Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), sc...Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), scanning electron microscopy(SEM), and electron backscatter diffraction(EBSD).The coating bonding strength is assessed by pull-out tests and scribing in accordance with GB/T 9286-1998.The results show that the Cu coating with a thickness of 30 μm deposited on GF/PEEK by magnetron sputtering has lower roughness, finer grain size, higher crystallinity, as well as better macroscopic compressive stress,bonding strength, and electrical conductivity than the Cu coating deposited by electroplating.展开更多
As promising catalysts for the degradation of organic pollutants,metal–organic frameworks(MOFs)often face limitations due to the particle agglomeration and challenging recovery in liquid-catalysis application,stemmin...As promising catalysts for the degradation of organic pollutants,metal–organic frameworks(MOFs)often face limitations due to the particle agglomeration and challenging recovery in liquid-catalysis application,stemming from their powdery nature.Engineering macroscopic structures from pulverous MOF is thus of great importance for broadening their practical applications.In this study,three-dimensional porous MOF aerogel catalysts were successfully fabricated for degrading organic dyes by activating peroxymonosulfate(PMS).MOF/gelatin aerogel(MOF/GA)catalysts were prepared by directly integrating bimetallic FeCo-BDC with gelatin solutions,followed by freeze-drying and low-temperature calcination.The FeCo-BDC-0.15/GA/PMS system exhibited remarkable performance in degrading various organic dyes,eliminating 99.2%of rhodamine B within a mere 5 min.Compared to the GA/PMS system,there was over a 300-fold increase in the reaction rate constant.Remarkably,high removal efficiency was maintained across varying conditions,including different solution pH,co-existing inorganic anions,and natural water matrices.Radical trapping experiments and electron paramagnetic resonance analysis revealed that the degradation involved radical(SO_(4)^(-)·)and non-radical routes(^(1)O_(2)),of which ^(1)O_(2) was dominant.Furthermore,even after a continuous 400-min reaction in a fixed-bed reactor at a liquid hourly space velocity of 27 h^(-1),the FeCo-BDC/GA composite sustained a degradation efficiency exceeding 98.7%.This work presents highly active MOF-gelatin aerogels for dye degradation and expands the potential for their large-scale,continuous treatment application in organic dye wastewater management.展开更多
The stability of lithium metal anodes essentially dictates the lifespan of high-energy-density lithium metal batteries.Lithium nitrate(LiNO_(3))is widely recognized as an effective additive to stabilize lithium metal ...The stability of lithium metal anodes essentially dictates the lifespan of high-energy-density lithium metal batteries.Lithium nitrate(LiNO_(3))is widely recognized as an effective additive to stabilize lithium metal anodes by forming LiN_(x)O_(y)-containing solid electrolyte interphase(SEI).However,its poor solubility in electrolytes,especially ester electrolytes,hinders its applications in lithium metal batteries.Herein,an organic nitrate,isosorbide nitrate(ISDN),is proposed to replace LiNO_(3).ISDNhas a high solubility of 3.3M in ester electrolytes due to the introduction of organic segments in the molecule.The decomposition of ISDN generates LiN_(x)O_(y)-rich SEI,enabling uniform lithium deposition.The lifespan of lithium metal batteries with ISDN significantly increases from 80 to 155 cycles under demanding conditions.Furthermore,a lithium metal pouch cell of 439Whkg^(−1) delivers 50 cycles.This work opens a new avenue to develop additives by molecular modifications for practical lithium metal batteries.展开更多
Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,th...Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,the poor chemical stability and low electron conductivity limited their activity,and single-functional sites in these frameworks hindered them to show multifunctional roles in catalytic systems.Herein,we have constructed novel metal organic polymers(Co-HAT-CN and Ni-HAT-CN)with dual catalytic centers(metal-N_(4) and metal-N_(2))to catalyze oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).By using different metal centers,the catalytic activity and selectivity were well-tuned.Among them,Co-HAT-CN catalyzed the ORR in a 4e^(-)pathway,with a half-wave potential of 0.8 V versus RHE,while the Ni-HAT-CN catalyze ORR in a 2e^(-)pathway with H_(2)O_(2) selectivity over 90%.Moreover,the Co-HAT-CN delivered an overpotential of 350 mV at 10 mA cm^(-2) with a corresponding Tafel slope of 24 mV dec^(-1) for OER in a 1.0 M KOH aqueous solution.The experimental results revealed that the activities toward ORR were due to the M-N_(4) sites in the frameworks,and both M-N_(4) and M-N_(2) sites contributed to the OER.This work gives us a new platform to construct bifunctional catalysts.展开更多
Aqueous zinc metal batteries feature intrinsic safety,but suffer from severe dendrite growth and water-derived side reactions.Many metal coatings have been explored for stabilizing Zn metal anode via a trialand-error ...Aqueous zinc metal batteries feature intrinsic safety,but suffer from severe dendrite growth and water-derived side reactions.Many metal coatings have been explored for stabilizing Zn metal anode via a trialand-error approach.Here,we propose an exercisable way to screen the potential metal coating on Zn anodes in view of de-polarization effect and dendrite-suppressing ability theoretically.As an output of this screening,cadmium(Cd) metal is checked experimentally.Therefore,symmetric ZnllZn cells using Cd coated Zn(Zn@Cd) exhibit an ultra-long cycle life of 3500 h(nearly 5 months) at a high current density of 10 mA cm^(-2),achieving a record-high cumulative capacity(35 A h cm^(-2)) compared to the previous reports.The full cells of Zn@Cd‖MnO_(2) display a markedly improved cycling performance under harsh conditions including a limited Zn supply(N/P ratio=1.7) and a high areal capacity(3.5 mA h cm^(-2)).The significance of this work lies in not only the first report of Cd coating for stabilizing Zn metal anode,but also a feasible way to screen the promising metal materials for other metal anodes.展开更多
Deep-level defects and random oriented configuration in perovskite crystallization process would cause the nonradiative recombination and further affect the performance of perovskite solar cells(PSCs).Herein,two metal...Deep-level defects and random oriented configuration in perovskite crystallization process would cause the nonradiative recombination and further affect the performance of perovskite solar cells(PSCs).Herein,two metal-organic frameworks(MOFs)with tunable Lewis-base passivation sites have been constructed(Cd-Httb and Cd-Httb-BDC,Httb=5-(4-(1H-1,2,4-triazole-1-yl)benzyl)-1h-tetrazole,BDC=1,4-dicarboxybenzene)to eliminate deep-level defects and simultaneously as nanostructured heterogeneous nucleation seed to assist the growth of large-grained perovskite films.Compared with the control and Cd-Httb,Cd-Httb-BDC designed with mix-ligands strategy exhibited the enhanced inducted effect on the crystallization and nucleation of high-quality perovskite films during annealing process.Consequently,the resultant Cd-Httb-BDC-modified device achieved higher power conversion efficiency(PCE)(22.18%)than the control(20.89%)and Cd-Httb(21.56%).Meanwhile,the unencapsulated Cd-Httb-BDC-modified device still maintained 90%of initial PCE after 1500 h in ambient conditions and exhibited enhanced thermal stability(85℃ in N_(2) atmosphere).This work presented a successful example of mixligands strategy on construction of high-quality MOF-assisted perovskite films for high-efficient and stable PSCs.展开更多
Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications,especially for the green ammonia(NH_(3))industry.A properly engineere...Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications,especially for the green ammonia(NH_(3))industry.A properly engineered electrocatalyst plays a vital role in the realization of superior catalytic performance.Among various types of promising nanomaterials,metal–organic frameworks(MOFs)are competitive candidates for developing efficient electrocatalytic NH_(3) synthesis from simple nitrogen-containing molecules or ions,such as N_(2) and NO_(3)^(−).In this review,recent advances in the development of electrocatalysts derived from MOFs for the electrosynthesis of NH_(3) are collected,categorized,and discussed,including their application in the N_(2) reduction reaction(NRR)and the NO_(3)^(−)reduction reaction(NO3RR).Firstly,the fundamental principles are illustrated,such as plausible mechanisms of NH_(3) generation from N_(2) and NO_(3)^(−),the apparatus of corresponding electrocatalysis,parameters for evaluation of reaction efficiency,and detection methods of yielding NH_(3).Then,the electrocatalysts for NRR processes are discussed in detail,including pristine MOFs,MOF-hybrids,MOF-derived N-doped porous carbons,single atomic catalysts from pyrolysis of MOFs,and other MOF-related materials.Subsequently,MOF-related NO3RR processes are also listed and discussed.Finally,the existing challenges and prospects for the rational design and fabrication of electrocatalysts from MOFs for electrochemical NH_(3) synthesis are presented,such as the evolution of investigation methods with artificial intelligence,innovation in synthetic methods of MOF-related catalysts,advancement of characterization techniques,and extended electrocatalytic reactions.展开更多
Deuterium(D_(2)) is one of the important fuel sources that power nuclear fusion reactors. The existing D_(2)/H_(2) separation technologies that obtain high-purity D_(2) are cost-intensive. Recent research has shown th...Deuterium(D_(2)) is one of the important fuel sources that power nuclear fusion reactors. The existing D_(2)/H_(2) separation technologies that obtain high-purity D_(2) are cost-intensive. Recent research has shown that metal-organic frameworks(MOFs) are of good potential for D_(2)/H_(2) separation application. In this work, a high-throughput computational screening of 12020 computation-ready experimental MOFs is carried out to determine the best MOFs for hydrogen isotope separation application. Meanwhile, the detailed structure-performance correlation is systematically investigated with the aid of machine learning. The results indicate that the ideal D_(2)/H_(2) adsorption selectivity calculated based on Henry coefficient is strongly correlated with the 1/ΔAD feature descriptor;that is, inverse of the adsorbility difference of the two adsorbates. Meanwhile, the machine learning(ML) results show that the prediction accuracy of all the four ML methods is significantly improved after the addition of this feature descriptor. In addition, the ML results based on extreme gradient boosting model also revealed that the 1/ΔAD descriptor has the highest relative importance compared to other commonly-used descriptors. To further explore the effect of hydrogen isotope separation in binary mixture, 1548 MOFs with ideal adsorption selectivity greater than 1.5 are simulated at equimolar conditions. The structure-performance relationship shows that high adsorption selectivity MOFs generally have smaller pore size(0.3-0.5 nm) and lower surface area. Among the top 200 performers, the materials mainly have the sql, pcu, cds, hxl, and ins topologies.Finally, three MOFs with high D_(2)/H_(2) selectivity and good D_(2) uptake are identified as the best candidates,of all which had one-dimensional channel pore. The findings obtained in this work may be helpful for the identification of potentially promising candidates for hydrogen isotope separation.展开更多
This review offers an overview of the latest developments in metal-covalent organic framework(MCOF)and covalent metal-organic framework(CMOF)materials,whose construction entails a combination of reversible coordinatio...This review offers an overview of the latest developments in metal-covalent organic framework(MCOF)and covalent metal-organic framework(CMOF)materials,whose construction entails a combination of reversible coordination and covalent bonding adapted from metal-organic frameworks(MOFs)and covalent organic frameworks(COFs),respectively.With an emphasis on the MCOF and CMOF structures,this review surveys their building blocks and topologies.Specifically,the frameworks are classified based on the dimensions of their components(building blocks),namely,discrete building blocks and one-dimensional infinite building blocks.For the first category,the materials are further divided into collections of two-and three-dimensional networks based on their topologies.For the second category,the recently emerging MCOFs with woven structures are covered.Finally,the state-of-the-art in MCOF and CMOF chemistry has been laid out for promising avenues in future developments.展开更多
The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous st...The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous structure and tunable chemical functionality,have shown enormous potential as energy storage materials for accommodating or transporting electrochemically active ions.In this perspective,we specifically focus on the current status and prospects of anionic MOF-based quasi-solid-state-electrolytes(anionic MOF-QSSEs)for lithium metal batteries(LMBs).An overview of the definition,design,and properties of anionic MOF-QSSEs is provided,including recent advances in the understanding of their ion transport mechanism.To illustrate the advantages of using anionic MOF-QSSEs as electrolytes for LMBs,a thorough comparison between anionic MOF-QSSEs and other well-studied electrolyte systems is made.With these in-depth understandings,viable techniques for tuning the chemical and topological properties of anionic MOF-QSSEs to increase Li+conductivity are discussed.Beyond modulation of the MOFs matrix,we envisage that solvent and solid-electrolyte interphase design as well as emerging fabrication techniques will aid in the design and practical application of anionic MOF-QSSEs.展开更多
Integrated electrocatalysts(IECs)containing well-defined functional materials directly grown on the current collector have sparked increasing interest in the fields of electrocatalysis owing to efficient activity,high...Integrated electrocatalysts(IECs)containing well-defined functional materials directly grown on the current collector have sparked increasing interest in the fields of electrocatalysis owing to efficient activity,high stability and the fact that they are easily assembled into devices.Recently,metal organic frameworks(MOFs)provide a promising platform for constructing advanced IECs because of their properties of low cost,large surface area and efficient structural tunability.In this review,the design principles of state-of-the-art IECs based on MOFs are presented,including by hydrothermal/solvothermal,template-directed,electrospinning,electrodeposition and other methods.The high performance of MOF-derived IECs has also been demonstrated in electrocatalytic gasinvolved reactions.This is promising for green energy storage and conversion.The structure-activity relationship and performance improvement mechanism of IECs are uncovered by discussing some in situ technologies for IECs.Finally,we provide an outlook on the challenges and prospects in this booming field.展开更多
The separation of C2H4from C_(2)H_(6)/C_(2)H_(4)mixture is of great importance but difficult and energy intensive. Adsorptive separation provides an alternative approach to ameliorate this situation. Here, we report a...The separation of C2H4from C_(2)H_(6)/C_(2)H_(4)mixture is of great importance but difficult and energy intensive. Adsorptive separation provides an alternative approach to ameliorate this situation. Here, we report a microporous metal–organic framework(MOF) BUT-315-a as a C_(2)H_(6)-selective adsorbent for the separation of C2H6/C2H4gas mixture. BUT-315-a combines good IAST selectivity of 2.35 with high C_(2)H_(6)uptake of 97.5 cm^(3)g^(-1), giving superior high separation potential ΔQ(2226 mmol L^(-1)) for equimolar C_(2)H_(6)/C_(2)H_(4) at 298 K. Impressively, such excellent performance can be preserved at higher temperatures of 313 and 323 K to accommodate industrial conditions. Efficient dynamic separation performance of BUT-315-a has been demonstrated by column breakthrough experiments under varied temperatures and gas ratios. Theoretical calculations further reveal multiple synergistic interactions between C_(2)H_(6) and the framework. This work highlights a new benchmark material for C_(2)H_(6)/C_(2)H_(4)separation and provides guidance for designing adsorbent for separation applications.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
The practical application of Li metal anodes(LMAs)is limited by uncontrolled dendrite growth and side reactions.Herein,we propose a new friction-induced strategy to produce high-performance thin Li anode(Li@CFO).By vi...The practical application of Li metal anodes(LMAs)is limited by uncontrolled dendrite growth and side reactions.Herein,we propose a new friction-induced strategy to produce high-performance thin Li anode(Li@CFO).By virtue of the in situ friction reaction between fluoropolymer grease and Li strips during rolling,a robust organic/inorganic hybrid interlayer(lithiophilic LiF/LiC_(6)framework hybridized-CF_(2)-O-CF_(2)-chains)was formed atop Li metal.The derived interface contributes to reversible Li plating/stripping behaviors by mitigating side reactions and decreasing the solvation degree at the interface.The Li@CFO||Li@CFO symmetrical cell exhibits a remarkable lifespan for 5,600 h(1.0 mA cm^(-2)and 1.0 mAh cm^(-2))and 1,350 cycles even at a harsh condition(18.0 mA cm^(-2)and 3.0 mAh cm^(-2)).When paired with high-loading LiFePO4 cathodes,the full cell lasts over 450 cycles at 1C with a high-capacity retention of 99.9%.This work provides a new friction-induced strategy for producing high-performance thin LMAs.展开更多
As more and more pollutants threaten human health, it is necessary and essential to develop sensitive, accurate and rapid methods and sensory materials to detect harmful substance. Metal-organic frameworks (MOFs) are ...As more and more pollutants threaten human health, it is necessary and essential to develop sensitive, accurate and rapid methods and sensory materials to detect harmful substance. Metal-organic frameworks (MOFs) are inorganic-organic hybrids assembled from inorganic metal ions or clusters and suitable organic ligands. Zinc-based MOFs (Zn-MOFs) have emerged as one of the most promising sensory material of MOFs for practical applications, and attracted significant attention due to structural diversity and incomparable stability properties. However, there are few reviews on systemic summary of synthesis design, mechanism and application of Zn-MOFs. In this review, we summarize the synthesis design methods, structure types and luminescence mechanism of Zn-MOFs sensor recognition in the past ten years and their applications in metal cations, anions, organic compounds and other analytes. Finally, we present a short conclusion, and look forward to the future development direction of Zn-MOFs.展开更多
The effectiveness of the corrosion protection of Nafion/Dimethysulfoxid (DMSO) organic coatings for AM50 magnesium alloy prepared by simple immersion and heat treatment was investigated. Its corrosion resistance and...The effectiveness of the corrosion protection of Nafion/Dimethysulfoxid (DMSO) organic coatings for AM50 magnesium alloy prepared by simple immersion and heat treatment was investigated. Its corrosion resistance and morphologies of the Nafion/DMSO organic coatings were studied by electrochemical corrosion testing and optical microscopy. The results show that Nafion/DMSO organic coatings can improve the corrosion resistance of AM50 magnesium alloy effectively. Also, the corrosion resistance increases with the surface density of the organic coatings.展开更多
Recent research activities on the formation of micro-defects and porosity in organic coatings were reviewed. The mechanisms of aggressive ionic conduction through organic coatings were analyzed. The micro-mechanisms f...Recent research activities on the formation of micro-defects and porosity in organic coatings were reviewed. The mechanisms of aggressive ionic conduction through organic coatings were analyzed. The micro-mechanisms for the failure behavior of coatings under corrosive environments were discussed in detail. These mechanisms included blistering (i. e. osmotic blistering, anodic blistering and cathodic blistering) in the coating, wet-adhesion loss at the substrate/coating interface, cathodic delamination of coating from the substrate. Based on these researches, it was found that the failure behavior of organic coatings is closely related to the micro-defects in coatings, regardless of the failure mode. Additionally, the general failure mode of a coating system was proposed to interpret the failure behavior of organic in corrosion environments. The topics discussed can provide some insights into the development of a methodology for designing fail-safe coating systems.展开更多
Corrosion of reinforced concrete is the most important cause of concrete structure deterioration. In the present study, the protective effect of the reinforcement mortars against corrosion is examined. In particular, ...Corrosion of reinforced concrete is the most important cause of concrete structure deterioration. In the present study, the protective effect of the reinforcement mortars against corrosion is examined. In particular, the chloride penetration resistance on reinforced cement mortars using organic coating as additive containing was studied. The aforementioned additive consists of corrosion inhibitor for protection of steel rebars against pitting corrosion. For the experimental procedure, four (4) different types of reinforced mortars were prepared. The corrosion protection of the additive was evaluated by electrochemical methods, (linear polarization resistance, Half-cell Potential Resistance and Electrochemical Impedance Spectroscopy). In addition, the mass loss of steel rebars against time of partially immersed in NaCl solution was carried out in the lab. The experimental results showed that in all examined cases the organic coating provides anticorrosion protection on steel rebars against chlorides.展开更多
The degradation coefficient is proposed to evaluate the degradation degree of organic coatings by directly analyzing the Bode plots of the electrochemical impedance spectroscopy (EIS) data.This paper investigated the ...The degradation coefficient is proposed to evaluate the degradation degree of organic coatings by directly analyzing the Bode plots of the electrochemical impedance spectroscopy (EIS) data.This paper investigated the degradation of phenolic epoxy coating/tinplate system by EIS and the degradation coefficient value,which correlates well with the results of breakpoint frequency and variation of phase angle at 10 Hz.Furthermore,the degradation process was confirmed by scanning electron microscope (SEM) and scanning probe microscopy (SPM).It is concluded that degradation coefficient can be used for the fast evaluation of degradation degree of organic coatings in practical applications.展开更多
CeO2 and Ce0.8M0.2O2-d films (M = Mn, Y, Gd, Sm, Nd and La) with (00l) preferred orientation have been prepared on biaxially textured Ni-W substrates by metal organic decomposition (MOD) method. The factors infl...CeO2 and Ce0.8M0.2O2-d films (M = Mn, Y, Gd, Sm, Nd and La) with (00l) preferred orientation have been prepared on biaxially textured Ni-W substrates by metal organic decomposition (MOD) method. The factors influencing the formation of cracks on the surface of these CeO2 and doped CeO2 films on Ni-W substrates were explored by X-ray diffraction (XRD), scanning electron microscopy (SEM) analysis, atomic force microscopy (AFM) and differential scanning calorimetry (DSC). The results indicate that many factors, such as the change of the ionic radii of doping cations, the transformation of crystal structure and the formation of oxygen vacancies in lattices at high annealing temperature, may be related to the formation of cracks on the surface of these films. However, the crack formation shows no dependence on the crystal lattice mismatch degree of the films with Ni-W substrates. Moreover, the suppression of surface cracks is related to the change of intrinsic elasticity of CeO2 film with doping of cations with a larger radius. SEM and AFM investigations of Ce0.8M0.2O2-d (M = Y, Gd, Sm, Nd and La) films reveal the dense, smooth and crack-free microstructure, and their lattice parameters match well with that of YBCO, illuminating that they are potentially suitable to be as buffer layer, especially as cap layer in multi-layer architecture of buffer layer for coated conductors.展开更多
基金Funded by Shenzhen-Hong Kong Innovative Collaborative Research and Development Program (Nos.SGLH20181109 110802117, CityU 9240014)Innovation Project of Southwestern Institute of Physics (Nos.202001XWCXYD002, 202301XWCX003)CNNC Young Talent Program (No.2023JZYF-01)。
文摘Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), scanning electron microscopy(SEM), and electron backscatter diffraction(EBSD).The coating bonding strength is assessed by pull-out tests and scribing in accordance with GB/T 9286-1998.The results show that the Cu coating with a thickness of 30 μm deposited on GF/PEEK by magnetron sputtering has lower roughness, finer grain size, higher crystallinity, as well as better macroscopic compressive stress,bonding strength, and electrical conductivity than the Cu coating deposited by electroplating.
基金funded by the Natural Science Foundation of Fujian Province(2023J05180)the President's Foundation of Minnan Normal University(KJ2021011).
文摘As promising catalysts for the degradation of organic pollutants,metal–organic frameworks(MOFs)often face limitations due to the particle agglomeration and challenging recovery in liquid-catalysis application,stemming from their powdery nature.Engineering macroscopic structures from pulverous MOF is thus of great importance for broadening their practical applications.In this study,three-dimensional porous MOF aerogel catalysts were successfully fabricated for degrading organic dyes by activating peroxymonosulfate(PMS).MOF/gelatin aerogel(MOF/GA)catalysts were prepared by directly integrating bimetallic FeCo-BDC with gelatin solutions,followed by freeze-drying and low-temperature calcination.The FeCo-BDC-0.15/GA/PMS system exhibited remarkable performance in degrading various organic dyes,eliminating 99.2%of rhodamine B within a mere 5 min.Compared to the GA/PMS system,there was over a 300-fold increase in the reaction rate constant.Remarkably,high removal efficiency was maintained across varying conditions,including different solution pH,co-existing inorganic anions,and natural water matrices.Radical trapping experiments and electron paramagnetic resonance analysis revealed that the degradation involved radical(SO_(4)^(-)·)and non-radical routes(^(1)O_(2)),of which ^(1)O_(2) was dominant.Furthermore,even after a continuous 400-min reaction in a fixed-bed reactor at a liquid hourly space velocity of 27 h^(-1),the FeCo-BDC/GA composite sustained a degradation efficiency exceeding 98.7%.This work presents highly active MOF-gelatin aerogels for dye degradation and expands the potential for their large-scale,continuous treatment application in organic dye wastewater management.
基金supported by the Key Research and Development Program of Yunnan Province(202103A A080019)S&T Program of Hebei(22344402D)+4 种基金National Key Research and Development Program(2021YFB2400300)National Natural Science Foundation of China(22108149)China Postdoctoral Science Foundation(2021M700404)Scientific and Technological Key Project of Shanxi Province(20191102003)Beijing Institute of Technology Research Fund Program for Young Scholars.
文摘The stability of lithium metal anodes essentially dictates the lifespan of high-energy-density lithium metal batteries.Lithium nitrate(LiNO_(3))is widely recognized as an effective additive to stabilize lithium metal anodes by forming LiN_(x)O_(y)-containing solid electrolyte interphase(SEI).However,its poor solubility in electrolytes,especially ester electrolytes,hinders its applications in lithium metal batteries.Herein,an organic nitrate,isosorbide nitrate(ISDN),is proposed to replace LiNO_(3).ISDNhas a high solubility of 3.3M in ester electrolytes due to the introduction of organic segments in the molecule.The decomposition of ISDN generates LiN_(x)O_(y)-rich SEI,enabling uniform lithium deposition.The lifespan of lithium metal batteries with ISDN significantly increases from 80 to 155 cycles under demanding conditions.Furthermore,a lithium metal pouch cell of 439Whkg^(−1) delivers 50 cycles.This work opens a new avenue to develop additives by molecular modifications for practical lithium metal batteries.
基金support from the Natural Science Foundation of Shanghai (20ZR1464000)G.Zeng acknowledges the support from the National Natural Science Foundation of China (21878322,22075309)the Science and Technology Commission of Shanghai Municipality (19ZR1479200,22ZR1470100)。
文摘Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,the poor chemical stability and low electron conductivity limited their activity,and single-functional sites in these frameworks hindered them to show multifunctional roles in catalytic systems.Herein,we have constructed novel metal organic polymers(Co-HAT-CN and Ni-HAT-CN)with dual catalytic centers(metal-N_(4) and metal-N_(2))to catalyze oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).By using different metal centers,the catalytic activity and selectivity were well-tuned.Among them,Co-HAT-CN catalyzed the ORR in a 4e^(-)pathway,with a half-wave potential of 0.8 V versus RHE,while the Ni-HAT-CN catalyze ORR in a 2e^(-)pathway with H_(2)O_(2) selectivity over 90%.Moreover,the Co-HAT-CN delivered an overpotential of 350 mV at 10 mA cm^(-2) with a corresponding Tafel slope of 24 mV dec^(-1) for OER in a 1.0 M KOH aqueous solution.The experimental results revealed that the activities toward ORR were due to the M-N_(4) sites in the frameworks,and both M-N_(4) and M-N_(2) sites contributed to the OER.This work gives us a new platform to construct bifunctional catalysts.
基金supported by the National Nature Science Foundation of China (22105118)the Nature Science Foundation of Shandong Provinces (ZR2021QB095)the China Postdoctoral Science Foundation (2020TQ0183 and 2021M701979)。
文摘Aqueous zinc metal batteries feature intrinsic safety,but suffer from severe dendrite growth and water-derived side reactions.Many metal coatings have been explored for stabilizing Zn metal anode via a trialand-error approach.Here,we propose an exercisable way to screen the potential metal coating on Zn anodes in view of de-polarization effect and dendrite-suppressing ability theoretically.As an output of this screening,cadmium(Cd) metal is checked experimentally.Therefore,symmetric ZnllZn cells using Cd coated Zn(Zn@Cd) exhibit an ultra-long cycle life of 3500 h(nearly 5 months) at a high current density of 10 mA cm^(-2),achieving a record-high cumulative capacity(35 A h cm^(-2)) compared to the previous reports.The full cells of Zn@Cd‖MnO_(2) display a markedly improved cycling performance under harsh conditions including a limited Zn supply(N/P ratio=1.7) and a high areal capacity(3.5 mA h cm^(-2)).The significance of this work lies in not only the first report of Cd coating for stabilizing Zn metal anode,but also a feasible way to screen the promising metal materials for other metal anodes.
基金supported by the National Natural Science Foundation of China(22072034,22001050,and 21873025)the China Postdoctoral Science Foundation(2020T130147,2020M681084,and 2022M710949)+1 种基金the Postdoctoral Foundation of Heilongjiang Province(LBH-Z19059)the Natural Science Foundation of Heilongjiang Youth Fund(YQ2021B002).
文摘Deep-level defects and random oriented configuration in perovskite crystallization process would cause the nonradiative recombination and further affect the performance of perovskite solar cells(PSCs).Herein,two metal-organic frameworks(MOFs)with tunable Lewis-base passivation sites have been constructed(Cd-Httb and Cd-Httb-BDC,Httb=5-(4-(1H-1,2,4-triazole-1-yl)benzyl)-1h-tetrazole,BDC=1,4-dicarboxybenzene)to eliminate deep-level defects and simultaneously as nanostructured heterogeneous nucleation seed to assist the growth of large-grained perovskite films.Compared with the control and Cd-Httb,Cd-Httb-BDC designed with mix-ligands strategy exhibited the enhanced inducted effect on the crystallization and nucleation of high-quality perovskite films during annealing process.Consequently,the resultant Cd-Httb-BDC-modified device achieved higher power conversion efficiency(PCE)(22.18%)than the control(20.89%)and Cd-Httb(21.56%).Meanwhile,the unencapsulated Cd-Httb-BDC-modified device still maintained 90%of initial PCE after 1500 h in ambient conditions and exhibited enhanced thermal stability(85℃ in N_(2) atmosphere).This work presented a successful example of mixligands strategy on construction of high-quality MOF-assisted perovskite films for high-efficient and stable PSCs.
基金support from the Natural Science Foundation of Liaoning Province(general program)(2020-MS-137)T.J.White would like to thank the MOE2019-T2-2-032 grant and Monetary Academic Resources for Research Grant 001561-00001 in Nanyang Technological University,Singapore+9 种基金T.Ma would like to thank the National Natural Science Foundation of China(Nos.52071171,52202248)Liaoning BaiQianWan Talents Program(LNBQW2018B0048)Shenyang Science and Technology Project(21-108-9-04)Australian Research Council(ARC)through Future Fellowship(FT210100298,FT210100806)Discovery Project(DP220100603)Linkage Project(LP210100467,LP210200504,LP210200345,LP220100088)Industrial Transformation Training Centre(IC180100005)schemesthe Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077)F.Wei would like to thank the A^(*)STAR career development fund C210112054Singapore structural metal alloy program grant No.A18b1B0061.A.K.Cheetham would like to thank the Ras al Khaimah Centre for Advanced Materials.
文摘Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications,especially for the green ammonia(NH_(3))industry.A properly engineered electrocatalyst plays a vital role in the realization of superior catalytic performance.Among various types of promising nanomaterials,metal–organic frameworks(MOFs)are competitive candidates for developing efficient electrocatalytic NH_(3) synthesis from simple nitrogen-containing molecules or ions,such as N_(2) and NO_(3)^(−).In this review,recent advances in the development of electrocatalysts derived from MOFs for the electrosynthesis of NH_(3) are collected,categorized,and discussed,including their application in the N_(2) reduction reaction(NRR)and the NO_(3)^(−)reduction reaction(NO3RR).Firstly,the fundamental principles are illustrated,such as plausible mechanisms of NH_(3) generation from N_(2) and NO_(3)^(−),the apparatus of corresponding electrocatalysis,parameters for evaluation of reaction efficiency,and detection methods of yielding NH_(3).Then,the electrocatalysts for NRR processes are discussed in detail,including pristine MOFs,MOF-hybrids,MOF-derived N-doped porous carbons,single atomic catalysts from pyrolysis of MOFs,and other MOF-related materials.Subsequently,MOF-related NO3RR processes are also listed and discussed.Finally,the existing challenges and prospects for the rational design and fabrication of electrocatalysts from MOFs for electrochemical NH_(3) synthesis are presented,such as the evolution of investigation methods with artificial intelligence,innovation in synthetic methods of MOF-related catalysts,advancement of characterization techniques,and extended electrocatalytic reactions.
基金supported by the National Natural Science Foundation of China (22078004)the Research Development Fund from Xi’an Jiaotong-Liverpool University (RDF-16-02-03 and RDF15-01-23)key program special fund (KSF-E-03)。
文摘Deuterium(D_(2)) is one of the important fuel sources that power nuclear fusion reactors. The existing D_(2)/H_(2) separation technologies that obtain high-purity D_(2) are cost-intensive. Recent research has shown that metal-organic frameworks(MOFs) are of good potential for D_(2)/H_(2) separation application. In this work, a high-throughput computational screening of 12020 computation-ready experimental MOFs is carried out to determine the best MOFs for hydrogen isotope separation application. Meanwhile, the detailed structure-performance correlation is systematically investigated with the aid of machine learning. The results indicate that the ideal D_(2)/H_(2) adsorption selectivity calculated based on Henry coefficient is strongly correlated with the 1/ΔAD feature descriptor;that is, inverse of the adsorbility difference of the two adsorbates. Meanwhile, the machine learning(ML) results show that the prediction accuracy of all the four ML methods is significantly improved after the addition of this feature descriptor. In addition, the ML results based on extreme gradient boosting model also revealed that the 1/ΔAD descriptor has the highest relative importance compared to other commonly-used descriptors. To further explore the effect of hydrogen isotope separation in binary mixture, 1548 MOFs with ideal adsorption selectivity greater than 1.5 are simulated at equimolar conditions. The structure-performance relationship shows that high adsorption selectivity MOFs generally have smaller pore size(0.3-0.5 nm) and lower surface area. Among the top 200 performers, the materials mainly have the sql, pcu, cds, hxl, and ins topologies.Finally, three MOFs with high D_(2)/H_(2) selectivity and good D_(2) uptake are identified as the best candidates,of all which had one-dimensional channel pore. The findings obtained in this work may be helpful for the identification of potentially promising candidates for hydrogen isotope separation.
基金financially supported by the National Natural Science Foundation of China(No.22176135)the Fundamental Research Funds for the Central Universities in China(No.YJ201976)。
文摘This review offers an overview of the latest developments in metal-covalent organic framework(MCOF)and covalent metal-organic framework(CMOF)materials,whose construction entails a combination of reversible coordination and covalent bonding adapted from metal-organic frameworks(MOFs)and covalent organic frameworks(COFs),respectively.With an emphasis on the MCOF and CMOF structures,this review surveys their building blocks and topologies.Specifically,the frameworks are classified based on the dimensions of their components(building blocks),namely,discrete building blocks and one-dimensional infinite building blocks.For the first category,the materials are further divided into collections of two-and three-dimensional networks based on their topologies.For the second category,the recently emerging MCOFs with woven structures are covered.Finally,the state-of-the-art in MCOF and CMOF chemistry has been laid out for promising avenues in future developments.
基金financially supported by the Scientific Research Startup Funds from Tsinghua Shenzhen International Graduate School。
文摘The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous structure and tunable chemical functionality,have shown enormous potential as energy storage materials for accommodating or transporting electrochemically active ions.In this perspective,we specifically focus on the current status and prospects of anionic MOF-based quasi-solid-state-electrolytes(anionic MOF-QSSEs)for lithium metal batteries(LMBs).An overview of the definition,design,and properties of anionic MOF-QSSEs is provided,including recent advances in the understanding of their ion transport mechanism.To illustrate the advantages of using anionic MOF-QSSEs as electrolytes for LMBs,a thorough comparison between anionic MOF-QSSEs and other well-studied electrolyte systems is made.With these in-depth understandings,viable techniques for tuning the chemical and topological properties of anionic MOF-QSSEs to increase Li+conductivity are discussed.Beyond modulation of the MOFs matrix,we envisage that solvent and solid-electrolyte interphase design as well as emerging fabrication techniques will aid in the design and practical application of anionic MOF-QSSEs.
基金supported by National Natural Science Foundation of China(22090031,21922501,22109004)China Postdoctoral Science Foundation(2021M690319)。
文摘Integrated electrocatalysts(IECs)containing well-defined functional materials directly grown on the current collector have sparked increasing interest in the fields of electrocatalysis owing to efficient activity,high stability and the fact that they are easily assembled into devices.Recently,metal organic frameworks(MOFs)provide a promising platform for constructing advanced IECs because of their properties of low cost,large surface area and efficient structural tunability.In this review,the design principles of state-of-the-art IECs based on MOFs are presented,including by hydrothermal/solvothermal,template-directed,electrospinning,electrodeposition and other methods.The high performance of MOF-derived IECs has also been demonstrated in electrocatalytic gasinvolved reactions.This is promising for green energy storage and conversion.The structure-activity relationship and performance improvement mechanism of IECs are uncovered by discussing some in situ technologies for IECs.Finally,we provide an outlook on the challenges and prospects in this booming field.
基金the financial support of the National Natural Science Foundation of China (No. 22038001)。
文摘The separation of C2H4from C_(2)H_(6)/C_(2)H_(4)mixture is of great importance but difficult and energy intensive. Adsorptive separation provides an alternative approach to ameliorate this situation. Here, we report a microporous metal–organic framework(MOF) BUT-315-a as a C_(2)H_(6)-selective adsorbent for the separation of C2H6/C2H4gas mixture. BUT-315-a combines good IAST selectivity of 2.35 with high C_(2)H_(6)uptake of 97.5 cm^(3)g^(-1), giving superior high separation potential ΔQ(2226 mmol L^(-1)) for equimolar C_(2)H_(6)/C_(2)H_(4) at 298 K. Impressively, such excellent performance can be preserved at higher temperatures of 313 and 323 K to accommodate industrial conditions. Efficient dynamic separation performance of BUT-315-a has been demonstrated by column breakthrough experiments under varied temperatures and gas ratios. Theoretical calculations further reveal multiple synergistic interactions between C_(2)H_(6) and the framework. This work highlights a new benchmark material for C_(2)H_(6)/C_(2)H_(4)separation and provides guidance for designing adsorbent for separation applications.
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This work was supported by the National Natural Science Foundation of China(U1904216 and U22A20141)the Natural Science Foundation of Changsha City(kq2208258).
文摘The practical application of Li metal anodes(LMAs)is limited by uncontrolled dendrite growth and side reactions.Herein,we propose a new friction-induced strategy to produce high-performance thin Li anode(Li@CFO).By virtue of the in situ friction reaction between fluoropolymer grease and Li strips during rolling,a robust organic/inorganic hybrid interlayer(lithiophilic LiF/LiC_(6)framework hybridized-CF_(2)-O-CF_(2)-chains)was formed atop Li metal.The derived interface contributes to reversible Li plating/stripping behaviors by mitigating side reactions and decreasing the solvation degree at the interface.The Li@CFO||Li@CFO symmetrical cell exhibits a remarkable lifespan for 5,600 h(1.0 mA cm^(-2)and 1.0 mAh cm^(-2))and 1,350 cycles even at a harsh condition(18.0 mA cm^(-2)and 3.0 mAh cm^(-2)).When paired with high-loading LiFePO4 cathodes,the full cell lasts over 450 cycles at 1C with a high-capacity retention of 99.9%.This work provides a new friction-induced strategy for producing high-performance thin LMAs.
文摘As more and more pollutants threaten human health, it is necessary and essential to develop sensitive, accurate and rapid methods and sensory materials to detect harmful substance. Metal-organic frameworks (MOFs) are inorganic-organic hybrids assembled from inorganic metal ions or clusters and suitable organic ligands. Zinc-based MOFs (Zn-MOFs) have emerged as one of the most promising sensory material of MOFs for practical applications, and attracted significant attention due to structural diversity and incomparable stability properties. However, there are few reviews on systemic summary of synthesis design, mechanism and application of Zn-MOFs. In this review, we summarize the synthesis design methods, structure types and luminescence mechanism of Zn-MOFs sensor recognition in the past ten years and their applications in metal cations, anions, organic compounds and other analytes. Finally, we present a short conclusion, and look forward to the future development direction of Zn-MOFs.
文摘The effectiveness of the corrosion protection of Nafion/Dimethysulfoxid (DMSO) organic coatings for AM50 magnesium alloy prepared by simple immersion and heat treatment was investigated. Its corrosion resistance and morphologies of the Nafion/DMSO organic coatings were studied by electrochemical corrosion testing and optical microscopy. The results show that Nafion/DMSO organic coatings can improve the corrosion resistance of AM50 magnesium alloy effectively. Also, the corrosion resistance increases with the surface density of the organic coatings.
基金Project(50235030) supported by the National Natural Science Foundation of China project(G1999065009) supported by the National Basic Research Program of China project(2003AA331130) supported by the Hi-tech Research and Development Program of China
文摘Recent research activities on the formation of micro-defects and porosity in organic coatings were reviewed. The mechanisms of aggressive ionic conduction through organic coatings were analyzed. The micro-mechanisms for the failure behavior of coatings under corrosive environments were discussed in detail. These mechanisms included blistering (i. e. osmotic blistering, anodic blistering and cathodic blistering) in the coating, wet-adhesion loss at the substrate/coating interface, cathodic delamination of coating from the substrate. Based on these researches, it was found that the failure behavior of organic coatings is closely related to the micro-defects in coatings, regardless of the failure mode. Additionally, the general failure mode of a coating system was proposed to interpret the failure behavior of organic in corrosion environments. The topics discussed can provide some insights into the development of a methodology for designing fail-safe coating systems.
文摘Corrosion of reinforced concrete is the most important cause of concrete structure deterioration. In the present study, the protective effect of the reinforcement mortars against corrosion is examined. In particular, the chloride penetration resistance on reinforced cement mortars using organic coating as additive containing was studied. The aforementioned additive consists of corrosion inhibitor for protection of steel rebars against pitting corrosion. For the experimental procedure, four (4) different types of reinforced mortars were prepared. The corrosion protection of the additive was evaluated by electrochemical methods, (linear polarization resistance, Half-cell Potential Resistance and Electrochemical Impedance Spectroscopy). In addition, the mass loss of steel rebars against time of partially immersed in NaCl solution was carried out in the lab. The experimental results showed that in all examined cases the organic coating provides anticorrosion protection on steel rebars against chlorides.
基金Supported by Major State Basic Research Program of China ("973"Program,No. 2011CB610500)
文摘The degradation coefficient is proposed to evaluate the degradation degree of organic coatings by directly analyzing the Bode plots of the electrochemical impedance spectroscopy (EIS) data.This paper investigated the degradation of phenolic epoxy coating/tinplate system by EIS and the degradation coefficient value,which correlates well with the results of breakpoint frequency and variation of phase angle at 10 Hz.Furthermore,the degradation process was confirmed by scanning electron microscope (SEM) and scanning probe microscopy (SPM).It is concluded that degradation coefficient can be used for the fast evaluation of degradation degree of organic coatings in practical applications.
基金Funded by the National Natural Science Foundation of ChinaNational 863 Program of China(Nos.50872115and2009AA03Z203)
文摘CeO2 and Ce0.8M0.2O2-d films (M = Mn, Y, Gd, Sm, Nd and La) with (00l) preferred orientation have been prepared on biaxially textured Ni-W substrates by metal organic decomposition (MOD) method. The factors influencing the formation of cracks on the surface of these CeO2 and doped CeO2 films on Ni-W substrates were explored by X-ray diffraction (XRD), scanning electron microscopy (SEM) analysis, atomic force microscopy (AFM) and differential scanning calorimetry (DSC). The results indicate that many factors, such as the change of the ionic radii of doping cations, the transformation of crystal structure and the formation of oxygen vacancies in lattices at high annealing temperature, may be related to the formation of cracks on the surface of these films. However, the crack formation shows no dependence on the crystal lattice mismatch degree of the films with Ni-W substrates. Moreover, the suppression of surface cracks is related to the change of intrinsic elasticity of CeO2 film with doping of cations with a larger radius. SEM and AFM investigations of Ce0.8M0.2O2-d (M = Y, Gd, Sm, Nd and La) films reveal the dense, smooth and crack-free microstructure, and their lattice parameters match well with that of YBCO, illuminating that they are potentially suitable to be as buffer layer, especially as cap layer in multi-layer architecture of buffer layer for coated conductors.