Biological nanotechnologies based on functional nanoplatforms have synergistically catalyzed the emergence of cancer therapies.As a subtype of metal-organic frameworks(MOFs),zeolitic imidazolate frameworks(ZIFs)have e...Biological nanotechnologies based on functional nanoplatforms have synergistically catalyzed the emergence of cancer therapies.As a subtype of metal-organic frameworks(MOFs),zeolitic imidazolate frameworks(ZIFs)have exploded in popularity in the field of biomaterials as excellent protective materials with the advantages of conformational flexibility,thermal and chemical stability,and functional controllability.With these superior properties,the applications of ZIF-based materials in combination with various therapies for cancer treatment have grown rapidly in recent years,showing remarkable achievements and great potential.This review elucidates the recent advancements in the use of ZIFs as drug delivery agents for cancer therapy.The structures,synthesis methods,properties,and various modifiers of ZIFs used in oncotherapy are presented.Recent advances in the application of ZIF-based nanoparticles as single or combination tumor treatments are reviewed.Furthermore,the future prospects,potential limitations,and challenges of the application of ZIF-based nanomaterials in cancer treatment are discussed.We except to fully explore the potential of ZIF-based materials to present a clear outline for their application as an effective cancer treatment to help them achieve early clinical application.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
(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under...(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.展开更多
Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nano...Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.展开更多
The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic ...The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic frameworks(MOFs)are ideal self-sacrificing templates for the construction of carbon-based EMW absorbers.In this work,bimetallic FeMn-MOF-derived MnFe_(2)O_(4)/C/graphene composites were fabricated via a two-step route of solvothermal reaction and the following pyrolysis treatment.The results re-veal the evolution of the microscopic morphology of carbon skeletons from loofah-like to octahedral and then to polyhedron and pomegran-ate after the adjustment of the Fe^(3+)to Mn^(2+)molar ratio.Furthermore,at the Fe^(3+)to Mn^(2+)molar ratio of 2:1,the obtained MnFe_(2)O_(4)/C/graphene composite exhibited the highest EMW absorption capacity.Specifically,a minimum reflection loss of-72.7 dB and a max-imum effective absorption bandwidth of 5.1 GHz were achieved at a low filling ratio of 10wt%.In addition,the possible EMW absorp-tion mechanism of MnFe_(2)O_(4)/C/graphene composites was proposed.Therefore,the results of this work will contribute to the construction of broadband and efficient carbon-based EMW absorbers derived from MOFs.展开更多
Exploring efficient microwave absorbing materials(MAMs)has gradually become a hot topic in recent years because it is crucial in both civil and military fields.Metal-organic framework(MOF)has great potential due to it...Exploring efficient microwave absorbing materials(MAMs)has gradually become a hot topic in recent years because it is crucial in both civil and military fields.Metal-organic framework(MOF)has great potential due to its unique composition and bonding mode,which has advantages such as large specific surface area,high porosity,adjustable structure,and designable composition.Herein,MOF-derived MAMs are highlighted based on morphology and structure.The synthesis strategies of MOF-derived MAMs of different dimensions are discussed.On this basis,the structure-activity relationships can be deeply explored through the precise control of material structure and property by atomic engineering.Finally,perspectives are given for the existing problems of MOF-derived MAMs,which will open a new horizon and promote the development of MAMs.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
Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded...Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded organic frameworks(HOFs)have promising application potential for embedding enzymes.In fact,no metal involvement is required,and HOFs exhibit superior biocompatibility,and free access to substrates in mesoporous channels.Herein,a facile in situ growth approach was proposed for the self-assembly of alcohol dehydrogenase encapsulated in HOF.The micron-scale bio-catalytic composite was rapidly synthesized under mild conditions(aqueous phase and ambient temperature)with a controllable embedding rate.The high crystallinity and periodic arrangement channels of HOF were preserved at a high enzyme encapsulation efficiency of 59%.This bio-composite improved the tolerance of the enzyme to the acid-base environment and retained 81%of its initial activity after five cycles of batch hydrogenation involving NADH coenzyme.Based on this controllably synthesized bio-catalytic material and a common lipase,we further developed a two-stage cascade microchemical system and achieved the continuous production of chiral hydroxybutyric acid(R-3-HBA).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
The Fushan Depression is one of the petroliferous depressions in the Beibuwan Basin,South China Sea.Previous studies have preliminarily explored the origin and source of crude oils in some areas of this depression.Nev...The Fushan Depression is one of the petroliferous depressions in the Beibuwan Basin,South China Sea.Previous studies have preliminarily explored the origin and source of crude oils in some areas of this depression.Nevertheless,no systematic investigations on the classification and origin of oils and hy-drocarbon migration processes have been made for the entire petroleum system in this depression,which has significantly hindered the hydrocarbon exploration in the region.A total of 32 mudstone and 58 oil samples from the Fushan Depression were analyzed to definite the detailed oil-source correlation within the sequence and sedimentary framework.The organic matter of third member of Paleogene Liushagang Formation(Els(3))source rocks,both deltaic and lacustrine mudstone,are algal-dominated with high abundance of C_(23)tricyclic terpane and C_(30)4-methylsteranes.The deltaic source rocks occur-ring in the first member(Els_(1))and second member(Els_(2))of the Paleogene Liushagang Formation are characterized by high abundance of C_(19+20)tricyclic terpane and oleanane,reflecting a more terrestrial plants contribution.While lacustrine source rocks of Els_(1)and Els_(2)display the reduced input of terrige-nous organic matter with relatively low abundance of C 19+20 tricyclic terpane and oleanane.Three types of oils were identified by their biomarker compositions in this study.Most of the oils discovered in the Huachang and Bailian Els_(1)reservoir belong to group A and were derived from lacustrine source rocks of Els_(1)and Els_(2).Group B oils are found within the Els_(1)and Els_(2)reservoirs,showing a close relation to the deltaic source rocks of Els_(1)and Els_(2),respectively.Group C oils,occurring in the Els3 reservoirs,have a good affinity with the Els3 source rocks.The spatial distribution and accumulation of different groups of oils are mainly controlled by the sedimentary facies and specific structural conditions.The Els_(2)reservoir in the Yong'an area belonging to Group B oil,are adjacent to the source kitchen and could be considered as the favorable exploration area in the future.展开更多
Coating microdefects and localized corrosion in coating/metal system are inevitable,accelerating the degradation of metal infrastructure.Early evaluating coating microdefects and detecting corrosion sites are urgent y...Coating microdefects and localized corrosion in coating/metal system are inevitable,accelerating the degradation of metal infrastructure.Early evaluating coating microdefects and detecting corrosion sites are urgent yet remain challenge to achieve.Herein,we propose a robust,universal and efficient fluorescence-based strategy for hierarchical warning of coating damage and metal corrosion by introducing the concepts of damage-induced fluorescence enhancement effect(DIE)and ionic-recognition induced quenching effect(RIQ).The coatings with dualresponsiveness for coating defect and steel corrosion are constructed by incorporating synthesized nanoprobes composed of metal organic frameworks(Ni–Zn-MOFs)loaded with Rhodamine B(RhB@MOFs).The initial damage to the coating causes an immediate intensification of fluorescence,while the specific ionic-recognition characteristic of RhB with Fe3t results in an evident fluorescence quenching,enabling the detection of coating damage and corrosion.Importantly,this nanoprobes are insensitive to the coating matrix and exhibit stable corrosion warning capability across various coating systems.Meanwhile,electrochemical investigations indicate that the impedance values of RM/EP maintain above 10^(8)Ωcm^(2)even after 60 days of immersion.Therefore,the incorporation of fluorescent nanoprobes greatly inhibits the intrusion of electrolytes into polymer and improves the corrosion protection performance of the coating.This powerful strategy towards dual-level damage warning provides insights for the development of long-term smart protective materials.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
Transition metal sulfides have great potential as anode mterials for sodium-ion batteries(SIBs)due to their high theoretical specific capacities.However,the inferior intrinsic conductivity and large volume variation d...Transition metal sulfides have great potential as anode mterials for sodium-ion batteries(SIBs)due to their high theoretical specific capacities.However,the inferior intrinsic conductivity and large volume variation during sodiation-desodiation processes seriously affect its high-rate and long-cyde performance,unbeneficial for the application as fast-charging and long-cycling SIBs anode.Herein,the three-dimensional porous Cu_(1.81)S/nitrogen-doped carbon frameworks(Cu_(1.81)S/NC)are synthesized by the simple and facile sol-gel and annealing processes,which can accommodate the volumetric expansion of Cu_(1.81)S nanoparticles and accelerate the transmission of ions and electrons during Na^(+)insertion/extraction processes,exhibiting the excellent rate capability(250.6 mA·g^(-1)at 20.0 A·g^(-1))and outstanding cycling stability(70% capacity retention for 6000 cycles at 10.0 A·g^(-1))for SIBs.Moreover,the Na-ion full cells coupled with Na_(3)V_(2)(PO_(4))_(3)/C cathode also demonstrate the satisfactory reversible specific capacity of 330.5 mAh·g^(-1)at 5.0 A·g^(-1)and long-cycle performance with the 86.9% capacity retention at 2.0 A·g^(-1)after 750 cycles.This work proposes a promising way for the conversionbased metal sulfides for the applications as fast-charging sodium-ion battery anode.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
Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1....Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.展开更多
Metal-organic frameworks(MOFs)are import-ant as possible energy storage materials.Nitrogen-doped iron-cobalt MOFs were synthesized by a one-pot solvo-thermal method using CoCl_(3)·6H_(2)O and FeCl_(3)·6H_(2)...Metal-organic frameworks(MOFs)are import-ant as possible energy storage materials.Nitrogen-doped iron-cobalt MOFs were synthesized by a one-pot solvo-thermal method using CoCl_(3)·6H_(2)O and FeCl_(3)·6H_(2)O dis-solved in N,N-dimethylformamide,and were converted into Fe-Co embedded in N-doped porous carbon polyhedra by pyrolysis in a nitrogen atmosphere.During pyrolysis,the or-ganic ligands transformed into N-doped porous carbon which improved their structural stability and also their electrical contact with other materials.The Fe and Co are tightly bound together because of their encapsulation by the carbon nitride and are well dispersed in the carbon matrix,and improve the material’s conductivity and stability and provide additional capacity.When used as the anode for lithium-ion batteries,the material gives an initial capacity of up to 2230.7 mAh g^(-1)and a reversible capa-city of 1146.3 mAh g^(-1)is retained after 500 cycles at a current density of 0.5 A g^(-1),making it an excellent candidate for this purpose.展开更多
Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imida...Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imidazol-1-yl)phenyl]amine(tipa)ligand,whose molecular formula is(Me_(2)CH_(2))_(2)[Mg_(3)(Ti_(4)L_(6))(tipa)(H_(2)O)_(12)](PTC‑378).The Ti_(4)L_(6)tetrahedral cages serve as robust building units,while the Mg^(2+)ions and tipa ligands provide structural stability and tunable optical properties.The resulting PTC‑378 film exhibited intriguing third-order NLO property,which was systematically investigated using Z-scan techniques.Our results demonstrate that the synergistic interaction between Ti_(4)L_(6)cages andπ-conjugated ligands significantly enhances the NLO performance of the materials.CCDC:2453909.展开更多
Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as...Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms,the obtained Pt-on-Co/C400 catalysts exhib-ited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency(TOF)value of 3022 min^(-1)at 303 K.Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability,and there were no changes in the catalyst structures and catalytic activities after 10 cycles.展开更多
The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNT...The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNTs)during the growth process of MOF crystals,synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure.Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin.Simultaneously,the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency.X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT changed the electron cloud density on the catalytic active center Co,optimizing the electronic structure.Consequently,the E_(1/2) of the TCPPCo-MOF-CNT catalyst under neutral conditions reached 0.77 V(vs.RHE),outperforming the catalyst without CNTs.When the TCPPCo-MOF-CNT was employed as the cathode catalyst in assembling microbial fuel cells(MFCs)with Nafion-117 as the proton exchange membrane,the maxi-mum power density of MFCs reached approximately 500 mW·m^(-2).展开更多
基金National Natural Science Foundation of China(52073278)the“Medical Science+X”Cross-innovation Team of the Norman Bethune Health Science of Jilin University(2022JBGS10)+2 种基金the Jilin Province Science and Technology Development Program(20190201044JC20230101045JC)the Education Department of Jilin Province(JJKH20231205KJ).
文摘Biological nanotechnologies based on functional nanoplatforms have synergistically catalyzed the emergence of cancer therapies.As a subtype of metal-organic frameworks(MOFs),zeolitic imidazolate frameworks(ZIFs)have exploded in popularity in the field of biomaterials as excellent protective materials with the advantages of conformational flexibility,thermal and chemical stability,and functional controllability.With these superior properties,the applications of ZIF-based materials in combination with various therapies for cancer treatment have grown rapidly in recent years,showing remarkable achievements and great potential.This review elucidates the recent advancements in the use of ZIFs as drug delivery agents for cancer therapy.The structures,synthesis methods,properties,and various modifiers of ZIFs used in oncotherapy are presented.Recent advances in the application of ZIF-based nanoparticles as single or combination tumor treatments are reviewed.Furthermore,the future prospects,potential limitations,and challenges of the application of ZIF-based nanomaterials in cancer treatment are discussed.We except to fully explore the potential of ZIF-based materials to present a clear outline for their application as an effective cancer treatment to help them achieve early clinical application.
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.
文摘(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.
文摘Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.
基金supported by the Natural Science Research Project of the Anhui Educational Committee,China(No.2022AH050827)the Open Research Fund Program of Anhui Province Key Laboratory of Specialty Polymers,Anhui University of Science and Technology,China(No.AHKLSP23-12)the Joint National-Local Engineering Research Center for Safe and Precise Coal Mining Fund,China(No.EC2022020)。
文摘The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic frameworks(MOFs)are ideal self-sacrificing templates for the construction of carbon-based EMW absorbers.In this work,bimetallic FeMn-MOF-derived MnFe_(2)O_(4)/C/graphene composites were fabricated via a two-step route of solvothermal reaction and the following pyrolysis treatment.The results re-veal the evolution of the microscopic morphology of carbon skeletons from loofah-like to octahedral and then to polyhedron and pomegran-ate after the adjustment of the Fe^(3+)to Mn^(2+)molar ratio.Furthermore,at the Fe^(3+)to Mn^(2+)molar ratio of 2:1,the obtained MnFe_(2)O_(4)/C/graphene composite exhibited the highest EMW absorption capacity.Specifically,a minimum reflection loss of-72.7 dB and a max-imum effective absorption bandwidth of 5.1 GHz were achieved at a low filling ratio of 10wt%.In addition,the possible EMW absorp-tion mechanism of MnFe_(2)O_(4)/C/graphene composites was proposed.Therefore,the results of this work will contribute to the construction of broadband and efficient carbon-based EMW absorbers derived from MOFs.
基金supported by the National Natural Science Foundation of China(Nos.52373280,52177014 and 52273257).
文摘Exploring efficient microwave absorbing materials(MAMs)has gradually become a hot topic in recent years because it is crucial in both civil and military fields.Metal-organic framework(MOF)has great potential due to its unique composition and bonding mode,which has advantages such as large specific surface area,high porosity,adjustable structure,and designable composition.Herein,MOF-derived MAMs are highlighted based on morphology and structure.The synthesis strategies of MOF-derived MAMs of different dimensions are discussed.On this basis,the structure-activity relationships can be deeply explored through the precise control of material structure and property by atomic engineering.Finally,perspectives are given for the existing problems of MOF-derived MAMs,which will open a new horizon and promote the development of MAMs.
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 Key Research and Development Program of China(2019YFA0905100)the National Natural Science Foundation of China(21991102,22378227).
文摘Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded organic frameworks(HOFs)have promising application potential for embedding enzymes.In fact,no metal involvement is required,and HOFs exhibit superior biocompatibility,and free access to substrates in mesoporous channels.Herein,a facile in situ growth approach was proposed for the self-assembly of alcohol dehydrogenase encapsulated in HOF.The micron-scale bio-catalytic composite was rapidly synthesized under mild conditions(aqueous phase and ambient temperature)with a controllable embedding rate.The high crystallinity and periodic arrangement channels of HOF were preserved at a high enzyme encapsulation efficiency of 59%.This bio-composite improved the tolerance of the enzyme to the acid-base environment and retained 81%of its initial activity after five cycles of batch hydrogenation involving NADH coenzyme.Based on this controllably synthesized bio-catalytic material and a common lipase,we further developed a two-stage cascade microchemical system and achieved the continuous production of chiral hydroxybutyric acid(R-3-HBA).
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funded by the South Oil Exploration and Development Company of PetroChina(2021-HNYJ-010).
文摘The Fushan Depression is one of the petroliferous depressions in the Beibuwan Basin,South China Sea.Previous studies have preliminarily explored the origin and source of crude oils in some areas of this depression.Nevertheless,no systematic investigations on the classification and origin of oils and hy-drocarbon migration processes have been made for the entire petroleum system in this depression,which has significantly hindered the hydrocarbon exploration in the region.A total of 32 mudstone and 58 oil samples from the Fushan Depression were analyzed to definite the detailed oil-source correlation within the sequence and sedimentary framework.The organic matter of third member of Paleogene Liushagang Formation(Els(3))source rocks,both deltaic and lacustrine mudstone,are algal-dominated with high abundance of C_(23)tricyclic terpane and C_(30)4-methylsteranes.The deltaic source rocks occur-ring in the first member(Els_(1))and second member(Els_(2))of the Paleogene Liushagang Formation are characterized by high abundance of C_(19+20)tricyclic terpane and oleanane,reflecting a more terrestrial plants contribution.While lacustrine source rocks of Els_(1)and Els_(2)display the reduced input of terrige-nous organic matter with relatively low abundance of C 19+20 tricyclic terpane and oleanane.Three types of oils were identified by their biomarker compositions in this study.Most of the oils discovered in the Huachang and Bailian Els_(1)reservoir belong to group A and were derived from lacustrine source rocks of Els_(1)and Els_(2).Group B oils are found within the Els_(1)and Els_(2)reservoirs,showing a close relation to the deltaic source rocks of Els_(1)and Els_(2),respectively.Group C oils,occurring in the Els3 reservoirs,have a good affinity with the Els3 source rocks.The spatial distribution and accumulation of different groups of oils are mainly controlled by the sedimentary facies and specific structural conditions.The Els_(2)reservoir in the Yong'an area belonging to Group B oil,are adjacent to the source kitchen and could be considered as the favorable exploration area in the future.
基金support by the National Natural Science Foundation of China(52201077)the Natural Science Foundation of Shandong Province(ZR2022QE191)+1 种基金Elite Scheme of Shandong University of Science and Technology(0104060541123)Talent introduction and Research Start-up Fund of Shandong University of Science and Technology(0104060510124).
文摘Coating microdefects and localized corrosion in coating/metal system are inevitable,accelerating the degradation of metal infrastructure.Early evaluating coating microdefects and detecting corrosion sites are urgent yet remain challenge to achieve.Herein,we propose a robust,universal and efficient fluorescence-based strategy for hierarchical warning of coating damage and metal corrosion by introducing the concepts of damage-induced fluorescence enhancement effect(DIE)and ionic-recognition induced quenching effect(RIQ).The coatings with dualresponsiveness for coating defect and steel corrosion are constructed by incorporating synthesized nanoprobes composed of metal organic frameworks(Ni–Zn-MOFs)loaded with Rhodamine B(RhB@MOFs).The initial damage to the coating causes an immediate intensification of fluorescence,while the specific ionic-recognition characteristic of RhB with Fe3t results in an evident fluorescence quenching,enabling the detection of coating damage and corrosion.Importantly,this nanoprobes are insensitive to the coating matrix and exhibit stable corrosion warning capability across various coating systems.Meanwhile,electrochemical investigations indicate that the impedance values of RM/EP maintain above 10^(8)Ωcm^(2)even after 60 days of immersion.Therefore,the incorporation of fluorescent nanoprobes greatly inhibits the intrusion of electrolytes into polymer and improves the corrosion protection performance of the coating.This powerful strategy towards dual-level damage warning provides insights for the development of long-term smart protective materials.
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financially supported by the National Natural Science Foundation of China(Nos.U1904173 and 52272219)the Key Research Projects of Henan Provincial Department of Education(No.19A150043)+2 种基金the Natural Science Foundation of Henan Province(Nos.202300410330 and 222300420276)the Nanhu Scholars Program for Young Scholars of Xinyang Normal Universitythe Xinyang Normal University Analysis&Testing Center。
文摘Transition metal sulfides have great potential as anode mterials for sodium-ion batteries(SIBs)due to their high theoretical specific capacities.However,the inferior intrinsic conductivity and large volume variation during sodiation-desodiation processes seriously affect its high-rate and long-cyde performance,unbeneficial for the application as fast-charging and long-cycling SIBs anode.Herein,the three-dimensional porous Cu_(1.81)S/nitrogen-doped carbon frameworks(Cu_(1.81)S/NC)are synthesized by the simple and facile sol-gel and annealing processes,which can accommodate the volumetric expansion of Cu_(1.81)S nanoparticles and accelerate the transmission of ions and electrons during Na^(+)insertion/extraction processes,exhibiting the excellent rate capability(250.6 mA·g^(-1)at 20.0 A·g^(-1))and outstanding cycling stability(70% capacity retention for 6000 cycles at 10.0 A·g^(-1))for SIBs.Moreover,the Na-ion full cells coupled with Na_(3)V_(2)(PO_(4))_(3)/C cathode also demonstrate the satisfactory reversible specific capacity of 330.5 mAh·g^(-1)at 5.0 A·g^(-1)and long-cycle performance with the 86.9% capacity retention at 2.0 A·g^(-1)after 750 cycles.This work proposes a promising way for the conversionbased metal sulfides for the applications as fast-charging sodium-ion battery anode.
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.
文摘Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.
文摘Metal-organic frameworks(MOFs)are import-ant as possible energy storage materials.Nitrogen-doped iron-cobalt MOFs were synthesized by a one-pot solvo-thermal method using CoCl_(3)·6H_(2)O and FeCl_(3)·6H_(2)O dis-solved in N,N-dimethylformamide,and were converted into Fe-Co embedded in N-doped porous carbon polyhedra by pyrolysis in a nitrogen atmosphere.During pyrolysis,the or-ganic ligands transformed into N-doped porous carbon which improved their structural stability and also their electrical contact with other materials.The Fe and Co are tightly bound together because of their encapsulation by the carbon nitride and are well dispersed in the carbon matrix,and improve the material’s conductivity and stability and provide additional capacity.When used as the anode for lithium-ion batteries,the material gives an initial capacity of up to 2230.7 mAh g^(-1)and a reversible capa-city of 1146.3 mAh g^(-1)is retained after 500 cycles at a current density of 0.5 A g^(-1),making it an excellent candidate for this purpose.
文摘Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imidazol-1-yl)phenyl]amine(tipa)ligand,whose molecular formula is(Me_(2)CH_(2))_(2)[Mg_(3)(Ti_(4)L_(6))(tipa)(H_(2)O)_(12)](PTC‑378).The Ti_(4)L_(6)tetrahedral cages serve as robust building units,while the Mg^(2+)ions and tipa ligands provide structural stability and tunable optical properties.The resulting PTC‑378 film exhibited intriguing third-order NLO property,which was systematically investigated using Z-scan techniques.Our results demonstrate that the synergistic interaction between Ti_(4)L_(6)cages andπ-conjugated ligands significantly enhances the NLO performance of the materials.CCDC:2453909.
文摘Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms,the obtained Pt-on-Co/C400 catalysts exhib-ited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency(TOF)value of 3022 min^(-1)at 303 K.Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability,and there were no changes in the catalyst structures and catalytic activities after 10 cycles.
基金the financial support from the National Natural Science Foundation of China(No.22178307)China Southern Power Grid(Grant Nos.0470002022030103HX00002-01).
文摘The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNTs)during the growth process of MOF crystals,synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure.Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin.Simultaneously,the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency.X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT changed the electron cloud density on the catalytic active center Co,optimizing the electronic structure.Consequently,the E_(1/2) of the TCPPCo-MOF-CNT catalyst under neutral conditions reached 0.77 V(vs.RHE),outperforming the catalyst without CNTs.When the TCPPCo-MOF-CNT was employed as the cathode catalyst in assembling microbial fuel cells(MFCs)with Nafion-117 as the proton exchange membrane,the maxi-mum power density of MFCs reached approximately 500 mW·m^(-2).
