Elucidation of Abnormal Potential Responses of Cation-Selective Electrodes with Solid-State Membranes to Aqueous Solutions of CuCl2 and CdI2

An empirical solution to abnormal potential responses, showing peaks of emf, of commercial Cu2+- and Cd2+-selective electrodes with solid-state membranes was proposed for aqueous solutions of CuCl2 and CdI2. The two-step processes of Mn+ + Yn? (s: solid phase) MY(s) and MY(s) + 2X? X2MY2?(s) (n = 1, 2) at a test solution/electrode-interface were considered as a model. Here, Mn+, Yn?, and X? refer to a divalent or univalent cation, functional groups of electrode materials, and a halide ion (X? = Cl?, Br?, I?), respectively. By applying electrochemical potentials to these processes at n = 2, we derived an equation. Regression analyses based on the equation reproduced well the plots of emf versus log 2(*[M]t) for the Cd(II) and Cu(II) systems: *[M]t denotes a total concentration of species relevant to M2+ in a bulk of the aqueous solution. Also, we obtained log Ks(CdBr2) = 4.28 ? 0.22, log Ks(CdI2) = 6.98 ? 0.05, log Ks(CuCl2) = 3.96 ? 0.09, and log Ks(CuBr2) = 11.4 at 25?C. The magnitude in ?log Ks reflected that in the logarithmic solubility product, log {*[M2+](*[X?])2}, for bulk water, where *[M2+] or *[X?] denotes a molar concentration of the bulk solu-tion of M2+ or X? at equilibrium, respectively. Moreover, a mixture of CuSO4 with NaCl at the molar ratio of 1:1 yielded a plot similar to that of CuCl2.

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.

Design strategies and recent advancements of solid-state supercapacitor operating in wide temperature range

Solid-state supercapacitors(SSCs)are emerging as one of the promising energy storage devices due to their high safety,superior power density,and excellent cycling life.However,performance degradation and safety issues under extreme conditions are the main challenges for the practical application.With the expansion of human activities,such as space missions,polar exploration,and so on,the investigation of SSC with wide temperature tolerance,high energy density,power density,and sustainability is highly desired.In this review,the effects of temperature on SSC are systematically illustrated and clarified,including the properties of the electrolyte,ion diffusion,and reaction dynamics of the supercapacitor.Subsequently,we summarize the recent advances in wide-temperature-range SSCs from the aspect of electrolyte modification,electrode design,and interface adjustment between electrode and electrolyte,especially with critical concerns on ionic conductivity and cycling stability.In the end,a perspective is presented,expecting to promote the practical application of the SSC in harsh conditions.

A Review on Engineering Design for Enhancing Interfacial Contact in Solid-State Lithium–Sulfur Batteries

The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high interfacial impedances existing between the SSEs and the electrodes(both lithium anodes and sulfur cathodes)hinder the charge transfer and intensify the uneven deposition of lithium,which ultimately result in insufficient capacity utilization and poor cycling stability.Hence,the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries.In this review,we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes,and summarize recent progresses of their applications in solidstate Li–S batteries.Moreover,the challenges and perspectives of rational interfacial design in practical solid-state Li–S batteries are outlined as well.We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.

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.

Construction and Application of a PVC Membrane Enoxacin Ion-selective Electrode Based on a Needle-shaped Inner Reference Electrode

A PVC membrane enoxacin ion-selective electrode based on a needle-shaped inner reference electrode was prepared. A Ag/AgCl wire was used as the substrate of this electrode. It was previously coated with a thin sheet of urea-formaldehyde resin containing Cl - ions to form a needle-shaped inner reference electrode, then the inner reference electrode was coated with a thin sheet of a PVC membrane containing an enoxacin tetraphenylborate ion-pair complex. The influences of various ion-pair complexes, concentrations of the active components in the membrane and the plasticizers on the performance of the electrode were studied by orthogonal design. The linear response range of the electrode was 7.9×10 -5 -1.0×10 -2 mol/L. The detection limit was 2.0×10 -5 mol/L. The slope was 30.4 mV/decade(25 ℃). The electrode can be used for the potentiometric determination of enoxacin tablets directly. The average recovery was 100.4%, and the RSD was 0.9%. The results agreed with those determined by the method in Chinese Pharmacopoeia.

Potentiometric Urea Biosensor Based on Ion-Selective Electrode by Different Immobilization Procedures

Enzyme was immobilized on an ammonium ion-selective electrode by different methods.An ion-selective electrode is not completely ion-specific,and interfering ions react with the ion-selective electrode membrane,altering the measured potential.Therefore,the characteristics of the effect of other ions on ammonium ion-selective electrode-based urea biosensors are considered.Based on the experimental results,the urea biosensor based on entrapment had a high response voltage of around 189 mV and fast response time of around 16 sec.Moreover,selectivity of the urea biosensor in different interfering ions was considered to elucidate the characteristics of ammonium ion-selective electrode-based biosensors.

STUDY OF CALCIUM ION-SELECTIVE ELECTRODE BASED ON A NEW NEUTRAL CARRIER

A calcium ion-setective eletrode based on a new neutral carrier was studied.The electrode gives a Nernstian response in the rang 5.9-1 Pa and the response is stable in a wide pH range.Logarithms of setectivity coefficents are -2.3 Li(+),-3.5 Na(+),-4.0 K(+),-3.7NH_4(+),-4.5 Mg(2+) and -4.4Zn(2+).

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...

Newly Design Porous/Sponge Red Phosphorus@Graphene and Highly Conductive Ni2P Electrode for Asymmetric Solid State Supercapacitive Device With Excellent Performance

Supercapacitors have attracted much attention in the field of electrochemical energy storage.However,material preparation,stability,performance as well as power density limit their applications in many fields.Herein,a sponge-like red phosphorus@graphene(rP@rGO)negative electrode and a Ni2P positive electrode were prepared using a simple one-step method.Both electrodes showed excellent performances(294 F g^−1 and 1526.6 F g^−1 for rP@rGO and Ni2P,respectively),which seem to be the highest among all rP@rGO-and Ni2P-based electrodes reported so far.The asymmetric solid-state supercapacitor was assembled by sandwiching a gel electrolyte-soaked cellulose paper between rP@rGO and Ni2P as the negative and positive electrodes.Compared to other asymmetric devices,the device,which attained a high operating window of up to 1.6 V,showed high energy and power density values of 41.66 and 1200 W kg−1,respectively.It also has an excellent cyclic stability up to 88%after various consecutive charge/discharge tests.Additionally,the device could power commercial light emitting diodes and fans for 30 s.So,the ease of the synthesis method and excellent performance of the prepared electrode materials mat have significant potential for energy storage applications.

Electrode connection optimization for both temperature difference and purification of lanthanum rod during solid-state electrotransport

In order to solve the problem of large temperature difference between the center and ends of the metallic rod in the purification process of solid-state electrotransport(SSE),three types of electrode connections of tantalum and the corresponding rods of metallic lanthanum were designed,the temperature distributions of three kinds of rod were measured,and the influence of temperature difference on the purification effect of solid-state electrotransport was investigated.The results indicate that the maximum temperature difference of the rod will be significantly reduced through decreasing the cross section of electrode connection to make its unit length resistance close to that of rod,or increasing the unit length resistance of the section at both ends of the rod.When these two measures are adopted at the same time,the effect of decreasing rod temperature difference is the best in the present study,and the maximum temperature difference of the rod can be reduced to 29℃when the maximum temperature of the rod is 820℃.The migration velocity of the impurities at rod ends can be obviously improved after the rod temperature difference is reduced,which enables the purification effect and efficiency of solid-state electrotransport to be greatly raised;it is also found that the major impurities iron in metallic lanthanum migrates more easily than oxygen and carbon during the purification of metal lanthanum with solid-state electrotransport.

New All-solid-state Carbonate Ion-selective Electrode with Ag2CO3-BaCO3 as Sensitive Films

A new all-solid-state carbonate ion-selective electrode was fabricated via electrochemical and ion-exchange reactions with Ag nanoparticles and Ag2CO3-BaCO3 as ion-to-electron transducer and ion-selective layer, respectively. This paper presented the detailed procedures of the construction of the electrode, the applications of the electrode in various experiments, and the corresponding chemical reaction principles involved. The fabricated electrode was characterized by means of scanning electron microscopy（SEM）, energy dispersive spectrometer（EDS）, and electrochemical analyses. The electrode exhibited stable linear responses to carbonate anions（10-5--10-1 mol/L） with average Slope of the curve being -26.56 mV per decade, and showed negligible responses to NO3, SO2-, and Sal- anions. The electrode was further used to measure the concentration of carbonate anions in boiler water. The measured concentration was lower than that determined via titration. Overall, the electrode exhibited the advantages of miniaturized size, robust construction, and compatibility with other equipment and thus could be ideally integrated into various sensor platforms to collect chemical data from industrial heat exchangers.

Ion Selective Electrode Array Analysis Using Variable Step-Size Generalized Simulated Annealing

A global optimum location algorithm called Variable Step-Size Generalized Simulated Annealing(VSGSA) was applied to treating the data obtained by using an array of ion-electrodes in solutions containing mixtures of Na+, K+, Ca2+. Unlike traditional optimization algorithms such as simplex procedure, VSGSA can be used to determine the model parameters without any priori information about the analytical system under investigation and overcome the disadvantage of simplex method which might converge to local extrema depending on the starting positions. The algorithm was applied to po-tentiometric determination of ions in mixture solutions.

Binding mechanism of halide ions to bovine serum albumin and hemoglobin: investigated by ion selective-electrode

The binding mechanism of the interactions of halide ions (F–, Br– and I–) with bovine serum albumin (BSA) and hemoglobin (Hb) were studied at different temperatures, by using ion-selective electrodes. The experimental data were treated according to Klotz equation, and the number of binding sites and the binding constants were determined. The results show that the binding sites of F– on protein molecules are more than those of Br– and I–. Additionally, the number of the binding sites for halide ions on protein molecules increases with increasing temperature. This study also indicates that the binding constants for the interactions of halide ions with proteins gradually decrease as the size of halide ions and temperature increases. These behaviors were reasonably interpreted with the structural and thermodynamic factors. The thermodynamic functions at different temperatures were calculated with thermodynamic equations, and the enthalpy change for the interactions were also determined by isothermal titration calorimetry (ITC) at 298.15 K, which indicate that the interactions of halide ions with proteins are mainly electrostatic interaction.

Coulometric Response of H-Selective Solid-Contact Ion-Selective Electrodes and Its Application in Flexible Sensors+

The analytical performance of H+-selective solid-contact ion-selective electrodes(SCISEs)based on solid contact polyaniline doped with chloride(PANI(Cl))and poly(3,4-ethylenedioxythiophene)doped with poly(styrene sulfonate)(PEDOT(PSS))was characterized by a developed coulometric signal transduction method.PEDOT(PSS)solid contact is covered by PVC based H+-selective membrane.The obtained coulometric signal demonstrates that the cumulated charge can be amplified by increasing the capacitance of solid contact.SCISEs covered with spin-coated membrane behave faster amperometric response than electrodes with drop-cast mem-brane.In contrast to earlier works,the amperometric response and impedance spectrum demonstrates H+transfer through SCISEs is independent from the thickness of membrane.The exceptional behavior of PANI(Cl)H+-SCISEs shows that the capacitance estimated from impedance spectrum at low frequency 10 mHz and coulometric signal of PANI(Cl)based SCISEs is influenced by the applied po-tentials,whereas PEDOT(PSS)solid contact is independent from the chosen applied potentials.Furthermore,preliminary investiga-tions of coulometric signal transduction on flexible pH sensor implies its potential applications in wearable sensors for sweat ion concentration detection.

Nonaqueous potassium-ion full-cells:Mapping the progress and identifying missing puzzle pieces

This review addresses the growing interest for potassium-ion full-cells(KIFCs)in view of the transition from potassium-ion half-cells(KIHCs)toward commercial K-ion batteries(KIBs).It focuses on the key parameters of KIFCs such as the electrode/electrolyte interfaces challenge,major barriers,and recent advancements in KIFCs.The strategies for enhancing KIFC performance,including interfaces co ntrol,electrolyte optimization,electrodes capacity ratio,electrode material screening and electrode design,are discussed.The review highlights the need to evaluate KIBs in full-cell configurations as half-cell results are strongly impacted by the K metal reactivity.It also emphasizes the importance of understanding solid electrolyte interphase(SEI)formation in KIFCs and explores promising nonaqueous as well as quasiand all-solid-state electrolytes options.This review thus paves the way for practical,cost-effective,and scalable KIBs as energy storage systems by offering insights and guidance for future research.

Structural Isomers:Small Change with Big Difference in Anion Storage

Organic electrode materials are promising for batteries.However,the reported organic electrodes are often facing the challenges of low specific capacity,low voltage,poor rate capability and vague charge storage mechanisms,etc.Isomers are good platform to investigate the charge storage mechanisms and enhance the performance of batteries,which,however,have not been focused in batteries.Herein,two isomers are reported for batteries.As a result,the isomer tetrathiafulvalene(TTF)could store two monovalent anions reversibly,deriving an average discharge voltage of 1.05 V and a specific capacity of 220 mAh g−1 at a current density of 2 C.On the other hand,the other isomer tetrathianaphthalene could only reversibly store one monovalent anion and upon further oxidation,it would undergo an irreversible solid-state molecular rearrangement to TTF.The molecular rearrangement was confirmed by electrochemical performances,X-ray diffraction patterns,nuclear magnetic resonance spectra,and 1H detected heteronuclear multiple bond correlation spectra.These results suggested the small structural change could lead to a big difference in anion storage,and we hope this work will stimulate more attention to the structural design for boosting the performance of organic batteries.

Synthesis of a Tweezer-like Bis(phenylthiapropoxy)calix[4]-arene as a Cation/π Enhanced Sensor for Ion-Selective Electrodes

Two novel 25,27-dihydroxy-26,28-bis(3-phenylthiapropoxy)-calixarene (3) and 25,27-dihydroxy-26,28-bis(3-phenylthia-propoxy)-5,11,17,23-tetra-tert-butylcalixarene (4) were synthesized for the evaluation of their ion-selectivity in ion-selective electrodes (ISEs). ISEs based on 3 and 4 as neutral ionophores were prepared, and their selectivity coefficients for Ag + (lg K pot Ag,M) were investigated against other alkali metal, alkaline-earth metal, aluminum, thallium (I), lead and some transition metal ions using the separate solution method (SSM). These ISEs showed excellent Ag + selectivity over most of the interfering cations examined, except for Hg 2+ and Fe 2+ having relative smaller interference (lg K pot Ag,M≤-2.1).

Comparison of three measurement models of soil nitrate-nitrogen based on ion-selective electrodes

Ion-selective electrode(ISE)is a quick and low-cost method of soil nitrate nitrogen(N)detection.The measurement models of soil nitrate-N based on ISEs includes the linear regression model,multiple linear regression model and BP neural network model,and so on.Three models were analyzed in theory,measurement experiments of validation samples and soil nitrate-N concentrations were carried out in this study,and the measurement accuracies of the three models were compared.The results showed that,in the measurement experiments of validation samples and soil nitrate-N concentrations,BP neural network model had the highest accuracy(the average relative errors between results of the BP neural network model and the reference values were 5.07%and 8.81%,respectively)among the three models,multiple linear regression model had the second highest accuracy(the average relative errors between results of the multiple linear regression model and the reference values were 7.70%and 10.51%,respectively),linear regression model couldn’t exclude the interference of chloride ions so that it had the lowest accuracy(the average relative errors between results of the linear regression model and the reference values were 11.16%and 12.28%,respectively)among the three models.The BP neural network model can effectively restrain the interference of chloride ions,and it has a high accuracy for the measurement of soil nitrate-N concentration,so that the BP neural network model can be used to measure soil nitrate-N concentration accurately.

A novel Ce(Ⅳ)ion-selective polyvinyl chloride membrane electrode based on HDEHP and HEH/EHP

A novel Ce（Ⅳ） ion-selective polyvinyl chloride（PVC） membrane electrode based on HDEHP and HEH/EHP as ionophore was successfully prepared. The factors affecting the response of Ce（Ⅳ） ion were investigated, such as membrane composition, internal solution, concentration of SO_4^（2–）, and acidity in test solution. The best performance was obtained using the membrane with PVC：DBP：HDEHP：HEH/EHP：OA mass ratio of 75：175：5：5：5. The proposed electrode exhibited a Nernstian slope of 30.44 mV/decade for Ce（Ⅳ） ion over a linear concentration range of 1×10^（–5）–1×10^（–1） mol/L with the detection limit of 9.0×10^（-6） mol/L. The electrode showed stable response within the SO_4^（2–） concentration range of 0.1–1 mol/L and the acidity range of 0.25–1.2 mol/L H＋. The proposed electrode showed high selectivity for Ce（Ⅳ） over a wide variety of interfering ions and a fast response time. It was used as an indicator in the potentiometric titration of Ce（Ⅳ） solution with H_2O_2 solution, and could also be used for the determination of Ce（Ⅳ） in real Ce（Ⅳ）-containing aqueous samples.