Water pollution is an increasingly serious environmental problem because many pollutants have carcinogenic effects on humans and aquatic organisms.Metal organic framework(MOF),made up of metal ions and multifunctional...Water pollution is an increasingly serious environmental problem because many pollutants have carcinogenic effects on humans and aquatic organisms.Metal organic framework(MOF),made up of metal ions and multifunctional organic ligands,has been one of the most concerned materials because of its adjustable and regular pore structure.MOFs have always shown attractive advantages in membrane separation and adsorption technologies,among which water-stable MOFs are particularly prominent in wastewater treatment(WWT)applications.This review systematically summarizes the application of MOF membranes in membrane filtration,membrane pervaporation and membrane distillation.Also,the adsorption mechanisms of heavy metals,dyes and antibacterials in wastewater have been concluded.In order to tap the full application potential of pristine MOFs in sustainable wastewater treatment,current challenges are discussed in detail and future research directions are proposed.展开更多
The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity...The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity and flexible electronic structure.Herein,density functional theory simulations were addressed to predict the electronic structure regulations of CoFc-MOF by nickel doping,which demonstrated that the well-proposed CoNiFc-MOFs delivered a small energy barrier,promoted conductivity,and well-regulated d-band center.Inspired by these,a series of sea-urchin-like CoNiFc-MOFs were successfully synthesized via a facile solvothermal method.Moreover,the synchrotron X-ray and X-ray photoelectron spectroscopy measurements manifested that the introduction of nickel could tailor the electronic structure of the catalyst and induce the directional transfer of electrons,thus optimizing the rate-determining step of^(*)O→^(*)OOH during the OER process and yielding decent overpotentials of 209 and 252 mV at 10 and 200 mA cm^(−2),respectively,with a small Tafel slope of 39 mV dec^(−1).This work presents a new paradigm for developing highly efficient and durable MOF-based electrocatalysts for OER.展开更多
The development of economical,efficient,and robust electrocatalysts toward the hydrogen evolution reaction(HER)is highly imperative for the rapid advancement of renewable H2 energy-associated technologies.Extensive ut...The development of economical,efficient,and robust electrocatalysts toward the hydrogen evolution reaction(HER)is highly imperative for the rapid advancement of renewable H2 energy-associated technologies.Extensive utilization of the heterointerface effect can endow the catalysts with remarkably boosted electrocatalytic performance due to the modified electronic state of active sites.Herein,we demonstrate deliberate crafting of CoP/CoO heterojunction porous nanotubes(abbreviated as CoP/CoO PNTs hereafter)using a self-sacrificial template-engaged strategy.Precise control over the Kirkendall diffusion process of the presynthesized cobalt–aspartic acid complex nanowires is indispensable for the formation of CoP/CoO heterostructures.The topochemical transformation strategy of the reactive templates enables uniform and maximized construction of CoP/CoO heterojunctions throughout all the porous nanotubes.The establishment of CoP/CoO heterojunctions could considerably modify the electronic configuration of the active sites and also improve the electric conductivity,which endows the resultant CoP/CoO PNTs with enhanced intrinsic activity.Simultaneously,the hollow and porous nanotube architectures allow sufficient accessibility of exterior/interior surfaces and molecular permeability,drastically promoting the reaction kinetics.Consequently,when used as HER electrocatalysts,the well-designed CoP/CoO PNTs show Pt-like activity,with an overpotential of only 61 mV at 10mA cm^(−2) and excellent stability in 1.0M KOH medium,exceeding those of the vast majority of the previously reported nonprecious candidates.Density functional theory calculations further substantiate that the construction of CoP/CoO heterojunctions enables optimization of the Gibbs free energies for water adsorption and H adsorption,resulting in boosted HER intrinsic activity.The present study may provide in-depth insights into the fundamental mechanisms of heterojunction-induced electronic regulation,which may pave the way for the rational design of advanced Earth-abundant electrocatalysts in the future.展开更多
Metal–organic framework-based compounds have recently gained great attention because of their unique porous structure,ordered porosity,and high specific surface area.Benefiting from these superior properties,metal–o...Metal–organic framework-based compounds have recently gained great attention because of their unique porous structure,ordered porosity,and high specific surface area.Benefiting from these superior properties,metal–organic framework-based compounds have been proven to be one of the most potential candidates for environmental governance and remediation.In this review,the different types of metal–organic framework-based compounds are first summarized.Further,the various environmental applications of metal–organic framework-based compounds including organic pollutant removal,toxic and hazardous gas capture,heavy metal ion detection,gas separation,water harvesting,air purification,and carbon dioxide reduction reactions are discussed in detail.In the end,the opportunities and challenges for the future development of metal–organic framework-based compounds for environmental applications are highlighted.展开更多
AIM:To investigate different methods of creating incomplete intestinal obstruction in a rat model and to compare their electrophysiologic,morphologic and histologic characteristics. METHODS:Rat ileum was partially obs...AIM:To investigate different methods of creating incomplete intestinal obstruction in a rat model and to compare their electrophysiologic,morphologic and histologic characteristics. METHODS:Rat ileum was partially obstructed by the respective application of:braided silk(penetrated the mesentery and surrounded intestine);half ligation (penetrated directly and ligated 1/2 cross-section of the intestine);wide pipe(6 mm in width,surrounded the intestine);narrow pipe(2 mm in width,surrounded the intestine).A control was also included(no obstruction). Various behavioral and electrophysiologic variables, as well as morphologic and immunohistochemical observations were recorded by blinded investigators at different time points(12,24,48,72 h),including daily general condition,ileal wet weight and circumference, macromorphous and micromorphous intestine,bowel movement capability in vivo and in vitro,slow wave and neural electrical activity,and the number of c-Kit positive interstitial cells of Cajal(ICC). RESULTS:Despite being of a similar general condition, these methods resulted in different levels of obstruction in each group compared with the control at different time points(12,24,48,72 h).However,these fields of the wide pipe rat showed significantly differences when compared with the other three obstructed groups at 12 to 72 h,including macroscopic and histological presentation,intestinal transit ratio and contractility,circumference and wet weight,amplitude and frequency of nerve electrical discharge and slow wave,and ICC numbers(all P<0.01). CONCLUSION:The wide pipe rat method is significantly more reliable and stable than the other methods of obstruction,demonstrating that use of the wide pipe method can be a useful model of incomplete intestinal obstruction.展开更多
The practical application of Li-S batteries is largely impeded by the“shuttle effect”generated at the cathode which results in a short life cycle of the battery.To address this issue,this work discloses a bimetallic...The practical application of Li-S batteries is largely impeded by the“shuttle effect”generated at the cathode which results in a short life cycle of the battery.To address this issue,this work discloses a bimetallic metal-organic framework(MOF)as a sulfur host material based on Al-MOF,commonly called(Al)MIL-53.To obtain a high-adsorption capacity to lithium polysulfides(Li_(2)S_(x),4≤x≤8),we present an effective strategy to incorporate sulfiphilic metal ion(Cu^(2+))with high-binding energy to Li_(2)S_(x) into the framework.Through a one-step hydrothermal method,Cu^(2+) is homogeneously dispersed in Al-MOF,producing a bimetallic Al/Cu-MOF as advanced cathode material.The macroscopic Li2S4 solution permeation test indicates that the Al/Cu-MOF has better adsorption capacity to lithium polysulfides than monometallic Al-MOF.The sulfur-transfusing process is executed via a melt-diffusion method to obtain the sulfur-containing Al/CuMOF(Al/Cu-MOF-S).The assembled Li-S batteries with Al/Cu-MOF-S yield improved cyclic performance,much better than that of monometallic AlMOF as sulfur host.It is shown that chemical immobilization is an effective method for polysulfide adsorption than physical confinement and the bimetallic Al/Cu-MOF,formed by incorporation of sulfiphilic Cu^(2+) into porous MOF,will provide a novel and powerful approach for efficient sulfur host materials.展开更多
Transition-metal selenides(M_xSe_y,M = Fe,Co,Ni)and their composites exhibit good storage capacities for sodium and lithium ions and occupy a unique position in research on sodium-ion and lithium-ion batteries.MxSey a...Transition-metal selenides(M_xSe_y,M = Fe,Co,Ni)and their composites exhibit good storage capacities for sodium and lithium ions and occupy a unique position in research on sodium-ion and lithium-ion batteries.MxSey and their composites are used as active materials to improve catalytic activity.However,low electrical conductivity,poor cycle stability,and low rate performance severely limit their applications.This review provides a comprehensive introduction to and understanding of the current research progress of M_xSe_y and their composites.Moreover,this review proposes a broader research platform for these materials,including various bioelectrocatalytic performance tests,lithium-sulfur batteries,and fuel cells.The synthesis method and related mechanisms of M_xSe_y and their composites are reviewed,and the effects of material morphologies on their electrochemical performance are discussed.The advantages and disadvantages of M_xSe_y and their composites as well as possible strategies for improving the storage and conversion of electrochemical energy are also summarized.展开更多
Because of features,such as adjustable structures,high porosity,and high crystallinity,metal-organic frameworks(MOFs)deservedly have received considerable attention.Nevertheless,there is still room for improvements in...Because of features,such as adjustable structures,high porosity,and high crystallinity,metal-organic frameworks(MOFs)deservedly have received considerable attention.Nevertheless,there is still room for improvements in the electrical conductivity and chemical stability of some MOFs,because of which they cannot be utilized as electrode materials.Fortunately,MOF derivatives have received widespread attention in recent years,especially phosphide materials,which are widely used in practical applications because of their outstanding conductivity,excellent specific surface area,and standout charge mobility.In this review,the latest developments of MOF-derived phosphides in electrocatalysis related to energy,including the excellent performance in terms of electrochemical energy storage and ingenious strategies,and diversified synthetic approaches are emphasized and summarized.Additionally,the arduous task and feasible proposals of MOF-derived phosphides are also discussed.展开更多
Lithium-sulfur batteries(LSBs)are considered promising new energy storage systems given their outstanding theoretical energy densities.Nevertheless,issues such as low electrical conductivity and severe volume expansio...Lithium-sulfur batteries(LSBs)are considered promising new energy storage systems given their outstanding theoretical energy densities.Nevertheless,issues such as low electrical conductivity and severe volume expansion,along with the formation of polysulfides during cycling,restrict their practical applications.To overcome these issues,it is necessary to find suitable and effective sulfur host materials.Metal-organic frameworks(MOFs),which are porous crystalline materials in the bourgeoning developmental stages,have demonstrated enormous potential in LSBs owing to their high porosity and tunable porous structure.Herein,we provide a comprehensive overview of MOF-based sulfur-loaded materials and discuss the charge/discharge mechanisms,strategies of enhancing battery performance,sulfur loading methods,and applications in LSBs.An outlook on future directions,prospects,and possible obstacles for the development of these materials is also provided.展开更多
The search for non-precious and efficient electrocatalysts towards the oxygen evolution reaction(OER)is of vital importance for the future advancement of multifarious renewable energy conversion/storage technologies.E...The search for non-precious and efficient electrocatalysts towards the oxygen evolution reaction(OER)is of vital importance for the future advancement of multifarious renewable energy conversion/storage technologies.Electronic modulation via heteroatom doping is recognized as one of the most forceful leverages to enhance the electrocatalytic activity.Herein,we demonstrate a delicate strategy for the in-situ confinement of S-doped Ni O nanoparticles into N-doped carbon nanotube/nanofiber-coupled hierarchical branched superstructures(labeled as S-Ni O@N-C NT/NFs).The developed strategy simultaneously combines enhanced thermodynamics via electronic regulation with accelerated kinetics via nanoarchitectonics.The S-doping into Ni O lattice and the 1 D/1 D-integrated hierarchical branched carbon substrate confer the resultant S-Ni O@N-C NT/NFs with regulated electronic configuration,enriched oxygen vacancies,convenient mass diffusion pathways and superior architectural robustness.Thereby,the SNi O@N-C NT/NFs display outstanding OER properties with an overpotential of 277 m V at 10 m A cm^(-2)and impressive long-term durability in KOH medium.Density functional theory(DFT)calculations further corroborate that introducing S-dopant significantly enhances the interaction with key oxygenate intermediates and narrow the band gap.More encouragingly,a rechargeable Zn-air battery using an air-cathode of Pt/C+S-Ni O@N-C NT/NFs exhibits a lower charge voltage and preferable cycling stability in comparison with the commercial Pt/C+Ru O_(2)counterpart.This study highlighting the concurrent consideration of electronic regulation,architectural design and nanocarbon hybridization may shed light on the future exploration of economical and efficient electrocatalysts.展开更多
Metal–organic frameworks(MOFs),which are generally considered to be crystalline materials comprising metal centers and organic ligands,have attracted growing attention because of their controllable structures and hig...Metal–organic frameworks(MOFs),which are generally considered to be crystalline materials comprising metal centers and organic ligands,have attracted growing attention because of their controllable structures and high porosity.MOFs based on transition metals(Fe,Co,Ni)are highly effi cient electrode materials for electrochemical energy storage.In this review,the characteristics of Fe-MOFs,Co-MOFs,Ni-MOFs,and their derivatives are summarized,and the relationships between the structures and performance are unveiled in depth.Additionally,their applications in lithium–ion batteries,lithium–sulfur batteries,and supercapacitors are discussed.This review sheds light on the development of MOFs and their derivatives to realize excellent electrochemical performance.展开更多
Metal-organic frameworks(MOFs)with high porosity and variable structure have attracted extensive attention in the field of electrochemistry,but their poor conductivity and stability have limited their development.Mate...Metal-organic frameworks(MOFs)with high porosity and variable structure have attracted extensive attention in the field of electrochemistry,but their poor conductivity and stability have limited their development.Materials derived from MOFs can maintain the structural diversity and porosity characteristics of MOFs while improving their electrical conductivity and stability.Metal phosphides play an important role in electrochemistry because they possess rich active sites,unique physicochemical properties,and a porous structure.Published results show that MOF-derived metal-phosphides materials have great promise in the field of electrochemistry due to their controllable structure,high specific surface area,high stability and excellent electrical conductivity.MOF-derived metal-phosphides with significant electrochemical properties can be obtained by simply,economical and scalable synthetic methods.This work reviews the application of MOF-derived metal phosphides in electrochemistry.Specifically,the synthesis methodology and morphological characterization of MOFs derived metal-phosphides and their application in electrochemistry are described.Based on recent scientific advances,we discuss the challenges and opportunities for future research on MOF-derived metal-phosphides materials.展开更多
Tin-based materials with high theoretical capacity and suitable working voltage are ideal anode materials for lithium-ion batteries(LIBs). However, to overcome their shortcomings(volume expansion and inferior stabilit...Tin-based materials with high theoretical capacity and suitable working voltage are ideal anode materials for lithium-ion batteries(LIBs). However, to overcome their shortcomings(volume expansion and inferior stability), the preparation processes are usually complicated and expensive. Herein, a tin-based metal-organic complex(tin 1,2-benzenedicarboxylic acid, Sn-BDC)with one-dimensional microbelt morphology is synthesized by a facile, rapid and low-cost co-precipitation method, and served as anode material for LIBs without any post-treatment. Sn-BDC exhibits a high reversible capacity with609/440 m Ah·g^(-1) at 50/2000 m A·g^(-1), and robust cycling stability of 856 m Ah·g^(-1) after 200 cycles at 200 m A·g^(-1),which are obviously superior to that of the Sn Ox/C counterparts. Moreover, an electrochemical reconstruction perspective on the lithium storage mechanism of Sn-BDC is proposed by systematic ex-situ characterizations. The reconstructed SnO_(2) replaces Sn-BDC and becomes the active material in the subsequent cycles. As the by-product of the lithiation reaction, the formed Li-based metal-organic complex(Li-BDC, wrapped around the reconstructed SnO_(2)) plays an important role in alleviating volume expansion and accelerating the charge transfer kinetics.This work is beneficial to design and construct the new electrode materials based on the electrochemical reconstruction for advanced LIBs.展开更多
The controllable morphology and composition of catalysts are crucial to improving the electrocatalytic activity of oxygen evolution reaction(OER).Herein,we construct a bimetallic heterostructure by sulfidation and hyd...The controllable morphology and composition of catalysts are crucial to improving the electrocatalytic activity of oxygen evolution reaction(OER).Herein,we construct a bimetallic heterostructure by sulfidation and hydrothermal methods,and the layered ReS_(2)is vertically aligned on Prussian blue-derived hollow Co_(9)S_(8)nanocubes(Co_(9)S_(8)@ReS_(2)).The core-shell structure of Co_(9)S_(8)@ReS_(2)can effectively prevent the restacking of layered ReS_(2),expose the abundant surface area and improve the utilization of electrocatalytic sites,resulting in fast electrolyte diffusion and charge transfer during OER.Due to the synergistic effect of the core-shell morphology and the formed bimetallic heterostructure,Co_(9)S_(8)@ReS_(2)exhibits excellent catalytic OER performance.At 10 mA/cm^(2),only 288 mV of overpotential is required with the Tafel slope of 73.3 mV/dec for Co_(9)S_(8)@ReS_(2),which are both lower than that of Co_(9)S_(8)and ReS_(2).Meanwhile,Co_(9)S_(8)@ReS_(2)exhibits high catalytic stability and low charge transfer resistance and the boosted active sites are confirmed by density functional theory.This work provides a rational design of the OER catalysts by constructing the bimetallic heterostructure.展开更多
To improve the efficiency of oxygen electrolysis,exploiting bifunctional electrocatalysts with excellent activity and stability is extremely important due to the four-electron transfer dynamics of oxygen evolution rea...To improve the efficiency of oxygen electrolysis,exploiting bifunctional electrocatalysts with excellent activity and stability is extremely important due to the four-electron transfer dynamics of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).Herein,a series of yolk-shell hollow polyhedrons(YHPs)embedded with NiCoFe ternary alloy and metal oxides,which are named YHP-x(x=1,2,3,4),were reported.By controlled etching multi-layered zeolitic imidazolate frameworks and following pyrolytic integration,YHPs are endowed with mass transfer tunnels,accessible inner active sites,and good electrical conductivity.Due to the synergetic effect of the alloy,metal oxides and the yolk-shell structure,YHP-1 exhibits excellent ORR performance with a half-wave potential of 0.79 V and YHP-2 displays superior OER performance with a low overpotential of 257 mV at 10 mA cm−2.The strategy described in this work can be extended to a number of hollow/yolk-shell electrocatalysts for water splitting and metal–air batteries.展开更多
In this work,taking NiSe_(2)as a prototype to be used as cocatalyst in photocatalytic hydrogen evolution,we demonstrate that the crystal phase of NiSe_(2)plays a vital role in determining the catalytic stability,rathe...In this work,taking NiSe_(2)as a prototype to be used as cocatalyst in photocatalytic hydrogen evolution,we demonstrate that the crystal phase of NiSe_(2)plays a vital role in determining the catalytic stability,rather than activity.Theoretical and experimental results indicate that the phase structure shows negligible influence to the charge transport and hydrogen adsorption capacity.When integrating with carbon nitride(CN)photocatalyst forming hybrids(m-NiSe_(2)/CN and p-NiSe_(2)/CN),the hybrids show comparable photocatalytic hydrogen evolution rates(3.26μmol/h and 3.75μmol/h).Unlike the comparable catalytic activity,we found that phase-engineered NiSe_(2)exhibits distinct stability,i.e.,m-NiSe_(2)can evolve H_(2) steadily,but p-NiSe_(2)shows a significant decrease in catalytic process(∼57.1%decrease in 25 h).The factor leading to different catalytic stability can be ascribed to the different surface conversion behavior during photocatalytic process,i.e.,chemical structure of m-NiSe_(2)can be well preserved in catalytic process,but partial p-NiSe_(2)tends to be converted to NiOOH.展开更多
Cu-based materials are seldom reported as oxygen evolution reaction(OER)electrocatalysts due to their inherent electron orbital configuration,which makes them difficult to adsorb oxygen-intermediates during OER.Reason...Cu-based materials are seldom reported as oxygen evolution reaction(OER)electrocatalysts due to their inherent electron orbital configuration,which makes them difficult to adsorb oxygen-intermediates during OER.Reasonably engineering the hierarchical architectures and the electronic structures can improve the performance of Cu-based OER catalysts,such as constructing multilevel morphology,inducing the porous materials,improving the Cu valence,building heterostructures,doping heteroatoms,etc.In this work,copper-1,3,5-benzenetricarboxylate(HKUST-1)octahedra in-situ grow on the Cu nanorod(NR)-supported N-doped carbon microplates,meanwhile an active layer of Cu(OH)_(2)forms on the surface of the original conductive Cu NRs.The octahedral HKUST-1,serving as a spacer between the microplates,greatly improves the porosity and increases the available active sites,facilitating the mass transport and electron transfer,thus resulting in greatly enhanced OER performance.展开更多
Metal-organic frameworks(MOFs)have received considerable attention because of their advantages of adjustable structure,high porosity,and rich active centers.Meanwhile,perovskite has attracted research interest due to ...Metal-organic frameworks(MOFs)have received considerable attention because of their advantages of adjustable structure,high porosity,and rich active centers.Meanwhile,perovskite has attracted research interest due to its unique highemission quantum yield and excellent optoelectronic properties.However,the instability of perovskites under certain conditions hinders their more comprehensive development.A novel strategy encapsulates perovskite in the pores of MOFs to protect it from external interference and increase the active centers,thus improving the performance of perovskite@MOF composites.In this review,the latest research progress in the synthesis strategy,function,and application of perovskite@MOF composites is systematically summarized.Additionally,the challenges of further developing perovskite@MOF composites are discussed.Hopefully,this review provides creative inspiration to advance future studies on perovskite@MOF composites in this emerging field.展开更多
Uncontrollable dendrite growth and side reactions resulting in short operating life and low Coulombic efficiency have severely hindered the further development of aqueous zinc-ion batteries(AZIBs).In this work,we desi...Uncontrollable dendrite growth and side reactions resulting in short operating life and low Coulombic efficiency have severely hindered the further development of aqueous zinc-ion batteries(AZIBs).In this work,we designed to grow zeolitic imidazolate framework-8(ZIF-8)uniformly on CuO nanosheets(NSs)and prepared carbon-coated CuZn alloy NSs(CuZn@C NSs)by calcination under H_(2)/Ar atmosphere.As reflected by extended X-ray absorption fine structure(EXAFS),density functional theory(DFT),in-situ Raman,the Cu–Zn and Zn–N bonds present in CuZn@C NSs act as zincophilic sites to uniformly absorb Zn ions and inhibit the formation of Zn dendrites.At the same time,CuZn@C NSs hinder the direct contact between zinc anode and electrolyte,preventing the occurrence of side reactions.More impressively,the symmetric cells constructed with CuZn@C NSs anodes exhibited excellent zinc plating/exfoliation performance and long life cycle at different current densities with low voltage hysteresis.In addition,low polarization,high capacity retention,long cycle life over 1000 cycles at 5 A∙g^(−1) were achieved when CuZn@C NSs were used as anodes for CuZn@C/V_(2)O_(5)full cells.展开更多
基金supported by the National Natural Science Foundation of China (NSFC-U1904215)Natural Science Foundation of Jiangsu Province (BK20200044)Changjiang scholars program of the Ministry of Education (Q2018270).
文摘Water pollution is an increasingly serious environmental problem because many pollutants have carcinogenic effects on humans and aquatic organisms.Metal organic framework(MOF),made up of metal ions and multifunctional organic ligands,has been one of the most concerned materials because of its adjustable and regular pore structure.MOFs have always shown attractive advantages in membrane separation and adsorption technologies,among which water-stable MOFs are particularly prominent in wastewater treatment(WWT)applications.This review systematically summarizes the application of MOF membranes in membrane filtration,membrane pervaporation and membrane distillation.Also,the adsorption mechanisms of heavy metals,dyes and antibacterials in wastewater have been concluded.In order to tap the full application potential of pristine MOFs in sustainable wastewater treatment,current challenges are discussed in detail and future research directions are proposed.
基金Changjiang Scholars Program of the Ministry of Education,Grant/Award Number:Q2018270Outstanding Youth Funding of Anhui Province,Grant/Award Number:OUFAH 1908085J10+2 种基金Jiangsu Students'Innovation and Entrepreneurship Training Program,Grant/Award Number:202111117079YNatural Science Foundation of Jiangsu Province,Grant/Award Number:BK20200044National Natural Science Foundation of China,Grant/Award Numbers:NSFC 21671004,NSFC 21975001,NSFC U1904215。
文摘The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity and flexible electronic structure.Herein,density functional theory simulations were addressed to predict the electronic structure regulations of CoFc-MOF by nickel doping,which demonstrated that the well-proposed CoNiFc-MOFs delivered a small energy barrier,promoted conductivity,and well-regulated d-band center.Inspired by these,a series of sea-urchin-like CoNiFc-MOFs were successfully synthesized via a facile solvothermal method.Moreover,the synchrotron X-ray and X-ray photoelectron spectroscopy measurements manifested that the introduction of nickel could tailor the electronic structure of the catalyst and induce the directional transfer of electrons,thus optimizing the rate-determining step of^(*)O→^(*)OOH during the OER process and yielding decent overpotentials of 209 and 252 mV at 10 and 200 mA cm^(−2),respectively,with a small Tafel slope of 39 mV dec^(−1).This work presents a new paradigm for developing highly efficient and durable MOF-based electrocatalysts for OER.
基金supported by the National Natural Science Foundation of China(Grant Nos.21972068,21875112,and 22075290)the Nanjing IPE Institute of Green Manufacturing Industrythe Beijing Natural Science Foundation(Grant No.Z200012).
文摘The development of economical,efficient,and robust electrocatalysts toward the hydrogen evolution reaction(HER)is highly imperative for the rapid advancement of renewable H2 energy-associated technologies.Extensive utilization of the heterointerface effect can endow the catalysts with remarkably boosted electrocatalytic performance due to the modified electronic state of active sites.Herein,we demonstrate deliberate crafting of CoP/CoO heterojunction porous nanotubes(abbreviated as CoP/CoO PNTs hereafter)using a self-sacrificial template-engaged strategy.Precise control over the Kirkendall diffusion process of the presynthesized cobalt–aspartic acid complex nanowires is indispensable for the formation of CoP/CoO heterostructures.The topochemical transformation strategy of the reactive templates enables uniform and maximized construction of CoP/CoO heterojunctions throughout all the porous nanotubes.The establishment of CoP/CoO heterojunctions could considerably modify the electronic configuration of the active sites and also improve the electric conductivity,which endows the resultant CoP/CoO PNTs with enhanced intrinsic activity.Simultaneously,the hollow and porous nanotube architectures allow sufficient accessibility of exterior/interior surfaces and molecular permeability,drastically promoting the reaction kinetics.Consequently,when used as HER electrocatalysts,the well-designed CoP/CoO PNTs show Pt-like activity,with an overpotential of only 61 mV at 10mA cm^(−2) and excellent stability in 1.0M KOH medium,exceeding those of the vast majority of the previously reported nonprecious candidates.Density functional theory calculations further substantiate that the construction of CoP/CoO heterojunctions enables optimization of the Gibbs free energies for water adsorption and H adsorption,resulting in boosted HER intrinsic activity.The present study may provide in-depth insights into the fundamental mechanisms of heterojunction-induced electronic regulation,which may pave the way for the rational design of advanced Earth-abundant electrocatalysts in the future.
基金supported by the National Natural Science Foundation of China(NSFC-U1904215,21671170)the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP).
文摘Metal–organic framework-based compounds have recently gained great attention because of their unique porous structure,ordered porosity,and high specific surface area.Benefiting from these superior properties,metal–organic framework-based compounds have been proven to be one of the most potential candidates for environmental governance and remediation.In this review,the different types of metal–organic framework-based compounds are first summarized.Further,the various environmental applications of metal–organic framework-based compounds including organic pollutant removal,toxic and hazardous gas capture,heavy metal ion detection,gas separation,water harvesting,air purification,and carbon dioxide reduction reactions are discussed in detail.In the end,the opportunities and challenges for the future development of metal–organic framework-based compounds for environmental applications are highlighted.
基金Supported by Higher Education Quality Project of Sichuan Province:Innovative Scientific Experiment Project of SichuanProvince,Grant No.SJCX201110Chengdu Medical College Innovative Scientific Experiment Project,Grant No.CX201220and CX201115
文摘AIM:To investigate different methods of creating incomplete intestinal obstruction in a rat model and to compare their electrophysiologic,morphologic and histologic characteristics. METHODS:Rat ileum was partially obstructed by the respective application of:braided silk(penetrated the mesentery and surrounded intestine);half ligation (penetrated directly and ligated 1/2 cross-section of the intestine);wide pipe(6 mm in width,surrounded the intestine);narrow pipe(2 mm in width,surrounded the intestine).A control was also included(no obstruction). Various behavioral and electrophysiologic variables, as well as morphologic and immunohistochemical observations were recorded by blinded investigators at different time points(12,24,48,72 h),including daily general condition,ileal wet weight and circumference, macromorphous and micromorphous intestine,bowel movement capability in vivo and in vitro,slow wave and neural electrical activity,and the number of c-Kit positive interstitial cells of Cajal(ICC). RESULTS:Despite being of a similar general condition, these methods resulted in different levels of obstruction in each group compared with the control at different time points(12,24,48,72 h).However,these fields of the wide pipe rat showed significantly differences when compared with the other three obstructed groups at 12 to 72 h,including macroscopic and histological presentation,intestinal transit ratio and contractility,circumference and wet weight,amplitude and frequency of nerve electrical discharge and slow wave,and ICC numbers(all P<0.01). CONCLUSION:The wide pipe rat method is significantly more reliable and stable than the other methods of obstruction,demonstrating that use of the wide pipe method can be a useful model of incomplete intestinal obstruction.
基金supported by the National Natural Science Foundation of China(U1904215)Natural Science Foundation of Jiangsu Province(BK20200044)+1 种基金Changjiang scholars program of the Ministry of Education(Q2018270)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX20_2805).
文摘The practical application of Li-S batteries is largely impeded by the“shuttle effect”generated at the cathode which results in a short life cycle of the battery.To address this issue,this work discloses a bimetallic metal-organic framework(MOF)as a sulfur host material based on Al-MOF,commonly called(Al)MIL-53.To obtain a high-adsorption capacity to lithium polysulfides(Li_(2)S_(x),4≤x≤8),we present an effective strategy to incorporate sulfiphilic metal ion(Cu^(2+))with high-binding energy to Li_(2)S_(x) into the framework.Through a one-step hydrothermal method,Cu^(2+) is homogeneously dispersed in Al-MOF,producing a bimetallic Al/Cu-MOF as advanced cathode material.The macroscopic Li2S4 solution permeation test indicates that the Al/Cu-MOF has better adsorption capacity to lithium polysulfides than monometallic Al-MOF.The sulfur-transfusing process is executed via a melt-diffusion method to obtain the sulfur-containing Al/CuMOF(Al/Cu-MOF-S).The assembled Li-S batteries with Al/Cu-MOF-S yield improved cyclic performance,much better than that of monometallic AlMOF as sulfur host.It is shown that chemical immobilization is an effective method for polysulfide adsorption than physical confinement and the bimetallic Al/Cu-MOF,formed by incorporation of sulfiphilic Cu^(2+) into porous MOF,will provide a novel and powerful approach for efficient sulfur host materials.
基金supported by the National Natural Science Foundation of China(NSFC-21671170,21673203, and 21201010)the Top-notch Academic Programs Project ofJiangsu Higher Education Institutions (TAPP)+3 种基金Program for New Century Excellent Talents of the University in China (NCET-130645)the Six Talent Plan (2015-XCL-030)Qinglan Projectthe Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Transition-metal selenides(M_xSe_y,M = Fe,Co,Ni)and their composites exhibit good storage capacities for sodium and lithium ions and occupy a unique position in research on sodium-ion and lithium-ion batteries.MxSey and their composites are used as active materials to improve catalytic activity.However,low electrical conductivity,poor cycle stability,and low rate performance severely limit their applications.This review provides a comprehensive introduction to and understanding of the current research progress of M_xSe_y and their composites.Moreover,this review proposes a broader research platform for these materials,including various bioelectrocatalytic performance tests,lithium-sulfur batteries,and fuel cells.The synthesis method and related mechanisms of M_xSe_y and their composites are reviewed,and the effects of material morphologies on their electrochemical performance are discussed.The advantages and disadvantages of M_xSe_y and their composites as well as possible strategies for improving the storage and conversion of electrochemical energy are also summarized.
基金This study was supported by the National Natural Science Foundation of China(NSFC-U1904215)Natural Science Foundation of Jiangsu Province(BK20200044)Program for Young Changjiang Scholars of the Ministry of Education,China(Q2018270).
文摘Because of features,such as adjustable structures,high porosity,and high crystallinity,metal-organic frameworks(MOFs)deservedly have received considerable attention.Nevertheless,there is still room for improvements in the electrical conductivity and chemical stability of some MOFs,because of which they cannot be utilized as electrode materials.Fortunately,MOF derivatives have received widespread attention in recent years,especially phosphide materials,which are widely used in practical applications because of their outstanding conductivity,excellent specific surface area,and standout charge mobility.In this review,the latest developments of MOF-derived phosphides in electrocatalysis related to energy,including the excellent performance in terms of electrochemical energy storage and ingenious strategies,and diversified synthetic approaches are emphasized and summarized.Additionally,the arduous task and feasible proposals of MOF-derived phosphides are also discussed.
基金supported by the National Natural Science Foundation of China (NSFC-U1904215, and 21671170)Changjiang scholars program of the Ministry of Education (Q2018270)+3 种基金the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions (TAPP)Program for New Century Excel ent Talents of the University in China (NCET-13-0645)the Six Talent Plan (2015-XCL-030)Qinglan Project of Jiangsu and Program for Colleges Natural Science Research in Jiangsu Province (18KJB150036)
文摘Lithium-sulfur batteries(LSBs)are considered promising new energy storage systems given their outstanding theoretical energy densities.Nevertheless,issues such as low electrical conductivity and severe volume expansion,along with the formation of polysulfides during cycling,restrict their practical applications.To overcome these issues,it is necessary to find suitable and effective sulfur host materials.Metal-organic frameworks(MOFs),which are porous crystalline materials in the bourgeoning developmental stages,have demonstrated enormous potential in LSBs owing to their high porosity and tunable porous structure.Herein,we provide a comprehensive overview of MOF-based sulfur-loaded materials and discuss the charge/discharge mechanisms,strategies of enhancing battery performance,sulfur loading methods,and applications in LSBs.An outlook on future directions,prospects,and possible obstacles for the development of these materials is also provided.
基金financially supported by the National Natural Science Foundation of China(21972068,21875112,22072067,21878047,22075290 and 21676056)the Qing Lan Project of Jiangsu Province(1107040167)+3 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX20_0121)the China Scholarship Council(CSC,202006090294)the Fundamental Research Funds for the Central Universities(3207042101D)A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)(1107047002)。
文摘The search for non-precious and efficient electrocatalysts towards the oxygen evolution reaction(OER)is of vital importance for the future advancement of multifarious renewable energy conversion/storage technologies.Electronic modulation via heteroatom doping is recognized as one of the most forceful leverages to enhance the electrocatalytic activity.Herein,we demonstrate a delicate strategy for the in-situ confinement of S-doped Ni O nanoparticles into N-doped carbon nanotube/nanofiber-coupled hierarchical branched superstructures(labeled as S-Ni O@N-C NT/NFs).The developed strategy simultaneously combines enhanced thermodynamics via electronic regulation with accelerated kinetics via nanoarchitectonics.The S-doping into Ni O lattice and the 1 D/1 D-integrated hierarchical branched carbon substrate confer the resultant S-Ni O@N-C NT/NFs with regulated electronic configuration,enriched oxygen vacancies,convenient mass diffusion pathways and superior architectural robustness.Thereby,the SNi O@N-C NT/NFs display outstanding OER properties with an overpotential of 277 m V at 10 m A cm^(-2)and impressive long-term durability in KOH medium.Density functional theory(DFT)calculations further corroborate that introducing S-dopant significantly enhances the interaction with key oxygenate intermediates and narrow the band gap.More encouragingly,a rechargeable Zn-air battery using an air-cathode of Pt/C+S-Ni O@N-C NT/NFs exhibits a lower charge voltage and preferable cycling stability in comparison with the commercial Pt/C+Ru O_(2)counterpart.This study highlighting the concurrent consideration of electronic regulation,architectural design and nanocarbon hybridization may shed light on the future exploration of economical and efficient electrocatalysts.
基金supported by the National Natural Science Foundation of China (Nos. NSFC-U1904215)the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions (TAPP)+2 种基金the Natural Science Foundation of Jiangsu Province (No. BK20200044)Program for Young Changjiang Scholars of the Ministry of Education,China (No. Q2018270)the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Metal–organic frameworks(MOFs),which are generally considered to be crystalline materials comprising metal centers and organic ligands,have attracted growing attention because of their controllable structures and high porosity.MOFs based on transition metals(Fe,Co,Ni)are highly effi cient electrode materials for electrochemical energy storage.In this review,the characteristics of Fe-MOFs,Co-MOFs,Ni-MOFs,and their derivatives are summarized,and the relationships between the structures and performance are unveiled in depth.Additionally,their applications in lithium–ion batteries,lithium–sulfur batteries,and supercapacitors are discussed.This review sheds light on the development of MOFs and their derivatives to realize excellent electrochemical performance.
基金supported by the National Natural Science Foundation of China(U1904215)Natural Science Foundation of Jiangsu Province(BK20200044)Changjiang scholars program of the Ministry of Education(Q2018270)。
文摘Metal-organic frameworks(MOFs)with high porosity and variable structure have attracted extensive attention in the field of electrochemistry,but their poor conductivity and stability have limited their development.Materials derived from MOFs can maintain the structural diversity and porosity characteristics of MOFs while improving their electrical conductivity and stability.Metal phosphides play an important role in electrochemistry because they possess rich active sites,unique physicochemical properties,and a porous structure.Published results show that MOF-derived metal-phosphides materials have great promise in the field of electrochemistry due to their controllable structure,high specific surface area,high stability and excellent electrical conductivity.MOF-derived metal-phosphides with significant electrochemical properties can be obtained by simply,economical and scalable synthetic methods.This work reviews the application of MOF-derived metal phosphides in electrochemistry.Specifically,the synthesis methodology and morphological characterization of MOFs derived metal-phosphides and their application in electrochemistry are described.Based on recent scientific advances,we discuss the challenges and opportunities for future research on MOF-derived metal-phosphides materials.
基金financially supported by the National Natural Science Foundations of China (Nos.51904152,21965033 and U2003216)the Natural Science Foundations of Henan Province (No.222300420502)+1 种基金the Program for Science&Technology Innovation Talents in Universities of Henan Province (No.20HASTIT020)the Key Science and Technology Program of Henan Province (No.222102240044)。
文摘Tin-based materials with high theoretical capacity and suitable working voltage are ideal anode materials for lithium-ion batteries(LIBs). However, to overcome their shortcomings(volume expansion and inferior stability), the preparation processes are usually complicated and expensive. Herein, a tin-based metal-organic complex(tin 1,2-benzenedicarboxylic acid, Sn-BDC)with one-dimensional microbelt morphology is synthesized by a facile, rapid and low-cost co-precipitation method, and served as anode material for LIBs without any post-treatment. Sn-BDC exhibits a high reversible capacity with609/440 m Ah·g^(-1) at 50/2000 m A·g^(-1), and robust cycling stability of 856 m Ah·g^(-1) after 200 cycles at 200 m A·g^(-1),which are obviously superior to that of the Sn Ox/C counterparts. Moreover, an electrochemical reconstruction perspective on the lithium storage mechanism of Sn-BDC is proposed by systematic ex-situ characterizations. The reconstructed SnO_(2) replaces Sn-BDC and becomes the active material in the subsequent cycles. As the by-product of the lithiation reaction, the formed Li-based metal-organic complex(Li-BDC, wrapped around the reconstructed SnO_(2)) plays an important role in alleviating volume expansion and accelerating the charge transfer kinetics.This work is beneficial to design and construct the new electrode materials based on the electrochemical reconstruction for advanced LIBs.
基金supported by the Natural Science Research of the Jiangsu Higher Education Institutions of China(No.18KJB150034)Six Talent Peaks Project of Jiangsu Province(No.XCL-103)‘High-End Talent Project’of Yangzhou University。
文摘The controllable morphology and composition of catalysts are crucial to improving the electrocatalytic activity of oxygen evolution reaction(OER).Herein,we construct a bimetallic heterostructure by sulfidation and hydrothermal methods,and the layered ReS_(2)is vertically aligned on Prussian blue-derived hollow Co_(9)S_(8)nanocubes(Co_(9)S_(8)@ReS_(2)).The core-shell structure of Co_(9)S_(8)@ReS_(2)can effectively prevent the restacking of layered ReS_(2),expose the abundant surface area and improve the utilization of electrocatalytic sites,resulting in fast electrolyte diffusion and charge transfer during OER.Due to the synergistic effect of the core-shell morphology and the formed bimetallic heterostructure,Co_(9)S_(8)@ReS_(2)exhibits excellent catalytic OER performance.At 10 mA/cm^(2),only 288 mV of overpotential is required with the Tafel slope of 73.3 mV/dec for Co_(9)S_(8)@ReS_(2),which are both lower than that of Co_(9)S_(8)and ReS_(2).Meanwhile,Co_(9)S_(8)@ReS_(2)exhibits high catalytic stability and low charge transfer resistance and the boosted active sites are confirmed by density functional theory.This work provides a rational design of the OER catalysts by constructing the bimetallic heterostructure.
基金This study was financially supported by the Program for the National Natural Science Foundation of China(Nos.NSFC-21901221,21671170,21673203 and U1904215)the Natural Science Foundation of Jiangsu Province(No.BK20190870)+1 种基金Changjiang Scholars Program of the Ministry of Education(No.Q2018270)the Top Talent Project of Yangzhou University.
文摘To improve the efficiency of oxygen electrolysis,exploiting bifunctional electrocatalysts with excellent activity and stability is extremely important due to the four-electron transfer dynamics of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).Herein,a series of yolk-shell hollow polyhedrons(YHPs)embedded with NiCoFe ternary alloy and metal oxides,which are named YHP-x(x=1,2,3,4),were reported.By controlled etching multi-layered zeolitic imidazolate frameworks and following pyrolytic integration,YHPs are endowed with mass transfer tunnels,accessible inner active sites,and good electrical conductivity.Due to the synergetic effect of the alloy,metal oxides and the yolk-shell structure,YHP-1 exhibits excellent ORR performance with a half-wave potential of 0.79 V and YHP-2 displays superior OER performance with a low overpotential of 257 mV at 10 mA cm−2.The strategy described in this work can be extended to a number of hollow/yolk-shell electrocatalysts for water splitting and metal–air batteries.
基金the financial support by Natural Science Foundation of Jiangsu Province(No.BK20210827)China Postdoctoral Science Foundation(No.2021M700117)+3 种基金National Natural Science Foundation of China(Nos.U1904215 and 41977085)Program for Young Changjiang Scholars of the Ministry of Education(No.Q2018270)Six Talent Peaks Project in Jiangsu Province(No.TD-JNHB-012)333 Project in Jiangsu Province(No.BRA2020300).
文摘In this work,taking NiSe_(2)as a prototype to be used as cocatalyst in photocatalytic hydrogen evolution,we demonstrate that the crystal phase of NiSe_(2)plays a vital role in determining the catalytic stability,rather than activity.Theoretical and experimental results indicate that the phase structure shows negligible influence to the charge transport and hydrogen adsorption capacity.When integrating with carbon nitride(CN)photocatalyst forming hybrids(m-NiSe_(2)/CN and p-NiSe_(2)/CN),the hybrids show comparable photocatalytic hydrogen evolution rates(3.26μmol/h and 3.75μmol/h).Unlike the comparable catalytic activity,we found that phase-engineered NiSe_(2)exhibits distinct stability,i.e.,m-NiSe_(2)can evolve H_(2) steadily,but p-NiSe_(2)shows a significant decrease in catalytic process(∼57.1%decrease in 25 h).The factor leading to different catalytic stability can be ascribed to the different surface conversion behavior during photocatalytic process,i.e.,chemical structure of m-NiSe_(2)can be well preserved in catalytic process,but partial p-NiSe_(2)tends to be converted to NiOOH.
基金the National Natural Science Foundation of China(Nos.U1904215 and 21875207)the Natural Science Foundation of Jiangsu Province(No.BK20200044)the Shenzhen Key Laboratory of Micro/Nano-Porous Functional Materials(SKLPM,No.ZDSYS20210709112802010).
文摘Cu-based materials are seldom reported as oxygen evolution reaction(OER)electrocatalysts due to their inherent electron orbital configuration,which makes them difficult to adsorb oxygen-intermediates during OER.Reasonably engineering the hierarchical architectures and the electronic structures can improve the performance of Cu-based OER catalysts,such as constructing multilevel morphology,inducing the porous materials,improving the Cu valence,building heterostructures,doping heteroatoms,etc.In this work,copper-1,3,5-benzenetricarboxylate(HKUST-1)octahedra in-situ grow on the Cu nanorod(NR)-supported N-doped carbon microplates,meanwhile an active layer of Cu(OH)_(2)forms on the surface of the original conductive Cu NRs.The octahedral HKUST-1,serving as a spacer between the microplates,greatly improves the porosity and increases the available active sites,facilitating the mass transport and electron transfer,thus resulting in greatly enhanced OER performance.
基金supported by the National Natural Science Foundation of China(NSFC-U1904215)the Natural Science Foundation of Jiangsu Province(BK20200044)the Program for Young Changjiang Scholars of the Ministry of Education,China(Q2018270).
文摘Metal-organic frameworks(MOFs)have received considerable attention because of their advantages of adjustable structure,high porosity,and rich active centers.Meanwhile,perovskite has attracted research interest due to its unique highemission quantum yield and excellent optoelectronic properties.However,the instability of perovskites under certain conditions hinders their more comprehensive development.A novel strategy encapsulates perovskite in the pores of MOFs to protect it from external interference and increase the active centers,thus improving the performance of perovskite@MOF composites.In this review,the latest research progress in the synthesis strategy,function,and application of perovskite@MOF composites is systematically summarized.Additionally,the challenges of further developing perovskite@MOF composites are discussed.Hopefully,this review provides creative inspiration to advance future studies on perovskite@MOF composites in this emerging field.
基金the National Natural Science Foundation of China(Nos.NSFC-U1904215,21805192,and 12102422)the Natural Science Foundation of Jiangsu Province(No.BK20200044)+2 种基金the Top-notch Academic Programs Project(TAPP)of Jiangsu Higher Education Institutions,and the Program for Young Changjiang Scholars of the Ministry of Education,China(No.Q2018270)We also acknowledge the Priority Academic Program Development of Jiangsu Higher Education Institutions.Y.Y.L.acknowledges the Guangdong Basic and Applied Basic Research Foundation(No.2019A1515110735)the Natural Science Research Project of Anhui Educational Committee for Excellent Young Scholars(No.2022AH030152).
文摘Uncontrollable dendrite growth and side reactions resulting in short operating life and low Coulombic efficiency have severely hindered the further development of aqueous zinc-ion batteries(AZIBs).In this work,we designed to grow zeolitic imidazolate framework-8(ZIF-8)uniformly on CuO nanosheets(NSs)and prepared carbon-coated CuZn alloy NSs(CuZn@C NSs)by calcination under H_(2)/Ar atmosphere.As reflected by extended X-ray absorption fine structure(EXAFS),density functional theory(DFT),in-situ Raman,the Cu–Zn and Zn–N bonds present in CuZn@C NSs act as zincophilic sites to uniformly absorb Zn ions and inhibit the formation of Zn dendrites.At the same time,CuZn@C NSs hinder the direct contact between zinc anode and electrolyte,preventing the occurrence of side reactions.More impressively,the symmetric cells constructed with CuZn@C NSs anodes exhibited excellent zinc plating/exfoliation performance and long life cycle at different current densities with low voltage hysteresis.In addition,low polarization,high capacity retention,long cycle life over 1000 cycles at 5 A∙g^(−1) were achieved when CuZn@C NSs were used as anodes for CuZn@C/V_(2)O_(5)full cells.
