Electrochemical synthesis of trimetallic nickel-iron-copper nanoparticles via potential-cycling for high current density anion exchange membrane water-splitting applications

Hydrogen is known for its elevated energy density and environmental compatibility and is a promising alternative to fossil fuels.Alkaline water electrolysis utilizing renewable energy sources has emerged as a means to obtain high-purity hydrogen.Nevertheless,electrocatalysts used in the process are fabricated using conventional wet chemical synthesis methods,such as sol-gel,hydrothermal,or surfactantassisted approaches,which often necessitate intricate pretreatment procedures and are vulnerable to post-treatment contamination.Therefore,this study introduces a streamlined and environmentally conscious one-step potential-cycling approach to generate a highly efficient trimetallic nickel-iron-copper electrocatalyst in situ on nickel foam.The synthesized material exhibited remarkable performance,requiring a mere 476 mV to drive electrochemical water splitting at 100 mA cm^(-2)current density in alkaline solution.Furthermore,this material was integrated into an anion exchange membrane watersplitting device and achieved an exceptionally high current density of 1 A cm^(-2)at a low cell voltage of2.13 V,outperforming the noble-metal benchmark(2.51 V).Additionally,ex situ characterizations were employed to detect transformations in the active sites during the catalytic process,revealing the structural transformations and providing inspiration for further design of electrocatalysts.

Towards high-performance and robust anion exchange membranes(AEMs)for water electrolysis:Super-acid-catalyzed synthesis of AEMs

The increasing demand for hydrogen energy to address environmental issues and achieve carbon neutrality has elevated interest in green hydrogen production,which does not rely on fossil fuels.Among various hydrogen production technologies,anion exchange membrane water electrolyzer(AEMWE)has emerged as a next-generation technology known for its high hydrogen production efficiency and its ability to use non-metal catalysts.However,this technology faces significant challenges,particularly in terms of the membrane durability and low ionic conductivity.To address these challenges,research efforts have focused on developing membranes with a new backbone structure and anion exchange groups to enhance durability and ionic conductivity.Notably,the super-acid-catalyzed condensation(SACC)synthesis method stands out due to its user convenience,the ability to create high molecular weight(MW)polymers,and the use of oxygen-tolerant organic catalysts.Although the synthesis of anion exchange membranes(AEMs)using the SACC method began in 2015,and despite growing interest in this synthesis approach,there remains a scarcity of review papers focusing on AEMs synthesized using the SACC method.The review covers the basics of SACC synthesis,presents various polymers synthesized using this method,and summarizes the development of these polymers,particularly their building blocks including aryl,ketone,and anion exchange groups.We systematically describe the effects of changes in the molecular structure of each polymer component,conducted by various research groups,on the mechanical properties,conductivity,and operational stability of the membrane.This review will provide insights into the development of AEMs with superior performance and operational stability suitable for water electrolysis applications.

Development of advanced anion exchange membrane from the view of the performance of water electrolysis cell

Green hydrogen produced by water electrolysis combined with renewable energy is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.Among water electrolysis technologies,the anion exchange membrane(AEM) water electrolysis has gained intensive attention and is considered as the next-generation emerging technology due to its potential advantages,such as the use of low-cost non-noble metal catalysts,the relatively mature stack assembly process,etc.However,the AEM water electrolyzer is still in the early development stage of the kW-level stack,which is mainly attributed to severe performance decay caused by the core component,i.e.,AEM.Here,the review comprehensively presents the recent progress of advanced AEM from the view of the performance of water electrolysis cells.Herein,fundamental principles and critical components of AEM water electrolyzers are introduced,and work conditions of AEM water electrolyzers and AEM performance improvement strategies are discussed.The challenges and perspectives are also analyzed.

Durable poly(binaphthyl-co-p-terphenyl piperidinium)-based anion exchange membranes with dual side chains

Building well-developed ion-conductive highways is highly desirable for anion exchange membranes(AEMs).Grafting side chain is a highly effective approach for constructing a well-defined phaseseparated morphological structure and forming unblocked ion pathways in AEMs for fast ion transport.Fluorination of side chains can further enhance phase separation due to the superhydrophobic nature of fluorine groups.However,their electronic effect on the alkaline stability of side chains and membranes is rarely reported.Here,fluorine-containing and fluorine-free side chains are introduced into the polyaromatic backbone in proper configuration to investigate the impact of the fluorine terminal group on the stability of the side chains and membrane properties.The poly(binaphthyl-co-p-terphenyl piperidinium)AEM(QBNp TP)has the highest molecular weight and most dimensional stability due to its favorable backbone arrangement among ortho-and meta-terphenyl based AEMs.Importantly,by introducing both a fluorinated piperidinium side chain and a hexane chain into the p-terphenyl-based backbone,the prepared AEM(QBNp TP-QFC)presents an enhanced conductivity(150.6 m S cm^(-1))and a constrained swelling at 80℃.The electronic effect of fluorinated side chains is contemplated by experiments and simulations.The results demonstrate that the presence of strong electro-withdrawing fluorine groups weakens the electronic cloud of adjacent C atoms,increasing OH^(-)attack on the C atom and improving the stability of piperidinium cations.Hence QBNp TP-QFC possesses a robust alkaline stability at 80℃(95.3%conductivity retention after testing in 2 M Na OH for 2160 h).An excellent peak power density of 1.44 W cm^(-2)and a remarkable durability at 80℃(4.5%voltage loss after 100 h)can be observed.

Electrochemical reconstruction of non-noble metal-based heterostructure nanorod arrays electrodes for highly stable anion exchange membrane seawater electrolysis

Direct seawater electrolysis for hydrogen production has been regarded as a viable route to utilize surplus renewable energy and address the climate crisis.However,the harsh electrochemical environment of seawater,particularly the presence of aggressive Cl^(-),has been proven to be prone to parasitic chloride ion oxidation and corrosion reactions,thus restricting seawater electrolyzer lifetime.Herein,hierarchical structure(Ni,Fe)O(OH)@NiCoS nanorod arrays(NAs)catalysts with heterointerfaces and localized oxygen vacancies were synthesized at nickel foam substrates via the combination of hydrothermal and annealing methods to boost seawater dissociation.The hiera rchical nanostructure of NiCoS NAs enhanced electrode charge transfer rate and active surface area to accelerate oxygen evolution reaction(OER)and generated sulfate gradient layers to repulsive aggressive Cl^(-).The fabricated heterostructure and vacancies of(Ni,Fe)O(OH)tuned catalyst electronic structure into an electrophilic state to enhance the binding affinity of hydroxyl intermediates and facilitate the structural transformation into amorphousγ-NiFeOOH for promoting OER.Furthermore,through operando electrochemistry techniques,we found that theγ-NiFeOOH possessing an unsaturated coordination environment and lattice-oxygen-participated OER mechanism can minimize electrode Cl^(-)corrosion enabled by stabilizing the adsorption of OH*intermediates,making it one of the best OER catalysts in the seawater medium reported to date.Consequently,these catalysts can deliver current densities of 100 and 500 mA cm-2for boosting OER at minimal overpotentials of 245and 316 mV,respectively,and thus prevent chloride ion oxidation simultaneously.Impressively,a highly stable anion exchange membrane(AEM)seawater electrolyzer based on the non-noble metal heterostructure electrodes reached a record low degradation rate under 100μV h-1at constant industrial current densities of 400 and 600 mA cm-2over 300 h,which exhibits a promising future for the nonprecious and stable AEMWE in the direct seawater electrolysis industry.

Technical factors affecting the performance of anion exchange membrane water electrolyzer

Anion exchange membrane(AEM)electrolysis is a promising membrane-based green hydrogen production technology.However,AEM electrolysis still remains in its infancy,and the performance of AEM electrolyzers is far behind that of well-developed alkaline and proton exchange membrane electrolyzers.Therefore,breaking through the technical barriers of AEM electrolyzers is critical.On the basis of the analysis of the electrochemical performance tested in a single cell,electrochemical impedance spectroscopy,and the number of active sites,we evaluated the main technical factors that affect AEM electrolyzers.These factors included catalyst layer manufacturing(e.g.,catalyst,carbon black,and anionic ionomer)loadings,membrane electrode assembly,and testing conditions(e.g.,the KOH concentration in the electrolyte,electrolyte feeding mode,and operating temperature).The underlying mechanisms of the effects of these factors on AEM electrolyzer performance were also revealed.The irreversible voltage loss in the AEM electrolyzer was concluded to be mainly associated with the kinetics of the electrode reaction and the transport of electrons,ions,and gas-phase products involved in electrolysis.Based on the study results,the performance and stability of AEM electrolyzers were significantly improved.

Poly(Ionic Liquid) as an Anion Exchange Membrane for a 3.3 V Copper–Lithium Battery

Metal–metal battery bears great potential for next-generation large-scale energy storage system because of its simple manufacture process and low production cost.However,the cross-over of metal cations from the cathode to the anode causes a loss in capacity and influences battery stability.Herein,a coating of poly(ionic liquid)(PIL)with poly(diallyldimethylammonium bis(trifluoromethanesulfonyl)imide)(PDADMA^(+)TFSI^(−))on a commercial polypropylene(PP)separator serves as an anion exchange membrane for a 3.3 V copper–lithium battery.The PIL has a positively charged polymer backbone that can block the migration of copper ions,thus improving Coulombic efficiency,long-term cycling stability and inhibiting self-discharge of the battery.It can also facilitate the conduction of anions through the membrane and reduce polarization,especially for fast charging/discharging.Bruce-Vincent method gives the transport number in the electrolyte to be 0.25 and 0.04 for PP separator without and with PIL coating,respectively.This suggests that the PIL layer reduces the contribution of the internal current due to cation transport.The use of PIL as a coating layer for commercial PP separator is a cost-effective way to improve overall electrochemical performance of copper–lithium batteries.Compared to PP and polyacrylic acid(PAA)/PP separators,the PIL/PP membrane raises the Coulombic efficiency to 99%and decreases the average discharge voltage drop to about 0.09 V when the current density is increased from 0.1 to 1 mA cm^(−2).

Chemical Oxidation Effects on Anion Exchange and Nitrate Sorption Capacity of Biochar for Ruminal Methanogenesis Inhibition

The chemical composition of biochar is determined by the chemical profile of the material the by-product is made of and the pyrolysis conditions. Analysis of commercial biochar detected similarities to the chemical profile of hardwood, which was used as an object of pyrolysis for biochar production and showed the presence of bridge-forming cations, such as manganese, iron, and sodium. Despite frequently being reported in existing literature, the current study showed that the redox potential of biochar is not associated with biochar’s ability to recover certain anions. No association was detected between biochar’s redox potential and the material nitrate sorption capacity. In fact, higher redox potential values were associated with lower nitrate absorption. In the case of the anion exchange capacity of biochar, a direct association between this electrochemical property of the by-product and its redox potential was observed. However, redox potential’s impact on anion exchange capacity can be inhibited by the presence of organic compounds in biochar’s chemical profile. The chemical oxidation of biochar is a complex process and is a research priority for a potential role to mitigate enteric methanogenesis in livestock.

Application of monodispersive anion exchangers in sorption and separation of Y^3＋ from Nd^3＋ and Sm^3＋ complexes with dcta

Rare earth complexes with trans-1,2-diaminocyclohexane-N,N,N ,N -tetraacetic acid （DCTA） of the Ln（dcta） type exhibited an unusual sequence of affinity on the polystyrene anion exchangers： pm^3＋〉Nd^3＋〉Sm^3＋〉Pr^3＋〉Ce^3＋〉Eu^3＋〉Gd^3＋〉La^3＋〉Sc^3＋〉Tb^3＋〉Dy^3＋〉 Ho^3＋〉Y^3＋〉Er^3＋〉Tm^3＋〉Yb3＋〉Lu^3＋[1]. Taking into account the position of Y^3＋, Sm^3＋, and Nd^3＋ in this affinity series, for the monodispersive polystyrene anion exchangers, Lewatit MonoPlus M 500, Lewatit MonoPlus M 600, Lewatit MonoPlus MP 500, Lewatit MonoPlus MP 64, and for the heterodispersive anion exchanger, Lewatit MP 62, the weight （Dg） and bed （Dv） distribution coefficients of these complexes and working ion exchange capacities （Cw） were determined. Based on these values, purifications of Y^3＋ from Nd^3＋ and Y^3＋ from Sm^3＋ in the macro-micro component system on these anion exchangers were studied. The application potential of this method was highlighted for the separation of Y^3＋ in the presence of Nd^3＋ and Sm^3＋. With 1 L of monodispersive and strongly basic polystyrene gel anion exchanger Lewatit MonoPlus M 500 in the acetate form, it is possible to obtain approximately 79 g Y2O3 purified from Nd2O3 and 70 g Y2O3 purified from Sm2O3 in the same process condition.

Expression and Purification of Hydrophilic Domains of Bovine Anion Exchanger,Member 1 and Electrogenic Sodium Bicarbonate Cotransporter 1

[ Objective] To express and purify the intracellular hydrophilic domains of bovine membrane carrier proteins：anion exchanger, member 1 （AE1） and electregenic sodium bicarbonate cotransporter 1 （NBCel）, which were associated with bicarbonate ion transport. [ Method] The hydrophilic domains of bovine AE1 and NBCel were amplified by PCR and inserted into the prokaryotic expression vector pET-28a, respectively. The recombinant plasmids were transformed into the expression strain E. coli BL21 （DE3） and then induced by IPTG. The expressed proteins were purified by nickel ion affinity chromatography and analyzed by 15% SDS-PAGE. [Result] The hydrophilic domains of bovine AE1 and NBCel were amplified respectively by PCR and expressed by prokaryotic expression system with the induction of IPTG. They were mainly expressed in the cyto- plasm of E. coli and high-purity was achieved by nickel ion affinity chromatography. [Condusion] The expression of the hydrophilic domains of bovine AE1 and NBCel provides a major exit route for preparation of antibodies and the regulatory mechanisms of carrier proteins.

One-Step Fabrication of Methylthiazole-Functionalized Anion Exchange Membranes for Diffusion Dialysis

Anion exchange membranesusing brominated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO) as starting material were prepared from one-step functionalization by 4-methylthiazole (MTz). The obtain membranes with high thermal stability and mechanical strength showed satisfied diffusion dialysis performance for acid recovery. Specifically, when the optimal membrane was evaluated to recover acid from the simulated iron polishing waste solution (1.0 mol·L-1 FeCl2 + 0.2 mol·L-1 HCl), its acid diffusion coefficient (UH+) was 0.019 m h-1 and separation factor was 40.1 at 25°C, both of these two parameters are much higher than the corresponding values of the commercial DF-120 membrane, suggesting the great potential in the practical application for acid recovery.

Mechanism and kinetics study on removal of Iron from phosphoric acid by cation exchange resin

Iron element is one of the main impurities in wet-process phosphoric acid and it has a significant impact on the subsequent phosphorus chemical products. This paper studied the feasibility of using Sinco-430 cation exchange resin for iron removal from phosphoric acid. The specific surface area and the total exchange capacity of resin were 8.91 m2·g-1 and 5.18 mmol·g-1, respectively. The sorption mechanism was determined by FTIR and XPS and the results indicated that iron was combined with-SO3 H in resin. The removal process was studied as a function of temperature, H3 PO4 content and mass ratio between resin and solution. The unit mass of resin to remove iron was 0.058 g·g-1 resin when the operating parameters were T = 50 ℃, H3 PO4 content = 27.61 wt%and S/L = 0.1, respectively. Kinetics study demonstrated that pseudo-second-order reaction model fits this study best and the calculated activation energy of overall reaction is 29.10 kJ·mol-1. The overall reaction process was mainly controlled by pore diffusion.

Soil exchangeable base cations along a chronosequence of Caragana microphylla plantation in a semi-arid sandy land,China

As a pioneer leguminous shrub species for vegetation re-establishment, Caragana microphylla is widely distributed in the semi-fixed and fixed sandy lands of the Horqin region, North China. C. microphylla planta- tions modify organic carbon （SOC）, nitrogen （N） and phosphorus dynamics, bulk density and water-holding capacity and biological activities in soils, but little is known with regard to soil exchange properties. Variation in soil ex- changeable base cations was examined under C. microphylla plantations with an age sequence of 0, 5, 10, and 22 years in the Horqin Sandy Land, and at the depth of 0-10, 10-20, and 20-30 cm, respectively. C. microphylla has been planted on the non-vegetated sand dunes with similar physical-chemical soil properties. The results showed that exchangeable calcium （Ca）, magnesium （Mg）, and potassium （K）, and cation exchange capacity （CEC） were significantly increased, and Ca saturation tended to decrease, while Mg and K saturations were increased with the plantation years. No difference was observed for exchangeable sodium （Na） neither with plantation years nor at soil depths. Of all the base cations and soil layers, exchangeable K at the depth of 0-10 cm accumulated most quickly, and it increased by 1.76, 3.16, and 4.25 times, respectively after C. microphylla was planted for 5, 10, and 22 years. Exchangeable Ca, Mg, and K, and CEC were significantly （P〈0.001） and positively correlated with SOC, total N, pH and electrical conductivity （EC）. Soil pH and SOC are regarded as the main factors influencing the variation in ex- changeable cations, and the preferential absorption of cations by plants and different leaching rates of base cations that modify cation saturations under C. microphylla plantation. It is concluded that as a nitrogen-fixation species, C. microphylla plantation is beneficial to increasing exchangeable base cations and CEC in soils, and therefore can improve soil fertility and create favorable microenvironments for plants and creatures in the semi-arid sandy land ecosystems.

Spatial Variability of Soil Cation Exchange Capacity in Hilly Tea Plantation Soils Under Different Sampling Scales

Studies on the spatial variability of the soil cation exchange capacity （CEC） were made to provide a theoretical basis for an ecological tea plantation and management of soil fertilizer in the tea plantation. Geostatistics were used to analyze the spatial variability of soil CEC in the tea plantation site on Mengding Mountain in Sichuan Province of China on two sampling scales. It was found that, （1） on the small scale, the soil CEC was intensively spatially correlative, the rate of nugget to sill was 18.84% and the spatially dependent range was 1 818 m, and structural factors were the main factors that affected the spatial variability of the soil CEC; （2） on the microscale, the soil CEC was also consumingly spatially dependent, and the rate of nugget to sill was 16.52%, the spatially dependent range was 311 m, and the main factors affecting the spatial variability were just the same as mentioned earlier. On the small scale, soil CEC had a stronger anisotropic structure on the slope aspect, and a weaker one on the lateral side. According to the ordinary Kriging method, the equivalence of soil CEC distributed along the lateral aspect of the slope from northeast to southwest, and the soil CEC reduced as the elevation went down. On the microscale, the anisotropic structure was different from that measured on the small scale. It had a stronger anisotropic structure on the aspect that was near the aspect of the slope, and a weaker one near the lateral aspect of the slope. The soil CEC distributed along the lateral aspect of the slope and some distributed in the form of plots. From the top to the bottom of the slope, the soil CEC increased initially, and then reduced, and finally increased.

Cokriging of Soil Cation Exchange Capacity Using the First Principal Component Derived from Soil Physico-Chemical Properties

As soil cation exchange capacity （CEC） is a vital indicator of soil quality and pollutant sequestration capacity,a study was conducted to evaluate cokriging of CEC with the principal components derived from soil physico-chemical properties.In Qingdao,China,107 soil samples were collected.Soil CEC was estimated by using 86 soil samples for prediction and 21 soil samples for test.The first two principal components （PC1 and PC2） together explained 60.2% of the total variance of soil physico-chemical properties.The PC1 was highly correlated with CEC （r=0.76,P0.01）,whereas there was no significant correlation between CEC and PC2 （r=0.03）.The PC1 was then used as an auxiliary variable for the prediction of soil CEC.Mean error （ME） and root mean square error （RMSE） of kriging for the test dataset were-1.76 and 3.67 cmolc kg-1,and ME and RMSE of cokriging for the test dataset were-1.47 and 2.95 cmolc kg-1,respectively.The cross-validation R2 for the prediction dataset was 0.24 for kriging and 0.39 for cokriging.The results show that cokriging with PC1 is more reliable than kriging for spatial interpolation.In addition,principal components have the highest potential for cokriging predictions when the principal components have good correlations with the primary variables.

Separation of Clay Minerals from Host Sediments Using Cation Exchange Resins

Classic physical and chemical treatments applied to separating clay minerals from the host sediments are often difficult or aggressive for clay minerals. A technique using cation exchange resins (amberlite IRC\|50H and amberlite IR\|120) is used to separate clay minerals from the host sediments. The technique is based on the exchange of cations in the minerals that may be associated clay minerals in sediments, such as Ca and Mg from dolomite; Ca from calcite, gypsum and francolite with cations carried by resin radicals. The associated minerals such as gypsum, calcite, dolomite and francolite are removed in descending order. Separation of clay minerals using cation exchange resins is less aggressive than that by other classic treatments. The efficiency of amberlite IRC\|50H in the removal of associated minerals is greater than that of amberlite IR\|120.

Influence of Types and Charges of Exchangeable Cations on Ciprofloxacin Sorption by Montmorillonite

As one of the most important soil components, montmorillonite plays a vital role in transport and retention of organic pollutants in soils. Ciprofloxacin （CIP）, an antibiotic of fluoroquiolones, has been frequently detected in water and soil environments due to its wide use in human and veterinary medicine. In this study, the adsorption of CIP onto different homoionic montmorillonite such as Na-, Ca- and Al-MMT was investigated, and the influence of types and charges of exchangeable cations in the interlayer of montmorillonite on CIP adsorption was evaluated. The results showed that different homoionic montmorillonite exhibited different sorption capacity of CIP. At pH 3, the sorption capacity of CIP decreased in the order Na-MMT Ca-MMT Al-MMT, following the lyotropic series. When solution pH increased to 11, the sorption capacity of CIP followed the order Ca-MMT Al-MMT Na-MMT. Accompanying CIP adsorption on Ca-MMT, a certain amount of Ca2＋ was released into solution. Compared to pH 3, the lower Ca concentration in solution at pH 11 indicated that the adsorption of CIP on Ca-MMT at strong alkaline pH was no longer via cation exchange, and surface complexation or cation bridging might contribute to CIP adsorption. The adsorption of CIP on Na- and Ca-MMT at pH 3 and 11 resulted in the expansion of d-spacing, indicative of intercalation of CIP into the interlayer space of the montmorillonite. However, a decrease of d-spacing was observed when CIP adsorbed on Al-MMT at pH 11, which might be attributed to the dissolution of Al-CIP complex formed between CIP and Al3＋ in the interlayer of montmorillonite. The results suggest that the types and charges of exchangeable cations in the interlayer of montmorillonite play an important role in CIP adsorption on montmorillonite.

Investigation of Polyacrylate Anion-Exchangers for Separation of Rare Earth Element Complexes with EDTA

The rare earth complexes with EDTA, Ln(edta), show an unusual sequence of affinity for the anion exchangers. The sorption and chromatographic separation of Y 3+ for Nd 3+ complexes with EDTA was studied by using the strongly basic gel and macroporous polyacrylate anion exchangers, Amberlite IRA 458 and Amberlite 958, and the weakly basic gel polyacrylate anion exchanger, Amberlite IRA 68. The investigations on sorption and separation of rare earth complexes with EDTA on the polyacrylate anion exchangers applied mainly in the environment protection so far indicate that they can be applied in anionexchange separation of lanthanide complexes with aminopolycarboxylic acids. It was shown that the weakly basic polyacrylate gel anion exchanger Amberlite IRA 68 is the most effective in purification of Y 3+ from Nd 3+ in comparison with the strongly basic anion exchangers of this type.

Comparison and Evaluation of Two Analytical Methods for Cation Exchange Capacity and Exchangeable Sodium Percentage of Five Soil Types in Central Sudan

Twenty-six soil samples were collected from five soil profiles at different climatological and ecological regions in central Sudan. Soil profile was dug in each studied area and morphological profile description was carried out for different horizons. All samples were analyzed using two different methods to determine Cation Exchange Capacity (CEC) and exchangeable sodium percentage (ESP). Statistical analysis (T-test) was used in order to investigate the differences between soil samples for the studied locations. Significant differences appeared when compared the two methods for CEC determination at Gedaref area, Wad Medani and Nile flood plain and that appeared in evaluation of ESP at Nile flood plain and Shambat area. The results also revealed that, the developed method used in this study was more practical, simple and reliable for determination of CEC and ESP as the currently used in most soil laboratories. In addition, it will be safer than the other methods in some problematic soils. The adoption of this developed method is advisable because it is less time consuming as it omits the washing step. In contrast, the old method cannot be a good substitute in laboratories which have no possibility to determine sodium by using flame photometer. We conclude that when the developed method is used to determine CEC and ESP time will be saved, that fewer amounts of chemicals will be used and that accurate results will be achieved.