Comprehensive Summary This work systematically reviews recent progresses in the applications of MOF-derived materials modified 3D porous conductive framework as hosts for uniform lithium deposition in LMBs.A series of...Comprehensive Summary This work systematically reviews recent progresses in the applications of MOF-derived materials modified 3D porous conductive framework as hosts for uniform lithium deposition in LMBs.A series of commonly used lithiophilic materials and several kinds of representative MOF-derivation-modified 3D hosts as lithium metal anode(LMA)are presented.Finally,the challenges and future development of employing MOF-derived materials to modify the 3D porous conductive framework for LMA are included.展开更多
Developing highly efficient microwave absorbing materials(MAMs)to ameliorate the electromagnetic(EM)response and facilitate energy absorption is crucial in both the civil and military industries.Metal-organic framewor...Developing highly efficient microwave absorbing materials(MAMs)to ameliorate the electromagnetic(EM)response and facilitate energy absorption is crucial in both the civil and military industries.Metal-organic framework(MOF)derived nanoporous carbon composites have emerged as advanced MAMs ow-ing to their rich porosity,tunable compositions,facile functionalization,and morphology diversity.To-gether with the flourishing development of composition-tuning strategy,the rational dimension design and elaborate control over the architectures have also evolved into an effective approach to regulating their EM properties.Herein,we provide a comprehensive review of the recent advances in using di-mension and morphology modulation to adjust the microwave attenuation capacities for MOF-derived carbon composites.The underlying design rules and unique advantages for the MAMs of various dimen-sions were discussed with the selection of representative work,providing general concepts and insight on how to efficiently tune the morphologies.Accordingly,the fundamental dimension-morphology-function relationship was also elucidated.Finally,the challenges and perspectives of dimension design and mor-phology control over MOF-derived MAMs were also presented.展开更多
制备高效的OER电催化剂对水裂解制氢至关重要.具有丰富配位构型的MOFs可以衍生出各种优良的电催化材料.由于石墨炔(GDY)具有独特的可控合成特性,我们将其原位复合在MOF衍生的Co_(3)S_(4)/NF材料上,获得了自支撑电极GDY/Co_(3)S_(4)/NF,...制备高效的OER电催化剂对水裂解制氢至关重要.具有丰富配位构型的MOFs可以衍生出各种优良的电催化材料.由于石墨炔(GDY)具有独特的可控合成特性,我们将其原位复合在MOF衍生的Co_(3)S_(4)/NF材料上,获得了自支撑电极GDY/Co_(3)S_(4)/NF,大大提高了其OER催化性能.研究表明,GDY/Co_(3)S_(4)/NF在10 mA cm^(-2)电流密度下表现出223 mV的低过电位,在100 mA cm^(-2)的大电流密度下,能够稳定电解45小时左右,该材料显示出了巨大的实际应用潜力.结果表明,由于GDY独特的炔键和大孔结构,它可以通过强电子相互作用与Co_(3)S_(4)相互作用,从而调节电子结构并提供有效的电荷转移通道,从而大大提高了其电催化OER的性能.展开更多
A facile synthetic strategy based on a water-based process is developed for the preparation of metal-organic framework (MOF)-derived materials by revisiting the hydrolyzed non-porous metal-organic frameworks (h-MOF). ...A facile synthetic strategy based on a water-based process is developed for the preparation of metal-organic framework (MOF)-derived materials by revisiting the hydrolyzed non-porous metal-organic frameworks (h-MOF). The poor water stability of MOF has been recognized as key limitations for its commercialization and large-scale applications because the hydrolysis resulted in the complete loss of their functionalities. However, we found that the negative effect of hydrolysis on MOF can be nullified during the heat treatment. As similar to the intact MOF, h-MOF can be used as a precursor for the preparation of MOF-derived materials from porous MOF-derived carbons (MDCs) to MDC@ZnO composites. The property of h-MOF-derived materials is almost equivalent to that of MOF-derived materials. In addition, h-MOF turned the weakness of water instability to the strength of facile water-based process for hybridization. With the demonstration of the hybrid composite between h-MDC@ZnO and reduced graphene oxide (rGO) as a prototype example, it exhibited superior electrochemical performance when evaluated as an electrode material for lithium-ion batteries.展开更多
Phosphate removal is crucial for eutrophication control and water quality improvement.Electro-assisted adsorption,an eco-friendly elec-trosorption process,exhibited a promising potential for wastewater treatment.Howev...Phosphate removal is crucial for eutrophication control and water quality improvement.Electro-assisted adsorption,an eco-friendly elec-trosorption process,exhibited a promising potential for wastewater treatment.However,there are few works focused on phosphate electro-sorption,and reported electrodes cannot attach satisfactory removal capacities and rates.Herein,electro-assisted adsorption of phosphate via in-situ construction of La active centers on hierarchically porous carbon(LaPC)has been originally demonstrated.The resulted LaPC composite not only possessed a hierarchically porous structure with uniformly dispersed La active sites,but also provided good conductivity for interfacial electron transfer.The LaPC electrode achieved an ultrahigh phosphate electrosorption capability of 462.01 mg g^(-1) at 1 V,outperforming most existing electrodes.The superior phosphate removal performance originates from abundant active centers formed by the coupling of electricfield and capture sites.Besides,the stability and selectivity toward phosphate capture were maintained well even under comprehensive conditions.Moreover,a series of kinetics and isotherms models were employed to validate the electrosorption process.This work demonstrates a deep understanding and promotes a new level of phosphate electrosorption.展开更多
At present,commercial Li-ion batteries are hardly to satisfy the growing demand for high energy density,for this purpose,lithium metal batteries have attracted worldwide attention in recent years.However,its practical...At present,commercial Li-ion batteries are hardly to satisfy the growing demand for high energy density,for this purpose,lithium metal batteries have attracted worldwide attention in recent years.However,its practical applications are hindered by the formation of Li dendrites and volume effect during Li plating/stripping process,which leads to a lot of safety hazards.Herein,we first employed MOF-derived V_(2)O_(5) nanoparticles to decorate the carbon fiber cloth(CFC)backbone to acquire a lithiophilic 3D porous conductive framework(CFC@V_(2)O_(5)).Subsequently,the CFC@V_(2)O_(5) skeleton was permeated with molten Li to prepare CFC@V_(2)O_(5)@Li composite anode.The CFC@V_(2)O_(5)@Li composite anode can be stably cycled for more than 1650 h at high current density(5 mA·cm^(-2))and areal capacity(5 mA·h·cm^(–2)).The prepared full cell can initially maintain a high capacity of about 143 mA·h·g^(-1) even at a high current density of 5 C,and can still maintain 114 mA·h·g^(-1) after 1000 cycles.展开更多
The core reactions for fuel cells,rechargeable metal-air batteries,and hydrogen fuel production are the oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER),which are heav...The core reactions for fuel cells,rechargeable metal-air batteries,and hydrogen fuel production are the oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER),which are heavily dependent on the efficiency of electrocatalysts.Enormous attempts have previously been devoted in non-noble electrocatalysts born out of metal-organic frameworks(MOFs)for ORR,OER,and HER applications,due to the following advantageous reasons:(i)The significant porosity eases the electrolyte diffusion;(ii)the supreme catalyst-electrolyte contact area enhances the diffusion efficiency;and(iii)the electronic conductivity can be extensively increased owing to the unique construction block subunits for MOFs-derived electrocatalysis.Herein,the recent progress of MOFs-derived electrocatalysts including synthesis protocols,design engineering,DFT calculations roles,and energy applications is discussed and reviewed.It can be concluded that the elevated ORR,OER,and HER performances are attributed to an advantageously well-designed high-porosity structure,significant surface area,and plentiful active centers.Furthermore,the perspectives of MOF-derived electrocatalysts for the ORR,OER,and HER are presented.展开更多
Fe2O3 has become a promising anode material in lithium-ion batteries (LIBs) in light of its low cost, high theoretical capacity (1007 mA h g^−1) and abundant reserves on the earth. Nevertheless, the practical applicat...Fe2O3 has become a promising anode material in lithium-ion batteries (LIBs) in light of its low cost, high theoretical capacity (1007 mA h g^−1) and abundant reserves on the earth. Nevertheless, the practical application of Fe2O3 as the anode material in LIBs is greatly hindered by several severe issues, such as drastic capacity falloff, short cyclic life and huge volume change during the charge/discharge process. To tackle these limitations, carbon-coated Fe2O3 (Fe2O3@MOFC) composites with a hollow sea urchin nanostructure were prepared by an effective and controllable morphology-inherited strategy. Metal-organic framework (MOF)-coated FeOOH (FeOOH@-MIL-100(Fe)) was applied as the precursor and self-sacrificial template. During annealing, the outer MOF layer protected the structure of inner Fe2O3 from collapsing and converted to a carbon coating layer in situ. When applied as anode materials in LIBs, Fe2O3@MOFC composites showed an initial discharge capacity of 1366.9 mA h g^−1 and a capacity preservation of 1551.3 mA h g^−1 after 200 cycles at a current density of 0.1 A g^−1. When increasing the current density to 1 A g^−1, a reversible and high capacity of 1208.6 mA h g^−1 was obtained. The enhanced electrochemical performance was attributed to the MOF-derived carbon coating layers and the unique hollow sea urchin nanostructures. They mitigated the effects of volume expansion, increased the lithium-ion mobility of electrode, and stabilized the as-formed solid electrolyte interphase films.展开更多
Metal‐organic framework(MOF)‐derived nanomaterials have attracted widespread attention,because the excellent features,such as high surface area,porosity and tunable properties are inherited from MOFs.Moreover,the de...Metal‐organic framework(MOF)‐derived nanomaterials have attracted widespread attention,because the excellent features,such as high surface area,porosity and tunable properties are inherited from MOFs.Moreover,the derivatives avoid the poor conductivity and stability of MOFs.MOF‐derived nanomaterials can easily be regulated by a specific selection of metal nodes and organic linkers,resulting in multifunctionality in photocatalysis.MOF derivatives can be used not only as semiconductor photocatalysts,but also as co‐catalysts for photocatalytic hydrogen evolution,CO_(2) reduction,pollutants degradation,etc.This review focuses on the multifunctional applications of MOF derivatives in the field of photocatalysis.The researches in recent years are analyzed and summarized from the aspects of preparation,modification and application of MOF derivatives.At the end of the review,the development and challenges of MOF derivatives applied in photocatalysis in the future are put forward,in order to provide more references for further research in this field and bring new inspiration.展开更多
Metal-organic frameworks(MOFs)are a class of outstanding materials in Li-air batteries because of their high surface areas,tailorable pore sizes and diverse catalytic centers.However,MOF-based batteries are facing cha...Metal-organic frameworks(MOFs)are a class of outstanding materials in Li-air batteries because of their high surface areas,tailorable pore sizes and diverse catalytic centers.However,MOF-based batteries are facing challenges such as poor electronic conductivity and inferior long-cycle stability that limit their further development.This review first summarizes the progress of pristine MOFs and MOF-derived materials in Li-air batteries in the past 5 years,then provides a perspective for subsequent development of MOFs and their derivatives in this emerging field.展开更多
Designing novel electrode materials with unique structures is of great significance for improving the performance of lithium ion batteries(LIBs).Herein,copper-doped Co_(1-x)Te@nitrogen-doped carbon hollow nanoboxes(Cu...Designing novel electrode materials with unique structures is of great significance for improving the performance of lithium ion batteries(LIBs).Herein,copper-doped Co_(1-x)Te@nitrogen-doped carbon hollow nanoboxes(Cu-Co_(1-x)Te@NC HNBs)have been fabricated by chemical etching of Cu Co-ZIF nanoboxes,followed by a successive high-temperature tellurization process.The as-synthesized Cu-Co_(1-x)Te@NC HNBs composite demonstrated faster ionic and electronic diffusion kinetics than the pristine Co Te@NC HNBs electrode.The existence of Co-vacancy promotes the reduction of Gibbs free energy change(ΔG_(H^(*)))and effectively improves the Li~+diffusion coefficient.XPS and theoretical calculations show that performance improvement is ascribed to the electronic interactions between Cu-Co_(1-x)Te and nitrogen-doped carbon(NC)that trigger the shift of the p-band towards facilitation of interfacial charge transfer,which in turn helps boost up the lithium storage property.Besides,the proposed Cu-doping-induced Co-vacancy strategy can also be extended to other conversion-type cobalt-based material(CoSe_(2))in addition to asobtained Cu-Co_(1-x)Se_(2)@NC HNBs anodes for long-life and high-capacity LIBs.More importantly,the fabricated LiCoO_(2)//Cu-Co_(1-x)Te@NC HNBs full cell exhibits a high energy density of 403 Wh kg^(-1)and a power density of 6000 W kg^(-1).We show that the energy/power density reported herein is higher than that of previously studied cobalt-based anodes,indicating the potential application of Cu-Co_(1-x)Te@NC HNBs as a superior electrode material for LIBs.展开更多
The pursuit of high-mileage models results in the recurrence of lithium metal batteries(LMBs)to researchers’horizon.However,the lithium(Li)metal anode for LMBs undergoes the uncontrollable formation of Li dendrites a...The pursuit of high-mileage models results in the recurrence of lithium metal batteries(LMBs)to researchers’horizon.However,the lithium(Li)metal anode for LMBs undergoes the uncontrollable formation of Li dendrites and infinite volume change during cycling,impeding its practical application.To overcome these challenges,we developed a metal-organic framework(MOF)-derived pathway to construct lithiophilic three-dimensional(3D)skeleton using different substrates(e.g.,carbon cloth(CC)and Cu mesh)for dendrite-free lithium metal anodes.As a typical example,the MOF-derived ZnO/nitrogen-doped carbon(NC)nanosheet-modified 3D CC was well-constructed as a lithiophilic hierarchical host(CC@ZnO/NC@Li)for molten Li infiltration.Benefiting from the lithiophilic N-functional groups and LiZn alloy,the synthesized CC@ZnO/NC@Li composite anode promoted the uniform distribution of Li,resulting in a dendrite-free morphology.Meanwhile,the 3D conductive carbon skeleton enhanced the reaction kinetics and buffered the volume change of the electrode.The CC@ZnO/NC@Li composite anode presented a prolonged lifespan of over 1000 cycles at 5 mA cm^(−2) with a low overpotential of 19 mV.Coupled with a LiFePO_(4) cathode,the CC@ZnO/NC@Li composite anode also exhibited superior electrochemical properties in the full-cell system.This versatile strategy may open up the channel of designing multi-functional lithiophilic 3D hosts for the Li metal anode.展开更多
MOFs are among the most popular precursors and templates for deriving various porous materials,where the derivatives can inherit a large surface area,abundant active sites for targeted functionalities and a high degre...MOFs are among the most popular precursors and templates for deriving various porous materials,where the derivatives can inherit a large surface area,abundant active sites for targeted functionalities and a high degree of porosity inherited from their parent MOFs.Those unique structural features make them promising candidates in multiple applications.More interestingly,the structure and properties of these MOF derivatives can be modulated by the choice of the parent MOFs and the design in the conversion process.In this overview,the transformation pathways from MOFs into their porous derivatives,the principles underlying these transformations,and the behavior of the MOF components in the transition process are discussed.Recently,there has been tremendous progress in preserving and enhancing the surface area,the amount of active sites and the level of porosity of the MOF-derived materials for targeted applications,from the perspectives of both customizing the parent MOFs and tailoring the transformation process.To develop the rationally designed MOF-derived materials and thus to elucidate the precursor-process-product correlations,some typical examples of the MOF derivatives applied in electrochemical energy storage and conversion,water treatment,gas sensing,and biomedicine are discussed to demonstrate the effectiveness of the key design strategies.展开更多
Enhancing the selectivity of noble metal catalysts through electronic modulation is important for academic research and chemical industrial processes.Herein,we report a facile sacrificial template strategy for the syn...Enhancing the selectivity of noble metal catalysts through electronic modulation is important for academic research and chemical industrial processes.Herein,we report a facile sacrificial template strategy for the synthesis of PdZn intermetallic compound(3-4 nm)highly distributed in ZnO/nitrogen-decorated carbon hollow spheres(PdZn-ZnO/NCHS)to optimize the selectivity of Pd catalysts,which involves carbonization of a core-shell structured polystyrene(PS)@ZIF-8 precursor in an inert atmosphere,impregnation Pd precursor,and subsequent H2 reduction treatment.Due to the unique structural and compositional features,the developed PdZn-ZnO/NCHS delivers an excellent catalytic performance for the semihydrogenation of 2-methyl-3-butyn-2-ol(MBY)to 2-methyl-3-buten-2-ol(MBE)with high activity(>99%),high selectivity(96%),and good recyclability,outperforming the analog Pd on ZnO(Pd/ZnO)as well as the supported Pd nanoparticles(Pd/C and Pd/NC).Density functional theory(DFT)calculations reveal that the presence of Znδ+species in PdZn-ZnO/NCHS alters the adsorption modes of reactant and product,leading to a decrease of the adsorption strength and an enhancement of the energy barrier for overhydrogenation,which results in a kinetic favor for the selective transformation of MBY to MBE.In addition,PdZn-ZnO/NCHS was also very effective for the partial hydrogenation of dehydrolinalool to hydrolinalool.展开更多
The hydrogen evolution reaction(HER)as a fundamental process in electrocatalysis plays a significant role in clean energy technologies.For an energy-efficient HER,it demands an effective,durable,and low-cost catalyst ...The hydrogen evolution reaction(HER)as a fundamental process in electrocatalysis plays a significant role in clean energy technologies.For an energy-efficient HER,it demands an effective,durable,and low-cost catalyst to trigger proton reduction with minimal overpotential and fast kinetics.Here,we successfully fabricate a highly efficient HER catalyst of N-C/Co/Mo_(2)C holey nanorods with Co/b-Mo_(2)C nanoparticles uniformly embedded in nitrogen-doped carbon(N-C/Co/Mo_(2)C)by pyrolyzing the molybdate-coordinated zeolitic imidazolate framework(ZIF-67/MoO_(4)^(2-))holey nanorods,which result from the reaction between CoMoO_(4)and Me IM in a methanol/water/triethylamine mixed solution.The uniform distribution of MoO_(4)^(2-)in the ZIF-67/MoO_(4)^(2-)enables Co/β-Mo_(2)C nanoparticles to be welldistributed within nitrogen-doped carbon holey nanorods.This synthetic strategy endows the N-C/Co/Mo_(2)C catalyst with uniformly decorated bimetal,thus attaining excellent HER electrocatalytic activities with a small overpotential of 142.0 m V at 10 m A cm^(-2)and superior stability in 1.0 mol L^(-1)KOH aqueous solution.展开更多
Cu@MOF core-shell nanowires are synthesized by introducing oxidizable and CTAB-modified metal nanowires as self-engaged templates and supporting MOFs for a one-dimension nanostructure.The following thermal process is ...Cu@MOF core-shell nanowires are synthesized by introducing oxidizable and CTAB-modified metal nanowires as self-engaged templates and supporting MOFs for a one-dimension nanostructure.The following thermal process is controlled to obtain several one-dimension structure s ofCuCo-mixed materials,such as nanorods,single-shell and double-shell nanowires.The hollow structure for electrode materials enlarges the surface area,provides buffer space for electrolyte to accelerate the ion/charge transfers and for the structure to reduce injuries of volume expansion during cycling.Together with some other merits,such as adequate oxidation of the MOFs,small crystal grains of the material,and well-mixed Cu/Co oxides,the double-shell Cu@MOF nanowires(CuCo-DS5)applied for pseudocapacitors deliver advanced electrochemical performance with a specific capacitance of 563.8 F g^(-1)at 1 A g^(-1)as well as an outstanding cycling stability with a 92%retention after 3000 cycles at 5 A g^(-1).Meanwhile,an asymmetric pseudocapacitor constructed with the CuCo-DS5 and active carbon(AC)shows a high specific capacitance and energy density.展开更多
For photocatalytic materials,the composites formed by metal oxides and heteroatom-doped carbon have outstanding activity.Among them,metal-organic framework(MOF)derived composites,usually composed of metal oxide and ni...For photocatalytic materials,the composites formed by metal oxides and heteroatom-doped carbon have outstanding activity.Among them,metal-organic framework(MOF)derived composites,usually composed of metal oxide and nitrogen-doped carbon,is not only simple to prepare,but also have far-exceeding catalytic performance than homogenous semiconductor.However,the relationship between the structure and performance in the photocatalytic system is still not clear.Here,we explored the tunable nitrogen configurations in sample N-ZnO@NC by controlling the thermal conversion of ZIF-8.Crucially,through exsitu and in-situ XPS characterization,it is found that the ZnO and nitrogen-doped carbon in N-ZnO@NC are connected by C-N-Zn bond,which enhances charge separation efficiency and becomes the origin of superior photocatalytic performance.DFT calculations further reveal the influence of different Zn-bonding nitrogen configurations on the adjusting of Fermi level and electron transfer.This study exhibits that the pyridine-N configuration in MOF-derived material is the main contributor for the improved performance and tunes Fermi level more appropriately than the pyrrolic-N,which can hold the key for future design of next-generation photocatalysts.展开更多
Metal-organic frameworks (MOFs) derived metallic nanoparticles embedded nano-porous carbon (NPC)composites have shown to be promising microwave absorbing materials. Although MOF precursors withdiverse compositions and...Metal-organic frameworks (MOFs) derived metallic nanoparticles embedded nano-porous carbon (NPC)composites have shown to be promising microwave absorbing materials. Although MOF precursors withdiverse compositions and morphologies have been extensively investigated, anionic MOFs are rarelyexplored for this utility. In addition to the metal sites and ligands on the MOF framework, the guestcounter-cations in the void provide supplementary parameters to tune the capability of microwaveabsorption. Herein, we applied an anionic NixCoy-MOF featuring N-rich ligands and hierarchical porousstructures as a precursor for microwave absorption. The obtained dielectric-magnetic Ni_(x)Co_(y)@NPCcomposites with rich N dopants and multiple hetero-interfaces promote the microwave attenuationcapability through enhanced dipole/interfacial relaxation. The synergistic effects of magnetic loss andconduction loss induced by metallic nanoparticles (NPs) and porous graphitic layers further facilitate themicrowave dissipation. More significantly, impedance matching can be effectively improved by tuningthe Co/Ni amount in the precursors to realize the modulation of electromagnetic parameters. Conse-quently, Ni@NPC exhibits the optimal electromagnetic wave (EMW) absorption with minimum reflectionloss of 66 dB at only 2 mm and broad effective absorption band covering 4.56 GHz at a thin thickness of2.07 mm, making this material promising absorber for EMW elimination.展开更多
The hierarchical hollow structures of electrode materials s of supercapacitors is effective for the large specific surface area and fast ions and charge transports.Cu nanowires as self-engaged templates provide sites ...The hierarchical hollow structures of electrode materials s of supercapacitors is effective for the large specific surface area and fast ions and charge transports.Cu nanowires as self-engaged templates provide sites and paths for the nucleation and growth of the ZIF-67.Meanwhile,Cu atoms can disperse into metal organic frameworks(MOFs)to form Cu-Co mixed oxides and construct heterostructures.In this case,Cu nanowires are used as a template and an activated part to improve the internal electronic structures.The electrochemical performance can be improved due to these features.Herein,Cu nanowires and MOFs are combined via a mild and efficient approach to fabricate Cu-Co-O/CuO electrode materials.This electrode exhibits excellent electrochemical performance with a specific capacitance of 834.1 F g^(-1) at 1 A g^(-1).The assembled asymmetric supercapacitor(ASC)shows an ultra-high energy density of 40.7 W h kg^(-1) at a power density of 915 W kg^(-1) and a good capacitance retention after 8000 cycles in a 2 M KOH aqueous solution.The results otained in this work indicate a strategy of the combination of reactive metals with metal organic frameworks used as electrode materials for electrochemical supercapacitors.展开更多
基金the National Natural Science Foundation of China(Nos.21701083 and 22179054).
文摘Comprehensive Summary This work systematically reviews recent progresses in the applications of MOF-derived materials modified 3D porous conductive framework as hosts for uniform lithium deposition in LMBs.A series of commonly used lithiophilic materials and several kinds of representative MOF-derivation-modified 3D hosts as lithium metal anode(LMA)are presented.Finally,the challenges and future development of employing MOF-derived materials to modify the 3D porous conductive framework for LMA are included.
基金supported by t he Shanghai Science&Tech-nology Committee(No.22ZR1403300)the Fundamental Research Funds for the Central Universities(No.2232020A-02)the Na-tional Natural Science Foundation of China(Nos.51871053 and 91963204).
文摘Developing highly efficient microwave absorbing materials(MAMs)to ameliorate the electromagnetic(EM)response and facilitate energy absorption is crucial in both the civil and military industries.Metal-organic framework(MOF)derived nanoporous carbon composites have emerged as advanced MAMs ow-ing to their rich porosity,tunable compositions,facile functionalization,and morphology diversity.To-gether with the flourishing development of composition-tuning strategy,the rational dimension design and elaborate control over the architectures have also evolved into an effective approach to regulating their EM properties.Herein,we provide a comprehensive review of the recent advances in using di-mension and morphology modulation to adjust the microwave attenuation capacities for MOF-derived carbon composites.The underlying design rules and unique advantages for the MAMs of various dimen-sions were discussed with the selection of representative work,providing general concepts and insight on how to efficiently tune the morphologies.Accordingly,the fundamental dimension-morphology-function relationship was also elucidated.Finally,the challenges and perspectives of dimension design and mor-phology control over MOF-derived MAMs were also presented.
基金supported by the National Natural Science Foundation of China (22375148)the National Key R&D Program of China (2022YFA1502902)。
文摘制备高效的OER电催化剂对水裂解制氢至关重要.具有丰富配位构型的MOFs可以衍生出各种优良的电催化材料.由于石墨炔(GDY)具有独特的可控合成特性,我们将其原位复合在MOF衍生的Co_(3)S_(4)/NF材料上,获得了自支撑电极GDY/Co_(3)S_(4)/NF,大大提高了其OER催化性能.研究表明,GDY/Co_(3)S_(4)/NF在10 mA cm^(-2)电流密度下表现出223 mV的低过电位,在100 mA cm^(-2)的大电流密度下,能够稳定电解45小时左右,该材料显示出了巨大的实际应用潜力.结果表明,由于GDY独特的炔键和大孔结构,它可以通过强电子相互作用与Co_(3)S_(4)相互作用,从而调节电子结构并提供有效的电荷转移通道,从而大大提高了其电催化OER的性能.
文摘A facile synthetic strategy based on a water-based process is developed for the preparation of metal-organic framework (MOF)-derived materials by revisiting the hydrolyzed non-porous metal-organic frameworks (h-MOF). The poor water stability of MOF has been recognized as key limitations for its commercialization and large-scale applications because the hydrolysis resulted in the complete loss of their functionalities. However, we found that the negative effect of hydrolysis on MOF can be nullified during the heat treatment. As similar to the intact MOF, h-MOF can be used as a precursor for the preparation of MOF-derived materials from porous MOF-derived carbons (MDCs) to MDC@ZnO composites. The property of h-MOF-derived materials is almost equivalent to that of MOF-derived materials. In addition, h-MOF turned the weakness of water instability to the strength of facile water-based process for hybridization. With the demonstration of the hybrid composite between h-MDC@ZnO and reduced graphene oxide (rGO) as a prototype example, it exhibited superior electrochemical performance when evaluated as an electrode material for lithium-ion batteries.
基金This work is financially supported by the National Science Foundation of Tianjin(17JCYBJC23300).
文摘Phosphate removal is crucial for eutrophication control and water quality improvement.Electro-assisted adsorption,an eco-friendly elec-trosorption process,exhibited a promising potential for wastewater treatment.However,there are few works focused on phosphate electro-sorption,and reported electrodes cannot attach satisfactory removal capacities and rates.Herein,electro-assisted adsorption of phosphate via in-situ construction of La active centers on hierarchically porous carbon(LaPC)has been originally demonstrated.The resulted LaPC composite not only possessed a hierarchically porous structure with uniformly dispersed La active sites,but also provided good conductivity for interfacial electron transfer.The LaPC electrode achieved an ultrahigh phosphate electrosorption capability of 462.01 mg g^(-1) at 1 V,outperforming most existing electrodes.The superior phosphate removal performance originates from abundant active centers formed by the coupling of electricfield and capture sites.Besides,the stability and selectivity toward phosphate capture were maintained well even under comprehensive conditions.Moreover,a series of kinetics and isotherms models were employed to validate the electrosorption process.This work demonstrates a deep understanding and promotes a new level of phosphate electrosorption.
基金supported by National Natural Science Foundation of China(21701083).
文摘At present,commercial Li-ion batteries are hardly to satisfy the growing demand for high energy density,for this purpose,lithium metal batteries have attracted worldwide attention in recent years.However,its practical applications are hindered by the formation of Li dendrites and volume effect during Li plating/stripping process,which leads to a lot of safety hazards.Herein,we first employed MOF-derived V_(2)O_(5) nanoparticles to decorate the carbon fiber cloth(CFC)backbone to acquire a lithiophilic 3D porous conductive framework(CFC@V_(2)O_(5)).Subsequently,the CFC@V_(2)O_(5) skeleton was permeated with molten Li to prepare CFC@V_(2)O_(5)@Li composite anode.The CFC@V_(2)O_(5)@Li composite anode can be stably cycled for more than 1650 h at high current density(5 mA·cm^(-2))and areal capacity(5 mA·h·cm^(–2)).The prepared full cell can initially maintain a high capacity of about 143 mA·h·g^(-1) even at a high current density of 5 C,and can still maintain 114 mA·h·g^(-1) after 1000 cycles.
基金This work was supported by the National Natural Science Foundation of China(22075223,51701146).
文摘The core reactions for fuel cells,rechargeable metal-air batteries,and hydrogen fuel production are the oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER),which are heavily dependent on the efficiency of electrocatalysts.Enormous attempts have previously been devoted in non-noble electrocatalysts born out of metal-organic frameworks(MOFs)for ORR,OER,and HER applications,due to the following advantageous reasons:(i)The significant porosity eases the electrolyte diffusion;(ii)the supreme catalyst-electrolyte contact area enhances the diffusion efficiency;and(iii)the electronic conductivity can be extensively increased owing to the unique construction block subunits for MOFs-derived electrocatalysis.Herein,the recent progress of MOFs-derived electrocatalysts including synthesis protocols,design engineering,DFT calculations roles,and energy applications is discussed and reviewed.It can be concluded that the elevated ORR,OER,and HER performances are attributed to an advantageously well-designed high-porosity structure,significant surface area,and plentiful active centers.Furthermore,the perspectives of MOF-derived electrocatalysts for the ORR,OER,and HER are presented.
基金financially supported by the National Key R&D Program of China (2017YFA0403402 and 2019YFA0405601)the National Natural Science Foundation of China(21773222,U1732272 and U1932214)the DNL Cooperation Fund,and Chinese Academy of Sciences (DNL180201)
文摘Fe2O3 has become a promising anode material in lithium-ion batteries (LIBs) in light of its low cost, high theoretical capacity (1007 mA h g^−1) and abundant reserves on the earth. Nevertheless, the practical application of Fe2O3 as the anode material in LIBs is greatly hindered by several severe issues, such as drastic capacity falloff, short cyclic life and huge volume change during the charge/discharge process. To tackle these limitations, carbon-coated Fe2O3 (Fe2O3@MOFC) composites with a hollow sea urchin nanostructure were prepared by an effective and controllable morphology-inherited strategy. Metal-organic framework (MOF)-coated FeOOH (FeOOH@-MIL-100(Fe)) was applied as the precursor and self-sacrificial template. During annealing, the outer MOF layer protected the structure of inner Fe2O3 from collapsing and converted to a carbon coating layer in situ. When applied as anode materials in LIBs, Fe2O3@MOFC composites showed an initial discharge capacity of 1366.9 mA h g^−1 and a capacity preservation of 1551.3 mA h g^−1 after 200 cycles at a current density of 0.1 A g^−1. When increasing the current density to 1 A g^−1, a reversible and high capacity of 1208.6 mA h g^−1 was obtained. The enhanced electrochemical performance was attributed to the MOF-derived carbon coating layers and the unique hollow sea urchin nanostructures. They mitigated the effects of volume expansion, increased the lithium-ion mobility of electrode, and stabilized the as-formed solid electrolyte interphase films.
文摘Metal‐organic framework(MOF)‐derived nanomaterials have attracted widespread attention,because the excellent features,such as high surface area,porosity and tunable properties are inherited from MOFs.Moreover,the derivatives avoid the poor conductivity and stability of MOFs.MOF‐derived nanomaterials can easily be regulated by a specific selection of metal nodes and organic linkers,resulting in multifunctionality in photocatalysis.MOF derivatives can be used not only as semiconductor photocatalysts,but also as co‐catalysts for photocatalytic hydrogen evolution,CO_(2) reduction,pollutants degradation,etc.This review focuses on the multifunctional applications of MOF derivatives in the field of photocatalysis.The researches in recent years are analyzed and summarized from the aspects of preparation,modification and application of MOF derivatives.At the end of the review,the development and challenges of MOF derivatives applied in photocatalysis in the future are put forward,in order to provide more references for further research in this field and bring new inspiration.
基金financially supported by the National Natural Science Foundation of China(Nos.21625102,21471018)the Beijing Municipal Science and Technology Project(No.Z181100004418001)the Beijing Institute of Technology Research Fund Program。
文摘Metal-organic frameworks(MOFs)are a class of outstanding materials in Li-air batteries because of their high surface areas,tailorable pore sizes and diverse catalytic centers.However,MOF-based batteries are facing challenges such as poor electronic conductivity and inferior long-cycle stability that limit their further development.This review first summarizes the progress of pristine MOFs and MOF-derived materials in Li-air batteries in the past 5 years,then provides a perspective for subsequent development of MOFs and their derivatives in this emerging field.
基金the Natural Science Foundation of Anhui Province Higher Education Institutions(No.KJ2021A0501)the Foundation of Scientific Research Project of Anhui Polytechnic University(No.Xjky2020090)+4 种基金the Anhui Laboratory of Functional Coordinated Complexes for Materials Chemistry and Application(Nos.LFCCMCA-01 and LFCCMCA-06)the Scientific Research Launch Project of Anhui Polytechnic University(No.2020YQQ057)the Innovation and Entrepreneurship Training Program for College Students in Anhui Province(No.S202110363265)the National Key Research and Development Program of China(2019YFA0705702)the National Natural Science Foundation of China(21902188)。
文摘Designing novel electrode materials with unique structures is of great significance for improving the performance of lithium ion batteries(LIBs).Herein,copper-doped Co_(1-x)Te@nitrogen-doped carbon hollow nanoboxes(Cu-Co_(1-x)Te@NC HNBs)have been fabricated by chemical etching of Cu Co-ZIF nanoboxes,followed by a successive high-temperature tellurization process.The as-synthesized Cu-Co_(1-x)Te@NC HNBs composite demonstrated faster ionic and electronic diffusion kinetics than the pristine Co Te@NC HNBs electrode.The existence of Co-vacancy promotes the reduction of Gibbs free energy change(ΔG_(H^(*)))and effectively improves the Li~+diffusion coefficient.XPS and theoretical calculations show that performance improvement is ascribed to the electronic interactions between Cu-Co_(1-x)Te and nitrogen-doped carbon(NC)that trigger the shift of the p-band towards facilitation of interfacial charge transfer,which in turn helps boost up the lithium storage property.Besides,the proposed Cu-doping-induced Co-vacancy strategy can also be extended to other conversion-type cobalt-based material(CoSe_(2))in addition to asobtained Cu-Co_(1-x)Se_(2)@NC HNBs anodes for long-life and high-capacity LIBs.More importantly,the fabricated LiCoO_(2)//Cu-Co_(1-x)Te@NC HNBs full cell exhibits a high energy density of 403 Wh kg^(-1)and a power density of 6000 W kg^(-1).We show that the energy/power density reported herein is higher than that of previously studied cobalt-based anodes,indicating the potential application of Cu-Co_(1-x)Te@NC HNBs as a superior electrode material for LIBs.
基金supported by the National Natural Science Foundation of China(51771076 and 51621001)Guangdong"Pearl River Talents Plan"(2017GC010218)+1 种基金the R&D Program in Key Areas of Guangdong Province(2020B0101030005)Guangdong Basic and Applied Basic Research Foundation(2020B1515120049)。
文摘The pursuit of high-mileage models results in the recurrence of lithium metal batteries(LMBs)to researchers’horizon.However,the lithium(Li)metal anode for LMBs undergoes the uncontrollable formation of Li dendrites and infinite volume change during cycling,impeding its practical application.To overcome these challenges,we developed a metal-organic framework(MOF)-derived pathway to construct lithiophilic three-dimensional(3D)skeleton using different substrates(e.g.,carbon cloth(CC)and Cu mesh)for dendrite-free lithium metal anodes.As a typical example,the MOF-derived ZnO/nitrogen-doped carbon(NC)nanosheet-modified 3D CC was well-constructed as a lithiophilic hierarchical host(CC@ZnO/NC@Li)for molten Li infiltration.Benefiting from the lithiophilic N-functional groups and LiZn alloy,the synthesized CC@ZnO/NC@Li composite anode promoted the uniform distribution of Li,resulting in a dendrite-free morphology.Meanwhile,the 3D conductive carbon skeleton enhanced the reaction kinetics and buffered the volume change of the electrode.The CC@ZnO/NC@Li composite anode presented a prolonged lifespan of over 1000 cycles at 5 mA cm^(−2) with a low overpotential of 19 mV.Coupled with a LiFePO_(4) cathode,the CC@ZnO/NC@Li composite anode also exhibited superior electrochemical properties in the full-cell system.This versatile strategy may open up the channel of designing multi-functional lithiophilic 3D hosts for the Li metal anode.
基金the National Research Foundation(NRF)Singapore for funding under NRF-CRP17-2017-01(R-284-000-165-281)for the research conducted at the National University of Singapore.
文摘MOFs are among the most popular precursors and templates for deriving various porous materials,where the derivatives can inherit a large surface area,abundant active sites for targeted functionalities and a high degree of porosity inherited from their parent MOFs.Those unique structural features make them promising candidates in multiple applications.More interestingly,the structure and properties of these MOF derivatives can be modulated by the choice of the parent MOFs and the design in the conversion process.In this overview,the transformation pathways from MOFs into their porous derivatives,the principles underlying these transformations,and the behavior of the MOF components in the transition process are discussed.Recently,there has been tremendous progress in preserving and enhancing the surface area,the amount of active sites and the level of porosity of the MOF-derived materials for targeted applications,from the perspectives of both customizing the parent MOFs and tailoring the transformation process.To develop the rationally designed MOF-derived materials and thus to elucidate the precursor-process-product correlations,some typical examples of the MOF derivatives applied in electrochemical energy storage and conversion,water treatment,gas sensing,and biomedicine are discussed to demonstrate the effectiveness of the key design strategies.
基金We thank the financial supports from the National Natural Science Foundation of China(No.21576243)the Natural Science Foundation of Zhejiang Province(Nos.LY18B060006,LY17B060001,and LY21B030003).
文摘Enhancing the selectivity of noble metal catalysts through electronic modulation is important for academic research and chemical industrial processes.Herein,we report a facile sacrificial template strategy for the synthesis of PdZn intermetallic compound(3-4 nm)highly distributed in ZnO/nitrogen-decorated carbon hollow spheres(PdZn-ZnO/NCHS)to optimize the selectivity of Pd catalysts,which involves carbonization of a core-shell structured polystyrene(PS)@ZIF-8 precursor in an inert atmosphere,impregnation Pd precursor,and subsequent H2 reduction treatment.Due to the unique structural and compositional features,the developed PdZn-ZnO/NCHS delivers an excellent catalytic performance for the semihydrogenation of 2-methyl-3-butyn-2-ol(MBY)to 2-methyl-3-buten-2-ol(MBE)with high activity(>99%),high selectivity(96%),and good recyclability,outperforming the analog Pd on ZnO(Pd/ZnO)as well as the supported Pd nanoparticles(Pd/C and Pd/NC).Density functional theory(DFT)calculations reveal that the presence of Znδ+species in PdZn-ZnO/NCHS alters the adsorption modes of reactant and product,leading to a decrease of the adsorption strength and an enhancement of the energy barrier for overhydrogenation,which results in a kinetic favor for the selective transformation of MBY to MBE.In addition,PdZn-ZnO/NCHS was also very effective for the partial hydrogenation of dehydrolinalool to hydrolinalool.
基金National Institute of Advanced Industrial Science and Technology(AIST)the Japan Society for the Promotion of Science(JSPS)for financial support。
文摘The hydrogen evolution reaction(HER)as a fundamental process in electrocatalysis plays a significant role in clean energy technologies.For an energy-efficient HER,it demands an effective,durable,and low-cost catalyst to trigger proton reduction with minimal overpotential and fast kinetics.Here,we successfully fabricate a highly efficient HER catalyst of N-C/Co/Mo_(2)C holey nanorods with Co/b-Mo_(2)C nanoparticles uniformly embedded in nitrogen-doped carbon(N-C/Co/Mo_(2)C)by pyrolyzing the molybdate-coordinated zeolitic imidazolate framework(ZIF-67/MoO_(4)^(2-))holey nanorods,which result from the reaction between CoMoO_(4)and Me IM in a methanol/water/triethylamine mixed solution.The uniform distribution of MoO_(4)^(2-)in the ZIF-67/MoO_(4)^(2-)enables Co/β-Mo_(2)C nanoparticles to be welldistributed within nitrogen-doped carbon holey nanorods.This synthetic strategy endows the N-C/Co/Mo_(2)C catalyst with uniformly decorated bimetal,thus attaining excellent HER electrocatalytic activities with a small overpotential of 142.0 m V at 10 m A cm^(-2)and superior stability in 1.0 mol L^(-1)KOH aqueous solution.
基金supported by the National Natural Science Fundsgrant number 51821091,51872233the Shaanxi Natural Science Funds grant number 2018JM5044。
文摘Cu@MOF core-shell nanowires are synthesized by introducing oxidizable and CTAB-modified metal nanowires as self-engaged templates and supporting MOFs for a one-dimension nanostructure.The following thermal process is controlled to obtain several one-dimension structure s ofCuCo-mixed materials,such as nanorods,single-shell and double-shell nanowires.The hollow structure for electrode materials enlarges the surface area,provides buffer space for electrolyte to accelerate the ion/charge transfers and for the structure to reduce injuries of volume expansion during cycling.Together with some other merits,such as adequate oxidation of the MOFs,small crystal grains of the material,and well-mixed Cu/Co oxides,the double-shell Cu@MOF nanowires(CuCo-DS5)applied for pseudocapacitors deliver advanced electrochemical performance with a specific capacitance of 563.8 F g^(-1)at 1 A g^(-1)as well as an outstanding cycling stability with a 92%retention after 3000 cycles at 5 A g^(-1).Meanwhile,an asymmetric pseudocapacitor constructed with the CuCo-DS5 and active carbon(AC)shows a high specific capacitance and energy density.
基金financially supported by National Natural Science Foundation of China(Nos.U20A20246 and 51872108)Fundamental Research Funds for the Central Universities(No.CCNU20TS006)。
文摘For photocatalytic materials,the composites formed by metal oxides and heteroatom-doped carbon have outstanding activity.Among them,metal-organic framework(MOF)derived composites,usually composed of metal oxide and nitrogen-doped carbon,is not only simple to prepare,but also have far-exceeding catalytic performance than homogenous semiconductor.However,the relationship between the structure and performance in the photocatalytic system is still not clear.Here,we explored the tunable nitrogen configurations in sample N-ZnO@NC by controlling the thermal conversion of ZIF-8.Crucially,through exsitu and in-situ XPS characterization,it is found that the ZnO and nitrogen-doped carbon in N-ZnO@NC are connected by C-N-Zn bond,which enhances charge separation efficiency and becomes the origin of superior photocatalytic performance.DFT calculations further reveal the influence of different Zn-bonding nitrogen configurations on the adjusting of Fermi level and electron transfer.This study exhibits that the pyridine-N configuration in MOF-derived material is the main contributor for the improved performance and tunes Fermi level more appropriately than the pyrrolic-N,which can hold the key for future design of next-generation photocatalysts.
基金This work was supported by Fundamental Research Funds for the Central Universities(No.2232020A-02)Shanghai Pujiang Pro-gram(No.19PJ1400200)+1 种基金Fundamental Research Funds for the Central Universities(No.2232019G-07)National Natural Science Foundation of China(No.51871053,No.91963204).
文摘Metal-organic frameworks (MOFs) derived metallic nanoparticles embedded nano-porous carbon (NPC)composites have shown to be promising microwave absorbing materials. Although MOF precursors withdiverse compositions and morphologies have been extensively investigated, anionic MOFs are rarelyexplored for this utility. In addition to the metal sites and ligands on the MOF framework, the guestcounter-cations in the void provide supplementary parameters to tune the capability of microwaveabsorption. Herein, we applied an anionic NixCoy-MOF featuring N-rich ligands and hierarchical porousstructures as a precursor for microwave absorption. The obtained dielectric-magnetic Ni_(x)Co_(y)@NPCcomposites with rich N dopants and multiple hetero-interfaces promote the microwave attenuationcapability through enhanced dipole/interfacial relaxation. The synergistic effects of magnetic loss andconduction loss induced by metallic nanoparticles (NPs) and porous graphitic layers further facilitate themicrowave dissipation. More significantly, impedance matching can be effectively improved by tuningthe Co/Ni amount in the precursors to realize the modulation of electromagnetic parameters. Conse-quently, Ni@NPC exhibits the optimal electromagnetic wave (EMW) absorption with minimum reflectionloss of 66 dB at only 2 mm and broad effective absorption band covering 4.56 GHz at a thin thickness of2.07 mm, making this material promising absorber for EMW elimination.
基金supported by the National Natural Science Funds[grant number 51821091,51872233]the Natural Science Foundation of Shaanxi Province[grant number 2018JM5044]。
文摘The hierarchical hollow structures of electrode materials s of supercapacitors is effective for the large specific surface area and fast ions and charge transports.Cu nanowires as self-engaged templates provide sites and paths for the nucleation and growth of the ZIF-67.Meanwhile,Cu atoms can disperse into metal organic frameworks(MOFs)to form Cu-Co mixed oxides and construct heterostructures.In this case,Cu nanowires are used as a template and an activated part to improve the internal electronic structures.The electrochemical performance can be improved due to these features.Herein,Cu nanowires and MOFs are combined via a mild and efficient approach to fabricate Cu-Co-O/CuO electrode materials.This electrode exhibits excellent electrochemical performance with a specific capacitance of 834.1 F g^(-1) at 1 A g^(-1).The assembled asymmetric supercapacitor(ASC)shows an ultra-high energy density of 40.7 W h kg^(-1) at a power density of 915 W kg^(-1) and a good capacitance retention after 8000 cycles in a 2 M KOH aqueous solution.The results otained in this work indicate a strategy of the combination of reactive metals with metal organic frameworks used as electrode materials for electrochemical supercapacitors.
