Conductive metal-organic frameworks: Recent advances in electrochemical energy-related applications and perspectives

Metal-organic frameworks(MOFs),typically constructed with metallic nodes and organic linkers,have influenced the development of modular solid materials.Their adjustable molecular structure provides a remarkable variety of MOF-based solid-state structures towards diverse applications.However,the low conductivity of traditional MOFs extremely hinders their applications in electronic and electrochemical devices.The emerging conductive MOFs,generally possessing twodimensional layered structures,are endowed with both the structural merits of common MOFs and exceptional electronic/ionic conductivities.Besides,the selection and optimization of ligands and metal centers,as well as synthetic methods enormously affects the intrinsic conductivity of conductive MOFs.The distinctive crystal structures and superb conductivity promise their appealing applications in electrochemical energy-related fields.In the review,we mainly summarize representative crystal features,conducting mechanisms and recent advances in rational design and synthesis of conductive MOFs,along with their versatile applications as electrodes for electrochemical capacitors and rechargeable batteries,and as catalysts towards electrocatalysis.Finally,the involved challenges and future trends/prospects of the conductive MOFs for electrochemical energyrelated applications are further proposed.

Conductive metal-organic frameworks promoting polysulfides transformation in lithium-sulfur batteries

Metal organic frameworks(MOFs) have been extensively investigated in Li-S batteries owing to high surface area, adjustable structures and abundant catalytic sites. Nevertheless, the insulating nature of traditional MOFs render retarded kinetics of polysulfides conversion, leading to insufficient utilization of sulfur. In comparison, conductive MOFs(c-MOFs) show great potential for promoting polysulfides transformation due to superb electronic conductivity. In this work, a nickel-catecholates based c-MOF, NiHHTP(HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene), is designed to regulate surface chemistry of self-supported carbon paper for advanced Li-S batteries. Taking advantage of the porous structure and high conductivity, the as-prepared Ni-HHTP is conducive to synergising strengthening the chemisorption of polysulfides and accelerating the reaction kinetics in Li-S batteries, significantly mitigating the polysulfides diffusion from the non-encapsulated sulfur cathode, therefore promoting polysulfides transformation in Li-S batteries. This work points out a promising modification strategy for developing advanced sulfur cathode in Li-S batteries.

Recent Progress of Conductive Metal-Organic Frameworks for Electrochemical Energy Storage

The development of reliable and low-cost energy storage systems is of considerable value in using renewable and clean energy sources,and exploring advanced electrodes with high reversible capacity,excellent rate performance,and long cycling life for Li/Na/Zn-ion batteries and supercapacitors is the key problem.Particularly because of their diverse structure,high specific surface area,and adjustable redox activity,electrically conductive metal-organic frameworks(c-MOFs)are considered promising candidates for these electrochemical applications,and a detailed overview of the recent progress of c-MOFs for electrochemical energy storage and their intrinsic energy storage mechanism helps realize a comprehensive and systematic understanding of this progress and further achieve highly efficient energy storage and conversion.Herein,the chemical structure of c-MOFs and their conductive mechanism are first introduced.Subsequently,a comprehensive summarization of the current applications of c-MOFs in energy storage systems,namely supercapacitors,LIBs,SIBs,and ZIBs,is presented.Finally,the prospects and challenges of c-MOFs toward much higher-performance energy storage devices are presented,which should illuminate the future scientific research and practical applications of c-MOFs in energy storage fields.

Dual-conductive metal-organic framework@MXene heterogeneity stabilizes lithium-ion storage

Although a few pristine metal-organic frameworks(MOFs) of graphene analogue topology exhibit high intrinsic electrical conductivity, their use in lithium-ion batteries(LIBs) is still hampered by unfavorable Li+adsorption energy(ΔEa). In this paper, an electroconductive ferrocene-based MOF@MXene heterostructure is built to provide stable anodes for Li+storage. Charge density difference and planar average potential charge density show substantial redistribution of charges at the interfaces, transferring from MXene to MOF layers. Moreover, density functional theory(DFT) calculations reveal that the interaction between MXene and MOF significantly increases the ΔEa. As a result, the heterostructure anode exhibits high capacities and outstanding cycling stability with a capacity retention of 80% after 5000 cycles at 5 A g^(-1), outperforming mono-component MXene and MOF. Furthermore, the heterostructure anode is built into a full cell with a commercial NCM 532 cathode, delivering a high energy density of 611 Wh kg^(-1)and power density of 7600 W kg^(-1). The developed conductive MOF@MXene heterogeneity for improved LIB offers valuable insights into the design of advanced electrode materials for energy storage.

Metal and ligand modification modulates the electrocatalytic HER,OER,and ORR activity of 2D conductive metal-organic frameworks

It is highly desirable to design efficient and stable hydrogen evolution reaction(HER)and oxygen evolution/reduction reaction(OER/ORR)electrocatalysts for the development of renewable energy technologies.Herein,density functional theory(DFT)calculations were conducted to systematically investigate a series of TMN_(x)O_(4-x)-HTT(TM=Fe,Co,Ni,Ru,Rh,Pd,Ir and Pt;HTT=hexahydroxy tetraazanaphthotetraphene)analogs of two-dimensional(2D)conductive metal-organic frameworks(MOFs)as potential electrocatalysts for the HER,OER and ORR.The thermodynamic and electrochemical stability simulations suggest that these designed catalysts are stable.Remarkably,CoO_(4)-HTT,RhN_(3)O_(1)-HTT and IrN3O1-HTT are predicted to be the most promising catalysts for the HER,OER and ORR,respectively,surpassing the catalytic activity of corresponding benchmark catalysts.The volcano plots were established based on the scaling relationship of adsorption Gibbs free energy of intermediates.The results reveal that regulating combinations of metal active centers and local coordination environments could effectively balance the interaction strength between intermediates and catalysts,thus achieving optimal catalytic activity.Our findings not only opt for the promising HER/OER/ORR electrocatalysts but also guide the design of efficient electrocatalysts based on 2D MOFs materials.

Two-Dimensional Conductive Metal-Organic Framework Reinforced Spinterface in Organic Spin Valves

Interface engineering in device fabrication is a significant but complicated issue.Although great successes have been achieved by conventional physical in situ or ex situ methods,it still suffers from complicated procedures.In this work,we present a facile method for fabricating phthalocyanine(Pc)-based two-dimensional conductive metal–organic framework(MOF)films.Based on PcM-Cu(M=Ni,Cu,H_(2))MOF films,spin valves with a vertical configuration of La_(0.67)Sr_(0.33)MnO_(3)/PcM-Cu MOFs/Co were constructed successfully,and exhibited notably high negative magnetoresistance(MR)up to -22% at 50 K.The penetrated Co atoms coordinated with the dehydrogenated hydroxy groups in the MOFs resulting in an antiferromagnetic layer of the PcM-Cu-Co hybrid structure.Interestingly,a significant exchange bias effect was demonstrated at the PcM-Cu MOF/Co interface,beneficial for the MR behavior.Thus,our present study provides new insights into developing high-performance organic spin valves via de novo molecular design.

Co3(hexahydroxytriphenylene)2:A conductive metal-organic framework for ambient electrocatalytic N2 reduction to NH3

As a carbon-neutral alternative to the Haber-Bosch process,electrochemical N2 reduction enables environment-friendly NH3 synthesis at ambient conditions but needs active electrocatalysts for the N2 reduction reaction.Here,we report that conductive metal-organic framework CO3(hexahydroxytriphenylene)2(Co3 HHTP2)nanoparticles act as an efficient catalyst for ambient electrochemical N2-to-NH3 fixation.When tested in 0.5 M LiClO4,such Co3 HHTP2 achieves a large NH3 yield of 22.14μg·h^-1·mg^-1 cat.with a faradaic efficiency of 3.34%at-0.40 V versus the reversible hydrogen electrode.This catalyst also shows high electrochemical stability and excellent selectivity toward NH3 synthesis.

A Pyrazine-Based 2D Conductive Metal-Organic Framework for Efficient Lithium Storage

The merits of intrinsic electrical conductivity, high specific surface area, tunable chemical composition and tailor-made properties enable two-dimensional conductive metal-organic frameworks (2D c-MOFs) as promising next-generation electrode materials in the field of energy storage and conversion. Herein, we have designed and synthesized a novel pyrazine-based 2D c-MOF (TPQG-Cu-MOF) bearing extended π-conjugated structure and abundant redox active sites. Thanks to the excellent redox reversibility of pyrazine units and CuO2 units, as well as the insolubility of the rigid framework skeleton, TPQG-Cu-MOF as the cathode material of lithium-ion battery exhibits a reversible specific capacity (150.2 mAh·g–1 at 20 mAh·g–1), good cycling stability (capacity retention of 82.6% after 500 cycles at 1 A·g–1) and excellent rate performance. Comprehensive ex-situ spectroscopic studies revealed the reversible redox activity of pyrazine units and CuO2 units of TPQG-Cu-MOF during the Li+ insertion/extraction process. The deepening fundamental understanding of the structure-property relationship was proposed, which might pave the way for further development of efficient MOF-based energy storage devices.

2D conductive metal-organic frameworks for electronics and spintronics

Two-dimensional(2D)materials showcase great potentials in both fundamental research and technology development,thanks to their unique chemical and physical properties that are usually not available in corresponding bulk counterparts.As an emerging class of 2D materials,2D conductive metal-organic frameworks(2D c-MOFs)exhibit the characteristics of pre-designable and tunable structures,excellent crystallinity,intrinsic porosity and superior conductivity.During the past decade,2D c-MOFs have been rapidly developed in electronics,sensors,energy storage devices,etc.In this review,the electrical,magnetic and quantum properties of 2D c-MOFs are surveyed in detail.Their applications in semiconductor,metal,superconductor,topological insulator and porous magnet are highlighted.We envision that the combination of 2D c-MOFs with quantum materials could evoke rich physics,flexible chemistry and potential applications in both electronics and spintronics.

Improvement of ionic conductivity of solid polymer electrolyte based on Cu-Al bimetallic metal-organic framework fabricated through molecular grafting

A composite solid electrolyte comprising a Cu-Al bimetallic metal-organic framework(CAB),lithium salt(LiTFSI)and polyethylene oxide(PEO)was fabricated through molecular grafting to enhance the ionic conductivity of the PEO-based electrolytes.Experimental and molecular dynamics simulation results indicated that the electrolyte with 10 wt.%CAB(PL-CAB-10%)exhibits high ionic conductivity(8.42×10~(-4)S/cm at 60℃),high Li+transference number(0.46),wide electrochemical window(4.91 V),good thermal stability,and outstanding mechanical properties.Furthermore,PL-CAB-10%exhibits excellent cycle stability in both Li-Li symmetric battery and Li/PL-CAB-10%/LiFePO4 asymmetric battery setups.These enhanced performances are primarily attributable to the introduction of the versatile CAB.The abundant metal sites in CAB can react with TFSI~-and PEO through Lewis acid-base interactions,promoting LiTFSI dissociation and improving ionic conductivity.Additionally,regular pores in CAB provide uniformly distributed sites for cation plating during cycling.

A Two-Dimensional Semiconductive Metal-Organic Framework for Highly Efficient Microwave Absorption

Comprehensive Summary Advanced microwave absorbing materials(MAMs)are urgently required to eliminate and attenuate microwaves to address the ubiquitous microwave radiations and interference.In this contribution,we report the microwave absorption application of a two-dimensional(2D)semiconductive metal-organic framework(MOF),i.e.,CuHT(HT=4-hydroxythiophenol),without any pyrolysis at high temperature.

Structural Characterization and Proton-conductive Property of a Lanthanide Metal-organic Framework Assembled from 1,2,4,5-Benzenetetracarboxylic Acid and Piperazine

The reaction of Pr（Ⅲ） salt with 1,2,4,5-benzenetetracarboxylic acid（H4betc） and piperazine（pip） yielded a lanthanide metal-organic framework {[Pr（betc）（H2O）2]（H2pip）0.5}n（1）under hydrothermal conditions. Compound 1 was characterized by single-crystal X-ray structural analysis, elemental analysis, IR, X-ray powder diffraction, and thermal gravimetric. Compound 1crystallizes in monoclinic, space group P21/n with a = 11.023（5）, b = 11.109（5）, c = 11.456（5） A, β = 110.065（5）°, V = 1317.7（9） A3, Mr = 471.14, Z = 4, F（000） = 920, Dc = 2.375 g/cm^3, μ（Mo Kα） = 3.761 mm-1, the final R = 0.0286 and w R = 0.0821（I 〉 2σ（I））. Compound 1 exhibits a 2D network with（4, 4） topology, and a 3D supramolecular framework formed by hydrogen-bonding interactions. The proton conductivity of compound 1 has been investigated at ~97% relative humidity and different temperature.

Accelerating Oxygen Electrocatalysis Kinetics on Metal-Organic Frameworks via Bond Length Optimization

Metal-organic frameworks(MOFs)have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity,but the limited catalytic activity and stability has hampered their practical use in water splitting.Herein,we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs(donated as AE-CoNDA)to serve as efficient catalyst for water splitting.AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm^(−2)and a small Tafel slope of 62 mV dec^(−1)with excellent stability over 100 h.After integrated AE-CoNDA onto BiVO_(4),photocurrent density of 4.3 mA cm^(−2)is achieved at 1.23 V.Experimental investigations demonstrate that the stretched Co-O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p,which accounts for the fast kinetics and high activity.Theoretical calculations reveal that the stretched Co-O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.

Metal-organic frameworks and their composites for advanced lithium-ion batteries:Synthesis,progress and prospects

Metal-organic frameworks(MOFs)are among the most promising materials for lithium-ion batteries(LIBs)owing to their high surface area,periodic porosity,adjustable pore size,and controllable chemical composition.For instance,their unique porous structures promote electrolyte penetration,ions transport,and make them ideal for battery separators.Regulating the chemical composition of MOF can introduce more active sites for electrochemical reactions.Therefore,MOFs and their related composites have been extensively and thoroughly explored for LIBs.However,the reported reviews solely include the applications of MOFs in the electrode materials of LIBs and rarely involve other aspects.A systematic review of the application of MOFs in LIBs is essential for understanding the mechanism of MOFs and better designing related MOFs battery materials.This review systematically evaluates the latest developments in pristine MOFs and MOF composites for LIB applications,including MOFs as the main materials(anode,cathode,separators,and electrolytes)to auxiliary materials(coating layers and additives for electrodes).Furthermore,the synthesis,modification methods,challenges,and prospects for the application of MOFs in LIBs are discussed.

Synergistic catalysis of the N-hydroxyphthalimide on flower-like bimetallic metal-organic frameworks for boosting oxidative desulfurization

Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.

Hollow Metal-Organic Framework/MXene/Nanocellulose Composite Films for Giga/Terahertz Electromagnetic Shielding and Photothermal Conversion

With the continuous advancement of communication technology,the escalating demand for electromagnetic shielding interference(EMI)materials with multifunctional and wideband EMI performance has become urgent.Controlling the electrical and magnetic components and designing the EMI material structure have attracted extensive interest,but remain a huge challenge.Herein,we reported the alternating electromagnetic structure composite films composed of hollow metal-organic frameworks/layered MXene/nanocellulose(HMN)by alternating vacuum-assisted filtration process.The HMN composite films exhibit excellent EMI shielding effectiveness performance in the GHz frequency(66.8 dB at Kaband)and THz frequency(114.6 dB at 0.1-4.0 THz).Besides,the HMN composite films also exhibit a high reflection loss of 39.7 dB at 0.7 THz with an effective absorption bandwidth up to 2.1 THz.Moreover,HMN composite films show remarkable photothermal conversion performance,which can reach 104.6℃under 2.0 Sun and 235.4℃under 0.8 W cm^(−2),respectively.The unique micro-and macrostructural design structures will absorb more incident electromagnetic waves via interfacial polarization/multiple scattering and produce more heat energy via the local surface plasmon resonance effect.These features make the HMN composite film a promising candidate for advanced EMI devices for future 6G communication and the protection of electronic equipment in cold environments.

Temperature-feedback two-photon-responsive metal-organic frameworks for efficient photothermal therapy

The realization of real-time thermal feedback for monitoring photothermal therapy(PTT)under near-infrared(NIR)light irradiation is of great interest and challenge for antitumor therapy.Herein,by assembling highly efficient photothermal conversion gold nanorods and a temperature-responsive probe((E)-4-(4-(diethylamino)styryl)-1-methylpyridin-1-ium,PyS)within MOF-199,an intelligent nanoplatform(AMPP)was fabricated for simultaneous chemodynamic therapy and NIR light-induced temperature-feedback PTT.The fluorescence intensity and temperature of the PyS probe are linearly related due to the restriction of the rotation of the characteristic monomethine bridge.Moreover,the copper ions resulting from the degradation of MOF-199 in an acidic microenvironment can convert H_(2)O_(2)into•OH,resulting in tumor ablation through a Fenton-like reaction,and this process can be accelerated by increasing the temperature.This study establishes a feasible platform for fabricating highly sensitive temperature sensors for efficient temperature-feedback PTT.

Photophysics of metal-organic frameworks:A brief overview

Metal-organic frameworks(MOFs),which are self-assembled porous coordination materials,have garnered considerable attention in the fields of optoelectronics,photovoltaic,photochemistry,and photocatalysis due to their diverse structures and excellent tunability.However,the performance of MOF-based optoelectronic applications currently falls short of the industry benchmark.To enhance the performance of MOF materials,it is imperative to undertake comprehensive investigations aimed at gaining a deeper understanding of photophysics and sequentially optimizing properties related to photocarrier transport,recombination,interaction,and transfer.By utilizing femtosecond laser pulses to excite MOFs,time-resolved optical spectroscopy offers a means to observe and characterize these ultrafast microscopic processes.This approach adds the time coordinate as a novel dimension for comprehending the interaction between light and MOFs.Accordingly,this review provides a comprehensive overview of the recent advancements in the photophysics of MOFs and additionally outlines potential avenues for exploring the time domain in the investigation of MOFs.

Expediting^(*)OH accumulation kinetics on metal-organic frameworks-derived CoOOH with CeO_(2) “accelerator” for electrocatalytic 5-hydroxymethylfurfural oxidation valorization

In this work,nickel foam supported CeO_(2)-modified CoBDC(BDC stands for terephthalic acid linker)metal-organic frameworks(NF/CoBDC@CeO_(2)) are prepared by hydrothermal and subsequent impregnation methods,which can be further transformed to NF/CoOOH@CeO_(2) by reconstruction during the electrocatalytic test.The obtained NF/CoOOH@CeO_(2) exhibits excellent performance in electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF) because the introduction of CeO_(2) can optimize the electronic structure of the heterointerface and accelerate the accumulation of ^(*)OH.It requires only a potential of 1.290 V_(RHE) to provide a current density of 50 mA cm^(-2) in 1.0 M KOH+50 mM HMF,which is 222 mV lower than that required in 1,0 M KOH(1.512 V_(RHE)).In addition,density-functional theory calculation results demonstrate that CeO_(2) biases the electrons to the CoOOH side at the heterointerface and promotes the adsorption of ^(*)OH and ^(*)HMF on the catalyst surface,which lower the reaction energy barrier and facilitate the electrocata lytic oxidation process.

Metal-organic-framework-derived copper-based catalyst for multicomponent C-S coupling reaction

Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.