Using Electrodeposition of Carboxylated Chitosan for Green Preparation of Copper Nanoclusters and Nanocomposite Films

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.

Reshaping Li–Mg hybrid batteries:Epitaxial electrodeposition and spatial confinement on MgMOF substrates via the lattice‐matching strategy

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.

Electrodeposition of chitosan/graphene oxide conduit to enhance peripheral nerve regeneration

Currently available commercial nerve guidance conduits have been applied in the repair of peripheral nerve defects.However,a conduit exhibiting good biocompatibility remains to be developed.In this work,a series of chitosan/graphene oxide(GO)films with concentrations of GO varying from 0-1 wt%(collectively referred to as CHGF-n)were prepared by an electrodeposition technique.The effects of CHGF-n on proliferation and adhesion abilities of Schwann cells were evaluated.The results showed that Schwann cells exhibited elongated spindle shapes and upregulated expression of nerve regeneration-related factors such as Krox20(a key myelination factor),Zeb2(essential for Schwann cell differentiation,myelination,and nerve repair),and transforming growth factorβ(a cytokine with regenerative functions).In addition,a nerve guidance conduit with a GO content of 0.25%(CHGFC-0.25)was implanted to repair a 10-mm sciatic nerve defect in rats.The results indicated improvements in sciatic functional index,electrophysiology,and sciatic nerve and gastrocnemius muscle histology compared with the CHGFC-0 group,and similar outcomes to the autograft group.In conclusion,we provide a candidate method for the repair of peripheral nerve defects using free-standing chitosan/GO nerve conduits produced by electrodeposition.

Inverse-opal structured TiO_(2) regulating electrodeposition behavior to enable stable lithium metal electrodes

Lithium metal anode is almost the ultimate choice for high-energy density rechargeable batteries, but its uneven electrochemical dissolution-deposition characteristics lead to poor cycle stability and lithium dendrites safety problems. The fundamental solution to the problems is to interfere electrodeposition process of lithium metal so that it can be carried out reversibly and stably. In this work, an inverse-opal structured TiO2membrane with a thickness of only ~1 μm is designed to regulate the electrodeposition behavior of lithium metal, in which the ordered channels homogenize mass transfer process, the anatase TiO_(2)walls of the ion channels reduce desolvation barrier of solvated lithium-ions, and the spherical cavities with a diameter of ~300 nm confine migration of the adsorbed lithium atoms during electrocrystallization to diminish overpotential of lithium. These systematic effects cover and essentially change the whole process of electrodeposition of lithium metal and eliminate the possibility of lithium dendrite formation. The as-obtained lithium metal electrode delivers a Coulombic efficiency of 99.86% in the 100th cycle, and maintains a low deposition overpotential of 0.01 V for 800 h.

Three-dimensional structural Cu^(6)Sn_(5)/carbon nanotubes alloy thin-film electrodes fabricated by in situ electrodeposition from the leaching solution of waste-printed circuit boards

Tin-based materials are very attractive anodes because of their high theoretical capacity,but their rapid capacity fading from volume expansions limits their practical applications during alloying and dealloying processes.Herein,the improved binder-free tin-copper intermetallic/carbon nanotubes(Cu6Sn5/CNTs)alloy thin-film electrodes are directly fabricated through efficient in situ electrodeposition from the leaching solution of treated waste-printed circuit boards(WPCBs).The characterization results show that the easily agglomerated Cu6Sn5 alloy nanoparticles are uniformly dispersed across the three-dimensional network when the CNTs concentration in the electrodeposition solution is maintained at 0.2 g·L−1.Moreover,the optimal Cu6Sn5/CNTs-0.2 alloy thin-film electrode can not only provide a decent discharge specific capacity of 458.35 mAh·g^(−1)after 50 cycles at 100 mA·g^(−1)within capacity retention of 82.58%but also deliver a relatively high reversible specific capacity of 518.24,445.52,418.18,345.33,and 278.05 mAh·g^(−1)at step-increased current density of 0.1,0.2,0.5,1.0,and 2.0 A·g^(−1),respectively.Therefore,the preparation process of the Cu6Sn5/CNTs-0.2 alloy thin-film electrode with improved electrochemical performance may provide a cost-effective strategy for the resource utilization of WPCBs to fabricate anode materials for lithium-ion batteries.

Effect of Electrodeposition Methods of Cuprous Oxide on Antibacterial Properties of Concrete

Three types of electrodeposition,DC electrodeposition,low-frequency pulsed electrodeposition and high-frequency pulsed electrodeposition,were used to deposit cuprous oxide on the concrete surface to improve the antibacterial properties of concrete.The effects of pulse deposition frequency on the antibacterial property of concrete were studied using sulfate-reducing bacteria(SRB)and Escherichia coli(E.coli)as model bacteria.The bacterial concentration and the antibacterial rate were measured to evaluate the antibacterial performance of concrete.The effects of different deposition methods on the elemental content of copper and the amount of copper ions exuded were studied.XRD and SEM were used to analyze the microstructure of the deposited layers.The experimental results show that the concrete treated by electrodeposition exhibited good antibacterial properties against SRB and E.coli.The antibacterial effect of cuprous oxide deposited on concrete by pulse method was better than that by direct current(DC)method.The antibacterial rate of concrete was positively correlated with the exudation rate of copper ion.As the pulse frequency increased,the deposits content on the surface was increased with an accompanying improvement in the antibacterial property.Besides,the pulsed current had an indiscernible effect on the composition of the sediments,which were all mainly composed of Cu_(2)O,but the morphology of the Cu_(2)O differed greatly.Cubic octahedral cuprous oxide had better antibacterial properties with the highest copper ion leaching rate compared with cubic and spherical cuprous oxide.

Electrodeposition of Al on AZ31 magnesium alloy in TMPAC-AlCl_3 ionic liquids

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.

Influence of sodium silicate on manganese electrodeposition in sulfate solution

The influences of sodium silicate on manganese electrodeposition in sulfate solution were investigated. Manganese electrodeposition experiments indicate that a certain amount of sodium silicate can improve cathode current efficiency and initial pH 7.0?8.0 is the optimized pH for high cathode current efficiency. The analyses of scanning electron microscopy (SEM) and X-ray diffraction (XRD) indicate the compact morphology and nanocrystalline structure of electrodeposits. X-ray photoelectron spectrometry (XPS) analysis shows that the elements of Mn, Si and O exist in the deposit. The solution chemistry calculations of sulfate electrolyte and sodium silicate solution indicate that species of Mn2+, MnSO4, Mn(SO4)2?2 , Mn2+, MnSiO3, Mn(NH3)2+, SiO32?and HSiO3? are the main active species during the process of manganese electrodeposition. The reaction trend between Mn2+ and Si-containing ions is confirmed by the thermodynamic analysis. In addition, polarization curve tests confirm that sodium silicate can increase the overpotential of hydrogen evolution reaction, and then indirectly improve the cathode current efficiency.

Electrodeposition behavior of bright nickel in air and water-stable betaine·HCl-ethylene glycol ionic liquid

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.

Electrodeposition and corrosion resistance of Ni-P-TiN composite coating on AZ91D magnesium alloy

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.

Electrodeposition of cobalt in double-membrane three-compartment electrolytic reactor

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.

Electrodeposition of As-Sb alloy from high arsenic-containing solutions

As-Sb alloy was electrodeposited from high arsenic-containing solutions. The influences of current density, Sb（3＋） concentration, reaction temperature and HCl concentration on the electrolyte composition, cell voltage and current efficiency were investigated. The surface morphology, composition and structure of the deposits were analyzed by scanning electron microscopy（SEM）, inductively coupled plasma mass spectrometry（ICP-MS） and X-ray diffraction（XRD）, respectively. The results show that the prepared As-Sb alloy shows an amorphous structure under all conditions. Under the optimized condition, i.e., 10 g/L As（3＋）, 2 g/L Sb（3＋）, 4 mol/L HCl, current density of 4 mA/cm2 and temperature of 20 °C, desired As-Sb alloy with a composition of 70.26% As and 29.74% Sb（mass fraction） is obtained. What is more, the current efficiency is as high as 94.74% and high arsenic removal rate is achieved under this condition.

CeO_2/Zn NANOCOMPOSITE COATING BY ELECTRODEPOSITION

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.

Fabrication of superaligned carbon nanotubes reinforced copper matrix laminar composite by electrodeposition

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.

FABRICATION OF Bi NANOWIRE ARRAY BY ELECTRODEPOSITION TECHNOLOGY

In the fabrication of Bi nanowire array thermoelectric materials,electrodeposition technology has been used to deposit bismuth into the nanopores of anodic alumina porous films.The experiments show that the temperature significantly affects the electrodepositing process,and the simple form of Bi 3+ in the solutions is helpful to the deposition of metal Bi.The pulse plating technique is necessary for the electrodeposition because of the diffusive difficulty of Bi 3+ into the nanopores of the films.The XRD analysis indicates that Bi nanowire arrays have been manufactured by this technology.

Electrodeposition of iridium from composite ionic liquid

In order to study the electrodeposition process of iridium in composite ionic liquid, the effects of N, N-dimethylacetamide（DMAC） on the viscosity, conductivity and electrochemical stability of composite ionic liquid BMIC-BMIBF4, as well as the electrochemical behavior of Ir Cl3 in this system were studied. Iridium（Ir） coatings were deposited at different constant potentials and characterized by SEM and XRD. The results show that the addition of DMAC can evidently decrease the viscosity of the composite system, increase conductivity and improve electrochemical stability of the composite system. Cyclic voltammograms of a Au electrode illustrate that the process controlled by diffusion rate is irreversible with the average charge transfer coefficient of 0.170 and average diffusion coefficient of 1.096×10-6 cm^2/s. In addition, SEM image shows that Ir film deposited at the reduction peak potential is dense and even, while XRD pattern shows that Ir deposit is polycrystalline structure.

Electrodeposition of Cu_2O/g-C_3N_4 heterojunction film on an FTO substrate for enhancing visible light photoelectrochemical water splitting

An immobilized Cu2O/g-C3N4 heterojunction film was successfully made on an FTO substrate by electrophoretic deposition of g-C3N4 on a Cu2O thin film.The photoelectrochemical（PEC） performance for water splitting by the Cu2O/g-C3N4 film was better than pure g-C3N4 and pure Cu2O film.Under-0.4 V external bias and visible light irradiation,the photocurrent density and PEC hydrogen evolution efficiency of the optimized Cu2O/g-C3N4 film was-1.38 mA/cm^2 and 0.48 mL h^-1 cm^-2,respectively.The enhanced PEC performance of Cu2O/g-C3N4 was attributed to the synergistic effect of light coupling and a matching energy band structure between g-C3N4 and Cu2O as well as the external bias.

Electrodeposition and characterization of nano-structured black nickel thin films

The electrodeposition and characterization of nano-structured black nickel coatings were presented. The influences of bath pH, electrodeposition time, stirring speed, temperature and current density on the color and microstructure of the electrodeposited nickel film were investigated through naked eyes, scanning electron microscopy （SEM） and X-ray diffraction （XRD） techniques. Meanwhile, the corrosion resistance of the optimized black nickel film was evaluated by the polarization measurement and electrochemical impedance spectroscopy （EIS） in the neutral 3.5% NaC1 solution. The results show that the color of the electrodeposited nickel film was highly dependent on the above technological parameters. The operating parameters were optimized mainly according to the color. The optimized black nickel film possesses nano-structure with an average grain diameter of about 50 nm. It also exhibits enhanced corrosion resistance when compared with white nickel coatings electrdodeposited under the same condition except the variation of the electroplating current density.

Microstructure and depositional mechanism of Ni-P coatings with nano-ceria particles by pulse electrodeposition

Nano-CeO2 （RE） particles were co-deposited into Ni-P binary composite coatings by applying pulse current （PC） under ultrasonic （U） field. Morphology, chemical content and crystal microstructure were characterized by environmental scanning electron microscopy （E-SEM） with energy dispersive X-ray analysis （EDXA）, XRD diffractometry and transmission electron microscopy （TEM）. Experimental results show that Ni-P coating reinforced with 15g/L nano-CeO2, in amorphous state and with compact structure, can be improved in the microhardness from HV0.2580 to HV0.2780 by annealing at 600 °C for 2 h. The highest content of codeposited Ce and deposition rate can reach 2.3% and 68 μm/h, respectively. Furthermore, the effect of RE adsorption and pulse overpotential on depositional mechanism was investigated. n-CeO2 particles or Ce4＋ ions with strong adsorption capacity acted as the catalytic nucleus to improve densification effectively. During annealing at 600 °C for 2 h, n-CeO2 particles will uniformly adsorb on crystal grain to preferentially pad and heal up gaps of cracking Ni boundaries, promoting dispersion strengthening with refiner-grained structure.

Electrodeposition of Cu coating with high corrosion resistance on Mg-3.0Nd-0.2Zn-0.4Zr magnesium alloy

To improve the corrosion resistance, electrodeposition of Cu coating on Mg-3.0Nd-0.2Zn-0.4Zr （mass fraction, %NZ30K） magnesium alloy via an appropriate pretreatment was investigated. The surface morphologies, compositions and microstructures of the pretreated films and Cu coating were characterized in detail. The results show that the activation film consists of fluoride and phosphates and Zn immersion film forms preferentially on the eutectic compound Mg12Nd phase region. A smooth, uniform and dense Cu coating is successfully obtained. Potentiodynamic polarization tests reveal that Cu coating can greatly improve the corrosion resistance of NZ30K magnesium alloy. Open circuit potential （OCP） and electrochemical impedance spectroscopy （EIS） tests during long-term immersion further demonstrate that Cu coating can provide an effective protection for NZ30K magnesium alloy from corrosion up to ~60 h, due to its dense structure and a stable passive film formed. In addition, Cu coating exhibits good adhesion to substrate as confirmed by thermal shock test.