Advances of Electrochemical and Electrochemiluminescent Sensors Based on Covalent Organic Frameworks

Covalent organic frameworks(COFs),a rapidly developing category of crystalline conjugated organic polymers,possess highly ordered structures,large specific surface areas,stable chemical properties,and tunable pore microenvironments.Since the first report of boroxine/boronate ester-linked COFs in 2005,COFs have rapidly gained popularity,showing important application prospects in various fields,such as sensing,catalysis,separation,and energy storage.Among them,COFs-based electrochemical(EC)sensors with upgraded analytical performance are arousing extensive interest.In this review,therefore,we summarize the basic properties and the general synthesis methods of COFs used in the field of electroanalytical chemistry,with special emphasis on their usages in the fabrication of chemical sensors,ions sensors,immunosensors,and aptasensors.Notably,the emerged COFs in the electrochemiluminescence(ECL)realm are thoroughly covered along with their preliminary applications.Additionally,final conclusions on state-of-the-art COFs are provided in terms of EC and ECL sensors,as well as challenges and prospects for extending and improving the research and applications of COFs in electroanalytical chemistry.

Boosting photocatalytic hydrogen evolution enabled by SiO_(2)-supporting chiral covalent organic frameworks with parallel stacking sequence

Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31% at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.

Dipole polarization modulating of vinylene-linked covalent organic frameworks for efficient photocatalytic hydrogen evolution

Photocatalytic hydrogen(H_(2))evolution using covalent organic frameworks(COFs)is an attractive and promising avenue for exploration,but one of its big challenges is low photo-induced charge separation.In this study,we present a straightforward and facile dipole polarization engineering strategy to enhance charge separation efficiency,achieved through atomic modulation(O,S,and Se)of the COF monomer.Our findings demonstrate that incorporating atoms with varying electronegativities into the COF matrix significantly influences the local dipole moment,thereby affecting charge separation efficiency and photostability,which in turn affects the rates of photocatalytic H_(2) evolution.As a result,the newly developed TMT-BO-COF,which contains highly electronegative O atoms,exhibits the lowest exciton binding energy,the highest efficiency in charge separation and transportation,and the longest lifetime of the active charges.This leads to an impressive average H_(2) production rate of 23.7 mmol g^(−1) h^(−1),which is 2.5 and 24.5 times higher than that of TMT-BS-COF(containing S atoms)and TMT-BSe-COF(containing Se atoms),respectively.A novel photocatalytic hydrogen evolution mechanism based on proton-coupled electron transfer on N in the structure of triazine rings in vinylene-linked COFs is proposed by theoretical calculations.Our findings provide new insights into the design of highly photoactive organic framework materials for H_(2) evolution and beyond.

Superior Anodic Lithium Storage in Core–Shell Heterostructures Composed of Carbon Nanotubes and Schiff-Base Covalent Organic Frameworks

Covalent organic frameworks(COFs)after undergoing the superlithiation process promise high-capacity anodes while suffering from sluggish reaction kinetics and low electrochemical utilization of redox-active sites.Herein,integrating carbon nanotubes(CNTs)with imine-linked covalent organic frameworks(COFs)was rationally executed by in-situ Schiff-base condensation between 1,1′-biphenyl]-3,3′,5,5′-tetracarbaldehyde and 1,4-diaminobenzene in the presence of CNTs to produce core–shell heterostructured composites(CNT@COF).Accordingly,the redox-active shell of COF nanoparticles around one-dimensional conductive CNTs synergistically creates robust three-dimensional hybrid architectures with high specific surface area,thus promoting electron transport and affording abundant active functional groups accessible for electrochemical utilization throughout the whole electrode.Remarkably,upon the full activation with a superlithiation process,the as-fabricated CNT@COF anode achieves a specific capacity of 2324 mAh g^(−1),which is the highest specific capacity among organic electrode materials reported so far.Meanwhile,the superior rate capability and excellent cycling stability are also obtained.The redox reaction mechanisms for the COF moiety were further revealed by Fourier-transform infrared spectroscopy in conjunction with X-ray photoelectron spectroscopy,involving the reversible redox reactions between lithium ions and C=N groups and gradual electrochemical activation of the unsaturated C=C bonds within COFs.

Superposition of dual electric fields in covalent organic frameworks for efficient photocatalytic hydrogen evolution

Covalent organic frameworks(COFs)are promising materials for converting solar energy into green hydrogen.However,limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen evolution reaction(HER).In this study,the intrinsically tunable internal bond electric field(IBEF)at the imine bonds of COFs was manipulated to cooperate with the internal molecular electric field(IMEF)induced by the donor-acceptor(D-A)structure for an efficient HER.The aligned orientation of IBEF and IMEF resulted in a remarkable H_(2) evolution rate of 57.3 mmol·g^(-1)·h^(-1)on TNCA,which was approximately 520 times higher than that of TCNA(0.11 mmol·g^(-1)·h^(-1))with the opposing electric field orientation.The superposition of the dual electric fields enables the IBEF to function as an accelerating field for electron transfer,kinetically facilitat-ing the migration of photogenerated electrons from D to A.Furthermore,theoretical calculations indicate that the inhomogeneous charge distribution at the C and N atoms in TNCA not only pro-vides a strong driving force for carrier transfer but also effectively hinders the return of free elec-trons to the valence band,improving the utilization of photoelectrons.This strategy of fabricating dual electric fields in COFs offers a novel approach to designing photocatalysts for clean energy synthesis.

All‑Covalent Organic Framework Nanofilms Assembled Lithium‑Ion Capacitor to Solve the Imbalanced Charge Storage Kinetics

Free-standing covalent organic framework(COFs)nanofilms exhibit a remarkable ability to rapidly intercalate/de-intercalate Li^(+) in lithium-ion batteries,while simultaneously exposing affluent active sites in supercapacitors.The development of these nanofilms offers a promising solution to address the persistent challenge of imbalanced charge storage kinetics between battery-type anode and capacitor-type cathode in lithium-ion capacitors(LICs).Herein,for the first time,custom-made COFBTMB-TP and COFTAPB-BPY nanofilms are synthesized as the anode and cathode,respectively,for an all-COF nanofilm-structured LIC.The COFBTMB-TP nanofilm with strong electronegative–CF3 groups enables tuning the partial electron cloud density for Li^(+) migration to ensure the rapid anode kinetic process.The thickness-regulated cathodic COFTAPB-BPY nanofilm can fit the anodic COF nanofilm in the capacity.Due to the aligned 1D channel,2D aromatic skeleton and accessible active sites of COF nanofilms,the whole COFTAPB-BPY//COFBTMB-TP LIC demonstrates a high energy density of 318 mWh cm^(−3) at a high-power density of 6 W cm^(−3),excellent rate capability,good cycle stability with the capacity retention rate of 77%after 5000-cycle.The COFTAPB-BPY//COFBTMB-TP LIC represents a new benchmark for currently reported film-type LICs and even film-type supercapacitors.After being comprehensively explored via ex situ XPS,7Li solid-state NMR analyses,and DFT calculation,it is found that the COFBTMB-TP nanofilm facilitates the reversible conversion of semi-ionic to ionic C–F bonds during lithium storage.COFBTMB-TP exhibits a strong interaction with Li^(+) due to the C–F,C=O,and C–N bonds,facilitating Li^(+) desolation and absorption from the electrolyte.This work addresses the challenge of imbalanced charge storage kinetics and capacity between the anode and cathode and also pave the way for future miniaturized and wearable LIC devices.

Challenges and Opportunities in Preserving Key Structural Features of 3D-Printed Metal/Covalent Organic Framework

Metal-organic framework(MOF)and covalent organic framework(COF)are a huge group of advanced porous materials exhibiting attractive and tunable microstructural features,such as large surface area,tunable pore size,and functional surfaces,which have significant values in various application areas.The emerging 3D printing technology further provides MOF and COFs(M/COFs)with higher designability of their macrostructure and demonstrates large achievements in their performance by shaping them into advanced 3D monoliths.However,the currently available 3D printing M/COFs strategy faces a major challenge of severe destruction of M/COFs’microstructural features,both during and after 3D printing.It is envisioned that preserving the microstructure of M/COFs in the 3D-printed monolith will bring a great improvement to the related applications.In this overview,the 3D-printed M/COFs are categorized into M/COF-mixed monoliths and M/COF-covered monoliths.Their differences in the properties,applications,and current research states are discussed.The up-to-date advancements in paste/scaffold composition and printing/covering methods to preserve the superior M/COF microstructure during 3D printing are further discussed for the two types of 3D-printed M/COF.Throughout the analysis of the current states of 3D-printed M/COFs,the expected future research direction to achieve a highly preserved microstructure in the 3D monolith is proposed.

Covalent Organic Framework with 3D Ordered Channel and Multi-Functional Groups Endows Zn Anode with Superior Stability

Achieving a highly robust zinc(Zn)metal anode is extremely important for improving the performance of aqueous Zn-ion batteries(AZIBs)for advancing“carbon neutrality”society,which is hampered by the uncontrollable growth of Zn dendrite and severe side reactions including hydrogen evolution reaction,corrosion,and passivation,etc.Herein,an interlayer containing fluorinated zincophilic covalent organic framework with sulfonic acid groups(COF-S-F)is developed on Zn metal(Zn@COF-S-F)as the artificial solid electrolyte interface(SEI).Sulfonic acid group(-SO_(3)H)in COF-S-F can effectively ameliorate the desolvation process of hydrated Zn ions,and the three-dimensional channel with fluoride group(-F)can provide interconnected channels for the favorable transport of Zn ions with ion-confinement effects,endowing Zn@COF-S-F with dendrite-free morphology and suppressed side reactions.Consequently,Zn@COF-S-F symmetric cell can stably cycle for 1,000 h with low average hysteresis voltage(50.5 m V)at the current density of 1.5 m A cm^(-2).Zn@COF-S-F|Mn O_(2)cell delivers the discharge specific capacity of 206.8 m Ah g^(-1)at the current density of 1.2 A g^(-1)after 800 cycles with high-capacity retention(87.9%).Enlightening,building artificial SEI on metallic Zn surface with targeted design has been proved as the effective strategy to foster the practical application of high-performance AZIBs.

A Solvent-Free Covalent Organic Framework Single-Ion Conductor Based on Ion-Dipole Interaction for All-Solid-State Lithium Organic Batteries

Single-ion conductors based on covalent organic frameworks(COFs)have garnered attention as a potential alternative to currently prevalent inorganic ion conductors owing to their structural uniqueness and chemical versatility.However,the sluggish Li+conduction has hindered their practical applications.Here,we present a class of solvent-free COF single-ion conductors(Li-COF@P)based on weak ion-dipole interaction as opposed to traditional strong ion-ion interaction.The ion(Li+from the COF)-dipole(oxygen from poly(ethylene glycol)diacrylate embedded in the COF pores)interaction in the Li-COF@P promotes ion dissociation and Li+migration via directional ionic channels.Driven by this single-ion transport behavior,the Li-COF@P enables reversible Li plating/stripping on Li-metal electrodes and stable cycling performance(88.3%after 2000 cycles)in organic batteries(Li metal anode||5,5’-dimethyl-2,2’-bis-p-benzoquinone(Me2BBQ)cathode)under ambient operating conditions,highlighting the electrochemical viability of the Li-COF@P for all-solid-state organic batteries.

Imide-pillared covalent organic framework protective films as stable zinc ion-conducting interphases for dendrite-free Zn metal anodes

The notorious growth of zinc dendrite and the water-induced corrosion of zinc metal anodes(ZMAs)restrict the practical development of aqueous zinc ion batteries(AZIBs).In this work,a zinc metallized,imide-pillared covalent organic framework(ZPC)protective film has been engineered as a stable Zn^(2+)ion-conducting interphase to modulate interfacial kinetics and suppress side reactions for ZMAs.Compared to bare Zn,ZPC@Zn exhibits a higher Zn^(2+)ionic conductivity,a larger Zn^(2+)transference number,a lower electronic conductivity,a smaller desolvation activation energy and correspondingly a significant suppression of corrosion,hydrogen evolution and Zn dendrites.Impressively,the ZPC@Zn||ZPC@Zn symmetric cell obtains a cycling lifespan over 3000 h under 5 mA cm^(-2)for 1 mA h cm^(-2).The ZPC@Zn||NH_(4)V_(4)O_(10)coin-type full battery delivers a specific capacity of 195.8 mA h g^(-1)with a retention rate of78.5%at 2 A g^(-1)after 1100 cycles,and the ZPC@Zn||NH_(4)V_(4)O_(10) pouch full cell shows a retention of70.1%in reversible capacity at 3 A g^(-1)after 1100 cycles.The present incorporation of imide-linked covalent organic frameworks in the surface modification of ZMAs will offer fresh perspectives in the search for ideal protective films for the practicality of AZIBs.

A novel fluorescence sensor for milk clotting enzyme chymosin using peptide as substrate and covalent organic framework nanosheet as fluorescence quencher

Chymosin is one of the critical enzymes in cheese making.Herein,we proposed a novel fluorometric assay for chymosin determination.Firstly,covalent organic frameworks(COF)were synthesized and exfoliated to 2-dimensional COF nanosheets(COF NS)by ultrasound treatment.Gold nanoparticles(Au NPs)were loaded with COF NS to prepare AuNPs/COF NS(Au@COF NS).Secondly,rhodamine B(RhB)modified substrate peptide(Pep)for chymosin was linked with Au@COF NS to construct a Pep-Au@COF NS nanocomposite.For the sensing principle,fluorescence of RhB was quenched by Au@COF NS and the fluorescence intensity was weak due to the fluorescence resonance energy transfer between COF NS and RhB of Pep.However,in the presence of chymosin,the RhB was released by specific cleavage of the substrate peptide by chymosin and resulted in the recovery of fluorescence.The increased fluorescence intensity was proportional to the increase of chymosin concentration and thus a“turn on”fluorescent sensor for chymosin was constructed.The sensor showed a linear range in the concentration of 0.05-60.00μg/mL for the detection of chymosin with a detection limit of 20 ng/mL.The sensor was used to quantify chymosin in rennet product with good selectivity,which has the potential applications in cheese manufacturing.

One stone two birds:electrochemical and colorimetric dual-mode biosensor based on copper peroxide/covalent organic framework nanocomposite for ultrasensentive norovirus detection

Norovirus(NoV)is regarded as one of the most common causes of foodborne diarrhea in the world.It is urgent to identify the pathogenic microorganism of the diarrhea in short time.In this work,we developed an electrochemical and colorimetric dual-mode detection for NoV based on the excellent dual catalytic properties of copper peroxide/COF-NH_(2)nanocomposite(CuO_(2)@COF-NH_(2)).For the colorimetric detection,NoV can be directly detected by the naked eye based on CuO_(2)@COF-NH_(2)as a laccase-like nonazyme using“peptide-NoV-antibody”recognition mode.The colorimetric assay displayed a wide and quality linear detection range from 1 copy/mL to 5000 copies/mL of NoV with a low limit of detection(LOD)of 0.125 copy/mL.For the electrochemical detection of NoV,CuO_(2)@COF-NH_(2)showed an oxidation peak of copper ion from Cu^(+)to Cu^(2+)using“peptide-NoV-antibody”recognition mode.The electrochemical assay showed a linear detection range was 1-5000 copies/mL with a LOD of 0.152 copy/mL.It's worthy to note that this assay does not need other electrical signal molecule,which provide the stable and sensitive electrochemial detection for NoV.The electrochemical and colorimetric dual-mode detection was used to detect NoV in foods and faceal samples,which has the potential for improving food safety and diagnosing of NoV-infected diarrhea.

Nitrogen ligands in two-dimensional covalent organic frameworks for metal catalysis

We introduced bipyridine ligands into a series of two‐dimensional （2D） covalent organic frame‐works （COFs） using 2,2’‐bipyridine‐5,5’‐dicarbaldehyde （2,2’‐BPyDCA） as a component in the mixed building blocks. The framework of the COFs was formed by the linkage of imine groups. The ligand content in the COFs was synthetically tuned by the content of 2,2’‐BPyDCA, and thus the amount of metal, palladium（II） acetate, bonded to the nitrogen ligands could be manipulated. Both the bipyri‐dine ligands and imine groups can coordinate with Pd（II） ions, but the loading position can be var‐ied, with one ligand favoring binding in the space between adjacent COFs’ layers and the other lig‐and favoring binding within the pores of the COFs. The Pd（II）‐loaded COFs exhibited good catalytic activity for the Heck reaction.

Water-selective hybrid membranes with improved interfacial compatibility from mussel-inspired dopamine-modified alginate and covalent organic frameworks

Hybrid membranes combining the merits of both polymer matrices and fillers have drawn extensive attention. The rational design of polymer–filler interface in hybrid membranes is vitally important for reducing the occurrence of void defects. Herein, imine-type covalent organic frameworks(COFs) were selected as the fillers due to their totally organic nature and multi-functionalities. Mussel-inspired dopamine-modified sodium alginate(Alg DA) was synthesized as the polymer matrix. The dopamine modification significantly improves the Alg DA–COF compatibility,which enhances the COF content up to 50 wt% in the hybrid membranes. The improved interfacial compatibility enhances the membrane separation selectivity. Accordingly, when utilized for dehydration of ethanol/water mixed solution(water concentration of 10 wt%), the hybrid membrane reveals high water concentration of ~98.7 wt% in permeate, and stable permeation flux larger than 1500 g·m-2·h-1. This work might afford useful insights for fabricating hybrid membranes with high separation selectivity by optimizing the polymer–filler interface.

Covalent organic frameworks as heterogeneous catalysts

Covalent organic frameworks （COFs）, established as an emerging class of crystalline porous polymers with high surface area, structural diversity, and esignability, attract much interest and exhibit potential applications in catalysis. In this review, we summarize the use of COFs as a versatile platform to develop heterogeneous catalysts for a variety of chemical reactions. Catalytic COFs are categorized in accordance with the types of active sites, involving single functional active sites, bifunctional active sites, and metal nanoparticles （NPs） embedded in pores. Special emphasis is placed on the deliberate or incidental synthesis strategies, the stability, the heterogeneity, and the shape/size selectivity for COF catalysis. Moreover, a description of the application of COFs as photocatalysts and electrocatalysts is presented. Finally, the prospects of COFs in catalysis and remaining issues in this field are indicated.

Asymmetric photocatalysis over robust covalent organic frameworks with tetrahydroquinoline linkage

The asymmetric photocatalytic organic synthesis(APOS)process is a sustainable and environmentally benign method for the production of optically active chemicals with sunlight as an energy source.However,it still lacks efficient semiconductors with tunable band structures and has a low recycling stability.Herein,we report the synthesis of tetrahydroquinoline-linked covalent organic frameworks(QH-COFs)with irreversible tetrahydroquinoline linkage as efficient semiconductors for the visible-light-driven asymmetricα-alkylation of aldehydes by merging with a chiral secondary amine.Up to 94%ee was obtained over QH-COFs,and the activity of QH-COFs was significantly higher than those of inorganic semiconductors(e.g.,Ti O2,Bi VO4,and WO3)under similar conditions,which is mainly attributed to their narrow band gap and suitable band edge.As far as we know,QH-COFs are the most active semiconductors for asymmetricα-alkylation of aldehydes ever reported.The QH-COFs were prepared via a one-pot Povarov cascade imine formation and cycloaddition reaction using Sc(OTf)3/Yb(OTf)3 as Lewis acid catalysts.Attributed to the tetrahydroquinoline linkage,QH-COFs showed extremely high recycling stability,which made practicals application possible.This work not only opens up a new avenue for asymmetric photocatalysis but also provides an efficient and general method for the construction of robust COFs.

Metal-Free 2D/2D van der Waals Heterojunction Based on Covalent Organic Frameworks for Highly Efficient Solar Energy Catalysis

Covalent organic frameworks(COFs)have emerged as a kind of rising star materials in photocatalysis.However,their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination rate.Herein,a novel metal-free 2D/2D van der Waals heterojunction,composed of a two-dimensional(2D)COF with ketoenamine linkage(TpPa-1-COF)and 2D defective hexagonal boron nitride(h-BN),is successfully constructed through in situ solvothermal method.Benefitting from the presence of VDW heterojunction,larger contact area and intimate electronic coupling can be formed between the interface of TpPa-1-COF and defective h-BN,which make contributions to promoting charge car-riers separation.The introduced defects can also endow the h-BN with porous structure,thus providing more reactive sites.Moreover,the TpPa-1-COF will undergo a structural transformation after being integrated with defective h-BN,which can enlarge the gap between the conduction band position of the h-BN and TpPa-1-COF,and suppress electron backflow,corroborated by experimental and density functional theory calculations results.Accordingly,the resulting porous h-BN/TpPa-1-COF metal-free VDW heterojunction displays out-standing solar energy catalytic activity for water splitting without co-catalysts,and the H_(2) evolution rate can reach up to 3.15 mmol g^(−1) h^(−1),which is about 67 times greater than that of pristine TpPa-1-COF,also surpassing that of state-of-the-art metal-free-based photocatalysts reported to date.In particular,it is the first work for constructing COFs-based heterojunctions with the help of h-BN,which may provide new avenue for designing highly efficient metal-free-based photocatalysts for H_(2) evolution.

Covalent organic frameworks-incorporated thin film composite membranes prepared by interfacial polymerization for efficient CO_(2) separation

Thin film composite(TFC)membranes with nanofillers additives for CO_(2)separation show promising applications in energy and environment-related fields.However,the poor compatibility between nanofillers and polymers in TFC membranes is the main problem.In this work,covalent organic frameworks(COFs,TpPa-1)with rich ANHA groups were incorporated into polyamide(PA)segment via in situ interfacial polymerization to prepare defect-free TFC membranes for CO_(2)/N_(2)separation.The formed covalent bonds between TpPa-1 and PA strengthen the interaction between nanofillers and polymers,thereby enhancing compatibility.Besides,the incorporated COFs disturb the rigid structure of the PA layer,and provide fast CO_(2)transfer channels.The incorporated COFs also increase the content of effective carriers,which enhances the CO_(2)facilitated transport.Consequently,in CO_(2)/N_(2)mixed gas separation test,the optimal TFC(TpPa_(0.025)-PIP-TMC/m PSf)membrane exhibits high CO_(2)permeance of 854 GPU and high CO_(2)/N_(2)selectivity of 148 at 0.15 MPa,CO_(2)permeance of 456 GPU(gas permeation unit)and CO_(2)/N_(2)selectivity of 92 at 0.5 MPa.In addition,the Tp Pa_(0.025)-PIP-TMC/m PSf membrane also achieves high permselectivty in CO_(2)/CH_(4)mixed gas separation test.Finally,the optimal TFC membrane showes good stability in the simulated flue gas test,revealing the application potential for CO_(2)capture from flue gas.

Recent Progress in Nanoscale Covalent Organic Frameworks for Cancer Diagnosis and Therapy

Covalent organic frameworks(COFs)as a type of porous and crystalline covalent organic polymer are built up from covalently linked and periodically arranged organic molecules.Their precise assembly,welldefined coordination network,and tunable porosity endow COFs with diverse characteristics such as low density,high crystallinity,porous structure,and large specific-surface area,as well as versatile functions and active sites that can be tuned at molecular and atomic level.These unique properties make them excellent candidate materials for biomedical applications,such as drug delivery,diagnostic imaging,and disease therapy.To realize these functions,the components,dimensions,and guest molecule loading into COFs have a great influence on their performance in various applications.In this review,we first introduce the influence of dimensions,building blocks,and synthetic conditions on the chemical stability,pore structure,and chemical interaction with guest molecules of COFs.Next,the applications of COFs in cancer diagnosis and therapy are summarized.Finally,some challenges for COFs in cancer therapy are noted and the problems to be solved in the future are proposed.

Structural survey of metal-covalent organic frameworks and covalent metal-organic frameworks

This review offers an overview of the latest developments in metal-covalent organic framework(MCOF)and covalent metal-organic framework(CMOF)materials,whose construction entails a combination of reversible coordination and covalent bonding adapted from metal-organic frameworks(MOFs)and covalent organic frameworks(COFs),respectively.With an emphasis on the MCOF and CMOF structures,this review surveys their building blocks and topologies.Specifically,the frameworks are classified based on the dimensions of their components(building blocks),namely,discrete building blocks and one-dimensional infinite building blocks.For the first category,the materials are further divided into collections of two-and three-dimensional networks based on their topologies.For the second category,the recently emerging MCOFs with woven structures are covered.Finally,the state-of-the-art in MCOF and CMOF chemistry has been laid out for promising avenues in future developments.