factors of the electrodeposition process and analyzed the corresponding mechanisms.Based on these,we emphasized the importance of the establishment of predictive models for dealing with the challenges in large-scale applications.展开更多
Electrochemical metallurgy at low temperature(<473 K)shows promise for the extraction and refinement of metals and alloys in a green and sustainable manner.However,the kinetics of the electrodeposition process is g...Electrochemical metallurgy at low temperature(<473 K)shows promise for the extraction and refinement of metals and alloys in a green and sustainable manner.However,the kinetics of the electrodeposition process is generally slow at low temperature,resulting in large overpotential and low current efficiency.Thus,the application of external physical fields has emerged as an effective strategy for improving the mass and charge transfer processes during electrochemical reactions.This review highlights the challenges associated with low-temperature electrochemical processes and briefly discusses recent achievements in optimizing electrodeposition processes through the use of external physical fields.The regulating effects on the optimization of the electrodeposition process and the strategies for select-ing various external physical fields,including magnetic,supergravity,and ultrasonic fields are summarized from the perspectives of equipment and mechanisms.Finally,advanced methods for in-situ characterization of external physical field-assisted electrodeposition processes are reviewed to gain a deeper understanding of metallic electrodeposition.An in-depth exploration of the mechanism by which external physical fields affect the electrode process is essential for enhancing the efficiency of metal extraction at low temperatures.展开更多
Building a superhydrophobic coating on a carbon steel substrate is an effective strategy for enhancing metal protection.A practical approach to producing a series of superhydrophobic Ni/SiO_(2)composite coatings(SSN)u...Building a superhydrophobic coating on a carbon steel substrate is an effective strategy for enhancing metal protection.A practical approach to producing a series of superhydrophobic Ni/SiO_(2)composite coatings(SSN)using one-step electrodeposition method is shown.The effect of processing parameters on surface structure and wettability was thoroughly explored,resulting in the identification of three typical surface morphologies.The prepared coating with petal-like structure(SSN-3)obtained under the optimum parameters exhibited the best water repellency,achieving a contact angle of 162.7°and a sliding angle of 4.1°.The droplet bouncing behavior on SSN coatings surface was studied,and the delayed icing time was recorded.Meanwhile,the mechanical stability and chemical corrosion resistance of SSN coatings were focused.The superhydrophobic SSN-3 coating with unique surface structure exhibited excellent reliability.The anticorrosion mechanism of SSN-3 coating was discussed,and its corrosion protection efficiency was up to 98.5%.The superior properties of the superhydrophobic SSN-3 coating make it suitable for diverse applications.展开更多
Hydrogen is considered as the promising energy carrier to substitute traditional fossil fuel,due to its cleanliness,renewability and high energy density.Water electrolysis is a simple and eonvenient technology for hyd...Hydrogen is considered as the promising energy carrier to substitute traditional fossil fuel,due to its cleanliness,renewability and high energy density.Water electrolysis is a simple and eonvenient technology for hydrogen production.The efficiency of water electrolysis for hydrogen production is limited by the electrocatalytic performances on hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).The exorbitant Pt-and Ir-/Ru-based electrocatalysts as optimal HER and OER electrocatalysts,respectively,restrict water electrolysis development.Recently,non-precious metal-based high-entropy electrocatalysts have exhibited excellent electrocatalytic activities and long-term stabilities for water electrolysis,as promising precious cataly st candidates.Therefore,the construction of the high-entropy electroc atalysts is vital to water electrolysis industry.Electrodeposition technology is an efficient method for the preparation of high-entropy electrocatalysts due to its simple,fast,energy-saving and environmental-friendly advantages.Multi-component co-precipitation facilely occurs during the electroredox in electrodeposition processes.High-entropy alloys,oxides,(oxy)hydroxides,phosphides and phosphorus sulfide oxides have been successfully prepared by galvanostatic,potentiostatic electrodeposition,cyclic voltammetry,pulse,nanodroplet-mediated and cathodic plasma electrodeposition techniques.Hence,introduction of the development of high-entropy electrocatalysts synthesized by electrodeposition technology is significant to researchers and industries.Challenges and outlooks are also concluded to boost the industrial application of electrodeposition in water electrolysis and other energy conversion areas.展开更多
Microplasma based on glow discharge could act as a non-contact gaseous electrode and has attracted much attention in both fundamental research and application. Herein, with microplasma as the anode,the electrodepositi...Microplasma based on glow discharge could act as a non-contact gaseous electrode and has attracted much attention in both fundamental research and application. Herein, with microplasma as the anode,the electrodeposition process of a series of metal and metal alloys in molten salt has been systemically studied. Four metal cations with different valence states, silver(Ag~+), nickel(Ni^(2+)), copper(Cu^(2+)), and iron(Fe^(3+)), could all be reduced on the solid cathode with high current efficiency and the corresponding metal products were of high purity. The electrodeposition of aluminum-lanthanum(Al-Ln) alloy on the aluminum cathode was also successfully carried out with microplasma as the anode, and the same alloy was obtained by using the conventional anode electrode. These results indicated that microplasma anode based on non-contact direct-current(DC) glow discharge is a promising electrode to be applied in molten salt electrolysis.展开更多
On the basis of coordinated electrodeposition of carboxylated chitosan(CCS),we presented a green method to prepare Cu NCs and Cu NCs/CCS nanocomposite films.The method shows a range of benefits,such as the convenient ...On the basis of coordinated electrodeposition of carboxylated chitosan(CCS),we presented a green method to prepare Cu NCs and Cu NCs/CCS nanocomposite films.The method shows a range of benefits,such as the convenient and eco-friendly process,mild conditions,and simple post-treatment.The experimental results reveal that a homogeneous deposited film(Cu NCs/CCS nanocomposite film)is generated on the Cu plate(the anode)after electrodeposition,which exhibits an obvious red florescence.The results from TEM observation suggest there are nanoparticles(with the average particle size of 2.3 nm)in the deposited film.Spectral analysis results both demonstrate the existence of Cu NCs in the deposited film.Moreover,the Cu NCs/CCS film modified electrode is directly created through electrodeposition of CCS,which enables promising application in the electrochemical sensing.By means of fluorescence properties of Cu NCs,the Cu NCs/CCS film also owns the potential in fluorescence detection.Therefore,this work builds a novel method for the green synthesis of Cu NCs,meanwhile it offers a convenient and new electrodeposition strategy to prepare polysaccharide-based Cu NCs nanocomposites for uses in functional nanocomposites and bioelectronic devices.展开更多
The emergence of Li–Mg hybrid batteries has been receiving attention,owing to their enhanced electrochemical kinetics and reduced overpotential.Nevertheless,the persistent challenge of uneven Mg electrodeposition rem...The emergence of Li–Mg hybrid batteries has been receiving attention,owing to their enhanced electrochemical kinetics and reduced overpotential.Nevertheless,the persistent challenge of uneven Mg electrodeposition remains a significant impediment to their practical integration.Herein,we developed an ingenious approach that centered around epitaxial electrocrystallization and meticulously controlled growth of magnesium crystals on a specialized MgMOF substrate.The chosen MgMOF substrate demonstrated a robust affinity for magnesium and showed minimal lattice misfit with Mg,establishing the crucial prerequisites for successful heteroepitaxial electrocrystallization.Moreover,the incorporation of periodic electric fields and successive nanochannels within the MgMOF structure created a spatially confined environment that considerably promoted uniform magnesium nucleation at the molecular scale.Taking inspiration from the“blockchain”concept prevalent in the realm of big data,we seamlessly integrated a conductive polypyrrole framework,acting as a connecting“chain,”to interlink the“blocks”comprising the MgMOF cavities.This innovative design significantly amplified charge‐transfer efficiency,thereby increasing overall electrochemical kinetics.The resulting architecture(MgMOF@PPy@CC)served as an exceptional host for heteroepitaxial Mg electrodeposition,showcasing remarkable electrostripping/plating kinetics and excellent cycling performance.Surprisingly,a symmetrical cell incorporating the MgMOF@PPy@CC electrode demonstrated impressive stability even under ultrahigh current density conditions(10mAcm^(–2)),maintaining operation for an extended 1200 h,surpassing previously reported benchmarks.Significantly,on coupling the MgMOF@PPy@CC anode with a Mo_(6)S_(8) cathode,the assembled battery showed an extended lifespan of 10,000 cycles at 70 C,with an outstanding capacity retention of 96.23%.This study provides a fresh perspective on the rational design of epitaxial electrocrystallization driven by metal–organic framework(MOF)substrates,paving the way toward the advancement of cuttingedge batteries.展开更多
Rare refractory metals(RRMs)play a significant role in fundamental industries,including electronics,chemical industry,machinery,etc.,and future advanced fields,such as aerospace and superconductivity.However,the tradi...Rare refractory metals(RRMs)play a significant role in fundamental industries,including electronics,chemical industry,machinery,etc.,and future advanced fields,such as aerospace and superconductivity.However,the traditional production processes of RRMs based on high-temperature thermal reduction cannot meet the requirements of low-energy consumption.This dilemma could be addressed efficiently by using a low-temperature electrodeposition strategy in ionic liquids(ILs).This review summarizes a panoramic view of the latest developments on the electrodeposition of RRMs in ILs after a brief review on the current industrial production methods of RRMs.Based on this,the electrochemical mechanism occurring at the cathode during the electrodeposition process of RRMs in different electrolytes and under different conditions is thoroughly discussed,because it is crucial for the successful production of pure RRMs.In addition,this review not only analyses the main challenges that hinder the industrial application of the electrodeposition of RRMs in ILs,but also proposes corresponding solutions.We hope this review can provide a valuable guidance for the fundamental research and industrial development of lowtemperature electrodeposition of RRMs.展开更多
α-Ni(OH)2 was synthesized from a NiCl2 solution by electrodeposition method.In order to conduct a systematic study on the effects of experimental parameters,a series of electrolyte initial pH values,current densities...α-Ni(OH)2 was synthesized from a NiCl2 solution by electrodeposition method.In order to conduct a systematic study on the effects of experimental parameters,a series of electrolyte initial pH values,current densities,electrodeposition temperatures,and electrodeposition time were used.Cyclic voltammetry results demonstrated a side reaction of Ni^2++2e→Ni.The X-ray diffraction analysis,Fourier-transform infrared spectrum,and the color of the product showed that pureα-Ni(OH)2 could be obtained in the initial pH value range of 2−5.86,current density range of 10−25 mA/cm^2,electrodeposition temperature range of 25−35℃,and electrodeposition time range of 1.0−3.0 h.When electrodeposition temperature increased to 45℃,a mixture ofα-Ni(OH)2 and metallic Ni was obtained.A current density higher than 30 mA/cm^2 resulted in the sample with features ofβ-Ni(OH)2.A small amount of metallic Ni existed in the as-prepared sample when current density decreased to 5 mA/cm^2.A slight increase of electrolyte pH was observed with increasing initial solution pH and current density.Electrodeposition mass revealed a slight decrease with initial pH decreasing and showed an almost linear increase with current density increasing.The slope of the curve for electrodeposition mass versus electrodeposition time remained stable in the first 2.0 h and then decreased.展开更多
Aluminum was electrodeposited with constant current on AZ31 magnesium alloy pretreated under optimized conditions from trimethyl-phenyl-ammonium chloride and anhydrous aluminum chloride （TMPAC-AlCl3） quaternary ammo...Aluminum was electrodeposited with constant current on AZ31 magnesium alloy pretreated under optimized conditions from trimethyl-phenyl-ammonium chloride and anhydrous aluminum chloride （TMPAC-AlCl3） quaternary ammonium room temperature ionic liquids with benzene as a co-solvent. The corrosion resistance of the as-deposited Al layers was evaluated in 3.5% NaCl solution by the electrochemical technologies. The Al depositions were characterized by scanning electron microscopy equipped with energy dispersion X-ray. The results show that the microstructures of the Al depositions have spherical equiaxed grains obtained at a high current density, and bulk grains at a low current density. The Al deposition obtained at 12.3 mA/cm2 has a smooth and compact surface. The electrochemical measurements indicate that the thicker Al deposition can more effectively protect the Mg substrate. The Al deposition with bulk grains hardly protects the AZ31 Mg substrate from corrosion owing to its porosity.展开更多
In order to improve the corrosion resistance and microhardness of AZ91D magnesium alloy, TiN nanoparticles were addedto fabricate Ni-P-TiN composite coating by electrodeposition. The surface, cross-section morphology ...In order to improve the corrosion resistance and microhardness of AZ91D magnesium alloy, TiN nanoparticles were addedto fabricate Ni-P-TiN composite coating by electrodeposition. The surface, cross-section morphology and composition wereexamined using SEM, EDS and XRD, and the corrosion resistance was checked by electrochemical technology. The results indicatethat TiN nanoparticles were doped successfully in the Ni-P matrix after a series of complex pretreatments including activation, zincimmersion and pre-electroplating, which enhances the stability of magnesium alloy in electrolyte and the adhesion betweenmagnesium alloy and composite coating. The microhardness of the Ni-P coating increases dramatically by adding TiN nanoparticlesand subsequent heat treatment. The corrosion experimental results indicate that the corrosion resistance of Ni-P-TiN compositecoating is much higher than that of uncoated AZ91D magnesium alloy and similar with Ni-P coating in short immersion time.However, TiN nanoparticles play a significant role in long-term corrosion resistance of composite coatings.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
The process parameters were optimized for the electrodeposition of cobalt from cobalt chloride solution in the membrane electrolytic reactor. Effects of parameters such as catholyte composition, current density and t...The process parameters were optimized for the electrodeposition of cobalt from cobalt chloride solution in the membrane electrolytic reactor. Effects of parameters such as catholyte composition, current density and temperature on the current efficiency, specific power consumption and quality of deposition were studied. The catholyte was a mixed solution of cobalt chloride, the initial middle electrolyte consisted of diluted hydrochloric acid, and the anolyte was sulfuric acid. An anion exchange membrane separated the catholyte from the middle electrolyte, and a cation exchange membrane separated the anolyte from the middle electrolyte. The results showed that a maximum current efficiency of 97.5% was attained under the optimum experimental condition of an catholyte composition of 80 g/L Co^2＋, 20 g/L H3BO3, 3 g/L NaF and pH of 4, at a cathode current density of 250 A/m2 and a temperature of 50 ℃ HCl could be produced in the middle compartment electrochemically up to 0.45 mol/L.展开更多
The nanocomposite coating is obtained by electrochemical deposition of the zinc plating solution with ceria nanoparticles (mean diameter 30 nm). The effect of ceria nanoparticles on the electrodeposited zinc coating i...The nanocomposite coating is obtained by electrochemical deposition of the zinc plating solution with ceria nanoparticles (mean diameter 30 nm). The effect of ceria nanoparticles on the electrodeposited zinc coating is stu died by weight loss test, inductively copuled plasma quantometer (ICP), scanning electron microscopy (SEM) and X ray diffraction (XRD), respectively. It is found that under the same electrodeposition conditions, the corrosion resistance of the nanocomposite coating increases obviously while that of the micron composite coating only improves slightly; The ceria content of the nanocomposite coating is more than that of the micron composite coating. Ceria nanoparticles modify the surface morphology and crystal structure of the zinc matrix in correlation with the increase of corrosion resistance.展开更多
A new kind of laminar metal matrix nanocomposite（MMC） was fabricated by an electrodeposition process with copper and superaligned carbon nanotubes film（SACNT film）.The SACNT film was put on a titanium plate and th...A new kind of laminar metal matrix nanocomposite（MMC） was fabricated by an electrodeposition process with copper and superaligned carbon nanotubes film（SACNT film）.The SACNT film was put on a titanium plate and then a layer of copper was electrodeposited on it.By repeating the above process,the laminar Cu/SACNT composite which contains dozens or hundreds of layers of copper and SACNT films was obtained.The thickness of a single copper layer was controlled by adjusting the process parameter easily and the thinnest layer is less than 2 μm.The microscopic observation shows that the directional alignment structure of SACNT is retained in the composite perfectly.The mechanical and electrical properties testing results show that the tensile and yield strengths of composites are improved obviously compared with those of pure copper,and the high conductivity is retained.This technology is a potential method to make applicable MMC which characterizes high volume fraction and directional alignment of carbon nanotubes.展开更多
基金support from the National Key Research and Development Program of China(2021YFB3201400,2021YFB3201401,2020YFC1908602)the National Natural Science Foundation of China(21904001 and 61774159)+1 种基金the Anhui Provincial Natural Science Foundation(2008085QF288)the Scientific Research Foundation for the Returned Overseas Chinese Scholars,Anhui Province(2020LCX032).
文摘Metal-organic framework(MOF)nanostructures have emerged as a prominent class of materials in the advancement of electrochemical sensors.The rational design of bimetallic MOF-functionalized microelectrode is of importance for improv-ing the electrochemical performance but still in great challenge.In this work,the bimetallic FeCo-MOF nanostructures were assembled onto a gold disk ultramicroelectrode(Au UME,5.2μm in diameter)via an in-situ electrodeposition method,which enhanced the sensitive detection of epinephrine(EP).The in-situ electrodeposited FeCo-MOF exhibited a character-istic nanoflower-like morphology and was uniformly dispersed on the Au UME.The FeCo-MOF/Au UME demonstrated excellent electrochemical performance on the detection of EP with a high sensitivity of 36.93μA·μmol^(-1)·L·cm^(-2)and a low detection limit of 1.28μmol·L^(-1).It can be attributed to the nonlinear diffusion of EP onto the ultra-micro working substrate,coupled with synergistical catalytic activity of the bimetallic Fe,Co within MOF structure.Furthermore,the FeCo-MOF/Au UME has been successful applied to the analysis of EP in human serum samples,yielding high recovery rates.These results not only contribute to the expansion of the research area of electrochemical sensors,but also provide novel insights and directions into the development of high-performance MOF-based electrochemical sensors.
文摘Electrochromic(EC)smart windows utilizing a reversible metal electrodeposition device(RMED)offer a compelling alternative for dynamically regulating transmissions of optical and thermal energy.An EC device(ECD)is constructed by reversible metal electrodeposition(RME)of Bi/Cu on WO_(3)·xH_(2)O film electrodeposited onto fluorine-doped tin oxide(FTO)transparent conductive glass.The electrolyte consists of CuCl_(2),BiCl_(3),KCl and HCl aqueous solution,supplying necessary components for both electrochemical and electrodeposition processes.The ECD shows ability to rapidly transition between colorless and black states,which achieves a large optical modulation of 77.0%at 570 nm.In the black state,the ECD exhibits a near-zero transmittance in the wavelength range of 400-1100 nm while maintaining 96.6%of its initial optical modulation after coloration/bleaching cycling of 60000 s,exhibiting good cyclic stability.This RMED has relatively high stability under open-circuit voltage and also possesses excellent heat insulation performance.The results offer a solution to overcome the poor cyclic stability of RMEDs and improve the optical modulation of ECDs.
文摘pH-dependent multiple equilibria in cobalt sulfate-gluconate baths were calculated using stability constants adopted from literature.Changes of the bath speciation were then discussed in terms of spectrophotometric experiments and buffering properties of the solutions(pH 3-10).Cyclic voltammetry indicated changes in electrochemical behavior of cobalt species caused by different ionic compositions of the electrolytes.Tafel slopes were calculated and discussed in relation to electroreduction of cobalt species.Chronoamperometric studies showed 3D instantaneous nucleation of cobalt followed by diffusion-controlled growth,but it was disturbed at higher pH due to the release of cation from gluconate complexes as a limiting step.Diffusion coefficients of cobalt species were found.Changes in the pH were also reflected by modifications of morphology(SEM),development of preferred orientation planes(XRD,texture coefficients)and current efficiency,but not the thickness of the coatings deposited at constant potential of-1.0 V(vs Ag/AgCl).Anodic stripping analysis showed changes in anodic responses originated from the existence of preferentially oriented planes in cobalt layers.
基金supported by the National Natural Science Foundation of China(No.22179085).
文摘Aqueous zinc-ion batteries(AZIBs)are attractive for large-scale energy storage due to their safety and low cost,but practical use is limited by dendrite growth,hydrogen evolution,and passivation.Traditional solutions often introduce additional complexity without addressing the root cause:unstable zinc deposition.Recent advancements now focus on controlling zinc crystallographic orientation to fundamentally suppress inhomogeneous nucleation and growth.The(002)basal plane supports smooth,reversible growth and can be promoted via heteroepitaxy or homoepitaxy,enabling long cycle life even at high rates.However,emerging studies show that Zn(100)and Zn(101)orientations may offer comparable benefits through faster kinetics and reduced parasitic reactions.Scalable,non-epitaxial methods,such as electrolyte tuning and pressure control also show promise.Despite these advances,balancing thermodynamic stability with kinetic performance remains a major challenge.Future research should integrate orientation control with strategies against corrosion and calendar aging to enable practical,highperformance AZIBs.
基金supported by the Key Research and Development Program of Shanxi Province(202102130501007)the Natural Science Foundation of Shanxi Province(202403021212109,202203021211173)the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2024L039).
文摘Zinc(Zn)-based materials show broad application prospects for bone repair due to their biodegradability and good biocompatibility.In particular,Zn metal foam has unique interconnected pore structure that facilitates inward growth of new bone tissue,making it ideal candidates for orthopedic implants.However,pure Zn metal foam shows poor mechanical property,high degradation rate,and unsatisfactory osteogenic activity.Herein,Zinc-manganese(Zn-Mn)alloy foams were electrodeposited in Zn and Mn-containing electrolytes to overcome the concerns.The results showed that Mn could be incorporated into the foams in the form of MnZn_(13).Zn-Mn alloy foams showed better mechanical property and osteogenic activity as well as moderate degradation rate when compared with pure Zn metal foam.In addition,these properties could also be regulated by preparation process.The peak stress and osteogenic activity increased with deposition current(0.3‒0.5 A)and electrolyte pH(3‒5),but decreased with electrolyte temperature(20‒40℃),while the degradation rate exhibited opposite tendency,which suggests high deposition current and electrolyte pH and low electrolyte temperature can fabricate Zn-Mn alloy foam with favorable mechanical property,moderate degradation rate,and osteogenic activity.These findings provide a valuable reference for the design and fabrication of novel Zn-based biodegradable materials.
基金financially supported from the National Natural Science Foundation of China(Nos.52274291,52204305)Beijing Institute of Technology Research Fund Program for Young Scholars,China(No.1740011182102).
文摘The development of low-energy consumption and environmentally friendly electrodeposition of metal/alloy films or coatings is presently one of the primary topics for the research community.For this purpose,deep eutectic solvents(DESs)are valued as electrolytes for their advantages of low operating temperature and wide electrochemical windows.At present,there is large amount of literature on this emerging field,but there are no specialized reviews of these studies.Here,after a brief introduction of DESs’concept and history,we comprehensively reviewed the lastest progress on the metal/alloy electrodeposition in DESs.Additionally,we discussed the key influence factors of the electrodeposition process and analyzed the corresponding mechanisms.Based on these,we emphasized the importance of the establishment of predictive models for dealing with the challenges in large-scale applications.
基金supported by Southern Marine Science and Engineering Guangdong Laboratory(Zhuhai)(No.SML2023SP243)the National Key Research and Development Program of China(No.2022YFC2906100)the National Natural Science Foundation of China(No.92475202)are acknowledged.
文摘Electrochemical metallurgy at low temperature(<473 K)shows promise for the extraction and refinement of metals and alloys in a green and sustainable manner.However,the kinetics of the electrodeposition process is generally slow at low temperature,resulting in large overpotential and low current efficiency.Thus,the application of external physical fields has emerged as an effective strategy for improving the mass and charge transfer processes during electrochemical reactions.This review highlights the challenges associated with low-temperature electrochemical processes and briefly discusses recent achievements in optimizing electrodeposition processes through the use of external physical fields.The regulating effects on the optimization of the electrodeposition process and the strategies for select-ing various external physical fields,including magnetic,supergravity,and ultrasonic fields are summarized from the perspectives of equipment and mechanisms.Finally,advanced methods for in-situ characterization of external physical field-assisted electrodeposition processes are reviewed to gain a deeper understanding of metallic electrodeposition.An in-depth exploration of the mechanism by which external physical fields affect the electrode process is essential for enhancing the efficiency of metal extraction at low temperatures.
基金the Natural Science Foundation of Chongqing of China(Nos.CSTB2024NSCQ-MSX1013 and cstc2021jcyj-msxmX1139)the Science and Technology Research Program of Chongqing Education Commission(Nos.KJZD-K202304502,KJQN202201214,KJQN202001243 and KJZD-M202301201)the Opening Project of Material Corrosion and Protection Key Laboratory of Sichuan province(No.2024CL05).
文摘Building a superhydrophobic coating on a carbon steel substrate is an effective strategy for enhancing metal protection.A practical approach to producing a series of superhydrophobic Ni/SiO_(2)composite coatings(SSN)using one-step electrodeposition method is shown.The effect of processing parameters on surface structure and wettability was thoroughly explored,resulting in the identification of three typical surface morphologies.The prepared coating with petal-like structure(SSN-3)obtained under the optimum parameters exhibited the best water repellency,achieving a contact angle of 162.7°and a sliding angle of 4.1°.The droplet bouncing behavior on SSN coatings surface was studied,and the delayed icing time was recorded.Meanwhile,the mechanical stability and chemical corrosion resistance of SSN coatings were focused.The superhydrophobic SSN-3 coating with unique surface structure exhibited excellent reliability.The anticorrosion mechanism of SSN-3 coating was discussed,and its corrosion protection efficiency was up to 98.5%.The superior properties of the superhydrophobic SSN-3 coating make it suitable for diverse applications.
基金financially supported by the Natural Science Foundation of Hebei Province(No.B2021208030)College Students Innovation Training Program(Nos.202206224 and S2021113409001)。
文摘Hydrogen is considered as the promising energy carrier to substitute traditional fossil fuel,due to its cleanliness,renewability and high energy density.Water electrolysis is a simple and eonvenient technology for hydrogen production.The efficiency of water electrolysis for hydrogen production is limited by the electrocatalytic performances on hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).The exorbitant Pt-and Ir-/Ru-based electrocatalysts as optimal HER and OER electrocatalysts,respectively,restrict water electrolysis development.Recently,non-precious metal-based high-entropy electrocatalysts have exhibited excellent electrocatalytic activities and long-term stabilities for water electrolysis,as promising precious cataly st candidates.Therefore,the construction of the high-entropy electroc atalysts is vital to water electrolysis industry.Electrodeposition technology is an efficient method for the preparation of high-entropy electrocatalysts due to its simple,fast,energy-saving and environmental-friendly advantages.Multi-component co-precipitation facilely occurs during the electroredox in electrodeposition processes.High-entropy alloys,oxides,(oxy)hydroxides,phosphides and phosphorus sulfide oxides have been successfully prepared by galvanostatic,potentiostatic electrodeposition,cyclic voltammetry,pulse,nanodroplet-mediated and cathodic plasma electrodeposition techniques.Hence,introduction of the development of high-entropy electrocatalysts synthesized by electrodeposition technology is significant to researchers and industries.Challenges and outlooks are also concluded to boost the industrial application of electrodeposition in water electrolysis and other energy conversion areas.
基金financially supported by the National Natural Science Foundation of China (Nos.21976104, 21906051)Young Elite Scientists Sponsorship Program (No.2021QNRC001) of China Association for Science and Technology。
文摘Microplasma based on glow discharge could act as a non-contact gaseous electrode and has attracted much attention in both fundamental research and application. Herein, with microplasma as the anode,the electrodeposition process of a series of metal and metal alloys in molten salt has been systemically studied. Four metal cations with different valence states, silver(Ag~+), nickel(Ni^(2+)), copper(Cu^(2+)), and iron(Fe^(3+)), could all be reduced on the solid cathode with high current efficiency and the corresponding metal products were of high purity. The electrodeposition of aluminum-lanthanum(Al-Ln) alloy on the aluminum cathode was also successfully carried out with microplasma as the anode, and the same alloy was obtained by using the conventional anode electrode. These results indicated that microplasma anode based on non-contact direct-current(DC) glow discharge is a promising electrode to be applied in molten salt electrolysis.
基金Funded by the National Natural Science Foundation of China(No.51873167)the Fundamental Research Funds for the Central Universities(WUT:2022-CL-A1-04)。
文摘On the basis of coordinated electrodeposition of carboxylated chitosan(CCS),we presented a green method to prepare Cu NCs and Cu NCs/CCS nanocomposite films.The method shows a range of benefits,such as the convenient and eco-friendly process,mild conditions,and simple post-treatment.The experimental results reveal that a homogeneous deposited film(Cu NCs/CCS nanocomposite film)is generated on the Cu plate(the anode)after electrodeposition,which exhibits an obvious red florescence.The results from TEM observation suggest there are nanoparticles(with the average particle size of 2.3 nm)in the deposited film.Spectral analysis results both demonstrate the existence of Cu NCs in the deposited film.Moreover,the Cu NCs/CCS film modified electrode is directly created through electrodeposition of CCS,which enables promising application in the electrochemical sensing.By means of fluorescence properties of Cu NCs,the Cu NCs/CCS film also owns the potential in fluorescence detection.Therefore,this work builds a novel method for the green synthesis of Cu NCs,meanwhile it offers a convenient and new electrodeposition strategy to prepare polysaccharide-based Cu NCs nanocomposites for uses in functional nanocomposites and bioelectronic devices.
基金National Natural Science Foundation of China,Grant/Award Number:31770608Postgraduate Research&Practice Innovation Program of Jiangsu Province,Grant/Award Number:KYCX22_1081Jiangsu Specially‐appointed Professorship Program,Grant/Award Number:Sujiaoshi[2016]20。
文摘The emergence of Li–Mg hybrid batteries has been receiving attention,owing to their enhanced electrochemical kinetics and reduced overpotential.Nevertheless,the persistent challenge of uneven Mg electrodeposition remains a significant impediment to their practical integration.Herein,we developed an ingenious approach that centered around epitaxial electrocrystallization and meticulously controlled growth of magnesium crystals on a specialized MgMOF substrate.The chosen MgMOF substrate demonstrated a robust affinity for magnesium and showed minimal lattice misfit with Mg,establishing the crucial prerequisites for successful heteroepitaxial electrocrystallization.Moreover,the incorporation of periodic electric fields and successive nanochannels within the MgMOF structure created a spatially confined environment that considerably promoted uniform magnesium nucleation at the molecular scale.Taking inspiration from the“blockchain”concept prevalent in the realm of big data,we seamlessly integrated a conductive polypyrrole framework,acting as a connecting“chain,”to interlink the“blocks”comprising the MgMOF cavities.This innovative design significantly amplified charge‐transfer efficiency,thereby increasing overall electrochemical kinetics.The resulting architecture(MgMOF@PPy@CC)served as an exceptional host for heteroepitaxial Mg electrodeposition,showcasing remarkable electrostripping/plating kinetics and excellent cycling performance.Surprisingly,a symmetrical cell incorporating the MgMOF@PPy@CC electrode demonstrated impressive stability even under ultrahigh current density conditions(10mAcm^(–2)),maintaining operation for an extended 1200 h,surpassing previously reported benchmarks.Significantly,on coupling the MgMOF@PPy@CC anode with a Mo_(6)S_(8) cathode,the assembled battery showed an extended lifespan of 10,000 cycles at 70 C,with an outstanding capacity retention of 96.23%.This study provides a fresh perspective on the rational design of epitaxial electrocrystallization driven by metal–organic framework(MOF)substrates,paving the way toward the advancement of cuttingedge batteries.
基金financially supported by the National Natural Science Foundation of China(No.52274291)Beijing Institute of Technology Research Fund Program for Young Scholars(No.1740011182102)the National Key R&D Program of China(No.2022YFC2906100)。
文摘Rare refractory metals(RRMs)play a significant role in fundamental industries,including electronics,chemical industry,machinery,etc.,and future advanced fields,such as aerospace and superconductivity.However,the traditional production processes of RRMs based on high-temperature thermal reduction cannot meet the requirements of low-energy consumption.This dilemma could be addressed efficiently by using a low-temperature electrodeposition strategy in ionic liquids(ILs).This review summarizes a panoramic view of the latest developments on the electrodeposition of RRMs in ILs after a brief review on the current industrial production methods of RRMs.Based on this,the electrochemical mechanism occurring at the cathode during the electrodeposition process of RRMs in different electrolytes and under different conditions is thoroughly discussed,because it is crucial for the successful production of pure RRMs.In addition,this review not only analyses the main challenges that hinder the industrial application of the electrodeposition of RRMs in ILs,but also proposes corresponding solutions.We hope this review can provide a valuable guidance for the fundamental research and industrial development of lowtemperature electrodeposition of RRMs.
基金Project(U1710257)supported by the National Natural Science Foundation of China。
文摘α-Ni(OH)2 was synthesized from a NiCl2 solution by electrodeposition method.In order to conduct a systematic study on the effects of experimental parameters,a series of electrolyte initial pH values,current densities,electrodeposition temperatures,and electrodeposition time were used.Cyclic voltammetry results demonstrated a side reaction of Ni^2++2e→Ni.The X-ray diffraction analysis,Fourier-transform infrared spectrum,and the color of the product showed that pureα-Ni(OH)2 could be obtained in the initial pH value range of 2−5.86,current density range of 10−25 mA/cm^2,electrodeposition temperature range of 25−35℃,and electrodeposition time range of 1.0−3.0 h.When electrodeposition temperature increased to 45℃,a mixture ofα-Ni(OH)2 and metallic Ni was obtained.A current density higher than 30 mA/cm^2 resulted in the sample with features ofβ-Ni(OH)2.A small amount of metallic Ni existed in the as-prepared sample when current density decreased to 5 mA/cm^2.A slight increase of electrolyte pH was observed with increasing initial solution pH and current density.Electrodeposition mass revealed a slight decrease with initial pH decreasing and showed an almost linear increase with current density increasing.The slope of the curve for electrodeposition mass versus electrodeposition time remained stable in the first 2.0 h and then decreased.
文摘Aluminum was electrodeposited with constant current on AZ31 magnesium alloy pretreated under optimized conditions from trimethyl-phenyl-ammonium chloride and anhydrous aluminum chloride （TMPAC-AlCl3） quaternary ammonium room temperature ionic liquids with benzene as a co-solvent. The corrosion resistance of the as-deposited Al layers was evaluated in 3.5% NaCl solution by the electrochemical technologies. The Al depositions were characterized by scanning electron microscopy equipped with energy dispersion X-ray. The results show that the microstructures of the Al depositions have spherical equiaxed grains obtained at a high current density, and bulk grains at a low current density. The Al deposition obtained at 12.3 mA/cm2 has a smooth and compact surface. The electrochemical measurements indicate that the thicker Al deposition can more effectively protect the Mg substrate. The Al deposition with bulk grains hardly protects the AZ31 Mg substrate from corrosion owing to its porosity.
基金Projects(51171172,51131005)supported by the National Natural Science Foundation of ChinaProject(R16E010001)supported by Zhejiang Provincial Natural Science Foundation of China+1 种基金Project(2015QNA3011)supported by Fundamental Research Funds for the Central Universities,ChinaProject(14DZ2261000)supported by Science and Technology Commission of Shanghai Municipality,China
文摘In order to improve the corrosion resistance and microhardness of AZ91D magnesium alloy, TiN nanoparticles were addedto fabricate Ni-P-TiN composite coating by electrodeposition. The surface, cross-section morphology and composition wereexamined using SEM, EDS and XRD, and the corrosion resistance was checked by electrochemical technology. The results indicatethat TiN nanoparticles were doped successfully in the Ni-P matrix after a series of complex pretreatments including activation, zincimmersion and pre-electroplating, which enhances the stability of magnesium alloy in electrolyte and the adhesion betweenmagnesium alloy and composite coating. The microhardness of the Ni-P coating increases dramatically by adding TiN nanoparticlesand subsequent heat treatment. The corrosion experimental results indicate that the corrosion resistance of Ni-P-TiN compositecoating is much higher than that of uncoated AZ91D magnesium alloy and similar with Ni-P coating in short immersion time.However, TiN nanoparticles play a significant role in long-term corrosion resistance of composite coatings.
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.
基金Project(2015016)supported by the Young Scholars Science Foundation of Lanzhou Jiaotong University,ChinaProject(2015BAE04B01)supported by the National Science-technology Support Program of ChinaProject(21466019)supported by the National Natural Science Foundation of China
文摘The process parameters were optimized for the electrodeposition of cobalt from cobalt chloride solution in the membrane electrolytic reactor. Effects of parameters such as catholyte composition, current density and temperature on the current efficiency, specific power consumption and quality of deposition were studied. The catholyte was a mixed solution of cobalt chloride, the initial middle electrolyte consisted of diluted hydrochloric acid, and the anolyte was sulfuric acid. An anion exchange membrane separated the catholyte from the middle electrolyte, and a cation exchange membrane separated the anolyte from the middle electrolyte. The results showed that a maximum current efficiency of 97.5% was attained under the optimum experimental condition of an catholyte composition of 80 g/L Co^2＋, 20 g/L H3BO3, 3 g/L NaF and pH of 4, at a cathode current density of 250 A/m2 and a temperature of 50 ℃ HCl could be produced in the middle compartment electrochemically up to 0.45 mol/L.
文摘The nanocomposite coating is obtained by electrochemical deposition of the zinc plating solution with ceria nanoparticles (mean diameter 30 nm). The effect of ceria nanoparticles on the electrodeposited zinc coating is stu died by weight loss test, inductively copuled plasma quantometer (ICP), scanning electron microscopy (SEM) and X ray diffraction (XRD), respectively. It is found that under the same electrodeposition conditions, the corrosion resistance of the nanocomposite coating increases obviously while that of the micron composite coating only improves slightly; The ceria content of the nanocomposite coating is more than that of the micron composite coating. Ceria nanoparticles modify the surface morphology and crystal structure of the zinc matrix in correlation with the increase of corrosion resistance.
基金Project(20111080980)supported by the Initiative Scientific Research Program,Tsinghua University,China
文摘A new kind of laminar metal matrix nanocomposite（MMC） was fabricated by an electrodeposition process with copper and superaligned carbon nanotubes film（SACNT film）.The SACNT film was put on a titanium plate and then a layer of copper was electrodeposited on it.By repeating the above process,the laminar Cu/SACNT composite which contains dozens or hundreds of layers of copper and SACNT films was obtained.The thickness of a single copper layer was controlled by adjusting the process parameter easily and the thinnest layer is less than 2 μm.The microscopic observation shows that the directional alignment structure of SACNT is retained in the composite perfectly.The mechanical and electrical properties testing results show that the tensile and yield strengths of composites are improved obviously compared with those of pure copper,and the high conductivity is retained.This technology is a potential method to make applicable MMC which characterizes high volume fraction and directional alignment of carbon nanotubes.
