Co/CoO heterojunction rich in oxygen vacancies introduced by O2 plasma embedded in mesoporous walls of carbon nanoboxes covered with carbon nanotubes for rechargeable zinc-air battery

Herein,Co/CoO heterojunction nanoparticles(NPs)rich in oxygen vacancies embedded in mesoporous walls of nitrogen-doped hollow carbon nanoboxes coupled with nitrogen-doped carbon nanotubes(P-Co/CoOV@NHCNB@NCNT)are well designed through zeolite-imidazole framework(ZIF-67)carbonization,chemical vapor deposition,and O_(2) plasma treatment.As a result,the threedimensional NHCNBs coupled with NCNTs and unique heterojunction with rich oxygen vacancies reduce the charge transport resistance and accelerate the catalytic reaction rate of the P-Co/CoOV@NHCNB@NCNT,and they display exceedingly good electrocatalytic performance for oxygen reduction reaction(ORR,halfwave potential[EORR,1/2=0.855 V vs.reversible hydrogen electrode])and oxygen evolution reaction(OER,overpotential(η_(OER,10)=377mV@10mA cm^(−2)),which exceeds that of the commercial Pt/C+RuO_(2) and most of the formerly reported electrocatalysts.Impressively,both the aqueous and flexible foldable all-solid-state rechargeable zinc-air batteries(ZABs)assembled with the P-Co/CoOV@NHCNB@NCNT catalyst reveal a large maximum power density and outstanding long-term cycling stability.First-principles density functional theory calculations show that the formation of heterojunctions and oxygen vacancies enhances conductivity,reduces reaction energy barriers,and accelerates reaction kinetics rates.This work opens up a new avenue for the facile construction of highly active,structurally stable,and cost-effective bifunctional catalysts for ZABs.

Groundwater recharge via precipitation in the Badain Jaran Desert,China

Precipitation infiltration serves as a significant source of groundwater in the Badain Jaran Desert.To investigate variations in precipitation infiltration within the desert,this study collected data on moisture content and temperature from the vadose zone through in-situ field monitoring.Utilizing these data,a numerical model is employed to explore the mechanism of groundwater recharge via precipitation.The results are as follows:(1)Moisture content and temperature in the shallow vadose zone exhibit significant seasonal variations,with moisture content diminishing with increasing depth;(2)Groundwater recharge via precipitation infiltration initially increases and then decreases with groundwater level depth(GWD).Peak groundwater recharge via precipitation occurs at a GWD of 0.75 m,decreasing to merely 0.012 cm at GWDs exceeding 2 m;(3)Groundwater is no longer susceptible to phreatic water evaporation when the GWD reaches approximately 3.7 m.Therefore,GWD plays a crucial role in governing groundwater recharge via precipitation in the Badain Jaran Desert.

Clogging caused by coupled grain migration and compaction effect during groundwater recharge for unconsolidated sandstone reservoir in groundwater-source heat pump

In unconsolidated sandstone reservoirs,presence of numerous movable grains and a complex grain size composition necessitates a clear understanding of the physical clogging process for effective groundwater recharge in groundwater-source heat pump systems.To investigate this,a series of seepage experiments was conducted under in situ stress conditions using unconsolidated sandstone samples with varying grain compositions.The clogging phenomenon arises from the combined effects of grain migration and compaction,wherein the migration of both original and secondary crushed fine-grain particles blocks the seepage channels.Notably,grain composition influences the migration and transport properties of the grains.For samples composed of smaller grains,the apparent permeability demonstrates a transition from stability to decrease.In contrast,samples with larger grains experience a skip at the stability stage and directly enter the decrease stage,with a minor exception of a slight increase observed.Furthermore,a unique failure mode characterized by diameter shrinkage in the upper part of the sample is observed due to the combined effects of grain migration and in situ stress-induced compaction.These testing results contribute to a better understanding of the clogging mechanism caused by the coupled effects of grain migration and compaction during groundwater recharge in unconsolidated sandstone reservoirs used in groundwater-source heat pump systems.

Dual-Defect Engineering Strategy Enables High-Durability Rechargeable Magnesium-Metal Batteries

Rechargeable magnesium-metal batteries(RMMBs)are promising next-generation secondary batteries;however,their development is inhibited by the low capacity and short cycle lifespan of cathodes.Although various strategies have been devised to enhance the Mg^(2+)migration kinetics and structural stability of cathodes,they fail to improve electronic conductivity,rendering the cathodes incompatible with magnesium-metal anodes.Herein,we propose a dual-defect engineering strategy,namely,the incorporation of Mg^(2+)pre-intercalation defect(P-Mgd)and oxygen defect(Od),to simultaneously improve the Mg^(2+)migration kinetics,structural stability,and electronic conductivity of the cathodes of RMMBs.Using lamellar V_(2)O_(5)·nH_(2)O as a demo cathode material,we prepare a cathode comprising Mg_(0.07)V_(2)O_(5)·1.4H_(2)O nanobelts composited with reduced graphene oxide(MVOH/rGO)with P-Mgd and Od.The Od enlarges interlayer spacing,accelerates Mg^(2+)migration kinetics,and prevents structural collapse,while the P-Mgd stabilizes the lamellar structure and increases electronic conductivity.Consequently,the MVOH/rGO cathode exhibits a high capacity of 197 mAh g^(−1),and the developed Mg foil//MVOH/rGO full cell demonstrates an incredible lifespan of 850 cycles at 0.1 A g^(−1),capable of powering a light-emitting diode.The proposed dual-defect engineering strategy provides new insights into developing high-durability,high-capacity cathodes,advancing the practical application of RMMBs,and other new secondary batteries.

Heteroatom anchors Fe-Mn dual-atom catalysts with bi-functional oxygen catalytic activity for low-temperature rechargeable flexible Zn-air batteries

M-N-C(M=Fe,Co,Ni,etc.) catalyst owns high catalytic activity in the oxygen catalytic reaction which is the most likely to replace the Pt-based catalysts.But it is still a challenge to further increase the active site density.This article constructs the high-efficiency FeMn-N/S-C-1000 catalyst to realize ORR/OER bifunctional catalysis by hetero-atom,bimetal(Fe,Mn) doped simultaneously strategy.When evaluated it as bi-functional electro-catalysts,FeMn-N/S-C-1000 exhibits excellent catalytic activity(E_(1/2)=0.924 V,E_(j=10)=1.617 V) in alkaline media,outperforms conventional Pt/C,RuO_(2) and most non-precious-metal catalysts reported recently,Such outstanding performance is owing to N,S co-coordinated with metal to form multi-types of single atom,dual atom active sites to carry out bi-catalysis.Importantly,nitrite poison test provides the proof that the active sites of FeMn-N/S-C are more than that of single-atom catalysts to promote catalytic reactions directly.To better understand the local structure of Fe and Mn active sites,XAS and DFT were employed to reveal that FeMn-N_5/S-C site plays the key role during catalysis.Notably,the FeMn-N/S-C-1000 based low-temperature rechargeable flexible Zn-air also exhibits superior discharge performance and extraordinary durability at-40℃.This work will provide a new idea to design diatomic catalysts applied in low-temperature rechargeable batteries.

Engineering single-atom Mn on nitrogen-doped carbon to regulate lithium-peroxide reaction kinetics for rechargeable lithium-oxygen batteries

Precision engineering of catalytic sites to guide more favorable pathways for Li_(2)O_(2) nucleation and decom-position represents an enticing kinetic strategy for mitigating overpotential,enhancing discharge capac-ity,and improving recycling stability of Li-O_(2) batteries.In this work,we employ metal-organic frameworks(MOFs)derivation and ion substitution strategies to construct atomically dispersed Mn-N_(4) moieties on hierarchical porous nitrogen-doped carbon(Mn SAs-NC)with the aim of reducing the over-potential and improving the cycling stability of Li-O_(2) batteries.The porous structure provides more chan-nels for mass transfer and exposes more highly active sites for electrocatalytic reactions,thus promoting the formation and decomposition of Li_(2)O_(2).The Li-O_(2) batteries with Mn SAs-NC cathode achieve lower overpotential,higher specific capacity(14290 mA h g^(-1) at 100 mAg^(-1)),and superior cycle stability(>100 cycles at 200 mA g^(-1))compared with the Mn NPs-NC and NC.Density functional theory(DFT)cal-culations reveal that the construction of Mn-N_(4) moiety tunes the charge distribution of the pyridinic N-rich vacancy and balances the affinity of the intermediates(LiO_(2) and Li_(2)O_(2)).The initial nucleation of Li_(2)O_(2) on Mn SAs-NC favors the O_(2)-→LiO_(2)→Li_(2)O_(2) surface-adsorption pathway,which mitigates the overpoten-tials of the oxygen reduction(ORR)and oxygen evolution reaction(OER).As a result,Mn SAs-NC with Mn-N_(4) moiety effectively facilitates the Li_(2)O_(2) nucleation and enables its reversible decomposition.This work establishes a methodology for constructing carbon-based electrocatalysts with high activity and selectivity for Li-O_(2)batteries.

A perspective on the key factors of safety for rechargeable magnesium batteries

Rechargeable Mg batteries(RMBs)have become one of the best subsitutes for lithium-ion batteries due to the high volumetric capacity,abundant resources,and uniform plating behavior of Mg metal anode.However,the safety hazard induced by the formation of high-modulue Mg dendrites under a high current density(10 mA cm^(-1))was still revealed in recent years.It has forced researchers to re-examine the safety of RMBs.In this review,the intrinsic safety factors of key components in RMBs,such as uneven plating,pitting and flammability of Mg anode,heat release and crystalline water decomposition of cathode,strong corrosion,low oxidition stability and flammability of electrolytes,and soforth,are systematacially summarized.Their origins,formation mechanisms,and possible safety hazards are deeply discussed.To develop high-performance Mg anode,current strategies including designing artificial SEI,three-dimensional substrates,and Mg alloys are summarized.For practical electrolytes,the configurations of boron-centered anions and simple Mg salts and the functionalized solvent with high boiling point and low flammability are suggested to comprehensively design.In addition,the future study should more focus on the investigation on the thermal runaway and decomposition of cathode materials and separa-tors.This review aims to provide fundamental insights into the relationship between electrochemistry and safety,further promoting the sustainable development of RMBs.

Estimation of Groundwater Recharge Using Water Table Fluctuation Method in Bamako and Surrounding Areas, Mali

Bamako’s geographic and demographic expansion is sure to increase the need for water, and the slow development of the water supply network seems unable to meet this need. The knowledge of the approximate quantity of water reaching the groundwater is crucial, given the high dependence of this city and its surrounding area on groundwater. The aim of this study is to estimate the average groundwater recharge on a monthly scale, based on measurements taken over a 24-month period by using Water Table Fluctuation (WTF). The monthly recharge values obtained from the 15 piezometers in the study area by using WTF method vary from 1.04 to 38.81 mm with an average value of 9.74 mm. As part of the precipitations, these values represent respectively 1.29%, 48.52% and 12.17% of monthly average precipitation. It appears in this study that despite the piezometers belonging to the same climatic zone, the recharge rate can be different because of many factors such as the thickness of the aquifers, the soil and geology type, the local land cover and land use activities.

Optimizing groundwater recharge plan in North China Plain to repair shallow groundwater depression zone, China

The North China Plain is one of the main grain producing areas in China. However, overexploitation has long been unsustainable since the water supply is mainly from groundwater. Since 2014,the South-to-North Water Diversion Project's central route has been charted to the integrated management of water supply and over-exploitation, which has alleviated the problem to a certain extent. Although the Ministry of Water Resources has made many efforts on groundwater recharge since 2018 most of which have been successful, the recharge has not yet been sufficiently focused on the repair of shallow groundwater depression zones. It still needs further optimization. This paper discusses this particular issue,proposes optimized recharge plan and provides the following recommendations:(1) Seven priority target areas are selected for groundwater recharge in alluvial and proluvial fans in the piedmont plain, and the storage capacity is estimated to be 181.00×10~8 m~3;(2) A recharge of 31.18×10~8 m~3/a is required by 2035 to achieve the repair target;(3) It is proposed to increase the recharge of Hutuo River, Dasha River and Tanghe River to 19.00×10~8 m~3/a and to rehabilitate Gaoliqing-Ningbailong Depression Zone;increase the recharge of Fuyang River, Zhanghe River and Anyang River to 7.05×10~8 m~3/a and rehabilitate Handan Feixiang-Guangping Depression Zone;increase the recharge of Luanhe River by 0.56×10~8 m~3/a and restore Tanghai Depression Zone and Luanan-Leting Depression Zone;moderately reduce the amount of water recharged to North Canal and Yongding River to prevent excessive rebound of groundwater;(4) Recharge through well is implemented on a pilot basis in areas of severe urban ground subsidence and coastal saltwater intrusion;(5) An early warning mechanism for groundwater quality risks in recharge areas is established to ensure the safety. The numerical groundwater flow model also proves reasonable groundwater level restoration in the depression zones by 2035.

Aerophilic Triphase Interface Tuned by Carbon Dots Driving Durable and Flexible Rechargeable Zn‑Air Batteries

Efficient bifunctional catalysts for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are vital for rechargeable Zn-air batteries(ZABs).Herein,an oxygen-respirable sponge-like Co@C–O–Cs catalyst with oxygen-rich active sites was designed and constructed for both ORR and OER by a facile carbon dot-assisted strategy.The aerophilic triphase interface of Co@C–O–Cs cathode efficiently boosts oxygen diffusion and transfer.The theoretical calculations and experimental studies revealed that the Co–C–COC active sites can redistribute the local charge density and lower the reaction energy barrier.The Co@C–O–Cs catalyst displays superior bifunctional catalytic activities with a half-wave potential of 0.82 V for ORR and an ultralow overpotential of 294 mV at 10 mA cm^(−2) for OER.Moreover,it can drive the liquid ZABs with high peak power density(106.4 mW cm^(−2)),specific capacity(720.7 mAh g^(−1)),outstanding long-term cycle stability(over 750 cycles at 10 mA cm^(−2)),and exhibits excellent feasibility in flexible all-solid-state ZABs.These findings provide new insights into the rational design of efficient bifunctional oxygen catalysts in rechargeable metal-air batteries.

3D printing critical materials for rechargeable batteries: from materials, design and optimization strategies to applications

Three-dimensional(3D)printing,an additive manufacturing technique,is widely employed for the fabrication of various electrochemical energy storage devices(EESDs),such as batteries and supercapacitors,ranging from nanoscale to macroscale.This technique offers excellent manufacturing flexibility,geometric designability,cost-effectiveness,and eco-friendliness.Recent studies have focused on the utilization of 3D-printed critical materials for EESDs,which have demonstrated remarkable electrochemical performances,including high energy densities and rate capabilities,attributed to improved ion/electron transport abilities and fast kinetics.However,there is a lack of comprehensive reviews summarizing and discussing the recent advancements in the structural design and application of 3D-printed critical materials for EESDs,particularly rechargeable batteries.In this review,we primarily concentrate on the current progress in 3D printing(3DP)critical materials for emerging batteries.We commence by outlining the key characteristics of major 3DP methods employed for fabricating EESDs,encompassing design principles,materials selection,and optimization strategies.Subsequently,we summarize the recent advancements in 3D-printed critical materials(anode,cathode,electrolyte,separator,and current collector)for secondary batteries,including conventional Li-ion(LIBs),Na-ion(SIBs),K-ion(KIBs)batteries,as well as Li/Na/K/Zn metal batteries,Zn-air batteries,and Ni–Fe batteries.Within these sections,we discuss the 3DP precursor,design principles of 3D structures,and working mechanisms of the electrodes.Finally,we address the major challenges and potential applications in the development of 3D-printed critical materials for rechargeable batteries.

Fundamentals,recent developments and prospects of lithium and non-lithium electrochemical rechargeable battery systems

The present and future energy requirements of mankind can be fulfilled with sustained research and development efforts by global scientists.The purpose of this review paper is to provide an overview of the fundamentals,recent advancements on Lithium and non-Lithium electrochemical rechargeable battery systems,and their future prospects.The initial part of this review paper is dedicated to the advancement and challenges faced by the conventional rechargeable batteries,such as lead-acid,Ni-Cd and Ni-MH batteries.The subsequent section of this review focuses on an in-depth analysis of two major categories of rechargeable batteries,namely lithium-based rechargeable battery systems and alternative non-Lithium rechargeable battery systems.The working principle,construction,and a few important research progress on Li-ion,Li-O_(2),Li-CO_(2) and Li-S batteries have been highlighted.The recent progress and challenges of the alternate batteries such as Na-ion,Na-S,Mg-ion,K-ion,Al-ion,Al-air,Zn-ion and Zn-air are also discussed in this review.The large gap between theoretical and practical electrochemical values for the alternate battery system must be filled by adopting a series of design architectures followed by modern instrumentation for developing next-generation batteries in a sustainable and efficient way.

Evolution of groundwater recharge-discharge balance in the Turpan Basin of China during 1959-2021

Groundwater overexploitation is a serious problem in the Turpan Basin,Xinjiang Uygur Autonomous Region of China,causing groundwater level declines and ecological and environmental problems such as the desiccation of karez wells and the shrinkage of lakes.Based on historical groundwater data and field survey data from 1959 to 2021,we comprehensively studied the evolution of groundwater recharge and discharge terms in the Turpan Basin using the groundwater equilibrium method,mathematical statistics,and GIS spatial analysis.The reasons for groundwater overexploitation were also discussed.The results indicated that groundwater recharge increased from 14.58×10^(8)m^(3)in 1959 to 15.69×10^(8)m^(3)in 1980,then continued to decrease to 6.77×10^(8)m^(3)in 2021.Groundwater discharge increased from 14.49×10^(8)m^(3)in 1959 to 16.02×10^(8)m^(3)in 1989,while continued to decrease to 9.97×10^(8)m^(3)in 2021.Since 1980,groundwater recharge-discharge balance has been broken,the decrease rate of groundwater recharge exceeded that of groundwater discharge and groundwater recharge was always lower than groundwater discharge,showing in a negative equilibrium,which caused the continuous decrease in groundwater level in the Turpan Basin.From 1980 to 2002,groundwater overexploitation increased rapidly,peaking from 2003 to 2011 with an average overexploitation rate of 4.79×10^(8)m^(3)/a;then,it slowed slightly from 2012 to 2021,and the cumulative groundwater overexploitation was 99.21×10^(8)m^(3)during 1980-2021.This research can provide a scientific foundation for the restoration and sustainable use of groundwater in the overexploited areas of the Turpan Basin.

Recharge processes limit the resource elements of Qarhan Salt Lake in western China and analogues in the evaporite basins

The Qarhan Salt Lake(QSL)in western China is K-Sr-Li-B-Br-Rb multi-resource coexisting Quaternary brine deposits.Significant research efforts have been directed to the origin of K-Li resources and evolutionary history of the QSL.However,the study on the different sources,recharge processes,and differential distribution patterns for these resource elements in brine deposits is still inadequate.Therefore,we measured Li-B concentrations and H-O-Sr-B isotopic compositions of different waters(river,spring,and brine)from the QSL,combined with the reported K-Sr contents and multiple isotopes of waters,to discuss the recharge,source of K-Sr-Li-B and their spatial distributions,by analogy with other evaporite basins in the world.The results show that:(1)the K-Li-B-Sr elemental concentrations of brines and their spatial distribution in the QSL are diverse;(2)high K and Sr values are distributed in Dabuxun and Qarhan sections,respectively,which are controlled by Ca-Cl springs in the northern QSL;on the contrary,Li and B values are enriched in the Bieletan section and are charged by thermal springs in the Kunlun Mountains;(3)the formation and evolution of Ca-Cl and thermal springs constrain fundamentally on the recharge processes of K-Sr and Li-B elements in the terminal salt lakes of the Qaidam Basin(QB);(4)some analogues of recharge processes limit the resource elements of the QSL and other salt lakes(Da Qaidam,Lop Nur,Zhabuye,Atacama,and Guayatayoc)in the world provides a reference for the resource exploration in deep formation waters in the evaporite basins.

Zinc–Bromine Rechargeable Batteries:From Device Configuration,Electrochemistry,Material to Performance Evaluation

Zinc–bromine rechargeable batteries(ZBRBs)are one of the most powerful candidates for next-generation energy storage due to their potentially lower material cost,deep discharge capability,non-flammable electrolytes,relatively long lifetime and good reversibility.However,many opportunities remain to improve the efficiency and stability of these batteries for long-life operation.Here,we discuss the device configurations,working mechanisms and performance evaluation of ZBRBs.Both non-flow(static)and flow-type cells are highlighted in detail in this review.The fundamental electrochemical aspects,including the key challenges and promising solutions,are discussed,with particular attention paid to zinc and bromine half-cells,as their performance plays a critical role in determining the electrochemical performance of the battery system.The following sections examine the key performance metrics of ZBRBs and assessment methods using various ex situ and in situ/operando techniques.The review concludes with insights into future developments and prospects for high-performance ZBRBs.

Assessing the impact of artificial recharge on groundwater in an overexploited aquifer: A case study in the Cheria Basin, North-East of Algeria

The Cheria region in Northeastern Algeria has been facing aquifer overexploitation by the agricultural sector and prolonged droughts,resulting in a considerable decline in groundwater levels.This study investigates the feasibility of implementing artificial recharge techniques to replenish the Eocene aquifer which serves as the primary water source in the Cheria region.A 3D transient numerical model,based on the finite difference method,was used to simulate groundwater flow from 2021 to 2031 using Visual MODFLOW Flex.During the modelling process,three scenarios were considered:(1)including pumping without a recharge,(2)recharge of the entire area through efficient infiltration without pumping,and(3)artificial recharge using river water infiltration basins at two sites,Draa Douamis sinkholes and Eocene limestone outcrops.The simulation results showed that aquifer exploitation without recharge caused significant drawdowns,which were 3 m to 7 m in the north-eastern part and 8 m to 12 m in the central and southern parts.In contrast,the second scenario,involving recharge without pumping,showed a rise in groundwater levels of 2 m to 2.7 m in the north-eastern part and 3 m to 3.62 m in the central and southern parts.The third scenario,employing artificial recharge,indicated a positive response to artificial recharge,with increased piezometric levels at the proposed sites,signifying a beneficial impact on the aquifer.These findings underline the potential of artificial recharge as a promising approach to address the groundwater depletion and environmental issues in the Cheria Basin.

Superior oxygen electrocatalyst derived from metal organic coordination polymers by instantaneous nucleation and epitaxial growth for rechargeable Li-O_(2) battery

Rechargeable aprotic Li-O_(2)batteries have attractea increasing attention due to their extremely high capacity,and it is very important to design appropriate strategies to synthesize efficient catalysts used as oxygen cathode.In present work,we present an expedient "instantaneous nucleation and epitaxial growth"(INEG) synthesis strategy for convenient and large-scale synthesis of ultrafine MOCPs nanoparticles(size 50-100 nm) with obvious advantages such as fast synthesis,high yields,low costs and reduced synthetic steps.The bimetallic Ru/Co-MOCPs are further pyrolyzed to obtain bimetallic Coand low content of Ru-based nanoparticles embedded within nitrogen-doped carbon(Ru/Co@N-C) as an efficient catalyst used in Li-O_(2)battery.The Ru/Co@N-C provides porous carbon framework for the ion transportation and O_(2)diffusion,and has large amounts of metal/nonmetal sites as active site to promote the oxygen reduction reaction(ORR)/oxygen evolution reaction(OER) in Li-O_(2)batteries.As a consequence,a high discharge specific capacity of 15246 mA h g^(-1)at 250 mA g^(-1), excellent rate capability at different current densities,and stable overpotential during cycling,are achieved.This work opened up a new understanding for the industrialized synthesis of ultrafine catalysts for Li-O_(2)batteries with excellent structural characteristics and electrochemical performance.

Electrolyte additive enhances the electrochemical performance of Cu for rechargeable Cu//Zn batteries

Cu-based cathodes in aqueous batteries become very attractive in view of high theoretical capacity,moderate operation voltage and rich reserves of raw materials.However,their applications are obstructed by serious side reactions.The side reaction mainly arises from the spontaneous formation of Cu_(2)O,which occupies the electrode surface and lowers the reaction reversibility.Here,Na_(2)EDTA is introduced to address these issues.Both experimental results and theoretical calculations indicate that the Na_(2)EDTA reshapes the solvation structure of Cu^(2+)and modifies the electrode/electrolyte interface.Therefore,the redox potential of Cu^(2+)/Cu_(2)O is reduced and the surface of Cu is protected from H2O,thereby inhibiting the formation of Cu_(2)O.Meanwhile,the change in the solvation structure reduces the electrostatic repulsion between Cu^(2+)and the cathode,leading to high local concentration and benefiting uniform deposition.The results shed light on the applications of rechargeable Cu-based batteries.

Metal-organic frameworks based single-atom catalysts for advanced fuel cells and rechargeable batteries

The next-generation energy storage systems such as fuel cells,metal-air batteries,and alkali metal(Li,Na)-chalcogen(S,Se)batteries have received increasing attention owing to their high energy density and low cost.However,one of the main obstacles of these systems is the poor reaction kinetics in the involved chemical reactions.Therefore,it is essential to incorporate suitable and efficient catalysts into the cell.These years,single-atom catalysts(SACs)are emerging as a frontier in catalysis due to their maximum atom efficiency and unique reaction selectivity.For SACs fabrication,metal-organic frameworks(MOFs)have been confirmed as promising templates or precursors due to their high metal loadings,structural adjustability,porosity,and tailorable catalytic site.In this review,we summarize effective strategies for fabricating SACs by MOFs with corresponding advanced characterization techniques and illustrate the key role of MOFs-based SACs in these batteries by explaining their reaction mechanisms and challenges.Finally,current applications,prospects,and opportunities for MOFs-based SACs in energy storage systems are discussed.

Schiff-base polymer derived FeCo-N-doped porous carbon flowers as bifunctional oxygen electrocatalyst for long-life rechargeable zinc-air batteries

Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient approach to construct a bifunctional oxygen reduction reaction(ORR)/oxygen evolution reaction(OER)electrocatalyst composed of N-doped porous carbon nanosheet flowers decorated with Fe Co nanoparticles(Fe Co/N-CF).Rational design of this catalyst is achieved by designing Schiff-base polymer with unique molecular structure via hydrogen bonding of cyanuramide and terephthalaldehyde polycondensate in the presence of metal cations.It exhibits excellent activity and stability for electrocatalysis of ORR/OER,enabling ZAB with a high peak power density of 172 m W cm^(-2)and a large specific capacity of 811 m A h g^(-1)Znat large current.The rechargeable ZAB demonstrates excellent durability for 1000 h with slight voltage decay,far outperforming a couple of precious Pt/Ir-based catalysts.Density functional theory(DFT)calculations reveal that high activity of bimetallic Fe Co stems from enhanced O_(2)and OH-adsorption and accelerated O_(2)dissociation by OAO bond activation.