Femtosecond laser fabrication of 3D vertically aligned micro-pore network on thick-film Li_(4)Ti_(5)O_(12)electrode for high-performance lithium storage

The development of energy storage devices with high energy density relies heavily on thick film electrodes,but it is challenging due to the limited ion transport kinetics inherent in thick electrodes.Here,we report on the preparation of a directional vertical array of micro-porous transport networks on LTO electrodes using a femtosecond laser processing strategy,enabling directional ion rapid transport and achieving good electrochemical performance in thick film electrodes.Various three-dimensional(3D)vertically aligned micro-pore networks are innovatively designed,and the structure,kinetics characteristics,and electrochemical performance of the prepared ion transport channels are analyzed and discussed by multiple characterization and testing methods.Furthermore,the rational mechanisms of electrode performance improvement are studied experimentally and simulated from two aspects of structural mechanics and transmission kinetics.The ion diffusion coefficient,rate performance at 60 C,and electrode interface area of the laser-optimized 60-15%micro-porous transport network electrodes increase by 25.2 times,2.2 times,and 2.15 times,respectively than those of untreated electrodes.Therefore,the preparation of 3D micro-porous transport networks by femtosecond laser on ultra-thick electrodes is a feasible way to develop high-energy batteries.In addition,the unique micro-porous transport network structure can be widely extended to design and explore other high-performance energy materials.

Semi-implantable device based on multiplexed microfilament electrode cluster for continuous monitoring of physiological ions

Modern medicine is increasingly interested in advanced sensors to detect and analyze biochemical indicators.Ion sensors based on potentiometric methods are a promising platform for monitoring physiological ions in biological subjects.Current semi-implantable devices are mainly based on single-parameter detection.Miniaturized semi-implantable electrodes for multiparameter sensing have more restrictions on the electrode size due to biocompatibility considerations,but reducing the electrode surface area could potentially limit electrode sensitivity.This study developed a semi-implantable device system comprising a multiplexed microfilament electrode cluster(MMEC)and a printed circuit board for real-time monitoring of intra-tissue K^(+),Ca^(2+),and Na^(+)concentrations.The electrode surface area was less important for the potentiometric sensing mechanism,suggesting the feasibility of using a tiny fiber-like electrode for potentiometric sensing.The MMEC device exhibited a broad linear response(K^(+):2–32 mmol/L;Ca^(2+):0.5–4 mmol/L;Na^(+):10–160 mmol/L),high sensitivity(about 20–45 mV/decade),temporal stability(>2weeks),and good selectivity(>80%)for the above ions.In vitro detection and in vivo subcutaneous and brain experiment results showed that the MMEC system exhibits good multi-ion monitoring performance in several complex environments.This work provides a platform for the continuous real-time monitoring of ion fluctuations in different situations and has implications for developing smart sensors to monitor human health.

Studies of Adsorption of Cadmium Ions by Biowaste Adsorbent from Aqueous Solutions with Ion-Selective Electrodes and ICP-OES

Using environment-friendly and low-cost biowaste adsorbents as toxic metal ion removal substrates from aqueous solutions has a great economic advantage. This work evaluated pumpkin and potato peel biowastes for the adsorption of cadmium ions. The biowastes were treated with acid or base. Batch experiments were carried out by introducing a known concentration of metal ion solution into the biowaste sorbent at various pH levels. The pH and metal ion concentration was monitored with pH and cadmium ion-selective electrode continuously for two hours, and the final concentration for the metal ion after 24 hours was measured with the cadmium electrode and then confirmed with ICP-OES. L-type isotherms were obtained that fit to Freundlich model. Adsorption isotherms showed chemical adsorption and the kinetics following the second order model. Equilibrium adsorption capacity is higher than 29 mg/g at pH 5.6 when the initial concentration is 220 ppm. Dynamic cadmium adsorption capacity is 17 mg/g from aqueous solution when the feed solution is 220 ppm with pumpkin peel biowaste sorbent. The biowaste materials can be regenerated with acid washing.

An AuNPs/Mesoporous NiO/Nickel Foam Nanocomposite as a Miniaturized Electrode for Heavy Metal Detection in Groundwater

Heavy metals,notably Pb2+and Cu^(2+),are some of the most persistent contaminants found in groundwater.Frequent monitoring of these metals,which relies on efficient,sensitive,cost-effective,and reliable methods,is a necessity.We present a nanocomposite-based miniaturized electrode for the concurrent measurement of Pb2+and Cu^(2+)by exploiting the electroanalytical technique of square wave voltammetry.We also propose a facile in situ hydrothermal calcination method to directly grow binder-free mesoporous Ni O on a three-dimensional nickel foam,which is then electrochemically seeded with gold nanoparticles(Au NPs).The meticulous design of a low-barrier Ohmic contact between mesoporous Ni O and Au NPs facilitates target-mediated nanochannel-confined electron transfer within mesoporous Ni O.As a result,the heavy metals Pb2+(0.020 mg.L^(-1)detection limit;2.0–16.0 mg.L^(-1)detection range)and Cu^(2+)(0.013 mg.L^(-1)detection limit;0.4–12.8 mg.L^(-1)detection range)can be detected simultaneously with high precision.Furthermore,other heavy metal ions and common interfering ions found in groundwater showed negligible impacts on the electrode’s performance,and the recovery rate of groundwater samples varied between 96.3%±2.1%and 109.4%±0.6%.The compactness,flexible shape,low power consumption,and ability to remotely operate our electrode pave the way for onsite detection of heavy metals in groundwater,thereby demonstrating the potential to revolutionize the field of environmental monitoring.

Hetero-interfacial nickel nitride/vanadium oxynitride porous nanosheets as trifunctional electrodes for HER,OER and sodium ion batteries

The development of single electrode with multifunctional purposes for electrochemical devices remains a symbolic challenge in recent technology.This work explores interfacially-rich transition metal nitride hybrid that consist of nickel nitride and vanadium oxynitride(VO_(0.26)N_(0.52))on robust carbon fiber(denoted CF/Ni_(3)N/VON)as trifunctional electrode for hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and sodium ion batteries(SIBs).The as-prepared CF/Ni_(3)N/VON exhibits low HER overpotential of 48 m V@10 m A cm^(-2),OER overpotential of 287 m V@10 m A cm^(-2),and sodium-ion anode storage reversible capacity of 555 m A h g^(-1)@0.2 C.Theoretical analyses reveal that the Ni_(3)N effectively facilitates hydrogen desorption for HER,increases the electrical conductivity for OER,and promotes the Na-ion storage intercalation process,while the VON substantially elevates the water dissociation kinetics for HER,accelerates the adsorption of OH*intermediate for OER and enhances the Na-ion surface adsorption storage process.Owing to the excellent HER and OER performances of the CF/Ni_(3)N/VON electrode,an overall water splitting device denoted as CF/Ni_(3)N/VON//CF/Ni_(3)N/VON was not only assembled showing an operating voltage of 1.63 V at current density of 10 m A cm^(-2)but was also successfully self-powered by the assembled CF/Ni_(3)N/VON//CF/Na_(3)V_(2)(PO_(4))_(3) flexible sodium ion battery.This work will contribute to the development of efficient and cost-effective flexible integrated electrochemical energy devices.

Determination of Boron Trifluoride in Boron Trifluoride Complex by Fluoride Ion Selective Electrode

A method was proposed to determine boron trifluoride in boron trifluoride complex using fluoride ion selective electrode(ISE). Hydroxide was chosen to mask aluminum for the determination of 0.01—0.1 mol/L of fluoride. The simulation indicated that the permissible aluminum masked at a certain p H value was limited and hardly related to F-concentration and boric acid. It is better to control p H value below 11.5 and the aluminum concentration within 0.025 mol/L to minimize the interference of hydroxide to the fluoride ISE. The decomposition conditions of boron trifluoride by aluminum chloride were investigated. It is found that the F-detection ratio will approach 1.0 if the Al/F molar ratio is 0.3—0.7 and aluminum concentration is no more than 0.02 mol/L when heated at 80 ℃ for 10 min. In one word, hydroxide is quite fit to mask aluminum for samples which contain high content of fluoride and aluminum and the BF3 content can be successfully determined by this method.

A Method of Determining Selectivity Coefficients Based on the Practical Slope of Ion Selective Electrodes

It is a problem to be solved that the experimental selectivity coefficients of ion selective electrodes (ISEs) depend on the activity. This paper studied the new method of determining selectivity coefficients. A mixed ion response equation, which was similar to Nicolsky-Eisenman (N-E) equation recommended by IUPAC, was proposed. The equation includes the practical response slope of ISEs to the primary ion and the interfering ion. The selectivity coefficient was defined by the equation instead of the N-E equation. The experimental part of the method is similar to that based on the N-E equation. The values of selectivity coefficients obtained with this method do not depend on the activity whether the electrodes exhibit the Nernst response or non-Nernst response. The feasibility of the new method is illustrated experimentally.

A New Type of Dibenzoyl Tartaric Acid Selective Electrode Based on Polymer Membrane Containing Calixarene Ionophore

A new type of di benzoyl tartaric acid selective electr ode has been developed. Three double\| arm calixarene derivatives were emp loyed as the neutral ionophores. The poly(vinyl chloride) membrane electrode containing an amide derivative of ca lixarene as the neutral carrier an d a dibutyl phthalate as the plastici zer exhibited the highest sensitivity for dibenzoyl tartaric acid. The slop e of linear portion was 27.8 mV per c oncertration decade. The electrode has a fast response and a long lifetime .

Surface engineering of ZnO electrocatalyst by N doping towards electrochemical CO_(2) reduction

The discovery of efficient,selective,and stable electrocatalysts can be a key point to produce the largescale chemical fuels via electrochemical CO_(2) reduction(ECR).In this study,an earth-abundant and nontoxic ZnO-based electrocatalyst was developed for use in gas-diffusion electrodes(GDE),and the effect of nitrogen(N)doping on the ECR activity of ZnO electrocatalysts was investigated.Initially,a ZnO nanosheet was prepared via the hydrothermal method,and nitridation was performed at different times to control the N-doping content.With an increase in the N-doping content,the morphological properties of the nanosheet changed significantly,namely,the 2D nanosheets transformed into irregularly shaped nanoparticles.Furthermore,the ECR performance of Zn O electrocatalysts with different N-doping content was assessed in 1.0 M KHCO_(3) electrolyte using a gas-diffusion electrode-based ECR cell.While the ECR activity increased after a small amount of N doping,it decreased for higher N doping content.Among them,the N:ZnO-1 h electrocatalysts showed the best CO selectivity,with a faradaic efficiency(FE_(CO))of 92.7%at-0.73 V vs.reversible hydrogen electrode(RHE),which was greater than that of an undoped Zn O electrocatalyst(FE_(CO)of 63.4%at-0.78 V_(RHE)).Also,the N:ZnO-1 h electrocatalyst exhibited outstanding durability for 16 h,with a partial current density of-92.1 mA cm^(-2).This improvement of N:ZnO-1 h electrocatalyst can be explained by density functional theory calculations,demonstrating that this improvement of N:ZnO-1 h electrocatalyst comes from(ⅰ)the optimized active sites lowering the free energy barrier for the rate-determining step(RDS),and(ⅱ)the modification of electronic structure enhancing the electron transfer rate by N doping.

A potential-responsive ion-pump system based on nickel hexacyanoferrate film for selective extraction of cesium ions

A nickel hexacyanoferrate(NiHCF)film electrode was prepared with NiHCF,conductive carbon black,and polyvinylidene difluoride,which was coated on graphite plate substrate for selective extraction of Cs^(+)ions by using electrochemically switched ion exchange(ESIX)technology.A potential-responsive ionpump system for efficient extraction of Cs+ions was designed,and the effect of wet film thicknesses,charging modes,flow rates,and chamber widths on Cs+ions extraction performance was investigated.In the system,the adsorption capacity and removal percentage of Cs^(+)ions on the NiHCF film electrode reached as high as 147.69 mg·g^(-1)and 92.47%,respectively.Furthermore,the NiHCF film electrode showed high selectivity for Cs^(+)ions and stability.After seven cycles of adsorption/desorption,the desorption percentage could reach about 100%.The excellent Cs^(+)extraction performance should be attributed to the strong driving force produced by the potential-responsive ion-pumping effect in the ESIX process,as well as the low ion transfer resistance of the film electrode which is caused by the special crystal structure of NiHCF.In addition,the NiHCF film electrode was implemented to work together with the bismuth oxybromide(BiOBr)film electrode to accomplish the simultaneous extraction of Cs^(+)and Br^(-).And the adsorption capacity and removal percentage of Br^(-)ions on the BiOBr film electrode reached 69.53 mg·g^(-1)and 77.32%,correspondingly.It is expected that such a potential-responsive ion-pump system based on NiHCF and BiOBr film electrodes could be used for the selective extraction and concentration of Cs^(+)and Br^(-)ions from salt lake brine.

Selective capture of silver ions from aqueous solution by series of azole derivatives-functionalized silica nanosheets

The introduction of bifunctional groups into low-cost adsorbents for selective adsorption of Ag(I) through synergistic effect will have a profound impact on the recovery of precious metals. Organo silica nanosheets(organo-Si NSs) functionalized by series of azole derivatives(2-mercaptoimidazole(MI), 2-mercaptobenzimidazole(MBT) and 1H-1,2,4-triazole-3-thiol(MTT)), are fabricated and employed for selective removal of Ag(I). The structures of the organo-Si NSs are investigated using several characterization methods. The results of batch adsorption experiments display that the maximum adsorption amounts are 70.3, 103.2 and 139.5 mg·g^(-1) on MI-Si NSs, MBI-Si NSs and MTT-Si NSs for Ag(I) ions, and reach rapid equilibrium within 10–30 min. The adsorption processes are chemisorption and fit pseudo-second-order kinetic model and Langmuir adsorption isotherm model. Notably, MTT-Si NSs is greatly selective for Ag(I) in multicomponent system, and the distribution coefficient value of Ag(I) ions reaches 2331.26 ml·g^(-1). The reusability of organo-Si NSs is verified by four cycles of regeneration tests with 0.1 mol·L^(-1) HNO_(3) as the eluent. A combination of experimental, structural along with theoretical analysis is conducted to proclaim the structure-adsorptivity relationship:(i) The adsorption mechanisms are attributed to complexation.(ii) The amino group and sulfhydryl group of MTT-Si NSs as well as MBISi NSs may have synergistic impacts on Ag(I) capture.(iii) The differences in adsorption behavior and selectivity of the three organo-Si NSs are mainly related to the form of function groups, charge density and steric hindrance of adsorbent. This work not only sheds light on the promise of functionalized organo-Si NSs for the rapid and selective removal/enrichment of Ag(I) ions in complex water systems,but also provides new insights for designing cost-effective Si NSs-based adsorbents.

A comparative study of four 20-membered N_2S_4-crown ethers as ionophores for polymeric membrane silver selective electrodes

Four 20-membered N_2S_4-monoazathiacrown ethers have been synthesized and explored as neutral ionophores for Ag^+-selective electrodes.Potentiometric responses reveal that the flexibility of the ligands has great effect on the selectivity and sensitivity to Ag^+ ions.The electrode based on ionophore 9,10,20,25-tetrahydro-5H,12H-tribenzo[b,n,r][1,7,10,16,4,13]tetrathiadiaza cycloicosine 6,13-(7H,14H)-dione(C) with 2-nitrophenyl octyl ether(o-NPOE) as solvent in a poly(vinyl chloride)(PVC) membrane matrix sho...

Constructing Bidirectional Fluorine-Rich Electrode/Electrolyte Interphase Via Solvent Redistribution toward Long-Term Sodium Battery

The high concentration electrolytes with specific solvation structure could passivate the electrodes to prolong battery cycle life but at the expense of increased cost,which limits the wide application in commercialization.The regular concentration(1_(M))electrolytes with suitable properties(viscosity,ionic conductivity,etc.)are cost-guaranteed,but undesired reactions would always occur and lead to battery degradation during long cycles.To promote the long-term cycle stability in a cost-effective way,this work constructs bidirectional fluorine-rich electrode/electrolyte interphase(EEI)by redistribution of solvents and electrochemical induction.The fluorinated effect with reasonable zoning planning restricts morphological disintegration,meanwhile,forms spatial confinement on cathode.In particular,the obtained cathode electrolyte interphase(CEI)gets the ample ability of Na^(+)transport,which benefits from the fluorinated organics arranged in the epitaxy and the hemi-carbonate content acting on the thickness.Thus,the electrochemical long cycling performance of F-NVPOFⅡF-CC full cells is significantly enhanced(the decay rate at 1 C per cycle is as low as 0.01%).Such a fluorine-rich EEI engineering is expected to take transitional layers against the degradation of cells and make ultra-long cycle batteries possible.

Direct Determination of Potassium-Sodium Activity Ratio in Soil Suspension with Two Ion-Selective Electrodes

A K+-selective electrode and a Na+-selective electrode were used to construct a measuring cell without liquid-junction for the determination of the ion activity ratio of K+ to Na+ in soil suspensions. The measured cell potential was not affected by the total electrolyte concentration when the total cation concentration was 10-1-10-3 mol L-1 and the concentration ratio CK+ / CNa+. was 10:1 to 1:50. When the concentration ratios were equal to 1and the total electrolyte concentrations were 10-2 and 10-3 mol L-1, the ion activity ratio measurement would not be affected by pH in the pH range of 3.5 to 11.5 and 4.4 to 11 respectively. Ions other than H+ have no remarkable influence on the measurement. The ion activity ratio of K+ to Na+ measured directly in soil suspension agree well with those in centrifuged supernant solution. The relative deviation was within 4%. From the measured ion activity ratio, the difference of the bonding energies of K+ and Na+ ions was calculated.

Selective Heating of Transition Metal Usings Hydrogen Plasma and Its Application to Formation of Nickel Silicide Electrodes for Silicon Ultralarge-Scale Integration Devices

We developed an apparatus for producing high-density hydrogen plasma. The atomic hydrogen density was 3.1 × 1021 m?3 at a pressure of 30 Pa, a microwave power of 1000 W, and a hydrogen gas flow rate of 10 sccm. We confirmed that the temperatures of transition-metal films increased to above 800。C within 5 s when they were exposed to hydrogen plasma formed using the apparatus. We applied this phenomenon to the selective heat treatment of nickel films deposited on silicon wafers and formed nickel silicide electrodes. We found that this heat phenomenon automatically stopped after the nickel slicidation reaction finished. To utilize this method, we can perform the nickel silicidation process without heating the other areas such as channel regions and improve the reliability of silicon ultralarge-scale integration devices.

PVC Membrane Selective Electrode for Determination of Cadmium(Ⅱ) Ion in Chocolate Samples

Benzil bis(carbohydrazone)(BBC) is prepared and explored as new N N Schiff's base, which plays the role of an excellent ion carrier in the construction of a Cd(II) ion membrane sensor. The tris(2-ethylhexyl) phosphate best performance corresponds to a membrane composition of 30% poly(vinyl chloride), 65%(TEHP), 3.5% BBC and 1.5% tetradodecyl-ammoniumtetrakis(4-chlorophenyl) borate(ETH 500). This sensor shows very good selectivity and sensitivity towards cadmium ion over a wide variety of cations, including alkali, alkaline earth, transition and heavy metal ions. The effect of membrane composition, selectivity, pH and influence of additive on the response properties of electrode were investigated. The response mechanism was discussed in the view of UV-spectroscopy. The electrode exhibits a Nernstian behavior(with slope of 29.7 mV per decade) over a very wide concentration range from 1.0×10?1 to 1.0×10?8 mol·L?1 with a detection limit of 3.2×10?8 mol·L?1. It shows rela-tively fast response time in whole concentration range(<8 s) and can be used for at least 10 weeks in the pH range of 2.0-9.0. The proposed sensor is successfully used for the determination of cadmium in different chocolate sam-ples and as indicator electrode in titration with ethylene diamine tetraacetate(EDTA).

Preparation of CeO_2 Nanoparticles and Its Application to Ion-selective Electrodes Based on Acetyl Cellulose

CeO2 nanoparticles with an average diameter of about 30 nm were prepared by sol-gel method at lower temperature. The gel, transformed from the aqueous solution of metal nitrate and citric acid, can be combusted completely at lower temperature. The redox behavior and the crystallization process of the dried gel were studied by thermogravimetric analysis and infrared spectroscopy. The synthesized powders were characterized by X-ray powder diffraction and transmission electron microscopy. In addition, rare earth elements ion-selective electrodes based on acetyl cellulose were prepared using ultra fine cerium oxide powders.

Fluorine in drinking water and urine in the urban and rural areas of northwestern China——Its determination by a fluoride ion selective electrode

In this study, the author determined fluorine in drinking water and urine of residents who are divided into four age groups (5, 12, 35-44, 65-74 aged), living in Huangling City, Shaanxi Province and at 6 villages of Qin'an County, Gansu Province, P.R.China. Some residents are living in fluorine exposure areas. A total of 929 residents (463 females and 466 males) involved in the study were selected from 7 tap water systems. Drinking water samples were collected from each area and analyzed using the fluoride ion-selective method. No positive correlation relationship was found between fluorine concentrations in urine and those in drinking water in the area where the fluorine concentrations of drinking water are within the range of 1-2 mg/L. The fluorine absorbed by resistents of different ages is different in amount. With the same concentrations of fluorine in drinking water, more fluorine would be absorbed by young residents than old residents. No difference can be seen in absorption amount of fluorine among different genders.

The Measurement of Membrane Potential and NO3 Activity in Root Cells Using Ion-Selective Microelectrodes

Remobilisation of nitrate in plants, especially in vacuole of plant, is mostly related to the qua- lity of agricultural products and the high nitrogen use efficiency in plants. Ion-selective microelectrodes offer a non-destructive and non-interruptive method to measure NO 3 gradients and electric potential differences across both the plasma membrane and tonoplast. Thus, a double-barrelled microelectrode backfilled with a membrane sensor for NO 3 embedded in poly vinyl chloride (PVC) can record the NO 3 activity in cytoplasm and vacuole of a cell. This paper presented how to make this kind of microelectrode and how to do the intracellular measurements on intact plants. Our result showed that nitrate activity was about 2.7 mmol L 1 in cytoplasm while 70 mmol L 1 in vacuole, which implicated that vacuole was a pool of nitrate in plants.

Effect of Preparation Process of Functional Polymer Active Materials on Properties of Gadolinium Ion Selective Electrode

Recently we have studied the rare earth ion-selective electrodes with active materials of the func-tional polymers and found that the process chosen for the functional polymers had an effect on the propertiesof gadolinium ion selective electrode besides the effects of their structures.1.Effect of preparation process of the grafted polymers on the properties ofgadolinium ion selective electrodesThe electrode membranes which consist of functional polymers as active materials were prepared by re-action of gadolinium chloride with the radiation grafted clmer of acrlic acid and polystyrene of which