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
Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of C...Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of Cu-BTC, a copper-based MOF, and its derivatives Cu TM-BTC via the substitution of transition metal(TM) elements at the Cu site for photocatalytic overall water splitting(POWS) have been studied. POWS of Cu-BTC suffers from the sluggish hydrogen evolution reaction due to the large overpotential of 2.02 V and limited solar utilization due to a wide HOMO-LUMO gap of 4.11 e V. Via TM substitution, the HOMO-LUMO gap narrows but still satisfies the redox potentials when taken 3d-TM of Cr, Fe, Co or Ni, 4d-TM of Rh or Pd, or 5d-TM of Re or Pt into consideration, benefiting for the light absorption. Furthermore, Cr and Re could serve as active sites for hydrogen evolution with remarkably lowered overpotentials of 0.79 V and 0.28 V, respectively;similarly, oxygen evolution activities could be enhanced by Fe, Co and Rh because of their reduced overpotentials which are less than 0.5 V. Therefore,our findings pave guidance for designing Cu-BTC derivatives in overall water splitting.展开更多
This study aims to construct a virtual twin testing framework for the safety of the intended functionality of intelligent connected vehicles to address the safety requirements of intelligent driving and transportation...This study aims to construct a virtual twin testing framework for the safety of the intended functionality of intelligent connected vehicles to address the safety requirements of intelligent driving and transportation systems.The research methods include the construction of a theoretical model of safety for intelligent connected vehicles based on the concept of virtual twins,the correlation study between key concepts and functional safety,and the application research of virtual twin technology in the safety testing of intelligent connected vehicles.The results reveal that the virtual twin testing framework can effectively enhance the functional safety of intelligent connected vehicles,reduce development costs,and shorten the product launch cycle.The conclusion suggests that this framework provides strong support for the healthy development of the intelligent connected vehicle industry and has a positive impact on the safety and efficiency of intelligent transportation systems.展开更多
The recovery of gold from waste electronic and electric equipment(WEEE) has gained great attention with the increased number of WEEE,because it can largely alleviate the pressure on the environment and resources.Coval...The recovery of gold from waste electronic and electric equipment(WEEE) has gained great attention with the increased number of WEEE,because it can largely alleviate the pressure on the environment and resources.Covalent organic frameworks(COFs) are ideal adsorbents for gold recovery owing to their large surface area,good stability,easily functionalized ability,periodic structures,and definitive nanopores.Herein,a cyano-functionalized COF(COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold.The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance,which possesses fast adsorption kinetics,high cycling stability,and adsorption capacity up to 663.67 mg/g.Excitingly,COF-CN showed extremely high selectivity for gold ions,even in the presence of various competing cations and anions.The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE.The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.展开更多
The integration of organic and inorganic materials has been widely used in various applications to generate novel functional nanomaterials characterized by unique properties.Functional crystalline framework nanosheets...The integration of organic and inorganic materials has been widely used in various applications to generate novel functional nanomaterials characterized by unique properties.Functional crystalline framework nanosheets and their synergistic effects have been studied recently for possessing the advantages of functional species as well as crystalline framework nanosheets.Hence,we have focused on the preparation methods and applications of functional crystalline framework nanosheets in this review.We introduced crystalline framework nanosheets and discussed the importance of integrating functional species with nanosheets to form functional crystalline framework nanosheets.Then,two aspects of the preparation methods of functional crystalline framework nanosheets were reviewed:in situ synthesis and post-synthesis modification.Subsequently,we discussed the properties of the crystalline framework nanosheets combined with various functional species and summarized their applications in catalysis,sensing,separation,and energy storage.Finally,we have shared our insights on the challenges of functional crystalline framework nanosheets,hoping to contribute to the knowledge base for optimizing the preparation methods,expanding categories,improving stability,and exploring potential applications.展开更多
As a new emerging class of highly crystalline advanced porous materials,metal–organic frameworks(MOFs)and covalent organic frameworks(COFs)have gained significant attention for photodynamic therapy(PDT)due to their s...As a new emerging class of highly crystalline advanced porous materials,metal–organic frameworks(MOFs)and covalent organic frameworks(COFs)have gained significant attention for photodynamic therapy(PDT)due to their structural regularity,inherent porosity,extensive functionality,design flexibility,and good biocompatibility.In this review,we summarize and illustrate the recent developments of MOF-and COF-based nanomedicines for PDT and its combined antitumor treatments.Furthermore,major challenges and future development prospects in this field are also discussed.展开更多
Lithium-selenium batteries,as an advanced rechargeable battery system,have attracted wide attention.However,its application is hurdled by the ambiguous underlying mechanism such as the unclear active phase and the key...Lithium-selenium batteries,as an advanced rechargeable battery system,have attracted wide attention.However,its application is hurdled by the ambiguous underlying mechanism such as the unclear active phase and the key role of the host materials.Herein,a three-dimensional(3D) functional matrix derived from the Co/Znmetal organic framework is synthesized to unravel the questions raised.It reveals that the strong interaction and voids in the 3D matrix serve to anchor the amorphous Se with high electrochemical properties.The obtained 3DC/Se exhibits 544.2 and 273.2 mAh·g^(-1) t current densities of 0.1C and 2.0C,respectively,with a diffusion-controlled mechanism.The excessive amount of Se beyond the loading capacity of the matrix leads to the formation of trigonal phase Se,which shows an unsatisfying electrochemical property.展开更多
The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative p...The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative potential of metal-organic frameworks(MOFs)as next-generation adsorbents for PM recovery,focusing on their synthesis,functionalization,and multiscale adsorption mechanisms.We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity,energy consumption,and secondary pollution.In contrast,MOFs offer tunable porosity,abundant active sites,and tunable surface chemistry,enabling efficient PM capture via synergistic physical and chemical adsorption.Advanced modification techniques,including direct synthesis and post-synthetic modification,are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au,Ag,Pt,and Pd.Key structure-property relationships are established through multiscale characterization and thermodynamic models,revealing the critical roles of hierarchical porosity,soft donor atoms,and framework stability.Industrial challenges,such as aqueous stability and scalability,are addressed via Zr-O bond strengthening,hydrophobic functionalization,and support immobilization.This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.展开更多
The rational design of high-performance CO_(2)adsorbents remains a critical challenge in addressing global carbon emissions,with metal-organic frameworks(MOFs)emerging as promising candidates due to their tunable pore...The rational design of high-performance CO_(2)adsorbents remains a critical challenge in addressing global carbon emissions,with metal-organic frameworks(MOFs)emerging as promising candidates due to their tunable pore environments.However,the lack of systematic guidelines for functional group selection has hindered their practical implementation in carbon capture applications.Here,this gap was addressed by developing a comprehensive design framework through high-throughput computational screening.Through construction of a topology-directed database of 4797,integrating 10 metal centers with 144 functionalized ligands(18 ligands modified by–NH_(2),–NO_(2),–CH_(3),–CF_(3),–SH_(2),–SO_(2),–OH,and–OLi)across 36 topologies,the fundamental structure–property relationships governing CO_(2)capture performance was established.Multi-metric evaluation reveals that–NO_(2),–SO_(2),and–OLi dramatically enhance CO_(2)selectivity over CH_4/N_(2)via selectivity(S_(ads)),working capacity(ΔN),adsorbent performance score(APS),sorbent selection parameter(S_(sp)),and renewability R.Specially,ΔN rises from 2.34(pristine)to 5.91–7.94 mmol g^(-1)and S_(ads)surges from 24.94/40.36 to 121.11/176.87(–NO_(2)),149.94/215.54(–SO_(2)),and 58.64/267.44(–OLi).Besides,the critical trade-off between adsorption strength and renewability demonstrates that enhanced performance comes at the cost of reduced renewability,where stronger CO_(2)affinity(isosteric heat of-29.15,-29.96,and-30.09 for–NO_(2),–SO_(2),and–OLi)compromises renewability(R reduced by -50%).To resolve this trade-off,a novel energy efficiency(η)metric was introduced,which holistically evaluates both adsorption performance(S_(ads),ΔN,APS,S_(sp),and R)and energy inputs(desorption heat,pressure-swing energy,net loss).This leads to the identification of–SO_(2)as the optimal functional group that balances exceptional CO_(2)capture(η=6.17/12.78 for CO_(2)over CH_4/N_(2)),surpassing the second higher of 4.74/8.80 in–CF_(3)and 0.99/2.18 in non-functionalized counterparts.Adopting high-throughput computational screening methods,this work provides both fundamental insights into host–vip interactions in functionalized MOFs and a practical framework for designing next-generation adsorbents,bridging the gap between materials discovery and process engineering considerations in carbon capture technologies.展开更多
Covalent organic frameworks(COFs)have lately emerged as a blooming class of potential materials for photocatalytic water splitting because of their high crystallinity,huge surface areas,and structural versatility.Howe...Covalent organic frameworks(COFs)have lately emerged as a blooming class of potential materials for photocatalytic water splitting because of their high crystallinity,huge surface areas,and structural versatility.However,the photocatalytic performance for most pure COFs face some limitations factors,such as the significant recombination of photogenerated carriers and slow charge transfer.Herein,a novel thioether-functionalized pyrene-based COF(S_(4)-COF)was effectively produced and chosen as a support for the immobilization of ultrafine gold nanoparticles(Au NPs).S_(4)-COF photocatalyst with Au as cocatalyst demonstrates remarkable photocatalytic activity with a H_(2) generation rate of 1377μmol g^(−1) h^(−1) under visible light(>420 nm),which is ca.4.5-fold increase comparing to that of pure S_(4)-COF(302μmol g^(−1) h^(−1)).Au NPs anchored on S_(4)-COF possess an ultrafine size distribution ranging from 1.75 to 6.25 nm with an average size centered at 3.8 nm,which benefits from the coordination interaction between thioether groups and Au.Meanwhile,the produced Au@S_(4)-COF can generate a stable photocatalytic H_(2) generation during the four recycles and preserve its crystallinity structure after the stability testing.The Au NPs anchored on the S_(4)-COF photocatalyst can greatly accelerate the separation of photogenerated carriers and increase charge transfer because of the combined function of Au NPs and thioether groups.Such a method can not only prevent the aggregation of Au NPs onto thioether-containing COFs to achieve long-term photostability but also allow uniform dispersion for an ordered structure of photocatalysts.This work provides a rational strategy for designing and preparing COF-based photocatalysts for solar-driven H_(2) production.展开更多
The design and synthesis of highly porous MOFs with excellent framework stability and optimized supramolecular host-vip interactions is an effective strategy to obtain high-performance MOF materials for targeted app...The design and synthesis of highly porous MOFs with excellent framework stability and optimized supramolecular host-vip interactions is an effective strategy to obtain high-performance MOF materials for targeted applications such as gas storage,separation,catalysis and so on.Herein,we designed and constructed a microporous(3,24)-connected rht-type acylamide functionalized MOF(HNUST-9)from dicopper(II)-paddlewheel clusters and a novel C_(2)-symmetric acylamide-linking hexacarboxylate.Interestingly,with a high density of strong CO_(2) binding sites including open copper(II)sites and acylamide groups integrated in the framework,although exhibiting moderate porosity(a BET surface area of 2429 m^(2) g^(−1)),the activated HNUST-9 shows an exceptionally high excess CO_(2) uptake capacity(21.8 mmol g^(−1) at 25 bar and 273 K),and efficient CO_(2) separation ability from CO_(2)/CH4 and CO_(2)/N_(2) binary gas mixtures under dynamic conditions at 1 bar and room temperature.Moreover,HNUST-9 demonstrates efficient catalytic activity for the CO_(2) cycloaddition with various epoxides in the presence of tetrabutylammonium bromide as the cocatalyst under mild,solvent-free conditions.展开更多
The efficient separation of deuterium from hydrogen remains a significant challenge due to the limitations of conventional techniques,such as cryogenic distillation and the Girdler-sulfide process combined with electr...The efficient separation of deuterium from hydrogen remains a significant challenge due to the limitations of conventional techniques,such as cryogenic distillation and the Girdler-sulfide process combined with electrolysis,which are char-acterized by substantial energy demands and relatively low separation coefficients.In contrast,the quantum sieving effect,based on porous materials,offers a promising approach to overcoming these challenges.This study presents a novel application of strong adsorption sites(μ3-OH group)within the nanoporous metal-organic framework of UiO-66 for hydrogen isotope separation.By incorporating diverse organic functional groups into UiO-66,we successfully synthesized four derivative materials:UiO-66-NH_(2),UiO-66-CH_(3),UiO-66-NO_(2),and UiO-66-Ph.Experimental data reveal that the introduction of these functional groups modulated the material’s pore size and channel polarity,significantly impacting its adsorption and separation performance for hydrogen isotopes.Notably,UiO-66-NH_(2),with the smallest pore size and highest channel polarity,exhibited superior hydrogen isotope adsorption capacity and selectivity,highlighting its potential as an effective adsorbent for isotope separation.展开更多
Multivariate metal-organic frameworks（MTV-MOFs） with different ratios of terephthalate（BDC） linker and amino-benzenedicarboxylate（BDC-NH2） linker were synthesized through both direct synthesis from linker mixtur...Multivariate metal-organic frameworks（MTV-MOFs） with different ratios of terephthalate（BDC） linker and amino-benzenedicarboxylate（BDC-NH2） linker were synthesized through both direct synthesis from linker mixture and linker exchange of activated single-linker MOFs. Functionality proportion was impacted by the thermodynamics during the one-pot MOF construction, resulting in preference of BDC over BDC-NH2 in the MTV-MOF, in agreement with the quantum mechanics calculations. The functionality difference also affects the thermodynamics in the linker exchange process, as indicated by the more effective linker exchange in BDC-NH2-based IRMOF-3 than in BDC-based MOF-5. Furthermore,the thermal decomposition temperatures and chemical integrity upon ambient air exposure of these MOFs with variate functionalities were investigated, and it reveals that higher proportion of BDC in the MTV-MOF crystals contribute to both higher thermal and higher chemical stabilities.展开更多
The development of C-H functionalization methods for directly converting C-H bonds into C-C bonds has drawn significant attention.These reactions typically require the concurrent involvement of distinct catalytic proc...The development of C-H functionalization methods for directly converting C-H bonds into C-C bonds has drawn significant attention.These reactions typically require the concurrent involvement of distinct catalytic processes,such as photoredox and transition metal catalysis.Combining the corresponding catalytic sites within a single catalyst,instead of adding extra cocatalysts,remains a significant challenge.Here,we present a novel pyridone-based hydrogen-bonded organic framework(HOF),named PFC-943,which exhibits exceptional visible-light absorption properties while integrating both photosensitizing and redox-active sites within its skeleton.Femtosecond transient absorption spectroscopy(fs-TA)reveals that the excited-state electrons of PFC-943 in ethanol exhibit an extended lifetime.Leveraging this unique excited-state electron behavior,PFC-943converts oxygen into highly reactive singlet oxygen(^(1)O_(2))via an energy transfer(En T)pathway and facilitates a key carbanion intermediate through a single electron transfer(SET)process.Consequently,the metal-free PFC-943 exhibits remarkable photocatalytic performance in C-H bond arylation reaction of quinoxalin-2(1H)-one.This work presents the first dual-functional HOF for radical-mediated C-H functionalization reactions,offering a novel approach to C-H bond functionalization.展开更多
The investigation of thermal transport properties of materials has become increasingly important in technological applications,including thermal management and energy conversion.Recently,ultrahigh or low thermal condu...The investigation of thermal transport properties of materials has become increasingly important in technological applications,including thermal management and energy conversion.Recently,ultrahigh or low thermal conductivity has been reported in nitride,boride,and chalcogenide by different strategies.However,the strategy to design oxide crystals with unique thermal properties is also a challenge.In this work,a new ternary oxide crystal Ga_(2)TeO_(6) is designed and expected to show high thermal conductivity due to its lone pairs-free octahedra connected along the caxis by sharing edges.The thermal conductivities of Ga_(2)TeO_(6) crystal are determined to be 19.2 and 23.9Wm^(-1) K^(-1) along the a-and c-axis directions at 323 K,respectively,which are significantly higher than those of most reported oxide crystals.First-principles calculations and crystal structure analyses reveal that the Ga_(2)TeO_(6) crystal shows high sound velocity and weak lattice anharmonicity due to lone pairs-free octahedra and highly symmetric group arrangement.The results suggest that much attention must be paid to the polyhedron with lone pairs and its arrangement in materials design to balance the functions and thermal properties.展开更多
Helicobacter pylori colonizes over 50%of people worldwide.Biofilm formation through penetrating gastric mucus and resistance acquired by H.pylori markedly reduces the efficacy of traditional antibiotics.The present tr...Helicobacter pylori colonizes over 50%of people worldwide.Biofilm formation through penetrating gastric mucus and resistance acquired by H.pylori markedly reduces the efficacy of traditional antibiotics.The present triple therapy and bismuth-based quadruple therapy inevitably causes intestinal flora disturbance and fails to address the excessive H.pylori-triggered inflammatory response.Herein,a mucus-permeable therapeutic platform(Cu-MOF@NF)that consists of copper-bearing metal-organic framework(Cu-MOF)loaded with nitrogen-doped carbon dots and naturally active polysaccharide fucoidan is developed.The experimental results demonstrate that Cu-MOF@NF can penetrate the mucus layer and hinder H.pylori from adhering on gastric epithelial cells of the stomach.Notably,released Cu2+can degrade the polysaccharides in the biofilm and interfere with the cyclic growing mode of"bacterioplankton↔biofilm",thereby preventing recurrent and persistent infection.Compared with traditional triple therapy,the Cu-MOF@NF not only possesses impressive antibacterial effect(even include multidrug-resistant strains),but also improves the inflammatory microenvironment without disrupting the balance of intestinal flora,providing a more efficient,safe,and antibiotic-free new approach to eradicating H.pylori.展开更多
Achieving efficient adsorption and separation of C_(2)H_(2)/CO_(2)mixtures is a goal that people have always pursued to improve the situation of high energy consumption brought by traditional separation technologies i...Achieving efficient adsorption and separation of C_(2)H_(2)/CO_(2)mixtures is a goal that people have always pursued to improve the situation of high energy consumption brought by traditional separation technologies in industry today.High-nuclearity metal cluster-based MOFs with different functionalities are promising for this separation,but it is a complicated and difficult task to precisely control their structures.The strategy of pore-space partition(PSP)is a powerful way to construct this type MOFs,which has the characteristic of isostructural relationship,and can be resulted in a similar performance for them.Therefore,it is an interesting work to explore the effect of MOFs property by adjusting the size of PSP dividers.Herein,three tetranuclear Cu(Ⅱ)cluster-based MOFs(FJU-112/113/114)with dual functionalities has been successfully obtained by PSP strategy with various lengths of divider units.With the highest microporosity and unique functional site,FJU-114 realized a good improvement in the adsorption and separation performance of C_(2)H_(2)/CO_(2).The gas adsorption and lab-scale C_(2)H_(2)/CO_(2)breakthrough experiments demonstrated that FJU-114 exhibits the highest adsorption uptake of 77 cm^(3)/g for C_(2)H_(2),and shows the best separation factor of 4.2 among three MOFs.The GCMC simulation reveals that a stronger adsorption binding site of C_(2)H_(2)in FJU-114a located in the cage II near the unchanged tetranuclear copper node,combined with its high microporosity to achieve the effect of dual functionalities for the improvement performance of C_(2)H_(2)adsorption and separation.展开更多
Metal-organic frameworks（MOFs） are a unique class of porous crystalline materials that have shown promise for a wide range of applications. MOFs have been explored as a new type of heterogeneous catalytic materials,...Metal-organic frameworks（MOFs） are a unique class of porous crystalline materials that have shown promise for a wide range of applications. MOFs have been explored as a new type of heterogeneous catalytic materials, because of their high surface area, uniform and tunable pores, facile functionalization and incorporation of catalytic active sites. The use of multi-functional sites MOF materials as catalysts for synergistic catalysis and tandem reactions has attracted increasing attention. In this review, we aim to introduce the construction of bi-or multi-functional MOF catalysts with cooperative or cascade functions via post-synthetic modification（PSM）.展开更多
Cancer is one of the most complex diseases and the second leading cause of mortality worldwide.Due to its poor prognosis and challenges in diagnosis,eradicating cancer remains highly difficult.The limitations associat...Cancer is one of the most complex diseases and the second leading cause of mortality worldwide.Due to its poor prognosis and challenges in diagnosis,eradicating cancer remains highly difficult.The limitations associated with conventional therapies have led to the emergence of copious therapeutic strategies such as chemotherapy,phototherapy,starvation therapy,radiotherapy and immunotherapy;however,limited therapeutic efficacy,poor tumor cell selectivity and substantial adverse effects remain significant concern.Attributed to the expeditious advancement of nanotechnology,the amalgamation of nanomaterials with therapeutic approaches provides an opportunity to address the shortcomings of conventional chemotherapy.Metal-organic frameworks(MOFs),which consist of bridging ligands and ions/clusters connected by coordination bonds,have been widely used in cancer therapy to address the limitations of currently therapeutic interventions,such as poor efficacy,low stability and severe side effects.This potential arises from their tuneable porosities,high specific surface area-to-volume ratio,tailorable diameters,tractable morphologies,variegated compositions,biocompatibility and facile functionalization.We summarized the role of MOF-based nanoplatforms along with mechanistic insights into emerging avenues-such as cuproptosis,ferroptosis,cell-penetrating and biomimetic MOFs,and tumor microenvironment-responsive MOFs-alongside recent advancements in mono-and multifunctional cancer therapeutics.Theragnostic and imaging functionalities,as well as regulatory considerations and future prospects of MOF-based nanoplatforms utilized in cancer treatment,are also discussed.展开更多
Controlled synthesis of two-dimensional covalent organic frameworks(2D COFs),including stoichiometric and sub-stoichiometric variations,is a topic of growing interest due to its potential in gas separation application...Controlled synthesis of two-dimensional covalent organic frameworks(2D COFs),including stoichiometric and sub-stoichiometric variations,is a topic of growing interest due to its potential in gas separation applications.In this study,we successfully synthesized three distinct 2D COFs by carefully adjusting solvent compositions and monomer ratios during the synthesis of[4+4]type COFs.These included a stoichiometric[4+4]type COF and two sub-stoichiometric[4+2]type COFs,featuring unreacted amino or formyl groups.The resulting COFs exhibit different gas adsorption and separation properties.Specifically,sub-stoichiometric COF-DA with residual amino groups shows comparable adsorption capacity for C_(2)H_(2),C_(2)H_(4),and CO_(2)to stoichiometric COF-DAPy.In contrast,sub-stoichiometric COF-Py with residual formyl groups displays enhanced adsorption selectivity for C_(2)H_(2)/C_(2)H_(4)and C_(2)H_(2)/CO_(2)separation,with the C_(2)H_(2)/C_(2)H_(4)selectivity being the highest among reported COFs,attributed to increased pore polarity resulting from the presence of formyl groups.This study not only offers an additional example of substoichiometric COF synthesis but also advocates for further exploration of sub-stoichiometric COF materials,particularly in the field of gas adsorption and separation.展开更多
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the financial support from National Natural Science Foundation of China (No. 21503097)Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. KYCX23_3905)。
文摘Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of Cu-BTC, a copper-based MOF, and its derivatives Cu TM-BTC via the substitution of transition metal(TM) elements at the Cu site for photocatalytic overall water splitting(POWS) have been studied. POWS of Cu-BTC suffers from the sluggish hydrogen evolution reaction due to the large overpotential of 2.02 V and limited solar utilization due to a wide HOMO-LUMO gap of 4.11 e V. Via TM substitution, the HOMO-LUMO gap narrows but still satisfies the redox potentials when taken 3d-TM of Cr, Fe, Co or Ni, 4d-TM of Rh or Pd, or 5d-TM of Re or Pt into consideration, benefiting for the light absorption. Furthermore, Cr and Re could serve as active sites for hydrogen evolution with remarkably lowered overpotentials of 0.79 V and 0.28 V, respectively;similarly, oxygen evolution activities could be enhanced by Fe, Co and Rh because of their reduced overpotentials which are less than 0.5 V. Therefore,our findings pave guidance for designing Cu-BTC derivatives in overall water splitting.
文摘This study aims to construct a virtual twin testing framework for the safety of the intended functionality of intelligent connected vehicles to address the safety requirements of intelligent driving and transportation systems.The research methods include the construction of a theoretical model of safety for intelligent connected vehicles based on the concept of virtual twins,the correlation study between key concepts and functional safety,and the application research of virtual twin technology in the safety testing of intelligent connected vehicles.The results reveal that the virtual twin testing framework can effectively enhance the functional safety of intelligent connected vehicles,reduce development costs,and shorten the product launch cycle.The conclusion suggests that this framework provides strong support for the healthy development of the intelligent connected vehicle industry and has a positive impact on the safety and efficiency of intelligent transportation systems.
基金financially supported by the National Natural Science Foundation of China (No.51972302)。
文摘The recovery of gold from waste electronic and electric equipment(WEEE) has gained great attention with the increased number of WEEE,because it can largely alleviate the pressure on the environment and resources.Covalent organic frameworks(COFs) are ideal adsorbents for gold recovery owing to their large surface area,good stability,easily functionalized ability,periodic structures,and definitive nanopores.Herein,a cyano-functionalized COF(COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold.The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance,which possesses fast adsorption kinetics,high cycling stability,and adsorption capacity up to 663.67 mg/g.Excitingly,COF-CN showed extremely high selectivity for gold ions,even in the presence of various competing cations and anions.The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE.The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.
基金financially supported by the National Natural Science Foundation of China (Nos.21727808,21971114,21908105,and 22205100)the Jiangsu Provincial Funds for Natural Science Foundation (No.BK20200090)。
文摘The integration of organic and inorganic materials has been widely used in various applications to generate novel functional nanomaterials characterized by unique properties.Functional crystalline framework nanosheets and their synergistic effects have been studied recently for possessing the advantages of functional species as well as crystalline framework nanosheets.Hence,we have focused on the preparation methods and applications of functional crystalline framework nanosheets in this review.We introduced crystalline framework nanosheets and discussed the importance of integrating functional species with nanosheets to form functional crystalline framework nanosheets.Then,two aspects of the preparation methods of functional crystalline framework nanosheets were reviewed:in situ synthesis and post-synthesis modification.Subsequently,we discussed the properties of the crystalline framework nanosheets combined with various functional species and summarized their applications in catalysis,sensing,separation,and energy storage.Finally,we have shared our insights on the challenges of functional crystalline framework nanosheets,hoping to contribute to the knowledge base for optimizing the preparation methods,expanding categories,improving stability,and exploring potential applications.
基金support from the NSFC(Grant No.21971153 and 21671122)Chang Jiang Scholars Program of ChinaTaishan Scholars Construction Project of Shandong Province.
文摘As a new emerging class of highly crystalline advanced porous materials,metal–organic frameworks(MOFs)and covalent organic frameworks(COFs)have gained significant attention for photodynamic therapy(PDT)due to their structural regularity,inherent porosity,extensive functionality,design flexibility,and good biocompatibility.In this review,we summarize and illustrate the recent developments of MOF-and COF-based nanomedicines for PDT and its combined antitumor treatments.Furthermore,major challenges and future development prospects in this field are also discussed.
基金financially supported by the National Natural Science Foundation of China (Nos.51901189 and 51802265)Shaanxi Provincial Key R&D Program (No.2021KWZ17)+1 种基金China Postdoctoral Science Foundation Grant (No. 2020M683552)the Natural Science Foundation of Chongqing (No.cstc2020jcyj-msxmX0859)。
文摘Lithium-selenium batteries,as an advanced rechargeable battery system,have attracted wide attention.However,its application is hurdled by the ambiguous underlying mechanism such as the unclear active phase and the key role of the host materials.Herein,a three-dimensional(3D) functional matrix derived from the Co/Znmetal organic framework is synthesized to unravel the questions raised.It reveals that the strong interaction and voids in the 3D matrix serve to anchor the amorphous Se with high electrochemical properties.The obtained 3DC/Se exhibits 544.2 and 273.2 mAh·g^(-1) t current densities of 0.1C and 2.0C,respectively,with a diffusion-controlled mechanism.The excessive amount of Se beyond the loading capacity of the matrix leads to the formation of trigonal phase Se,which shows an unsatisfying electrochemical property.
基金supported by the National Natural Science Foundation of China(No.52304329)the Yunnan Fundamental Research Projects(No.202201BE070001-003),Guo Lin would like to acknowledge Xing Dian talent support program of Yunnan Province.
文摘The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative potential of metal-organic frameworks(MOFs)as next-generation adsorbents for PM recovery,focusing on their synthesis,functionalization,and multiscale adsorption mechanisms.We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity,energy consumption,and secondary pollution.In contrast,MOFs offer tunable porosity,abundant active sites,and tunable surface chemistry,enabling efficient PM capture via synergistic physical and chemical adsorption.Advanced modification techniques,including direct synthesis and post-synthetic modification,are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au,Ag,Pt,and Pd.Key structure-property relationships are established through multiscale characterization and thermodynamic models,revealing the critical roles of hierarchical porosity,soft donor atoms,and framework stability.Industrial challenges,such as aqueous stability and scalability,are addressed via Zr-O bond strengthening,hydrophobic functionalization,and support immobilization.This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.
基金supported by The National Natural Science Foundation of China(22471289 and 22478430)Shandong Natural Science Foundation(ZR2022ME105 and ZR2023ME004)+4 种基金Qingdao Natural Science Foundation(23-2-1-232-zyyd-jch)Geological body description and key technologies of reservoir engineering of CCUS oil displacement(2021ZZ01-03)Science and Technology Major Project on New Oil and Gas Exploration and Development:Research on Comprehensive Control Technology for CO_(2)-Enhanced Miscible and Immiscible Displacement(2024ZD1406601)State Key Laboratory of Enhanced Oil Recovery of Open Fund Funded Project(2024-KFKT-19)the Fundamental Research Funds for the Central Universities(24CX06042A and 24CX06070A)。
文摘The rational design of high-performance CO_(2)adsorbents remains a critical challenge in addressing global carbon emissions,with metal-organic frameworks(MOFs)emerging as promising candidates due to their tunable pore environments.However,the lack of systematic guidelines for functional group selection has hindered their practical implementation in carbon capture applications.Here,this gap was addressed by developing a comprehensive design framework through high-throughput computational screening.Through construction of a topology-directed database of 4797,integrating 10 metal centers with 144 functionalized ligands(18 ligands modified by–NH_(2),–NO_(2),–CH_(3),–CF_(3),–SH_(2),–SO_(2),–OH,and–OLi)across 36 topologies,the fundamental structure–property relationships governing CO_(2)capture performance was established.Multi-metric evaluation reveals that–NO_(2),–SO_(2),and–OLi dramatically enhance CO_(2)selectivity over CH_4/N_(2)via selectivity(S_(ads)),working capacity(ΔN),adsorbent performance score(APS),sorbent selection parameter(S_(sp)),and renewability R.Specially,ΔN rises from 2.34(pristine)to 5.91–7.94 mmol g^(-1)and S_(ads)surges from 24.94/40.36 to 121.11/176.87(–NO_(2)),149.94/215.54(–SO_(2)),and 58.64/267.44(–OLi).Besides,the critical trade-off between adsorption strength and renewability demonstrates that enhanced performance comes at the cost of reduced renewability,where stronger CO_(2)affinity(isosteric heat of-29.15,-29.96,and-30.09 for–NO_(2),–SO_(2),and–OLi)compromises renewability(R reduced by -50%).To resolve this trade-off,a novel energy efficiency(η)metric was introduced,which holistically evaluates both adsorption performance(S_(ads),ΔN,APS,S_(sp),and R)and energy inputs(desorption heat,pressure-swing energy,net loss).This leads to the identification of–SO_(2)as the optimal functional group that balances exceptional CO_(2)capture(η=6.17/12.78 for CO_(2)over CH_4/N_(2)),surpassing the second higher of 4.74/8.80 in–CF_(3)and 0.99/2.18 in non-functionalized counterparts.Adopting high-throughput computational screening methods,this work provides both fundamental insights into host–vip interactions in functionalized MOFs and a practical framework for designing next-generation adsorbents,bridging the gap between materials discovery and process engineering considerations in carbon capture technologies.
文摘Covalent organic frameworks(COFs)have lately emerged as a blooming class of potential materials for photocatalytic water splitting because of their high crystallinity,huge surface areas,and structural versatility.However,the photocatalytic performance for most pure COFs face some limitations factors,such as the significant recombination of photogenerated carriers and slow charge transfer.Herein,a novel thioether-functionalized pyrene-based COF(S_(4)-COF)was effectively produced and chosen as a support for the immobilization of ultrafine gold nanoparticles(Au NPs).S_(4)-COF photocatalyst with Au as cocatalyst demonstrates remarkable photocatalytic activity with a H_(2) generation rate of 1377μmol g^(−1) h^(−1) under visible light(>420 nm),which is ca.4.5-fold increase comparing to that of pure S_(4)-COF(302μmol g^(−1) h^(−1)).Au NPs anchored on S_(4)-COF possess an ultrafine size distribution ranging from 1.75 to 6.25 nm with an average size centered at 3.8 nm,which benefits from the coordination interaction between thioether groups and Au.Meanwhile,the produced Au@S_(4)-COF can generate a stable photocatalytic H_(2) generation during the four recycles and preserve its crystallinity structure after the stability testing.The Au NPs anchored on the S_(4)-COF photocatalyst can greatly accelerate the separation of photogenerated carriers and increase charge transfer because of the combined function of Au NPs and thioether groups.Such a method can not only prevent the aggregation of Au NPs onto thioether-containing COFs to achieve long-term photostability but also allow uniform dispersion for an ordered structure of photocatalysts.This work provides a rational strategy for designing and preparing COF-based photocatalysts for solar-driven H_(2) production.
基金supported by the National Natural Science Foundation of China(Grant No.21973029 and 21401055)the Hunan Provincial Natural Science Foundation of China(Grant No.2018JJ2113 and 2017JJ2095)the Scientific Research Fund of Hunan Provincial Education Department(Grant No.19A178).
文摘The design and synthesis of highly porous MOFs with excellent framework stability and optimized supramolecular host-vip interactions is an effective strategy to obtain high-performance MOF materials for targeted applications such as gas storage,separation,catalysis and so on.Herein,we designed and constructed a microporous(3,24)-connected rht-type acylamide functionalized MOF(HNUST-9)from dicopper(II)-paddlewheel clusters and a novel C_(2)-symmetric acylamide-linking hexacarboxylate.Interestingly,with a high density of strong CO_(2) binding sites including open copper(II)sites and acylamide groups integrated in the framework,although exhibiting moderate porosity(a BET surface area of 2429 m^(2) g^(−1)),the activated HNUST-9 shows an exceptionally high excess CO_(2) uptake capacity(21.8 mmol g^(−1) at 25 bar and 273 K),and efficient CO_(2) separation ability from CO_(2)/CH4 and CO_(2)/N_(2) binary gas mixtures under dynamic conditions at 1 bar and room temperature.Moreover,HNUST-9 demonstrates efficient catalytic activity for the CO_(2) cycloaddition with various epoxides in the presence of tetrabutylammonium bromide as the cocatalyst under mild,solvent-free conditions.
基金supported by National Nature Science Foundation of China(22275191,22275186)the Self-deployment deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(CXZX-2022-GH01,CXZX-2022-JQ11)the Nature Science Foundation of Fujian Province(No.2022I0037).
文摘The efficient separation of deuterium from hydrogen remains a significant challenge due to the limitations of conventional techniques,such as cryogenic distillation and the Girdler-sulfide process combined with electrolysis,which are char-acterized by substantial energy demands and relatively low separation coefficients.In contrast,the quantum sieving effect,based on porous materials,offers a promising approach to overcoming these challenges.This study presents a novel application of strong adsorption sites(μ3-OH group)within the nanoporous metal-organic framework of UiO-66 for hydrogen isotope separation.By incorporating diverse organic functional groups into UiO-66,we successfully synthesized four derivative materials:UiO-66-NH_(2),UiO-66-CH_(3),UiO-66-NO_(2),and UiO-66-Ph.Experimental data reveal that the introduction of these functional groups modulated the material’s pore size and channel polarity,significantly impacting its adsorption and separation performance for hydrogen isotopes.Notably,UiO-66-NH_(2),with the smallest pore size and highest channel polarity,exhibited superior hydrogen isotope adsorption capacity and selectivity,highlighting its potential as an effective adsorbent for isotope separation.
基金supported by the "Top-Notch Students Training in Basic Disciplines" undergraduate program of Ministry of Education of China
文摘Multivariate metal-organic frameworks（MTV-MOFs） with different ratios of terephthalate（BDC） linker and amino-benzenedicarboxylate（BDC-NH2） linker were synthesized through both direct synthesis from linker mixture and linker exchange of activated single-linker MOFs. Functionality proportion was impacted by the thermodynamics during the one-pot MOF construction, resulting in preference of BDC over BDC-NH2 in the MTV-MOF, in agreement with the quantum mechanics calculations. The functionality difference also affects the thermodynamics in the linker exchange process, as indicated by the more effective linker exchange in BDC-NH2-based IRMOF-3 than in BDC-based MOF-5. Furthermore,the thermal decomposition temperatures and chemical integrity upon ambient air exposure of these MOFs with variate functionalities were investigated, and it reveals that higher proportion of BDC in the MTV-MOF crystals contribute to both higher thermal and higher chemical stabilities.
基金supported by the Natural Science Foundation of Fujian Province(2024J010040 and 2024J09054)the Chinese Academy of Sciences Youth Interdisciplinary Team(JCTD-2022-12)the National Natural Science Foundation of China(22272178)。
文摘The development of C-H functionalization methods for directly converting C-H bonds into C-C bonds has drawn significant attention.These reactions typically require the concurrent involvement of distinct catalytic processes,such as photoredox and transition metal catalysis.Combining the corresponding catalytic sites within a single catalyst,instead of adding extra cocatalysts,remains a significant challenge.Here,we present a novel pyridone-based hydrogen-bonded organic framework(HOF),named PFC-943,which exhibits exceptional visible-light absorption properties while integrating both photosensitizing and redox-active sites within its skeleton.Femtosecond transient absorption spectroscopy(fs-TA)reveals that the excited-state electrons of PFC-943 in ethanol exhibit an extended lifetime.Leveraging this unique excited-state electron behavior,PFC-943converts oxygen into highly reactive singlet oxygen(^(1)O_(2))via an energy transfer(En T)pathway and facilitates a key carbanion intermediate through a single electron transfer(SET)process.Consequently,the metal-free PFC-943 exhibits remarkable photocatalytic performance in C-H bond arylation reaction of quinoxalin-2(1H)-one.This work presents the first dual-functional HOF for radical-mediated C-H functionalization reactions,offering a novel approach to C-H bond functionalization.
基金supported by the National Natural Science Foundation of China(No.62175129)the Taishan Scholar of Shandong Province(No.tsqn202306014)the Qilu Young Scholar of Shandong University.
文摘The investigation of thermal transport properties of materials has become increasingly important in technological applications,including thermal management and energy conversion.Recently,ultrahigh or low thermal conductivity has been reported in nitride,boride,and chalcogenide by different strategies.However,the strategy to design oxide crystals with unique thermal properties is also a challenge.In this work,a new ternary oxide crystal Ga_(2)TeO_(6) is designed and expected to show high thermal conductivity due to its lone pairs-free octahedra connected along the caxis by sharing edges.The thermal conductivities of Ga_(2)TeO_(6) crystal are determined to be 19.2 and 23.9Wm^(-1) K^(-1) along the a-and c-axis directions at 323 K,respectively,which are significantly higher than those of most reported oxide crystals.First-principles calculations and crystal structure analyses reveal that the Ga_(2)TeO_(6) crystal shows high sound velocity and weak lattice anharmonicity due to lone pairs-free octahedra and highly symmetric group arrangement.The results suggest that much attention must be paid to the polyhedron with lone pairs and its arrangement in materials design to balance the functions and thermal properties.
基金funded by the National Natural Science Foundation of China(grant no.82170580 to Y.Z.)the Key Research and Development Program of Jiangxi Province(20212BBG73004 to X.W.)the Postdoctoral Fellowship Program of CPSF(GZB20230283 to W.Z.).
文摘Helicobacter pylori colonizes over 50%of people worldwide.Biofilm formation through penetrating gastric mucus and resistance acquired by H.pylori markedly reduces the efficacy of traditional antibiotics.The present triple therapy and bismuth-based quadruple therapy inevitably causes intestinal flora disturbance and fails to address the excessive H.pylori-triggered inflammatory response.Herein,a mucus-permeable therapeutic platform(Cu-MOF@NF)that consists of copper-bearing metal-organic framework(Cu-MOF)loaded with nitrogen-doped carbon dots and naturally active polysaccharide fucoidan is developed.The experimental results demonstrate that Cu-MOF@NF can penetrate the mucus layer and hinder H.pylori from adhering on gastric epithelial cells of the stomach.Notably,released Cu2+can degrade the polysaccharides in the biofilm and interfere with the cyclic growing mode of"bacterioplankton↔biofilm",thereby preventing recurrent and persistent infection.Compared with traditional triple therapy,the Cu-MOF@NF not only possesses impressive antibacterial effect(even include multidrug-resistant strains),but also improves the inflammatory microenvironment without disrupting the balance of intestinal flora,providing a more efficient,safe,and antibiotic-free new approach to eradicating H.pylori.
基金financially supported by the National Natural Science Foundation of China(Nos.21975044,21971038,21922810 and 22271046)the Fujian Provincial Department of Science and Technology(Nos.2023J01355,2023J011106 and 2022R1022001).
文摘Achieving efficient adsorption and separation of C_(2)H_(2)/CO_(2)mixtures is a goal that people have always pursued to improve the situation of high energy consumption brought by traditional separation technologies in industry today.High-nuclearity metal cluster-based MOFs with different functionalities are promising for this separation,but it is a complicated and difficult task to precisely control their structures.The strategy of pore-space partition(PSP)is a powerful way to construct this type MOFs,which has the characteristic of isostructural relationship,and can be resulted in a similar performance for them.Therefore,it is an interesting work to explore the effect of MOFs property by adjusting the size of PSP dividers.Herein,three tetranuclear Cu(Ⅱ)cluster-based MOFs(FJU-112/113/114)with dual functionalities has been successfully obtained by PSP strategy with various lengths of divider units.With the highest microporosity and unique functional site,FJU-114 realized a good improvement in the adsorption and separation performance of C_(2)H_(2)/CO_(2).The gas adsorption and lab-scale C_(2)H_(2)/CO_(2)breakthrough experiments demonstrated that FJU-114 exhibits the highest adsorption uptake of 77 cm^(3)/g for C_(2)H_(2),and shows the best separation factor of 4.2 among three MOFs.The GCMC simulation reveals that a stronger adsorption binding site of C_(2)H_(2)in FJU-114a located in the cage II near the unchanged tetranuclear copper node,combined with its high microporosity to achieve the effect of dual functionalities for the improvement performance of C_(2)H_(2)adsorption and separation.
基金supported by the National Natural Science Foundation of China (Nos. 21371069 and 21621001)
文摘Metal-organic frameworks（MOFs） are a unique class of porous crystalline materials that have shown promise for a wide range of applications. MOFs have been explored as a new type of heterogeneous catalytic materials, because of their high surface area, uniform and tunable pores, facile functionalization and incorporation of catalytic active sites. The use of multi-functional sites MOF materials as catalysts for synergistic catalysis and tandem reactions has attracted increasing attention. In this review, we aim to introduce the construction of bi-or multi-functional MOF catalysts with cooperative or cascade functions via post-synthetic modification（PSM）.
基金funding support by the Department of Pharmaceuticals(DoP),Ministry of Chemicals and Fertilizers,Govt.of India to“Pharmaceutical Innovation and Translational Research Lab”(PITRL),National Institute of Pharmaceutical Education and Research(NIPER),Hyderabad,INDIA.
文摘Cancer is one of the most complex diseases and the second leading cause of mortality worldwide.Due to its poor prognosis and challenges in diagnosis,eradicating cancer remains highly difficult.The limitations associated with conventional therapies have led to the emergence of copious therapeutic strategies such as chemotherapy,phototherapy,starvation therapy,radiotherapy and immunotherapy;however,limited therapeutic efficacy,poor tumor cell selectivity and substantial adverse effects remain significant concern.Attributed to the expeditious advancement of nanotechnology,the amalgamation of nanomaterials with therapeutic approaches provides an opportunity to address the shortcomings of conventional chemotherapy.Metal-organic frameworks(MOFs),which consist of bridging ligands and ions/clusters connected by coordination bonds,have been widely used in cancer therapy to address the limitations of currently therapeutic interventions,such as poor efficacy,low stability and severe side effects.This potential arises from their tuneable porosities,high specific surface area-to-volume ratio,tailorable diameters,tractable morphologies,variegated compositions,biocompatibility and facile functionalization.We summarized the role of MOF-based nanoplatforms along with mechanistic insights into emerging avenues-such as cuproptosis,ferroptosis,cell-penetrating and biomimetic MOFs,and tumor microenvironment-responsive MOFs-alongside recent advancements in mono-and multifunctional cancer therapeutics.Theragnostic and imaging functionalities,as well as regulatory considerations and future prospects of MOF-based nanoplatforms utilized in cancer treatment,are also discussed.
基金supported by the National Key Research and Development Project of China(No.2022YFE0113800)the National Natural Science Foundation of China(No.22375179)+1 种基金the startup grant(No.2019125016829)in Zhejiang University of Technologypartially supported by the National Innovation and Entrepreneurship Training Program(No.202310337063)。
文摘Controlled synthesis of two-dimensional covalent organic frameworks(2D COFs),including stoichiometric and sub-stoichiometric variations,is a topic of growing interest due to its potential in gas separation applications.In this study,we successfully synthesized three distinct 2D COFs by carefully adjusting solvent compositions and monomer ratios during the synthesis of[4+4]type COFs.These included a stoichiometric[4+4]type COF and two sub-stoichiometric[4+2]type COFs,featuring unreacted amino or formyl groups.The resulting COFs exhibit different gas adsorption and separation properties.Specifically,sub-stoichiometric COF-DA with residual amino groups shows comparable adsorption capacity for C_(2)H_(2),C_(2)H_(4),and CO_(2)to stoichiometric COF-DAPy.In contrast,sub-stoichiometric COF-Py with residual formyl groups displays enhanced adsorption selectivity for C_(2)H_(2)/C_(2)H_(4)and C_(2)H_(2)/CO_(2)separation,with the C_(2)H_(2)/C_(2)H_(4)selectivity being the highest among reported COFs,attributed to increased pore polarity resulting from the presence of formyl groups.This study not only offers an additional example of substoichiometric COF synthesis but also advocates for further exploration of sub-stoichiometric COF materials,particularly in the field of gas adsorption and separation.
