Textured Asymmetric Membrane Electrode Assemblies of Piezoelectric Phosphorene and Ti_(3)C_(2)T_(x)MXene Heterostructures for Enhanced Electrochemical Stability and Kinetics in LIBs

Black phosphorus with a superior theoretical capacity(2596 mAh g^(-1))and high conductivity is regarded as one of the powerful candidates for lithium-ion battery(LIB)anode materials,whereas the severe volume expansion and sluggish kinetics still impede its applications in LIBs.By contrast,the exfoliated two-dimensional phosphorene owns negligible volume variation,and its intrinsic piezoelectricity is considered to be beneficial to the Li-ion transfer kinetics,while its positive influence has not been discussed yet.Herein,a phosphorene/MXene heterostructure-textured nanopiezocomposite is proposed with even phosphorene distribution and enhanced piezo-electrochemical coupling as an applicable free-standing asymmetric membrane electrode beyond the skin effect for enhanced Li-ion storage.The experimental and simulation analysis reveals that the embedded phosphorene nanosheets not only provide abundant active sites for Li-ions,but also endow the nanocomposite with favorable piezoelectricity,thus promoting the Li-ion transfer kinetics by generating the piezoelectric field serving as an extra accelerator.By waltzing with the MXene framework,the optimized electrode exhibits enhanced kinetics and stability,achieving stable cycling performances for 1,000 cycles at 2 A g^(-1),and delivering a high reversible capacity of 524 m Ah g^(-1)at-20℃,indicating the positive influence of the structural merits of self-assembled nanopiezocomposites on promoting stability and kinetics.

Designing Membrane Electrode Assembly for Electrochemical CO_(2)Reduction:a Review

Currently, the electrochemical CO_(2) reduction reaction (CO_(2) RR) can realize the resource conversion of CO_(2) , which is a promising approach to carbon resource use. Important advancements have been made in exploring the CO_(2) RR performance and mechanism because of the rational design of electrolyzer systems, such as H-cells, flow cells, and catalysts. Considering the future development direction of this technology and large-scale application needs, membrane electrode assembly (MEA) systems can improve energy use efficiency and achieve large-scale CO_(2) conversion, which is considered the most promising technology for industrial applications. This review will concentrate on the research progress and present situation of the MEA component structure. This paper begins with the composition and construction of a gas diff usion electrode. Then, the application of ion-exchange membranes in MEA is introduced. Furthermore, the eff ects of pH and the anion and cation of the anolyte on MEA performance are explored. Additionally, we present the anode reaction type in MEA. Finally, the challenges in this field are summarized, and upcoming trends are projected. This review should offer researchers a clearer picture of MEA systems and provide important, timely, and valuable insights into rational electrolyzer design to facilitate further development of CO_(2) electrochemical reduction.

Progress and perspective of single-atom catalysts for membrane electrode assembly of fuel cells

A fuel cell is an energy conversion device that can continuously input fuel and oxidant into the device through an electrochemical reaction to release electrical energy.Although noble metals show good activity in fuel cell-related electrochemical reactions,their ever-increasing price considerably hinders their industrial application.Improvement of atom utilization efficiency is considered one of the most effective strategies to improve the mass activity of catalysts,and this allows for the use of fewer catalysts,saving greatly on the cost.Thus,single-atom catalysts(SACs)with an atom utilization efficiency of 100%have been widely developed,which show remarkable performance in fuel cells.In this review,we will describe recent progress on the development of SACs for membrane electrode assembly of fuel cell applications.First,we will introduce several effective routes for the synthesis of SACs.The reaction mechanism of the involved reactions will also be introduced as it is highly determinant of the final activity.Then,we will systematically summarize the application of Pt group metal(PGM)and nonprecious group metal(non-PGM)catalysts in membrane electrode assembly of fuel cells.This review will offer numerous experiences for developing potential industrialized fuel cell catalysts in the future.

SPE Membrane Electrode and Its Application to Chemical Sensor

The structure and proton conducting mechanism of solid polymer electrolyte (SPE) are described. Since the conductivity of electrolyte is important in SPE electrochemical cell research and development, we investigate quantitatively the conductivity of Nafion membrane and its dependence on temperature and relative humidity. Experimental results show that the conductivity of Nafion membrane increases with temperature and relative humidity. We also reports on the preparation and development of SPE membrane electrode with the emphasis on the mixture pressing method and impregnation-reduction process to prepare SPE composite electrode assemblies and their application to electrochemical sensors. We also investigate and fabricate a potentiometric electrochemical sensor of hydrogen and ethylene to measure the hydrogen and ethylene partial pressure.

Preparation and Optimization of Porous Membrane Electrodes via Gradient Coating in Hydrogen Fuel Cell

Fuel cells are considered to be one of the ideal alternatives to traditional fossil energy conversion devices.Membrane electrodes are the core components in the hydrogen fuel cells.Our work reported the synthesis of the Pt/C catalysts with different Pt loading,and by changing the Nafion content,hot pressing temperature and hot pressing pressure,the catalyst coated membrane(CCM)spraying process was optimized.Moreover,the three-dimensional structure model of the single battery membrane electrode was studied quantitatively,and the porous membrane electrode with gradient distribution was fabricated under optimized processing conditions,with excellent electrical performance.

A Novel Tetraiodocadmate（Ⅱ） - PVC Membrane Electrode for the Potentiometric Determination of Cadmium（Ⅱ）

A novel tetraiodocadmate（Ⅱ）-selective membrane electrode consisting of tetraiodo-cadmate（Ⅱ）-rhodamin B ion pair （TICRhB） dispersed in a PVC matrix plasticized with 2-nitrophenyl octyl ether （o-NPOE） was prepared. The sensor demonstrated a near-Nernstian response for 1×10^-2 to 2×10^-6 mol/L cadmium （Ⅱ） at 25℃ with an anionic slope of 29.0. It revealed very good selectivity for Cd^2＋ with negligible interference from many cations and anions, and could be used in a pH range of 3 to 6.

Recent advances in Pt catalysts and membrane electrode assemblies fabrication for proton exchange membrane fuel cells

Proton exchange membrane fuel cells(PEMFCs)have been identified as a highly promising means of achieving sustainable energy conversion.A crucial factor in enhancing the performance of PEMFCs for further potential energy applications is the advancement in the field of catalyst engineering that has led to remarkable performance enhancement in facilitating the oxygen reduction reaction(ORR).Subsequently,it is important to acknowledge that the techniques used in preparation of membrane electrode assemblies(MEAs),the vital constituents of PEMFCs,also possess direct and critical influence on exhibiting the full catalytic activity of meticulously crafted catalysts.Here,a succinct summary of the most recent advancements in Pt catalysts for ORR was offered and their underly catalytic mechanism were discussed.Then,both laboratory-scale and industrial-scale MEA fabrication techniques of Pt catalysts were summarized.Furthermore,a detailed analysis of the connections between materials,process,and performance in MEA fabrication was presented in order to facilitate the development of optimal catalyst layers.

Surface promotion of copper nanoparticles with alumina clusters derived from layered double hydroxide accelerates CO_(2)reduction to ethylene in membrane electrode assemblies

Electrochemical CO_(2)reduction has the vast potential to neutralize CO_(2)emission and valorizes this greenhouse gas into chemicals and fuels under mild conditions.Its commercial realization hinges on catalyst innovation as well as device engineering for enabling reactions at industrially relevant conditions.Copper has been widely examined for the selective production of multicarbon chemicals particularly ethylene,while there is still a substantial gap between the expected and the attainable.In this work,we report that the surface promotion of copper with alumina clusters is a viable strategy to enhance its electrocatalytic performance.AlOx-promoted Cu catalyst is derived from Cu-Al layered double hydroxide nanosheets after alkali etching and cathodic conversion.It can catalyze CO_(2)to ethylene and multicarbon products with great selectivity and stability far superior to pristine copper in both an H-cell and a zero-gap membrane electrode assembly(MEA)electrolyzer.The surface promotion effect is understood via computational simulations showing that alumina clusters can stabilize key reaction intermediates(*COOH and*OCCOH)along the reaction pathway.

Probing the Efficiency of PPMG-Based Composite Electrolytes for Applications of Proton Exchange Membrane Fuel Cell

PPMG-based composite electrolytes were fabricated via the solution method using the polyvinyl alcohol and polyvinylpyrrolidone blend reinforced with various contents of sulfonated inorganic filler.Sulfuric acid was employed as the sulfonating agent to functionalize the external surface of the inorganic filler,i.e.,graphene oxide.The proton conductivities of the newly prepared proton exchange membranes(PEMs)were increased by increasing the temperature and content of sulfonated graphene oxide(SGO),i.e.,ranging from 0.025 S/cm to 0.060 S/cm.The induction of the optimum level of SGO is determined to be an excellent route to enhance ionic conductivity.The single-cell performance test was conducted by sandwiching the newly prepared PEMs between an anode(0.2 mg/cm^(2) Pt/Ru)and a cathode(0.2 mg/cm^(2) Pt)to prepare membrane electrode assemblies,followed by hot pressing under a pressure of approximately 100 kg/cm^(2) at 60℃for 5–10 min.The highest power densities achieved with PPMG PEMs were 14.9 and 35.60 mW/cm^(2) at 25℃and 70℃,respectively,at ambient pressure with 100%relative humidity.Results showed that the newly prepared PEMs exhibit good electrochemical performance.The results indicated that the prepared composite membrane with 6 wt%filler can be used as an alternative membrane for applications of high-performance proton exchange membrane fuel cell.

An oxygen reduction sensor based on a novel type of porous carbon composite membrane electrode

The development of a simple, efficient and sensitive sensor for dissolved oxygen is proposed using a novel type of porous carbon composite membrane/glassy carbon electrode based on the low-cost common filter paper by a simple method. The resulting device exhibited excellent electrocatalytic activities toward the oxygen reduction reaction. Scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and electrochemical measurements demonstrated that the porous morphology and uniformly dispersed Fe;C nanoparticles of the PCCM play an important role in the oxygen reduction reaction. A linear response range from 2mmol/L up to 110 mmol/L and a detection limit of 1.4 mmol/L was obtained with this sensor. The repeatability of the proposed sensor,evaluated in terms of relative standard deviation, was 3.0%. The successful fabrication of PCCM/GC electrode may promote the development of new porous carbon oxygen reduction reaction material for the oxygen reduction sensor.

PtNi-W/C with Atomically Dispersed Tungsten Sites Toward Boosted ORR in Proton Exchange Membrane Fuel Cell Devices

The performance of proton exchange membrane fuel cells is heavily dependent on the microstructure of electrode catalyst especially at low catalyst loadings.This work shows a hybrid electrocatalyst consisting of PtNi-W alloy nanocrystals loaded on carbon surface with atomically dispersed W sites by a two-step straightforward method.Single-atomic W can be found on the carbon surface,which can form protonic acid sites and establish an extended proton transport network at the catalyst surface.When implemented in membrane electrode assembly as cathode at ultra-low loading of 0.05 mgPt cm^(−2),the peak power density of the cell is enhanced by 64.4%compared to that with the commercial Pt/C catalyst.The theoretical calculation suggests that the single-atomic W possesses a favorable energetics toward the formation of*OOH whereby the intermediates can be efficiently converted and further reduced to water,revealing a interfacial cascade catalysis facilitated by the single-atomic W.This work highlights a novel functional hybrid electrocatalyst design from the atomic level that enables to solve the bottle-neck issues at device level.

Enhancement of current density using effective membranes electrode assemblies for water electrolyser system

The goal of this study was to develop and design a composite proton exchange membrane（PEM） and membrane electrode assembly（MEA） that are suitable for the PEM based water electrolysis system. In particular,it focuses on the development of sulphonated polyether ether ketone（SPEEK） based membranes and caesium salt of silico-tungstic acid（Cs Si WA） matrix compared with one of the transition metal oxides such as titanium dioxide（TiO2）, silicon dioxide（SiO2） and zirconium dioxide（ZrO2）. The resultant membranes have been characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, ion exchange capacity（IEC）, water uptake and atomic force microscopy. Comparative studies on the performance of MEAs were also conducted utilizing impregnation-reduction and conventional brush coating methods. The PEM electrolysis performance of SPEEK-Cs Si WA-ZrO2 composite membrane was more superior than that of other membranes involved in this study. Electrochemical characterization shows that a maximum current density of 1.4 A/cm^2 was achieved at 60 °C, explained by an increased concentration of protonic sites available at the interface.

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.

Boosting the optimization of membrane electrode assembly in proton exchange membrane fuel cells guided by explainable artificial intelligence

The utilization of environmentally friendly hydrogen energy requires proton exchange membrane fuel cell de-vices that offer high power output while remaining affordable.However,the current optimization of their key component,i.e.,the membrane electrode assembly,is still based on intuition-guided,inefficient trial-and-error cycles due to its complexity.Hence,we introduce an innovative,explainable artificial intelligence(AI)tool trained as a reliable assistant for a variable analysis and optimum-value prediction.Among the 8 algorithms considered,the surrogate model built with an artificial neural network achieves high replaceability in the experimentally validated multiphysics simulation(R^(2)=0.99845)and a much lower computational cost.For interpretation,partial dependence plots and the Shapley value method are applied to black-box models to intelligently simulate the impact of each parameter on performance.These methods show that a tradeoff existed in the catalyst layer thickness.The AI-guided optimization suggestions regarding catalyst loading and the ion-omer content are fully supported by the experimental results,and the final product achieves 3.2 times the Pt utilization of commercial products with a time cost orders of magnitude smaller.

Electrochemical Removal of Chlorophenol Pollutants by Reactive Electrode Membranes: Scale-Up Strategy for Engineered Applications

Chlorophenols(CPs)are significant refractory pollutants that are highly toxic to humans and other organ-isms.Reactive electrode membranes(REMs)show considerable potential in the electrochemical removal of refractory pollutants by allowing flow-through operations with convection-enhanced mass transfer.However,relevant studies are commonly performed on the laboratory scale,and there is no straightfor-ward method that guarantees success in scaling up engineered REM reactors.In this study,we demon-strated that a tubular concentric electrode(TCE)configuration with a titanium suboxide ceramic anode and a stainless-steel cathode is suitable for large-scale CPs removal.Both theoretical and experi-mental results showed that the TCE configuration not only allows the electrode surface to be orthogonal to electric field lines everywhere,but also has an ohmic resistance that is inversely proportional to the length of the electrode.In addition,the TCE configuration can be operated in either the anode-to-cathode(AC)or the cathode-to-anode(CA)mode based on the flow direction,creating adjustable condi-tions for selective degradation of CPs.This was confirmed by 98%removal of 2,4-dichlorophenol(2,4-DCP)and 72.5%removal of chemical oxygen demand(COD)in the CA mode,in which the kinetic constant was one order of magnitude higher than that for the AC mode under flow-through single-pass operations.This can be explained by the lower activation energy and free energy in the CA mode,as revealed by the-oretical calculations and experimental measurements.The TCE configuration is also suitable for a numbering-up strategy to scale up the electrochemical reactor without increasing the ohmic resistance or decreasing the specific electrode area,achieving 99.4%removal of 2,4-DCP with an energy consump-tion of 1.5 kW·h·m^(-3) when three TCE modules were employed.This study presents a suitable electrode design configuration for the REM reactor,offering effective strategies to bridge the“Valley of Death”encountered when scaling up the electrochemical removal of CP pollutants.

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.

Synthesis of Mn(Ⅲ) Complexes of New "Tailed" Porphyrins and Their Application as Carriers for PVC Membrane SCN-Anion-Selective Electrode

Three new 'tailed' porphyrins and their corresponding Mn(Ⅲ) metalloporphyrins were synthesized and characterized. The potentiometric response characteristics of the PVC membrane electrode based on the Mn(Ⅲ) complexes of the three new 'tailed' porphyrins toward SCN- have been studied.

A Cu-Pd alloy catalyst with partial phase separation for the electrochemical CO_(2) reduction reaction

Cu catalysts can convert CO_(2) through an electrochemical reduction reaction into a variety of useful carbon-based products.However,this capability provides an obstacle to increasing the selectivity for a single product.Herein,we report a simple fabrication method for a Cu-Pd alloy catalyst for use in a membrane electrode assembly(MEA)-based CO_(2) electrolyzer for the electrochemical CO_(2) reduction reaction(ECRR)with high selectivity for CO production.When the composition of the Cu-Pd alloy catalyst was fabricated at 6:4,the selectivity for CO increased and the production of multi-carbon compounds and hydrogen is suppressed.Introducing a Cu-Pd alloy catalyst with 6:4 ratio as the cathode of the MEAbased CO_(2) electrolyzer showed a CO faradaic efficiency of 92.8%at 2.4 V_(cell).We assumed that these results contributed from the crystal planes on the surface of the Cu-Pd alloy.The phases of the Cu-Pd alloy catalyst were partially separated through annealing to fabricate a catalyst with high selectivity for CO at low voltage and C_(2)H_4 at high voltage.The results of CO-stripping testing confirmed that when Cu partially separates from the lattice of the Cu-Pd alloy,the desorption of~*CO is suppressed,suggesting that C-C coupling reaction is favored.

A cascade of in situ conversion of bicarbonate to CO_(2) and CO_(2) electroreduction in a flow cell with a Ni-N-S catalyst

Combination of CO_(2) capture using inorganic alkali with subsequently electrochemical conversion of the resultant HCO_(3)^(-)to high-value chemicals is a promising route of low cost and high efficiency.The electrochemical reduction of HCO_(3)^(-)is challenging due to the inaccessible of negatively charged molecular groups to the electrode surface.Herein,we adopt a comprehensive strategy to tackle this challenge,i.e.,cascade of in situ chemical conversion of HCO_(3)^(-)to CO_(2) and CO_(2) electrochemical reduction in a flow cell.With a tailored Ni-N-S single atom catalyst(SACs),where sulfur(S)atoms located in the second shell of Ni center,the CO_(2)electroreduction(CO_(2)ER)to CO is boosted.The experimental results and density functional theory(DFT)calculations reveal that the introduction of S increases the p electron density of N atoms near Ni atom,thereby stabilizing^(*)H over N and boosting the first proton coupled electron transfer process of CO_(2)ER,i.e.,^(*)+e^(-)+^(*)H+^(*)CO_(2)→^(*)COOH.As a result,the obtained catalyst exhibits a high faradaic efficiency(FE_(CO)~98%)and a low overpotential of 425 mV for CO production as well as a superior turnover frequency(TOF)of 47397 h^(-1),outcompeting most of the reported Ni SACs.More importantly,an extremely high FECOof 90%is achieved at 50 mA cm^(-2)in the designed membrane electrode assembly(MEA)cascade electrolyzer fed with liquid bicarbonate.This work not only highlights the significant role of the second coordination on the first coordination shell of the central metal for CO_(2)ER,but also provides an alternative and feasible strategy to realize the electrochemical conversion of HCO_(3)^(-)to high-value chemicals.

Mushroom Pulp Tissue-Based Membrane-Ferrocene-Modified L-Tyrosine Biosensor

A new approach for assembling amperometric mushroom pulp tissue based membrane electrode for determination of L tyrosine analysis is proposed. Ferrocene is used as a mediator of electron transfer between tyrosinase in mushroom tissue and a graphite electrode. The optimal operation conditions are studied. The linear response range of the biosensor is 2 0×10 -4 to 4 5×10 -3 mol·L -1 with response time of less than 5 min and lifetime of at least 30 d. The biosensor can be applied to practical sample analysis.