Surface coatings of two-dimensional metal-organic framework nanosheets enable stable zinc anodes

Aqueous zinc-ion batteries (ZIBs) have been considered as safe and scalable energy storage solutions,but the dendrite and corrosion issues of Zn anodes have hindered their further application.Herein,we demonstrate that two-dimensional metalorganic framework (MOF) nanosheets can act as protective coatings to prevent dendrite formation and hydrogen evolution of Zn anodes.The morphology of MOFs was tuned from octahedral nanoparticles (UiO-67-3D) to nanosheets (UiO-67-2D),leading to significantly enhanced protective performance.UiO-67-2D nanosheets-coated Zn anodes displayed smaller polarization,longer cycling lifetime and lower H_(2) evolution than those of UiO-67-3D nanoparticles in symmetrical cells,which has been attributed to the higher concentration of surface Zr-OH/H_(2)O to induce uniform Zn deposition and one-dimensional (1D) channels perpendicular to the Zn surface to regulate Zn^(2+) diffusion.The assembled UiO-67-2D@Zn||Mn_(2)O_(3)/C full cell shows a high capacity of240 m Ah g^(-1)at 1 A g^(-1) and excellent cycling stability.

Laminar Composite Solid Electrolyte with Poly(Ethylene Oxide)-Threaded Metal-Organic Framework Nanosheets for High-Performance All-Solid-State Lithium Battery

Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.

Magnetic and electronic properties of two-dimensional metal-organic frameworks TM_(3)(C_(2)NH)_(12)

The ferromagnetism of two-dimensional(2D)materials has aroused great interest in recent years,which may play an important role in the next-generation magnetic devices.Herein,a series of 2D transition metal-organic framework materials(TM-NH MOF,TM=Sc-Zn)are designed,and their electronic and magnetic characters are systematically studied by means of first-principles calculations.Their structural stabilities are examined through binding energies and ab-initio molecular dynamics simulations.Their optimized lattice constants are correlated to the central TM atoms.These 2D TM-NH MOF nanosheets exhibit various electronic and magnetic performances owing to the effective charge transfer and interaction between TM atoms and graphene linkers.Interestingly,Ni-and Zn-NH MOFs are nonmagnetic semiconductors(SM)with band gaps of 0.41 eV and 0.61 eV,respectively.Co-and Cu-NH MOFs are bipolar magnetic semiconductors(BMS),while Fe-NH MOF monolayer is a half-semiconductor(HSM).Furthermore,the elastic strain could tune their magnetic behaviors and transformation,which ascribes to the charge redistribution of TM-3d states.This work predicts several new 2D magnetic MOF materials,which are promising for applications in spintronics and nanoelectronics.

Room-temperature ferrimagnetism and size-modulated electronic structures in two-dimensional cluster-based metal-organic frameworks

Cluster-assembled materials have attracted particular attention for their complex hierarchical structures and unique properties.However,the majority of cluster-based assemblies developed so far are either non-magnetic or only exhibit magnetic ordering with a relatively low Curie temperature,limiting their applications in spintronics.Thus,two-dimensional(2D)cluster-assembled materials with room-temperature magnetism remain highly desirable.For this purpose,based on first principles calculations,we design a series of thermodynamically stable 2D cluster-based metal-organic frameworks(MOFs)Fe_(n)-(pyz)(n=1-6)by utilizing Fenmetal clusters as nodes and nitrogen-containing pyrazine ligands as organic linkers.These 2D cluster-based MOFs exhibit robust ferrimagnetic ordering due to the strong d-p direct exchange interaction between d-electron spin of Fe_(n)(n=1-6)clusters and charge transfer-induced p-electron spin of pyrazine ligands.In particular,the ferrimagnetic Curie temperatures are well above room temperature(up to 836 K).Additionally,altering the size of Fe_(n)clusters in Fe_(n)-(pyz)(n=1-6)MOFs results in diverse functional spintronic properties,including bipolar magnetic semiconductors,half semiconductors and Dirac half metals.Moreover,these 2D assembled MOFs possess sizable magnetic anisotropy energies,up to 9.16 me V per formula.

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.

Two-dimensional metal-organic framework nanosheet composites:Preparations and applications

As emerging two-dimensional materials, metal-organic framework(MOF) nanosheet composites possess many unique physical and chemical properties, thus being expected to be widely applied in gas separation and adsorption, energy conversion and storage, heterogeneous catalysis, sensing as well as biomedicine. In this review, we first introduce the methods for integrating MOF nanosheets with other materials to prepare multifunctional composites. Next, the applications of MOF nanosheet composites in versatile fields are summarized and discussed. We hope this review will be instructive for researchers in the aspects of designs, preparations and applications of MOF nanosheet composites.

MOF-derived zinc manganese oxide nanosheets with valence-controllable composition for high-performance Li storage

Zinc manganese oxide(ZMO)system represents a notable family of mixed transition metal oxides(MTMOs)because of their superiority of the high theoretical capacity,adequacy of natural content,and low cost.However,the methods to match both the reliable synthesis and the designable construction of large-sized two-dimensional(2D)ZMO nanosheets are still considered as grand challenges.Herein,we have successfully realized the preparation of 2D ZMO nanosheets with large lateral sizes up to~20 mm by simple pyrolysis of 2D metal–organic framework(MOF)nanosheets precursor.The growth mechanism of 2D MOF is proposed to be based on the lamellar micelles formed by polyvinyl pyrrolidone(PVP).The obtained 2D and porous ZMO nanosheets exhibit high specific capacity as well as good rate capability.More importantly,the as-prepared ZMO electrode shows a remarkable capacity increment upon cycling(from 832 mAh g^(-1) at the 2nd cycle to 1418 mAh g^(-1) at the 700th cycle,at 1 A g^(-1)).Through simple adjustment of the calcination temperature,the valence state of Mn species in the yielding ZMO samples can be fine-tuned.Through systematic investigation towards these ZMOs containing different Mn species,the extra specific capacity is revealed to be chiefly on account of the arising of the valence state of Mn upon the cycling process.Moreover,it is disclosed that the higher-valent Mn the pristine ZMO contains,the more additional capacity it gains upon cycling.We believe that this work will inspire more detailed analysis on the relationship between the valence state of Mn and extra capacity.

Atomically dispersed Mn-N_(x) catalysts derived from Mn-hexamine coordination frameworks for oxygen reduction reaction

Metal-organic frameworks recently have been burgeoning and used as precursors to obtain various metal-nitrogen-carbon catalysts for oxygen reduction reaction(ORR).Although rarely studied,Mn-N-C is a promising catalyst for ORR due to its weak Fenton reaction activity and strong graphitization catalysis.Here,we developed a facile strategy for anchoring the atomically dispersed nitrogen-coordinated single Mn sites on carbon nanosheets(MnNCS)from an Mn-hexamine coordination framework.The atomically dispersed Mn-N_(4) sites were dispersed on ultrathin carbon nanosheets with a hierarchically porous structure.The optimized MnNCS displayed an excellent ORR performance in half-cells(0.89 V vs.reversible hydrogen electrode(RHE)in base and 0.76 V vs.RHE in acid in half-wave potential)and Zn-air batteries(233 mW cm^(−2)in peak power density),along with significantly enhanced stability.Density functional theory calculations further corroborated that the Mn-N_(4)-C(12)site has favorable adsorption of*OH as the rate-determining step.These findings demonstrate that the metal-hexamine coordination framework can be used as a model system for the rational design of highly active atomic metal catalysts for energy applications.

Cobalt-embedded few-layered carbon nanosheets toward enhanced hydrogen evolution:Rational design and insight into structure-performance correlation

Over the past decades, the energy and concomitant environment issues, such as energy shortage, air pollution and global warming, have been becoming increasingly striking world-wide challenges [1,2]. Such a dilemma in turn appeals to the development and employment of clean and renewable energy.

Facile synthesis of ultrathin metal-organic framework nanosheets for Lewis acid catalysis

Ultrathin metalorganic framework (MOF) nanosheets are attracting great interest in catalysis due to their unique and intriguing two-dime nsional (2D) features. Although many progresses have been achieved, it is still highly desirable to develop novel strategies for controllable synthesis of the well-defined ultrathin MOF nanosheets. Herein we report a polyvinylpyrrolidone (PVP)-assisted route to synthesize the ultrathin Ni-MOF nanosheets characteristic of 1.5 nm in thickness, in which PVP is reacted with 2-aminoterephthalic acid (H2BDC-NH2) via formation of C=N bon d, followed by coord inatio n with Ni2+ io ns to form the ultrathi n MOF n anosheets. Impressively, when used in the Kno eve nagel condensation reactions of propane dinitrile with different aldehydes, ultrathin Ni-MOF nanosheets display the significantly enhanced catalytic activity and good stability in respect with the bulk Ni-MOF, mainly owing to the exposed active sites as well as facile mass transfer and diffusion of substrates and products.

In situ decomposition of metal-organic frameworks into ultrathin nanosheets for the oxygen evolution reaction

The oxygen evolution reaction （OER） is a pivotal process for water-splitting and many other energy technologies involving oxygen electrodes. Herein, a new synthesis strategy is proposed to prepare OER catalysts based on a simple yet flexible in situ decomposition of Co-based acetate hydroxide metal-organic frameworks （MOFs）. This process allows straightforward fabrication of various 2D hydroxide ultrathin nanosheets （UNSs） with excellent component controllability. The as-obtained Co-based hydroxide UNSs demonstrate superior catalytic activity for the OER due to the exposure of numerous active sites. In particular, the CoNi hydroxide UNSs exhibit low overpotentials （r/） of 324 and 372 mV at current densities of 10 and 100 mA-cm-2, respectively; a large turnover frequency （TOF） of 0.16 s-~ at T/= 380 mV; and a small Tafel slope of 33 mV.dec-~ in an alkaline environment. Importantly, these values are superior to those of the state-of-the- art IrO2 commercial electrocatalyst. This facile strategy enables the exploration of more efficient and economic OER electrocatalysts with various constituents and opens a promising avenue for large-scale fabrication of functional nanocatalysts for use in clean ener~：v technologies.

Metal-organic framework nanosheets: a class of glamorous low-dimensional materials with distinct structural and chemical natures

Metal-organic framework nanosheets have gained great attention because of the diversified structures,tunable chemical functionalities,large surface area and ultrathin thickness.In this review,we introduce the recent progress in the favorable applications for catalysis,sensing,energy storage and gas separation,which has significantly addressed the advantages of the nanosheets.A summary of nanosheet fabrication approaches is put forward to establish a comprehension on the origin of the MOF nanosheets.And at last but not the least,we present the concerns on the challenges and opportunities of these materials from our perspectives.

Two-dimensional d-πconjugated metal-organic framework based on hexahydroxytrinaphthylene

The development of new two-dimensional(2D)d-πconjugated metal-organic frameworks(MOFs)holds great promise for the construction of a new generation of porous and semiconductive materials.This paper describes the synthesis,structural characterization,and electronic properties of a new d-πconjugated 2D MOF based on the use of a new ligand 2,3,8,9,14,15-hexahydroxytrinaphthylene.The reticular self-assembly of this largeπ-conjugated organic building block with Cu(II)ions in a mixed solvent system of 1,3-dimethyl-2-imidazolidinone(DMI)and H2 O with the addition of ammonia water or ethylenediamine leads to a highly crystalline MOF Cu3(HHTN)2,which possesses pore aperture of 2.5 nm.Cu3(HHTN)2 MOF shows moderate electrical conductivity of 9.01×10^(-8)S·cm^(-1)at 385 K and temperature-dependent band gap ranging from 0.75 to 1.65 eV.After chemical oxidation by l2,the conductivity of Cu3(HHTN)2 can be increased by 360 times.This access to HHTN based MOF adds an important member to previously reported MOF systems with hexagonal lattice,paving the way towards systematic studies of structure-property relationships of semiconductive MOFs.

Two-dimensional copper metal-organic frameworks as antibacterial agents for biofilm treatment

Metal-organic frameworks(MOFs)composed of functional metal ions/clusters and suitable bridging ligands are highly designable,which have shown excellent catalytic activity as nanozymes and are promising for antibacterial therapy.Herein,twodimensional(2D)copper MOF nanosheets(Cu-MOF NSs)as effective antibacterial agents were prepared through a simple onestep method.The 2D Cu-MOF NSs displayed a peroxidase-like activity toward H_(2)O_(2)decomposition into highly cytotoxic hydroxyl radicals(·OH).Notably,the 2D morphology of Cu-MOF NSs provides a high density of Cu^(2+)/Cu^(+)surface active sites,which could efficiently oxidize the proteins and lipids on the bacterial surface and induce the death of bacteria.It is found that the as-prepared 2D Cu-MOF NSs exhibited antibacterial properties against Staphylococcus aureus(S.aureus)and could efficiently eradicate the biofilm of S.aureus.Up to 99.9%bacteria were killed at a Cu-MOF concentration of 4μg/m L.This study opens a new avenue for the design of MOF-based antibacterial agents to combat pathogenic bacterial infections.

Two-dimensional Metal-Organic Frameworks and Derivatives for Electrocatalysis

The most important topics in the world todav are environmental and resource issues.Ihe development of green and clean enerev is still one of the ereat challenges of social sustainable development.Two-dimensiona(2D)metal-organic frameworks(MOFs)and derivatives have exceptional potential as high-efhiciency electrocatalvsts for clean enerey technologies.This review summarizes various synthesis strategies and applications of 2D MOFs and derivatives in electrocatalysis.Firstly,we will outline the advantages and uniqueness of 2D MOFs and derivatives.as well as their applicable areas.Secondly,the svnthetic strategies of 2D MOFs and derivatives are briefly classified Fach category is summarized and we list classic representative fabrication methods,including specific fabrication methods and mechanisms,corresponding structural characteristics.and insights into the advantages and limitations of the svnthesis method.Thirdly,we separately classify and summarize the application of 2D MOFs and derivatives in electrocatalysis,including electrocatalytic water splitting,oxygen reduction reaction(ORR),CO reduction reaction(CO.RR),and other electrocatalvtic applications.Finally.the development prospects and existing challenges to 2D MOEs and derivatives are discussed.

Recent progress of two-dimensional metal-organic-frameworks:From synthesis to electrocatalytic oxygen evolution

High-performance electrocatalysts for oxygen evolution reaction(OER)are crucial for water splitting and metal-air batteries.Twodimensional(2D)metal-organic framework(MOF)has become a new class of efficient OER electrocatalysts due to the rich coordination unsaturated metal nodes,large specific surface area,and adjustable structures.In addition,because inheriting the original microstructure of MOFs and having stronger chemical and mechanical stability,metal/alloy/oxide,metal sulfide/selenide/phosphide,and other compounds derived from 2D MOFs have also shown their unique OER catalytic ability.Here,we briefly introduced the existing reaction mechanism and evaluation parameters of catalyst performance of OER,introduced the synthesis methods and corresponding characterization techniques of 2D MOFs and their derivatives,and summarized the latest progress of 2D MOFs and their derivatives as OER catalysts.Finally,we put forward some views and suggestions on the existing problems hindering the development of 2D MOFs as OER for advancing the field.

Two-dimensional Metal-Organic Frameworks as Electrocatalysts for Oxygen Evolution Reaction

Oxygen evolution reaction(OER)plays an important role in many electrochemical systems.However,its sluggish kinetics severely limits the development of next-generation energy technologies.Recently,two-dimensional(2D)metal-organic frameworks(MOFs)have attracted much attention as a class of promising electrocatalysts.Their diverse components and tunable structures provide a new platform to design and explore ideal eleclrocatalysts.The ultrathin characteristics including high specific surface area,abundant exposed metal sites and fast electronic transfer further promote the electrocatalytic performance of 2D MOFs.Therefore,many attempts have been made in svntliesizing 2D MOF-based electrocatalysts in recent years.This review focuses on the strategies to fabricate 2D MOFs with high electrocatalytic performances for OER.The discussion on challenge and development of their electrocatalytic application is also presented.

Two-Dimensional Metal-Organic Frameworks with Unique Oriented Layers for Oxygen Reduction Reaction:Tailoring the Activity through Exposed Crystal Facets

As one of the most important families of porous materials,metal–organic frameworks(MOFs)have well-defined atomic structures.This provides ideal models for investigating and understanding the relationships between structures and catalytic activities at the molecular level.However,the active sites on the edges of two-dimensional(2D)MOFs have rarely been studied,as they are less exposed to the surfaces.Here,for the first time,we synthesized and observed that the 2D layers could align perpendicular to the surface of a 2D zeolitic imidazolate framework L(ZIF-L)with a leaf-like morphology.Owing to this unique orientation,the active sites on the edges of the 2D crystal structure could mostly be exposed to the surfaces.Interestingly,when another layer of ZIF-L-Co was grown heteroepitaxially onto ZIF-L-Zn(ZIF-L-Zn@ZIF-L-Co),the two layers shared a common b axis but rotated by 90°in the ac plane.This demonstrated that we could control exposed facets of the 2D MOFs.The ZIF-L-Co with more exposed edge active sites exhibited high electrocatalytic activity for oxygen reduction reaction.This work provides a new concept of designing unique oriented layers in 2D MOFs to expose more edge-active sites for efficient electrocatalysis.

Two-dimensional cobalt metal-organic frameworks for efficient C_3H_6/CH_4 and C_3H_8/CH_4 hydrocarbon separation

A Co-based two-dimensional（2 D） microporous metal-organic frameworks, [Co2（TMTA）（DMF）2（H2O）2]·NO3-·DMF（UPC-32） has been synthesized based on 4,4’,4’’-（2,4,6-trimethylbenzene-1,3,5-triyl）tribenzoic acid（H3TMTA）. UPC-32 features a 2 D microporous framework exhibits high adsorption of H2（118.2 cm3/g, 1.05 wt%, at 77 K）, and adsorption heat（Qst） of CO2（34–46 k J/mol）. UPC-32 with narrow distance between layers（3.8 ？） exhibits high selectivity of C3H6/CH4（31.46） and C3H8/CH4（28.04） at298 K and 1 bar. It is the first 2 D Co-MOF that showed selective separation of C3 hydrocarbon from CH4.

Thermal expansion-quench of nickel metal-organic framework into nanosheets for efficient visible light CO_(2) reduction

Metal-organic framework nanosheets (MOF NNs) offer potential opportunities for many applications,but an efficient strategy for the scalable preparation of few-layered two-dimensional (2D) MOF NNs are still a major challenge.Herein,we present an efficient top-down method for the synthesis of the Ni-BDC(Ni_(2)(OH)_(2)(1,4-BDC);1,4-BDC=1,4-benzenedicarboxylate) nanosheets utilizing a novel thermal expansionquench method of the flowerlike bulky MOFs in liquid N2.The obtained Ni-BDC nanosheets exhibit significantly enhanced photocatalytic performance of reductive CO_(2)deoxygenation (7.0μmol h^(-1)mg^(-1)) under visible light illumination compared with the bulky MOFs,due to much higher surface area for CO_(2)adsorption,more abundant active sites exposed and stronger electron transport ability of the nanosheets.More importantly,this synthetic strategy can be extended to fabricate other MOF nanosheets which also exhibit significantly improved performance for deoxygenative CO_(2)reduction compared to their bulky counterparts.This work may provide a guideline for preparing other 2D layered photocatalysts materials to realize energy conversion applications.