Covalent triazine-based frameworks（CTFs） are important microporous materials with a wide range of applications.Here,we demonstrate an environmentally benign and economic synthetic pathway to CTFs.The monomers used f...Covalent triazine-based frameworks（CTFs） are important microporous materials with a wide range of applications.Here,we demonstrate an environmentally benign and economic synthetic pathway to CTFs.The monomers used for CTFs,aromatic nitriles,were obtained by cyanation using nontoxic potassium hexacyanoferrate（Ⅱ） in place of commonly used toxic cyanides.Then,the CTFs were synthesized by trimerization of the corresponding cyano monomers in molten zinc chloride.A series of CTFs was synthesized,and the highest Brunauer-Emmett-Teller surface area measured in this series was 2404 m^2/g.Among the synthesized CTFs,CTF_（DCP） exhibited excellent CO_2 adsorption properties,with a CO_2 uptake of 225 mg/g at 0℃.展开更多
Single-atom catalysts(SACs)have emerged as an advanced frontier in heterogeneous catalysis due to their potential to maximize the atomic efficiency.Herein,covalent triazine-based frameworks(CTFs)confining cobalt singl...Single-atom catalysts(SACs)have emerged as an advanced frontier in heterogeneous catalysis due to their potential to maximize the atomic efficiency.Herein,covalent triazine-based frameworks(CTFs)confining cobalt single atoms(Co-SA/CTF)photocatalysts have been synthesized and used for efficient CO_(2) reduction and hydrogen production under visible light irradiation.The resulted Co-SA/CTF demonstrate excellent photocatalytic activity,with the CO and H2 evolution rates reaching 1665.74μmol g^(−1) h^(−1) and 1293.18μmol g^(−1) h^(−1),respectively,far surpassing those of Co nanoparticles anchored CTF and pure CTF.A variety of instrumental analyses collectively indicated that Co single atoms sites served as the reaction center for activating the adsorbed CO_(2) molecules,which significantly improved the CO_(2) reduction performance.Additionally,the introduction of Co single atoms could accelerate the separation/transfer of photogenerated charge carriers,thus boosting the photocatalytic performance.This study envisions a novel strategy for designing efficient photocatalysts for energy conversion and showcases the application of CTFs as attractive support for confining metal single atoms.展开更多
In this work, a 2D covalent triazine-based framework was prepared by using 1,3-dicyanobenzo[c]thiophene（DCBT） as monomer to effectively capture CO. The resulting CTF-DCBT was characterized by FT-IR, XPS, PXRD, eleme...In this work, a 2D covalent triazine-based framework was prepared by using 1,3-dicyanobenzo[c]thiophene（DCBT） as monomer to effectively capture CO. The resulting CTF-DCBT was characterized by FT-IR, XPS, PXRD, elemental analysis, SEM, TEM, and Nadsorption-desorption.The results indicate that CTF-DCBT is partially crystalline and has ultramicropore（6.5 A?） as well as high heteroatom contents（11.24 wt% and 12.61 wt% for N and S, respectively）. In addition, the BET surface area and total pore volume of CTF-DCBT are 500 m/g and 0.26 cm/g, respectively. CTF-DCBT possesses excellent thermal stability（450 °C） and chemical stability towards boiling water, 4 M HCl, and 1 M Na OH.The COadsorption capacity of CTF-DCBT is 37.8 cm/g at 1 bar and 25 °C. After six adsorption-desorption cycles, there is no obvious loss of COuptake observed. Due to the ultramicropore and high heteroatom contents, CTF-DCBT has high isosteric heats of adsorption for COand high selectivities of COover Nand CH. At 25 °C, the CO/Nand CO/CHselectivities are 112.5 and 10.3, respectively, which are higher than those of most POFs. Breakthrough curves indicate that CTF-DCBT could effectively separate CO/Nand CO/CHmixtures.展开更多
Using the bottom-up method, we synthesized a series of perfluorinated covalent triazine-based frameworks(FCTFs) with porous structures for catalysis oxygen reduction reaction(ORR). The evolved FCTFs by high-temperatur...Using the bottom-up method, we synthesized a series of perfluorinated covalent triazine-based frameworks(FCTFs) with porous structures for catalysis oxygen reduction reaction(ORR). The evolved FCTFs by high-temperature carbonization show an apparent variation in electrocatalytic activity toward the ORR dependent on the type of F. The samples synthesized at 900 ℃(FCTF-900) exhibits advantages in terms of high activity, high durability, and methanol-tolerant as an efficient electrocatalyst for ORR, manifests a comparable or even better activity as compared with the commercial Pt/C catalysts not only in alkaline media but also in acidic and neutral electrolyte.展开更多
Flexible covalent organic framework(COF)film has drawn much attention as a promising functional material due to their unique molecular structure and self-supporting property.However,the traditional solvothermal method...Flexible covalent organic framework(COF)film has drawn much attention as a promising functional material due to their unique molecular structure and self-supporting property.However,the traditional solvothermal method of synthesizing flexible COF film is usually complicated,long-term duration and energy-consuming,making it unsuitable for scalable preparation.To address these limitations,a new method combining electrospinning and sacrificial template is proposed to quickly produce triazinebased COF fiber films at room temperature.The method is easy to operate and has a short reaction time(minimum 0.5 h)without dehydration and deoxygenation processes at room temperature,making it suitable for large-scale production(20 cm×30 cm).Different from the unprocessable of COF powder,COF films not only have good flexibility and mechanical properties,but also can be patterned with multiple functions to adapt to various application scenarios.Moreover,the functionality of triazine-structured COF is retained,enabling the use of the films in energy conversion and storage applications.Triazine-based COFs naturally have scalable conjugated structure,thus showing potential photocatalytic probability.Furthermore,the large pore structure of COF films enables loading of phase change materials endowing comprehensive properties of thermal management and flame retardance.This study proposes a strategy for the rapid synthesis of COF fiber films at room temperature and paves the way for multifunctional and high-performance COF based materials.展开更多
The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-ri...The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-rich-group triazine-based covalent organic framework(COF-TzDha)with a desolvation effect is designed as an interlayer for stable,dendrite-free LMA.The abundant triazine rings in COFTzDha as a donor effectively attract lithium ions,while the one-dimensional nanopore structure facilitates lithium-ion migration.The periodic arrangement of polar groups(-OH)in the backbone interacts with electrolyte components(DOL,DME,TFSI-)to form a hydrogen bonding network that slows solvent molecules transport.Therefore,COF-TzDha effectively desolvates lithium ions from the solvent sheath,promoting uniform lithium ion flux and Li plating/stripping.Theoretical calculations verify that COFTzDha with abundant adsorption sites and strong adsorption energy facilitates lithium ion desolvation.Consequently,the introduction of COF-TzDha obtains a high ion mobility(0.75).The Li|COF@PP|Li symmetric cell cycles stably for over 1200 h at 4 mA cm^(-2)/4.0 mA h cm^(-2).The Li|COF@PP|LiFePO_(4)full cell also displays highly stable cycling performance with 600 cycles(75.5%capacity retention,~100% Coulombic efficiency)at 1 C.This work verifies an effective strategy for inducing uniform Li deposition and achieving dendrite-free,stable LMA using a polar-rich-group COF interlayer with a desolvation effect.展开更多
Photoinduced molecular oxygen activation is crucial for artificial photosynthesis.However,metal-free semiconductor photocatalysts with high activation efficiency are still lacking up to now.Herein,two isomorphic tris(...Photoinduced molecular oxygen activation is crucial for artificial photosynthesis.However,metal-free semiconductor photocatalysts with high activation efficiency are still lacking up to now.Herein,two isomorphic tris(triazolo)triazine-based covalent organic frameworks were successfully constructed under solvothermal conditions.And they possess high crystallinity,inherent porosity with large surface area and good stability.Strong electron donor-acceptor skeletons expand the visible light harvesting,also facilitate the charge separation and thus lead to their superior activity of photoinduced molecular oxygen activation including photosynthesis of tetrahydroquinolines and hydrogen peroxide.This work provides a way to improve the efficiency of molecular oxygen activation through the rational design of COFs,and also opens new avenues for the construction of highly active and metal-free photocatalysts toward sustainable solar-to-chemical energy conversion.展开更多
Covalent organic frameworks(COFs)have great potential as adsorbents due to their customizable functionality,low density and high porosity.However,COFs powder exists with poor processing and recycling performance.Moreo...Covalent organic frameworks(COFs)have great potential as adsorbents due to their customizable functionality,low density and high porosity.However,COFs powder exists with poor processing and recycling performance.Moreover,due to the accumulation of COFs nanoparticles,it is not conducive to the full utilization of their surface functional groups.Currently,the strategy of COFs assembling into aerogel can be a good solution to this problem.Herein,we successfully synthesize composite aerogels(CSR)by in-situ self-assembly of two-dimensional COFs and graphene based on crosslinking of sodium alginate.Sodium alginate in the composite improves the mechanical properties of the aerogel,and graphene provides a template for the in-situ growth of COFs.Impressively,CSR aerogels with different COFs and sizes can be prepared by changing the moiety of the ligand and modulating the addition amount of COFs.The prepared CSR aerogels exhibit porous,low density,good processability and good mechanical properties.Among them,the density of CSR-N-1.6 is only 5 mg/cm3,which is the lowest density among the reported COF aerogels so far.Due to these remarkable properties,CSR aerogels perform excellent adsorption and recycling properties for the efficient and rapid removal of organic pollutants(organic dyes and antibiotics)from polluted water.In addition,it is also possible to visually recognize the presence of antibiotics by fluorescence detection.This work not only provides a new strategy for synthesizing COF aerogels,but also accelerates the practical application of COF aerogels and contributes to environmental remediation.展开更多
A sp^(2) carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for ...A sp^(2) carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(Ⅵ) removal.The morphology and structure of rBDATN-HCl were analyzed and identified by SEM,FTIR,XRD and solid-state13C NMR.It is found that the active functional groups,such as hydroxyl and amide,were introduced into BDATN after radiation reduction and acidification.The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(Ⅵ) above 99%after 60min of illumination with a solid-liquid ratio of 0.5 mg/mL,showing outstanding performance,which is attributed to the increase of dispersibility and adsorption sites of r BDATN-HCl.In comparison to the cBDATN-HCl synthesized with chemical reduction,rBDATN-HCl exhibits a better photoreduction performance for Cr(Ⅵ),demonstrating the advantages of radiation preparation of rBDATN-HCl.It is expected that more functionalized sp^(2) carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.展开更多
Zinc-ion batteries(ZIBs)are inexpensive and safe,but side reactions on the Zn anode and Zn dendrite growth hinder their practical applications.In this study,1,3,5-triformylphloroglycerol(Tp)and various diamine monomer...Zinc-ion batteries(ZIBs)are inexpensive and safe,but side reactions on the Zn anode and Zn dendrite growth hinder their practical applications.In this study,1,3,5-triformylphloroglycerol(Tp)and various diamine monomers(p-phenylenediamine(Pa),benzidine(BD),and 4,4"-diamino-p-terphenyl(DATP))were used to synthesize a series of two-dimensional covalent-organic frameworks(COFs).The resulting COFs were named TpPa,TpBD,and TpDATP,respectively,and they showed uniform zincophilic sites,different pore sizes,and high Young's moduli on the Zn anode.Among them,TpPa and TpBD showed lower surface work functions and higher ion transfer numbers,which were conducive to uniform galvanizing/stripping zinc and inhibited dendrite growth.Theoretical calculations showed that TpPa and TpBD had wider negative potential region and greater adsorption capacity for Zn2+than TpDATP,providing more electron donor sites to coordinate with Zn^(2+).Symmetric cells protected by TpPa and TpBD stably cycled for more than 2300 h,whereas TpDATP@Zn and the bare zinc symmetric cells failed after around 150 and200 h.The full cells containing TpPa and TpBD modification layers also showed excellent cycling capacity at 1 A/g.This study provides comprehensive insights into the construction of highly reversible Zn anodes via COF modification layers for advanced rechargeable ZIBs.展开更多
The light-driven CO_(2)reduction reaction(CO_(2)RR)to CO is a very effective way to address global warming.To avoid competition with water photolysis,metal-free gas-solid CO_(2)RR catalysts should be investigated.Cova...The light-driven CO_(2)reduction reaction(CO_(2)RR)to CO is a very effective way to address global warming.To avoid competition with water photolysis,metal-free gas-solid CO_(2)RR catalysts should be investigated.Covalent organic frameworks(COFs)offer a promising approach for CO_(2)transformation but lack high efficiency and selectivity in the absence of metals.Here,we have incorporated a pyridine nitrogen component into the imine-COF conjugated structure(Tp Pym).This innovative system has set a record of producing a CO yield of 1565μmol g^(-1)within 6 h.The soft X-ray absorption fine structure measurement proves that Tp Pym has both better conjugation and electron cloud enrichment.The electronic structure distribution delays the charge-carrier recombination,as evidenced by femtosecond transient absorption spectroscopy.The energy band diagram and theoretical calculation show that the conduction-band potential of Tp Pym is lower and the reduction reaction of CO_(2)to CO is more likely to occur.展开更多
Covalent organic frameworks(COFs)are newly developed crystalline substances that are garnering growing interest because of their ultrahigh porosity,crystalline nature,and easy-modified architecture,showing promise in ...Covalent organic frameworks(COFs)are newly developed crystalline substances that are garnering growing interest because of their ultrahigh porosity,crystalline nature,and easy-modified architecture,showing promise in the field of photocatalysis.However,it is difficult for pure COFs materials to achieve excellent photocatalytic hydrogen production due to their severe carrier recombination problems.To mitigate this crucial issue,establishing heterojunction is deemed an effective approach.Nonetheless,many of the metal-containing materials that have been used to construct heterojunctions with COFs own a number of drawbacks,including small specific surface area and rare active sites(for inorganic semiconductor materials),wider bandgaps and higher preparation costs(for MOFs).Therefore,it is necessary to choose metal-free materials that are easy to prepare.Red phosphorus(RP),as a semiconductor material without metal components,with suitable bandgap,moderate redox potential,relatively minimal toxicity,is affordable and readily available.Herein,a range of RP/TpPa-1-COF(RP/TP1C)composites have been successfully prepared through solvothermal method.The two-dimensional structure of the two materials causes strong interactions between the materials,and the construction of heterojunctions effectively inhibits the recombination of photogenic charge carriers.As a consequence,the 9%RP/TP1C composite,with the optimal photocatalytic ability,achieves a photocatalytic H2 evolution rate of 6.93 mmol g^(-1) h^(-1),demonstrating a 10.19-fold increase compared to that of bare RP and a 4.08-fold improvement over that of pure TP1C.This article offers a novel and innovative method for the advancement of efficient COF-based photocatalysts.展开更多
The high conductivity of electrocatalyst can eliminate the Schottky energy barrier at the interface of heterogeneous phases during an electrocatalytic reaction and accelerate the rapid electron transfer to the catalyt...The high conductivity of electrocatalyst can eliminate the Schottky energy barrier at the interface of heterogeneous phases during an electrocatalytic reaction and accelerate the rapid electron transfer to the catalytic active center.Therefore,the electronic conductivity is a vital parameter for oxygen reduction reaction(ORR).Covalent triazine frameworks(CTFs)have shown great potential application as electrocatalysts in ORR with a merit of the diverse building blocks.However,the intrinsic low conductivity and high impedance of CTFs could be significant setbacks in electrocatalytic application.Herein,CTFs were constructed by introducing F and N co-modification for efficient 2e^(-)ORR.Compared with the pristine CTF,the co-presence of F,N could increase the conductivity obviously by 1000-fold.As a result,F-N-CTF exhibits enhanced catalytic performance of H_(2)O_(2)generation and selectivity towards reaction pathways.This work reveals the importance of conductivity optimization for CTFs and provides guidance for designing high conductivity non-metallic organic semiconductor catalysts for 2e^(-)ORR.展开更多
Dimensionality has great influence on the photo/electro-catalysts properties of covalent organic frameworks(COFs) because of the different electronic and porous structures.However,very rare attention has been paid on ...Dimensionality has great influence on the photo/electro-catalysts properties of covalent organic frameworks(COFs) because of the different electronic and porous structures.However,very rare attention has been paid on the dimensionality and function correlations of COF materials.In the present work,one new two-dimensional phthalocyanine COF,namely 2D-NiPc-COF,and one new three-dimensional phthalocyanine COF,namely 3D-NiPc-COF,were fabricated according to the imide reaction between tetraanhydrides of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato nickel(Ⅱ) with [2,2-bipyridine]-5,5-diamine and tetrakis(4-aminophenyl) methane,respectively.The crystalline structures of both COFs are verified by the powder X-ray diffraction analysis,computational simulation,and high resolution transmission electron microscopy measurement.Notably,3D-NiPc-COF with dispersed conjugated modules has high utilization efficiency of NiPc electroactive sites of 26.8%,almost two times higher than the in-plane stacking2D-NiPc-COF measured by electrochemical measurement,in turn resulting in its superior electrocatalytic performance with high CO_(2)-to-CO Faradaic efficiency over 90% in a wide potential window,a large partial CO current density of-13.97 mA/cm^(2) at-0.9 V(vs.reversible hydrogen electrode) to 2D-NiPc-COF.Moreover,3D-NiPc-COF has higher turnover number and turnover frequency of 5741.6 and 0.18 s^(-1) at-0.8 V during 8 h lasting measurement.The present work provides an example for the investigation on the correlation between dimensionality and electrochemical properties of 2D and 3D phthalocyanine COFs.展开更多
Structured design helps to play out the coordination advantage and optimize the performance of electro-chemical reactions.In this work,hierarchical hollow microspheres(Co_(3)S_(4)@NiCo_(2)S_(4)) with unique core-shell...Structured design helps to play out the coordination advantage and optimize the performance of electro-chemical reactions.In this work,hierarchical hollow microspheres(Co_(3)S_(4)@NiCo_(2)S_(4)) with unique core-shell heterostructure were successfully prepared through simple template and solvothermal methods.Thanks to the hollow structure,cross-linked nanowire arrays,and in-situ coating of zeolite imidazole framework(ZIF),Co_(3)S_(4)@NiCo_(2)S_(4) demonstrated excellent electrochemical performance with a specific ca-pacitance of up to 2697.7 F g^(-1)at 1 A g^(-1) and cycling stability of 80.5% after 5000 cycles.The covalent organic framework(COF)derived nano carbon,which had undergone secondary calcination and ZnCl_(2) activation,also exhibited excellent double-layer energy storage performance.Compared to a single calci-nation,the incredible increase in capacitance was up to 208.5 times greater,reaching 291.9 F g^(-1)at 1 A g^(-1)while maintaining ultra-high rate performance(81.0%at 20 A g^(-1)).The hybrid supercapacitor,assem-bled with Co_(3)S_(4)@NiCo_(2)S_(4)as the cathode and COF-derived carbon as the anode,exhibited an extremely high energy density(79.7 Wh kg^(-1)at 693.5 W kg^(-1))and excellent cyclic stability(maintained 79.3%after 10,000 cycles of 20 A g^(-1)),further explaining the reliable and practical characteristics.This work provided reference for the structural optimization of transition metal sulfides and the high-temperature activation of COF-derived carbon.展开更多
Porous materials are excellent adsorbents for the removal of organic dyes from sewage and play a significant role in environmental restoration.Herein,two ferrocene(Fc)-based covalent organic frameworks(Fc-COFs),namely...Porous materials are excellent adsorbents for the removal of organic dyes from sewage and play a significant role in environmental restoration.Herein,two ferrocene(Fc)-based covalent organic frameworks(Fc-COFs),namely FcTF-COF and FcBD-COF,are successfully synthesized for the first time through a solvothermal method,and the obtained Fc-COFs powders are used to adsorb Congo red(CR)from water.The results show that both FcTF-COF and FcBD-COF have superb adsorption performance towards CR with ultrahigh adsorption capability of 1672.2 mg g−1 and 1983.7 mg g−1 at pH=4.0,respectively,outperforming the majority of the reported solid porous adsorbents.The maximum adsorption of both Fc-COFs agrees with the Sips adsorption isothermal model,indicating that their adsorption was dominated by heterogeneous adsorption.The Coulombic interactions,hydrogen bonding,π-πinteractions and ion-dipolar interactions should all contribute to their ultrahigh CR adsorption capability and high-pH resistance performance regardless of the pH in the range of 4-9.In addition,after five cycles,both COFs still remain their exceptional high CR adsorption capabilities.This study offers a prospective organic porous adsorbent with promising applications for organic dye removal in sewage processing.展开更多
Photocatalytic production of hydrogen peroxide(H_(2)O_(2))presents a promising strategy for environmental remediation and energy production.However,achieving clean and efficient H_(2)O_(2) production under ambient con...Photocatalytic production of hydrogen peroxide(H_(2)O_(2))presents a promising strategy for environmental remediation and energy production.However,achieving clean and efficient H_(2)O_(2) production under ambient conditions without organic sacrificial agents remains challenging.Enhancing the low crystallinity of covalent organic frameworks(COFs)can promote the separation and transmission of photo-generated carriers,thereby boosting their photocatalytic performance.Herein,we introduce a novel synthetic approach by substituting traditional acetic acid catalysts with organic base catalysts to enhance the crystallinity of β-ketoenamine-linked COF,TpBD-COF.Compared to TpBD-COF-A synthesized using acetic acid catalysts,TpBD-COF-B,synthesized with organic base catalysts,exhibited advancements including increased absorption intensity in the visible spectrum,reduced photoluminescence intensity,enhanced photo-generated carrier separation performance,and a 2.1-fold increase in photocatalytic H_(2)O_(2) production.Under visible light irradiation,TpBDCOF-B achieved a photocatalytic H_(2)O_(2) production rate of 533μmol/h/g using only air and water,without the need for organic sacrificial agents.Furthermore,TpBD-COF-B also exhibited good performance in long-term catalytic production experiments,tests with actual water bodies,and cyclic usage experiments.This study offers a strategy for enhancing the crystallinity of COFs to improve their photocatalytic activity,with promising applications in clean energy production and environmental remediation.展开更多
Covalent organic frameworks(COFs),as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions.However,the solvothermal synthesis...Covalent organic frameworks(COFs),as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions.However,the solvothermal synthesis of COFs is often time-consuming and conducted at a high temperature within a sealed vessel,and also requires a large amount of poisonous solvents,which is generally not available for scaling-up production and commercial application.In recent years,great efforts have been made to explore simple,green,and efficient approaches for COFs synthesis.In this comprehensive review,we summarized the advances in emergent strategies by highlighting their distinct features.Fundamental issues and future directions are also discussed with the object of bringing implications for large-scale and sustainable fabrication of COFs.展开更多
Solid-state electrolytes are considered to be the vital part of the next-generation solid-state batteries(SSBs),due to their high safety and long operation life span.However,the two major factors that impede the expec...Solid-state electrolytes are considered to be the vital part of the next-generation solid-state batteries(SSBs),due to their high safety and long operation life span.However,the two major factors that impede the expected performance of batteries are:the easy formation of lithium dendrites due to the concentration gradient of anions,and the low ionic conductivity at room temperature,which prevents reaching ideal electrochemical performance.Single-ion quasi-solid-state electrolytes(SIQSSEs)could provide higher safety and energy density,owing to absence of anion concentration gradient and solvent,as well as good lithium-ion transport ability.The porous covalent organic frameworks(COFs)are beneficial for con-structing appropriate lithium-ion transport pathway,due to the ordered 1D channel.In addition,the boroxine COFs(COF-5)offers strong ability of withdrawing anion part of lithium salt.Last but not the least,boron atom could play the role of coordinate site due to its electron deficiency.These advantages afford an opportunity to obtain a SIQSSE with high ionic conductivity and high lithium transference number(LTN)simultaneously.The COF-5 based SIQSSEs delivered a high ionic conductivity of 6.3×10^(-4)S·cm^(-1),with a high LTN of 0.92 and a wide electrochemical stable window(ESW)of 4.7 V at room temperature.The LiFePO4(LFP)/Li cells,which was assembled with COF-5 based SIQSSE,exhibited outstanding long cycle stability,high initial capacity and favorable rate performance.The results indicated COFs could be an ideal material for single-ion solid-state electrolytes in next-generation batteries.展开更多
Covalent organic frameworks(COFs)play a crucial role in metal-free electrocatalysts for promoting oxygen reduction reaction(ORR)due to their adjustable skeleton structure and catalytic activity.While it is true that n...Covalent organic frameworks(COFs)play a crucial role in metal-free electrocatalysts for promoting oxygen reduction reaction(ORR)due to their adjustable skeleton structure and catalytic activity.While it is true that numerous studies have explored COFs for ORR,the critical gap by providing a systematic framework for ligand-driven electronic state manipulation is essential for designing highly active COF-based ORR catalysts.Herein,a series of COF-based metal-free materials have been conceived and synthesized by linkage-engineered strategy with dicarboxaldehyde(BPC),bipyridine-dicarbaldehyde(BPA)and benzodithiophene(BDA)as electronic linkages.Consequently,by incorporating different linkages into COFs,the surface area,electronic state,hydrophobic properties and affinities towards intermediates are optimized.Notably,the benzodithiophene-linked COF(denoted as BDA-COF)has greater catalytic ability with a half-wave potential of 0.74 V vs.RHE and an onset potential of 0.86 V vs.RHE than dicarboxaldehyde(denoted as BPC-COF)and dicarbaldehyde(denoted as BPA-COF).Relevant characterizations,in situ techniques and theoretical calculations confirm that thiophene-S-based COF promotes the electronic migration and enhances the interaction with the intermediate.The result provides insight into for illustration of a high-performance COF-based electrocatalyst via a linkage-engineered approach.展开更多
基金supported by the National Natural Science Foundation of China(21373202,21525315)~~
文摘Covalent triazine-based frameworks（CTFs） are important microporous materials with a wide range of applications.Here,we demonstrate an environmentally benign and economic synthetic pathway to CTFs.The monomers used for CTFs,aromatic nitriles,were obtained by cyanation using nontoxic potassium hexacyanoferrate（Ⅱ） in place of commonly used toxic cyanides.Then,the CTFs were synthesized by trimerization of the corresponding cyano monomers in molten zinc chloride.A series of CTFs was synthesized,and the highest Brunauer-Emmett-Teller surface area measured in this series was 2404 m^2/g.Among the synthesized CTFs,CTF_（DCP） exhibited excellent CO_2 adsorption properties,with a CO_2 uptake of 225 mg/g at 0℃.
基金financially supported by the National Natural Science Foundation of China(Nos.51672047,21707173)the Youth Talent Support Program of Fujian Province(00387077)the National Natural Science Foundation of Fujian Province(Nos.2019J01648,2019J01226)。
文摘Single-atom catalysts(SACs)have emerged as an advanced frontier in heterogeneous catalysis due to their potential to maximize the atomic efficiency.Herein,covalent triazine-based frameworks(CTFs)confining cobalt single atoms(Co-SA/CTF)photocatalysts have been synthesized and used for efficient CO_(2) reduction and hydrogen production under visible light irradiation.The resulted Co-SA/CTF demonstrate excellent photocatalytic activity,with the CO and H2 evolution rates reaching 1665.74μmol g^(−1) h^(−1) and 1293.18μmol g^(−1) h^(−1),respectively,far surpassing those of Co nanoparticles anchored CTF and pure CTF.A variety of instrumental analyses collectively indicated that Co single atoms sites served as the reaction center for activating the adsorbed CO_(2) molecules,which significantly improved the CO_(2) reduction performance.Additionally,the introduction of Co single atoms could accelerate the separation/transfer of photogenerated charge carriers,thus boosting the photocatalytic performance.This study envisions a novel strategy for designing efficient photocatalysts for energy conversion and showcases the application of CTFs as attractive support for confining metal single atoms.
基金supported by the National Key R&D Program of China(2016YFB0600901)the Natural Science Foundation of China(grant nos.21536001 and 21606007)
文摘In this work, a 2D covalent triazine-based framework was prepared by using 1,3-dicyanobenzo[c]thiophene（DCBT） as monomer to effectively capture CO. The resulting CTF-DCBT was characterized by FT-IR, XPS, PXRD, elemental analysis, SEM, TEM, and Nadsorption-desorption.The results indicate that CTF-DCBT is partially crystalline and has ultramicropore（6.5 A?） as well as high heteroatom contents（11.24 wt% and 12.61 wt% for N and S, respectively）. In addition, the BET surface area and total pore volume of CTF-DCBT are 500 m/g and 0.26 cm/g, respectively. CTF-DCBT possesses excellent thermal stability（450 °C） and chemical stability towards boiling water, 4 M HCl, and 1 M Na OH.The COadsorption capacity of CTF-DCBT is 37.8 cm/g at 1 bar and 25 °C. After six adsorption-desorption cycles, there is no obvious loss of COuptake observed. Due to the ultramicropore and high heteroatom contents, CTF-DCBT has high isosteric heats of adsorption for COand high selectivities of COover Nand CH. At 25 °C, the CO/Nand CO/CHselectivities are 112.5 and 10.3, respectively, which are higher than those of most POFs. Breakthrough curves indicate that CTF-DCBT could effectively separate CO/Nand CO/CHmixtures.
基金Supported by the 1000 Plan Professorship for Young Talents,Hundred Talents Program of Fujian Provincethe Fujian Science and Technology Key Project(Item Number 2016H0043)
文摘Using the bottom-up method, we synthesized a series of perfluorinated covalent triazine-based frameworks(FCTFs) with porous structures for catalysis oxygen reduction reaction(ORR). The evolved FCTFs by high-temperature carbonization show an apparent variation in electrocatalytic activity toward the ORR dependent on the type of F. The samples synthesized at 900 ℃(FCTF-900) exhibits advantages in terms of high activity, high durability, and methanol-tolerant as an efficient electrocatalyst for ORR, manifests a comparable or even better activity as compared with the commercial Pt/C catalysts not only in alkaline media but also in acidic and neutral electrolyte.
基金financially supported by the National Key Research and Development Program of China(2022YFB3806500)the National Natural Science Foundation of China(22273100)+1 种基金Dalian-Institute of Chemical Physics(DICPI202440 and DICP I202218)Dalian-Science and Technology-Innovation Fund(2023JJ12GX023)。
文摘Flexible covalent organic framework(COF)film has drawn much attention as a promising functional material due to their unique molecular structure and self-supporting property.However,the traditional solvothermal method of synthesizing flexible COF film is usually complicated,long-term duration and energy-consuming,making it unsuitable for scalable preparation.To address these limitations,a new method combining electrospinning and sacrificial template is proposed to quickly produce triazinebased COF fiber films at room temperature.The method is easy to operate and has a short reaction time(minimum 0.5 h)without dehydration and deoxygenation processes at room temperature,making it suitable for large-scale production(20 cm×30 cm).Different from the unprocessable of COF powder,COF films not only have good flexibility and mechanical properties,but also can be patterned with multiple functions to adapt to various application scenarios.Moreover,the functionality of triazine-structured COF is retained,enabling the use of the films in energy conversion and storage applications.Triazine-based COFs naturally have scalable conjugated structure,thus showing potential photocatalytic probability.Furthermore,the large pore structure of COF films enables loading of phase change materials endowing comprehensive properties of thermal management and flame retardance.This study proposes a strategy for the rapid synthesis of COF fiber films at room temperature and paves the way for multifunctional and high-performance COF based materials.
基金supported by the National Natural Science Foundation of China(No.51972066)the Natural Science Foundation of Guangdong Province of China(No.2024A1515012499)。
文摘The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-rich-group triazine-based covalent organic framework(COF-TzDha)with a desolvation effect is designed as an interlayer for stable,dendrite-free LMA.The abundant triazine rings in COFTzDha as a donor effectively attract lithium ions,while the one-dimensional nanopore structure facilitates lithium-ion migration.The periodic arrangement of polar groups(-OH)in the backbone interacts with electrolyte components(DOL,DME,TFSI-)to form a hydrogen bonding network that slows solvent molecules transport.Therefore,COF-TzDha effectively desolvates lithium ions from the solvent sheath,promoting uniform lithium ion flux and Li plating/stripping.Theoretical calculations verify that COFTzDha with abundant adsorption sites and strong adsorption energy facilitates lithium ion desolvation.Consequently,the introduction of COF-TzDha obtains a high ion mobility(0.75).The Li|COF@PP|Li symmetric cell cycles stably for over 1200 h at 4 mA cm^(-2)/4.0 mA h cm^(-2).The Li|COF@PP|LiFePO_(4)full cell also displays highly stable cycling performance with 600 cycles(75.5%capacity retention,~100% Coulombic efficiency)at 1 C.This work verifies an effective strategy for inducing uniform Li deposition and achieving dendrite-free,stable LMA using a polar-rich-group COF interlayer with a desolvation effect.
文摘Photoinduced molecular oxygen activation is crucial for artificial photosynthesis.However,metal-free semiconductor photocatalysts with high activation efficiency are still lacking up to now.Herein,two isomorphic tris(triazolo)triazine-based covalent organic frameworks were successfully constructed under solvothermal conditions.And they possess high crystallinity,inherent porosity with large surface area and good stability.Strong electron donor-acceptor skeletons expand the visible light harvesting,also facilitate the charge separation and thus lead to their superior activity of photoinduced molecular oxygen activation including photosynthesis of tetrahydroquinolines and hydrogen peroxide.This work provides a way to improve the efficiency of molecular oxygen activation through the rational design of COFs,and also opens new avenues for the construction of highly active and metal-free photocatalysts toward sustainable solar-to-chemical energy conversion.
基金the financial support provided by the National Natural Science Foundation of China(Nos.22175094,21971113)。
文摘Covalent organic frameworks(COFs)have great potential as adsorbents due to their customizable functionality,low density and high porosity.However,COFs powder exists with poor processing and recycling performance.Moreover,due to the accumulation of COFs nanoparticles,it is not conducive to the full utilization of their surface functional groups.Currently,the strategy of COFs assembling into aerogel can be a good solution to this problem.Herein,we successfully synthesize composite aerogels(CSR)by in-situ self-assembly of two-dimensional COFs and graphene based on crosslinking of sodium alginate.Sodium alginate in the composite improves the mechanical properties of the aerogel,and graphene provides a template for the in-situ growth of COFs.Impressively,CSR aerogels with different COFs and sizes can be prepared by changing the moiety of the ligand and modulating the addition amount of COFs.The prepared CSR aerogels exhibit porous,low density,good processability and good mechanical properties.Among them,the density of CSR-N-1.6 is only 5 mg/cm3,which is the lowest density among the reported COF aerogels so far.Due to these remarkable properties,CSR aerogels perform excellent adsorption and recycling properties for the efficient and rapid removal of organic pollutants(organic dyes and antibiotics)from polluted water.In addition,it is also possible to visually recognize the presence of antibiotics by fluorescence detection.This work not only provides a new strategy for synthesizing COF aerogels,but also accelerates the practical application of COF aerogels and contributes to environmental remediation.
基金supported by the National Natural Science Foundation of China(No.U2067212)the National Science Fund for Distinguished Young Scholars(No.21925603).
文摘A sp^(2) carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(Ⅵ) removal.The morphology and structure of rBDATN-HCl were analyzed and identified by SEM,FTIR,XRD and solid-state13C NMR.It is found that the active functional groups,such as hydroxyl and amide,were introduced into BDATN after radiation reduction and acidification.The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(Ⅵ) above 99%after 60min of illumination with a solid-liquid ratio of 0.5 mg/mL,showing outstanding performance,which is attributed to the increase of dispersibility and adsorption sites of r BDATN-HCl.In comparison to the cBDATN-HCl synthesized with chemical reduction,rBDATN-HCl exhibits a better photoreduction performance for Cr(Ⅵ),demonstrating the advantages of radiation preparation of rBDATN-HCl.It is expected that more functionalized sp^(2) carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.
基金financially supported by the National Natural Science Foundation of China(62464010)Spring City Plan-Special Program for Young Talents(K202005007)+3 种基金Yunnan Talents Support Plan for Yong Talents(XDYC-QNRC-2022-0482)Yunnan Local Colleges Applied Basic Research Projects(202101BA070001-138)Key Laboratory of Artificial Microstructures in Yunnan Higher EducationFrontier Research Team of Kunming University 2023。
文摘Zinc-ion batteries(ZIBs)are inexpensive and safe,but side reactions on the Zn anode and Zn dendrite growth hinder their practical applications.In this study,1,3,5-triformylphloroglycerol(Tp)and various diamine monomers(p-phenylenediamine(Pa),benzidine(BD),and 4,4"-diamino-p-terphenyl(DATP))were used to synthesize a series of two-dimensional covalent-organic frameworks(COFs).The resulting COFs were named TpPa,TpBD,and TpDATP,respectively,and they showed uniform zincophilic sites,different pore sizes,and high Young's moduli on the Zn anode.Among them,TpPa and TpBD showed lower surface work functions and higher ion transfer numbers,which were conducive to uniform galvanizing/stripping zinc and inhibited dendrite growth.Theoretical calculations showed that TpPa and TpBD had wider negative potential region and greater adsorption capacity for Zn2+than TpDATP,providing more electron donor sites to coordinate with Zn^(2+).Symmetric cells protected by TpPa and TpBD stably cycled for more than 2300 h,whereas TpDATP@Zn and the bare zinc symmetric cells failed after around 150 and200 h.The full cells containing TpPa and TpBD modification layers also showed excellent cycling capacity at 1 A/g.This study provides comprehensive insights into the construction of highly reversible Zn anodes via COF modification layers for advanced rechargeable ZIBs.
基金supported by the National Natural Science Foundation of China(Nos.22375031,22202037,22472023)the Fundamental Research Funds for the Central Universities(Nos.2412023YQ001,2412023QD019,2412024QD014)+1 种基金supported by grants from the seventh batch of Jilin Province Youth Science and Technology Talent Lifting Project(No.QT202305)Science and Technology Development Plan Project of Jilin Province,China(No.20240101192JC)。
文摘The light-driven CO_(2)reduction reaction(CO_(2)RR)to CO is a very effective way to address global warming.To avoid competition with water photolysis,metal-free gas-solid CO_(2)RR catalysts should be investigated.Covalent organic frameworks(COFs)offer a promising approach for CO_(2)transformation but lack high efficiency and selectivity in the absence of metals.Here,we have incorporated a pyridine nitrogen component into the imine-COF conjugated structure(Tp Pym).This innovative system has set a record of producing a CO yield of 1565μmol g^(-1)within 6 h.The soft X-ray absorption fine structure measurement proves that Tp Pym has both better conjugation and electron cloud enrichment.The electronic structure distribution delays the charge-carrier recombination,as evidenced by femtosecond transient absorption spectroscopy.The energy band diagram and theoretical calculation show that the conduction-band potential of Tp Pym is lower and the reduction reaction of CO_(2)to CO is more likely to occur.
基金supported by the National Natural Science Foundation of China(Nos.52071171,52202248,22101105)Liaoning Province Centrally Guided Local Science and Technology Development Fund Program(2024JH6/100700010,2024JH6/100700011)+8 种基金Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(2024-35)Open Research Fund of Guangdong Advanced Carbon Materials Co.,Ltd.(Kargen-2024B1001),and Key Research Project of Department of Education of Liaoning Province(LJKZZ20220015)T.M.acknowledged the Australian Research Council(ARC)through Future Fellowship(FT210100298)Discovery Project(DP220100603)Linkage Project(LP210200504,LP220100088,LP230200897)Industrial Transformation Research Hub(IH240100009)schemesthe Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077)the Australian Renewable Energy Agency(ARENA)as part of ARENA's Transformative Research Accelerating Commercialisation Program(TM021)European Commission's Australia-Spain Network for Innovation and Research Excellence(AuSpire)。
文摘Covalent organic frameworks(COFs)are newly developed crystalline substances that are garnering growing interest because of their ultrahigh porosity,crystalline nature,and easy-modified architecture,showing promise in the field of photocatalysis.However,it is difficult for pure COFs materials to achieve excellent photocatalytic hydrogen production due to their severe carrier recombination problems.To mitigate this crucial issue,establishing heterojunction is deemed an effective approach.Nonetheless,many of the metal-containing materials that have been used to construct heterojunctions with COFs own a number of drawbacks,including small specific surface area and rare active sites(for inorganic semiconductor materials),wider bandgaps and higher preparation costs(for MOFs).Therefore,it is necessary to choose metal-free materials that are easy to prepare.Red phosphorus(RP),as a semiconductor material without metal components,with suitable bandgap,moderate redox potential,relatively minimal toxicity,is affordable and readily available.Herein,a range of RP/TpPa-1-COF(RP/TP1C)composites have been successfully prepared through solvothermal method.The two-dimensional structure of the two materials causes strong interactions between the materials,and the construction of heterojunctions effectively inhibits the recombination of photogenic charge carriers.As a consequence,the 9%RP/TP1C composite,with the optimal photocatalytic ability,achieves a photocatalytic H2 evolution rate of 6.93 mmol g^(-1) h^(-1),demonstrating a 10.19-fold increase compared to that of bare RP and a 4.08-fold improvement over that of pure TP1C.This article offers a novel and innovative method for the advancement of efficient COF-based photocatalysts.
基金the financial support by the National Natural Science Foundation of China(Nos.22205124,52172206)Natural Science Foundation of Shandong province(Nos.ZR2021QB070,ZR2023QB110)+2 种基金Basic Research Projects for the Pilot Project of Integrating Science and Education and Industry of Qilu University of Technology(Shandong Academy of Sciences)(Nos.2023PY024,2023PX108)Special Fund for Taishan Scholars Projectthe Development Plan of Youth Innovation Team in Colleges and Universities of Shandong Province。
文摘The high conductivity of electrocatalyst can eliminate the Schottky energy barrier at the interface of heterogeneous phases during an electrocatalytic reaction and accelerate the rapid electron transfer to the catalytic active center.Therefore,the electronic conductivity is a vital parameter for oxygen reduction reaction(ORR).Covalent triazine frameworks(CTFs)have shown great potential application as electrocatalysts in ORR with a merit of the diverse building blocks.However,the intrinsic low conductivity and high impedance of CTFs could be significant setbacks in electrocatalytic application.Herein,CTFs were constructed by introducing F and N co-modification for efficient 2e^(-)ORR.Compared with the pristine CTF,the co-presence of F,N could increase the conductivity obviously by 1000-fold.As a result,F-N-CTF exhibits enhanced catalytic performance of H_(2)O_(2)generation and selectivity towards reaction pathways.This work reveals the importance of conductivity optimization for CTFs and provides guidance for designing high conductivity non-metallic organic semiconductor catalysts for 2e^(-)ORR.
基金Financial support from the Natural Science Foundation(NSF) of China(Nos.22205015,22175020,and 22235001)the National Postdoctoral Program for Innovative Talents(No.BX20220032)+1 种基金the China Postdoctoral Science Foundation Funded Project(No.2022BG013)the Fundamental Research Funds for the Central Universities(Nos.00007709 and 00007770)。
文摘Dimensionality has great influence on the photo/electro-catalysts properties of covalent organic frameworks(COFs) because of the different electronic and porous structures.However,very rare attention has been paid on the dimensionality and function correlations of COF materials.In the present work,one new two-dimensional phthalocyanine COF,namely 2D-NiPc-COF,and one new three-dimensional phthalocyanine COF,namely 3D-NiPc-COF,were fabricated according to the imide reaction between tetraanhydrides of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato nickel(Ⅱ) with [2,2-bipyridine]-5,5-diamine and tetrakis(4-aminophenyl) methane,respectively.The crystalline structures of both COFs are verified by the powder X-ray diffraction analysis,computational simulation,and high resolution transmission electron microscopy measurement.Notably,3D-NiPc-COF with dispersed conjugated modules has high utilization efficiency of NiPc electroactive sites of 26.8%,almost two times higher than the in-plane stacking2D-NiPc-COF measured by electrochemical measurement,in turn resulting in its superior electrocatalytic performance with high CO_(2)-to-CO Faradaic efficiency over 90% in a wide potential window,a large partial CO current density of-13.97 mA/cm^(2) at-0.9 V(vs.reversible hydrogen electrode) to 2D-NiPc-COF.Moreover,3D-NiPc-COF has higher turnover number and turnover frequency of 5741.6 and 0.18 s^(-1) at-0.8 V during 8 h lasting measurement.The present work provides an example for the investigation on the correlation between dimensionality and electrochemical properties of 2D and 3D phthalocyanine COFs.
基金the College Students Innovative Practice Fund of Jiangsu University Industrial Center(ZXJG2023047)for funding this research.
文摘Structured design helps to play out the coordination advantage and optimize the performance of electro-chemical reactions.In this work,hierarchical hollow microspheres(Co_(3)S_(4)@NiCo_(2)S_(4)) with unique core-shell heterostructure were successfully prepared through simple template and solvothermal methods.Thanks to the hollow structure,cross-linked nanowire arrays,and in-situ coating of zeolite imidazole framework(ZIF),Co_(3)S_(4)@NiCo_(2)S_(4) demonstrated excellent electrochemical performance with a specific ca-pacitance of up to 2697.7 F g^(-1)at 1 A g^(-1) and cycling stability of 80.5% after 5000 cycles.The covalent organic framework(COF)derived nano carbon,which had undergone secondary calcination and ZnCl_(2) activation,also exhibited excellent double-layer energy storage performance.Compared to a single calci-nation,the incredible increase in capacitance was up to 208.5 times greater,reaching 291.9 F g^(-1)at 1 A g^(-1)while maintaining ultra-high rate performance(81.0%at 20 A g^(-1)).The hybrid supercapacitor,assem-bled with Co_(3)S_(4)@NiCo_(2)S_(4)as the cathode and COF-derived carbon as the anode,exhibited an extremely high energy density(79.7 Wh kg^(-1)at 693.5 W kg^(-1))and excellent cyclic stability(maintained 79.3%after 10,000 cycles of 20 A g^(-1)),further explaining the reliable and practical characteristics.This work provided reference for the structural optimization of transition metal sulfides and the high-temperature activation of COF-derived carbon.
基金supported by the National Nat-ural Science Foundation of China(22465012)the Key Research and Development Project of Hainan Province,China(ZDYF2024GXJS005)the Major Science and Technology Plan of Hainan Province,China(ZDKJ202016).
文摘Porous materials are excellent adsorbents for the removal of organic dyes from sewage and play a significant role in environmental restoration.Herein,two ferrocene(Fc)-based covalent organic frameworks(Fc-COFs),namely FcTF-COF and FcBD-COF,are successfully synthesized for the first time through a solvothermal method,and the obtained Fc-COFs powders are used to adsorb Congo red(CR)from water.The results show that both FcTF-COF and FcBD-COF have superb adsorption performance towards CR with ultrahigh adsorption capability of 1672.2 mg g−1 and 1983.7 mg g−1 at pH=4.0,respectively,outperforming the majority of the reported solid porous adsorbents.The maximum adsorption of both Fc-COFs agrees with the Sips adsorption isothermal model,indicating that their adsorption was dominated by heterogeneous adsorption.The Coulombic interactions,hydrogen bonding,π-πinteractions and ion-dipolar interactions should all contribute to their ultrahigh CR adsorption capability and high-pH resistance performance regardless of the pH in the range of 4-9.In addition,after five cycles,both COFs still remain their exceptional high CR adsorption capabilities.This study offers a prospective organic porous adsorbent with promising applications for organic dye removal in sewage processing.
基金jointly supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0750200)the National Key Research and Development Program of China(No.2023YFC3706600)the National Natural Science Foundation of China(Nos.22225605 and 22193051).
文摘Photocatalytic production of hydrogen peroxide(H_(2)O_(2))presents a promising strategy for environmental remediation and energy production.However,achieving clean and efficient H_(2)O_(2) production under ambient conditions without organic sacrificial agents remains challenging.Enhancing the low crystallinity of covalent organic frameworks(COFs)can promote the separation and transmission of photo-generated carriers,thereby boosting their photocatalytic performance.Herein,we introduce a novel synthetic approach by substituting traditional acetic acid catalysts with organic base catalysts to enhance the crystallinity of β-ketoenamine-linked COF,TpBD-COF.Compared to TpBD-COF-A synthesized using acetic acid catalysts,TpBD-COF-B,synthesized with organic base catalysts,exhibited advancements including increased absorption intensity in the visible spectrum,reduced photoluminescence intensity,enhanced photo-generated carrier separation performance,and a 2.1-fold increase in photocatalytic H_(2)O_(2) production.Under visible light irradiation,TpBDCOF-B achieved a photocatalytic H_(2)O_(2) production rate of 533μmol/h/g using only air and water,without the need for organic sacrificial agents.Furthermore,TpBD-COF-B also exhibited good performance in long-term catalytic production experiments,tests with actual water bodies,and cyclic usage experiments.This study offers a strategy for enhancing the crystallinity of COFs to improve their photocatalytic activity,with promising applications in clean energy production and environmental remediation.
基金financially supported by the National Natural Science Foundation of China(Nos.22322801,22108010,22278124)Fundamental Research Funds for the Central Universities(No.buctrc202135)。
文摘Covalent organic frameworks(COFs),as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions.However,the solvothermal synthesis of COFs is often time-consuming and conducted at a high temperature within a sealed vessel,and also requires a large amount of poisonous solvents,which is generally not available for scaling-up production and commercial application.In recent years,great efforts have been made to explore simple,green,and efficient approaches for COFs synthesis.In this comprehensive review,we summarized the advances in emergent strategies by highlighting their distinct features.Fundamental issues and future directions are also discussed with the object of bringing implications for large-scale and sustainable fabrication of COFs.
基金financially supported by the National Natural Science Foundation of China (Nos. 22075130 and 21875102)the Fundamental Research Funds for the Central Universities
文摘Solid-state electrolytes are considered to be the vital part of the next-generation solid-state batteries(SSBs),due to their high safety and long operation life span.However,the two major factors that impede the expected performance of batteries are:the easy formation of lithium dendrites due to the concentration gradient of anions,and the low ionic conductivity at room temperature,which prevents reaching ideal electrochemical performance.Single-ion quasi-solid-state electrolytes(SIQSSEs)could provide higher safety and energy density,owing to absence of anion concentration gradient and solvent,as well as good lithium-ion transport ability.The porous covalent organic frameworks(COFs)are beneficial for con-structing appropriate lithium-ion transport pathway,due to the ordered 1D channel.In addition,the boroxine COFs(COF-5)offers strong ability of withdrawing anion part of lithium salt.Last but not the least,boron atom could play the role of coordinate site due to its electron deficiency.These advantages afford an opportunity to obtain a SIQSSE with high ionic conductivity and high lithium transference number(LTN)simultaneously.The COF-5 based SIQSSEs delivered a high ionic conductivity of 6.3×10^(-4)S·cm^(-1),with a high LTN of 0.92 and a wide electrochemical stable window(ESW)of 4.7 V at room temperature.The LiFePO4(LFP)/Li cells,which was assembled with COF-5 based SIQSSE,exhibited outstanding long cycle stability,high initial capacity and favorable rate performance.The results indicated COFs could be an ideal material for single-ion solid-state electrolytes in next-generation batteries.
基金financial support provided by the National Natural Science Foundation of Yunnan Province(202301AS070040)Major Science and Technology Projects of Yunnan Province(202302AB080019-3)。
文摘Covalent organic frameworks(COFs)play a crucial role in metal-free electrocatalysts for promoting oxygen reduction reaction(ORR)due to their adjustable skeleton structure and catalytic activity.While it is true that numerous studies have explored COFs for ORR,the critical gap by providing a systematic framework for ligand-driven electronic state manipulation is essential for designing highly active COF-based ORR catalysts.Herein,a series of COF-based metal-free materials have been conceived and synthesized by linkage-engineered strategy with dicarboxaldehyde(BPC),bipyridine-dicarbaldehyde(BPA)and benzodithiophene(BDA)as electronic linkages.Consequently,by incorporating different linkages into COFs,the surface area,electronic state,hydrophobic properties and affinities towards intermediates are optimized.Notably,the benzodithiophene-linked COF(denoted as BDA-COF)has greater catalytic ability with a half-wave potential of 0.74 V vs.RHE and an onset potential of 0.86 V vs.RHE than dicarboxaldehyde(denoted as BPC-COF)and dicarbaldehyde(denoted as BPA-COF).Relevant characterizations,in situ techniques and theoretical calculations confirm that thiophene-S-based COF promotes the electronic migration and enhances the interaction with the intermediate.The result provides insight into for illustration of a high-performance COF-based electrocatalyst via a linkage-engineered approach.
