Room temperature phosphorescence(RTP)materials show potential applications in information security and optoelectronic devices,but it is still a challenge to achieve RTP in organic materials under water ambient due to ...Room temperature phosphorescence(RTP)materials show potential applications in information security and optoelectronic devices,but it is still a challenge to achieve RTP in organic materials under water ambient due to the unstable property of triplet states.Herein,water-induced RTP has been demonstrated in the organic microrod(OMR).Noting that the RTP intensity of the as-prepared OMR is greatly enhanced when water is introduced,and the reason for the enhancement can be attributed to the formation of hydrogen-bonded networks inside the OMR.The hydrogen-bonded networks can confine the molecular motion effectively,leading to the stability of triplet states;thus the lifetime of the OMR can reach 1.64 s after introducing water.By virtue of the long lifetime of the OMR in the presence of water,multilevel data encryption based on the OMR has been demonstrated.展开更多
A new method is proposed to quick predict the strength of intermolecular hydrogen bonds.The method is employed to produce the hydrogen-bonding potential energy curves of twenty-nine hydro-gen-bonded dimers.The calcula...A new method is proposed to quick predict the strength of intermolecular hydrogen bonds.The method is employed to produce the hydrogen-bonding potential energy curves of twenty-nine hydro-gen-bonded dimers.The calculation results show that the hydrogen-bonding potential energy curves obtained from this method are in good agreement with those obtained from MP2/6-31+G calculations by including the BSSE correction,which demonstrate that the method proposed in this work can be used to calculate the hydrogen-bonding interactions in peptides.展开更多
To develop porous organic frameworks,precise control of the stacking manner of two-dimensional porous motifs and structural characterization of the resultant framework are important.From these points of view,porous mo...To develop porous organic frameworks,precise control of the stacking manner of two-dimensional porous motifs and structural characterization of the resultant framework are important.From these points of view,porous molecular crystals formed through reversible intermolecular hydrogen bonds,such as;hydrogen-bonded organic frameworks(HOFs),can provide deep insight because of their high crystallinity,affording single-crystalline X-ray diffraction analysis.In this study,we demonstrate that the stacking manner of hydrogen-bonded hexagonal network(HexNet)sheets can be controlled by synchronizing a homological triangular macrocyclic tecton and a hydrogen-bonded cyclic supramolecular synthon called the phenylene triangle.A structure of the resultant HOF was crystallographically characterized and revealed to have a large channel aperture of 2.4 nm.The HOF also shows thermal stability up to 290°C,which is higher than that of the conventional HexNet frameworks.展开更多
Flexible-robust hydrogen-bonded organic frameworks(HOFs)are attracting increasing interest due to their excellent separation performance for important industrial gases,but the construction remains challenging.Herein,a...Flexible-robust hydrogen-bonded organic frameworks(HOFs)are attracting increasing interest due to their excellent separation performance for important industrial gases,but the construction remains challenging.Herein,a sticked-layer strategy is first proposed to construct a flexible-robust HOF,HOFFJU-8,from a donor(D)–π–acceptor(A)molecule 4,4′,4″,4‴-(pyrrolo[3,2-b]pyrrole-1,2,4,5-tetrayl)tetrabenzonitrile(DP-4CN).HOF-FJU-8 is amicroporous three-dimensional framework composed of two kinds of DP-4CN molecules,one acting as building units for the two-dimensional layer via C≡N···H–C hydrogen bond dimers and another as the sticks to link the layers along channels through D–Aπ···πinteractions.The activated framework HOF-FJU-8a possesses flexible-robust pore characteristics,as determined by the gas adsorption and in situ gas-loaded powder X-ray diffraction.HOF-FJU-8a exhibits adaptive adsorption and stronger binding affinity to C_(2)H_(2)rather than CO_(2)due to the flexible-robust nature,which can effectively separate acetylene and carbon dioxide mixtures.展开更多
Hydrogen-bonded organic frameworks(HOFs)are a recent class of porous materials that have garnered considerable research interest owing to their distinctive characteristics.HOFs can be constructed through judicious sel...Hydrogen-bonded organic frameworks(HOFs)are a recent class of porous materials that have garnered considerable research interest owing to their distinctive characteristics.HOFs can be constructed through judicious selection of H-bonding motifs,which are further enforced by other weak intermolecular interactions such asπ–πstacking,van der Waals forces,and framework interpenetration.Taking advantage of these interactions,we can expand the functional field of HOFs by introducing active molecules.Recently,researchers have made substantial advancements in using HOFs for chemical sensing,catalysis,proton conduction,biological applications,and others.The low bonding energy of H-bonds allows for precise control over the concentration of ligands in solvents,forming diverse HOF structures.These varied structures offer significant advantages for producing HOFs with photo-responsive and electro-responsive properties.However,the presence of H-bonds in HOFs results in their inherent lower stability compared to metal-organic frameworks(MOFs)and covalent-organic frameworks(COFs)formed via coordination and covalent bonds,respectively.As a result,the pursuit of stable and innovative HOF materials with novel functional sites remains an ongoing challenge.This review provides an overview of recent research progress in the development of new strategies for stable HOF synthesis and applications of HOFs with stimuli-responsive properties.We first classified all synthetic methods reported to date and discussed the stable HOFs synthesized,as well as their unique properties and applications.In addition,we summarized the applications of HOFs utilizing their synergistic responses to external stimuli,including photo,electrical,pressure,and chemical stimuli.We systematically reviewed stable HOF synthesis and applications,which may lead to a deeper understanding of the structure–activity relationship for these materials and guide future HOF design.展开更多
Nickel-rich layered oxide cathode(LiNi_(x)Co_(y)Mn_(1−x−y)O_(2),x>0.5,NCM)shows substantial potential for applications in longer-range electrical vehicles.However,the rapid capacity decay and serious safety concern...Nickel-rich layered oxide cathode(LiNi_(x)Co_(y)Mn_(1−x−y)O_(2),x>0.5,NCM)shows substantial potential for applications in longer-range electrical vehicles.However,the rapid capacity decay and serious safety concerns impede its practical viability.This work provides a hydrogen-bonded organic framework(HOF)modification strategy to simultaneously improve the electrochemical performance,thermal stability and incombustibility of separator.Melamine cyanurate(MCA),as a low-cost and reliable flame-retardant HOF,was implemented in the separator modification layer,which can prevent the battery short circuit even at a high temperature.In addition,the supermolecule properties of MCA provide unique physical and chemical microenvironment for regulating ion-transport behavior in electrolyte.The MCA coating layer enabled the nickel-rich layered oxide cathode with a high-capacity retention of 90.3%after 300 cycles at 1.0 C.Collectively,the usage of MCA in lithium-ion batteries(LIBs)affords a simple,low-cost and efficient strategy to improve the security and service life of nickel-rich layered cathodes.展开更多
The development of hydrogen-bonded organic frameworks(HOFs)faces significant constraints,primarily attributed to their fragile architectures and limited functionalization capabilities.To overcome these limitations,thi...The development of hydrogen-bonded organic frameworks(HOFs)faces significant constraints,primarily attributed to their fragile architectures and limited functionalization capabilities.To overcome these limitations,this work presents a new polymeron-HOF strategy by covalently tethering armor-like polymers onto the surface of HOFs.The application of this approach not only bolsters the stability of HOFs,but also facilitates the customization of their functional expansion in radionuclide sequestration.The optimized HOF-polymer materials display extraordinary ability in radionuclide sequestration,achieving uptake of I^(-)(0.699 g g^(-1)),IO_(3)^(-)(0.285 g g^(-1))and ReO_(4)^(-)(1.616 g g^(-1),setting a world record),fast adsorption kinetics(~100% removal within 45 s),and exceptional regeneration capability(>30 cycles)under continuous flow conditions.These outstanding performances benefit from the internal porous channels and surface imidazolium polymer coatings of HOFs,as proved by density functional theory calculation and molecular dynamics simulations.This work paves the way for the rational design of HOF-based hybrid materials tailored to versatile applications.展开更多
Hydrogen-bonded organic frameworks(HOFs)have emerged as a new class of crystalline porous materials,and their application in membrane technology needs to be explored.Herein,for the first time,we demonstrated the utili...Hydrogen-bonded organic frameworks(HOFs)have emerged as a new class of crystalline porous materials,and their application in membrane technology needs to be explored.Herein,for the first time,we demonstrated the utilization of HOF-based mixed-matrix membrane for CO_(2) separation.HOF-21,a unique metallo-hydrogen-bonded organic framework material,was designed and processed into nanofillers via amine modulator,uniformly dispersing with Pebax polymer.Featured with the mix-bonded framework,HOF-21 possessed moderate pore size of 0.35 nm and displayed excellent stability under humid feed gas.The chemical functions of multiple binding sites and continuous hydrogen-bonded network jointly facilitated the mass transport of CO_(2).The resulting HOF-21 mixed-matrix membrane exhibited a permeability above 750 Barrer,a selectivity of~40 for CO_(2)/CH_(4) and~60 for CO_(2)/N_(2),surpassing the 2008 Robeson upper bound.This work enlarges the family of mixed-matrix membranes and lays the foundation for HOF membrane development.展开更多
Safe confinement of fission iodine isotopes for long-term radioactive waste disposal remains a formidable challenge,as conventional sorbents provide inherently weak iodine-host interactions.We report here a novel halo...Safe confinement of fission iodine isotopes for long-term radioactive waste disposal remains a formidable challenge,as conventional sorbents provide inherently weak iodine-host interactions.We report here a novel halogen bond(X-bond)directed strategy to sequester volatile iodine in hydrogen-bonded(H-bonded)frameworks with unprecedented stability.Charge-assisted Hbonded frameworks bearing open halide sites are developed,showing distinctive iodine encapsulation behaviors without compromising the crystallinity.Direct crystallographic evidence indicates the formation of X-bonds,i.e.,I–I···Cl^(−) and I–I···Br^(−),within the confined pore channels.Unusual polyhalogen anions,i.e.,[I_(2)Cl_(2)]^(2−)and[I_(2)Br_(2)]^(2−),sustained in H-bonded frameworks are identified for the first time.The X-bond reinforced host-guest interaction affords robust iodine trapping without leaking out even at elevated temperatures up to 180℃.By integrating the halogen-bond chemistry with H-bonded frameworks,this study offers fresh concepts for developing effective host reservoirs to secure fission iodine isotopes from spent fuel reprocessing off-gases.展开更多
Porous organic molecular materials(POMMs)are an emergent class of molecular-based materials characterized by the formation of extended porous frameworks,mainly held by non-covalent interactions.POMMs represent a varie...Porous organic molecular materials(POMMs)are an emergent class of molecular-based materials characterized by the formation of extended porous frameworks,mainly held by non-covalent interactions.POMMs represent a variety of chemical families,such as hydrogen-bonded organic frameworks,porous organic salts,porous organic cages,C-H···πmicroporous crystals,supramolecular organic frameworks,π-organic frameworks,halogen-bonded organic framework,and intrinsically porous molecular materials.In some porous materials such as zeolites and metal organic frameworks,the integration of multiscale has been adopted to build materials with multifunctionality and optimized properties.Therefore,considering the significant role of hierarchy in porous materials and the growing importance of POMMs in the realm of synthetic porous materials,we consider it appropriate to dedicate for the first time a critical review covering both topics.Herein,we will provide a summary of literature examples showcasing hierarchical POMMs,with a focus on their main synthetic approaches,applications,and the advantages brought forth by introducing hierarchy.展开更多
By tactically integrating two different kinds of proton donors and acceptors into one supramolecular tecton, a new crystalline hydrogen-bonded organic framework(HOF-SXU-1) has been developed. HOF-SXU-1 features a rema...By tactically integrating two different kinds of proton donors and acceptors into one supramolecular tecton, a new crystalline hydrogen-bonded organic framework(HOF-SXU-1) has been developed. HOF-SXU-1 features a remarkable proton conductivity as high as 6.32 mS cm^(-1) and an extremely low activation energy of 0.16 eV at 160℃ under anhydrous N_(2) conditions.By contrast, under identical conditions, the organic precursors of HOF-SXU-1 only exhibit negligible proton conduction performance, demonstrating that the formation of HOF is crucial for excellent proton conduction performance.展开更多
Elasticity,as an emerging phenomenon of crystals,endows the newfangled properties on crystals owing to the altered local crystallinity in the deformed state,and hence attracts increasing research endeavors.However,onl...Elasticity,as an emerging phenomenon of crystals,endows the newfangled properties on crystals owing to the altered local crystallinity in the deformed state,and hence attracts increasing research endeavors.However,only a few molecular crystals and a limited number of one-dimensional coordination polymer crystals have exhibited such fantastic elastic response under mechanical stress.Herein,we report the first example of elastic hydrogen-bonded ionic framework(HIF)of{(CN_(3)H_(6))_(2)[Ti(μ_(2)-O)(SO_(4))_(2)]}n,assembled from one-dimensional negatively charged inorganic[Ti(μ_(2)-O)(SO_(4))_(2)]n 2n-chains and positively charged organic guanidinium cations via hydrogen bonds and electrostatic interactions.The slender prismatic single crystal exhibits remarkable elasticity with an optimal elastic bending strain(ε)of 2.5%.Impressively,the crystals give rise to two-dimensional elasticity owing to the equivalent crystallographic planes of the exposed faces and an unusual elastic response at liquid nitrogen temperature.The in-depth crystallographic analyses reveal hydrogen bonds and electrostatic interactions between anion chains and cations function like adhesive glue and account for such specific elastic properties,owing to the flexible and dynamic attributes of hydrogen bonds as they can work in a range of distance and orientation.And the channel in HIF provides space for bending with reduced strain.Incorporating these factors into low-dimensional crystals could be a general guidance for designing elastic crystals.Elasticity ganged with other intrinsic properties of HIF materials could inspire their newfangled applications in the near future.展开更多
Understanding the mechanisms underlying the assembly of nucleobases is a great challenge. The ability to deeply understand how nucleobases interact with themselves as well as with other molecules will allow us to gain...Understanding the mechanisms underlying the assembly of nucleobases is a great challenge. The ability to deeply understand how nucleobases interact with themselves as well as with other molecules will allow us to gain valuable insights into how we might be able to harness these interesting biological molecules to construct complex nanostructures and materials. Uracil and thymine derivatives have been reported for use in biological applications and in self-assembling triple hydrogen bonded systems. Either uracil or thymine possesses three binding sites （Site 1, Site 2, and Site 3） that can induce strong directional N-H...O=C hydrogen bonding interaction. In this paper, theoretical calculations are carded out on the structural features and binding energies of hydrogen-bonded dimers and trimers formed by uracil and thymine bases. We find that the hydrogen bonds formed through Site 1 are the strongest, those formed through Site 3 are next, while those formed through Site 2 are the weakest. The atoms in molecules analysis show that the electron densities at the bond critical points and the corresponding Laplacians have greater values for those hydrogen bonds formed through Site 1 than through Site 2. All these results indicate that a uracil （or thymine） would interact with another uracil or thymine most likely through Site 1 and least likely through Site 2. We also find that a simple summation rule roughly exists for the binding energies in these dimers and trimers.展开更多
Hydrogen-bonded polymer complex fiber of poly(ethylene oxide)(PEO)and poly(acrylic acid)(PAA)shows rubber elasticity in ambient environment,but the fiber has relatively low strength and weak stability.We apply the cat...Hydrogen-bonded polymer complex fiber of poly(ethylene oxide)(PEO)and poly(acrylic acid)(PAA)shows rubber elasticity in ambient environment,but the fiber has relatively low strength and weak stability.We apply the catechol chemistry and metal coordination to stabilize and strengthen the PEO/PAA fiber.PAA is grafted with dopamine(Dopa),and then combines with PEO to prepare fiber.PAA-Dopa in the fiber is crosslinked through oxidation induced dismutation and the metal ions are introduced through coordination.The cross-linking and coordination greatly improve the stability of the fiber against the erosion of alkaline water.Among four different metal coordination fibers,PEO/PAA-Dopa/Cu fiber keeps the excellent extensibility(~1000%)and presents much higher initial modulus(~7 MPa),ultimate strength(~20 MPa),and toughness(~60 MJ/m^(3))than its precursor PEO/PAA fiber.In addition,PEO/PAA-Dopa/Cu fiber shows quick recovery and large energy dissipation ratio compared with the PEO/PAA fiber.The distinct mechanical properties enhancement of the hydrogen-bonded complex fiber is attributed to the synergy of hydrogen bonds,coordination and covalent bond cross-linking.展开更多
Hydrogen-bonded organic frameworks(HOFs),an emerging porous macrocyclic materials linked by hydrogen-bond,hold potential for gas separation and storage,sensors,optical,and electrocatalysts.Here,HOF-based electrocataly...Hydrogen-bonded organic frameworks(HOFs),an emerging porous macrocyclic materials linked by hydrogen-bond,hold potential for gas separation and storage,sensors,optical,and electrocatalysts.Here,HOF-based electrocatalysts are rationally developed for nitrates reduction to ammonia,allowing not only to regulate wastewater pollution but also to accomplish carbon-neutral ammonia(NH_(3))synthesis.We preform high-throughput computational screening of thirty-six HOFs with various metals as active sites,denoted as HOF-M1,for nitrate reduction reaction(NO_(3)RR)toward NH_(3).We have implemented a hierarchical four-step screening strategy,and ultimately,HOF-Ti1 was selected based on its exceptional catalytic activity and selectivity in the NO_(3)RR process.Through additional analysis,we discovered that the d band center of the active metal sites serves as an effective parameter for designing and predicting the performance of HOFs in NO_(3)RR.This research not only showcases the immense potential of electrocatalysis in transforming NO_(3)RR into NH_(3)but also provides researchers with a compelling incentive to undertake further experimental investigations.展开更多
Developing smart room-temperature phosphorescence(RTP)materials with facile and efficient strategies have attracted increasing attention.Herein,tunable RTP materials with two phosphorescent sources and stepwise enhanc...Developing smart room-temperature phosphorescence(RTP)materials with facile and efficient strategies have attracted increasing attention.Herein,tunable RTP materials with two phosphorescent sources and stepwise enhanced phosphorescence in water are obtained through an in-situ self-assembly strategy based on the sensitization of phosphors by trimesic acid(TMA)through simple doping and the rigidification of phosphors by hydrogen-bonded organic frameworks(HOFs).As expected,doped TMA+phosphors simultaneously promote the RTP emission of phosphors and maintain TMA phosphorescence.In-situ assembled HOF(MATMA)@phosphors facilitate smart RTP emission in water due to the coexistence of phosphorescent HOF(MA-TMA)host and phosphors guest.Additionally,such RTP materials with good processability demonstrate the application potential in information security,benefitting from their varied afterglow lifetimes and easy luminous recognition in the darkness.This work will inspire the design of dual phosphorescent source RTP systems and provide new strategies for the development of smart RTP materials in water.展开更多
Gas hydrate is a promising alternative for gas capture and storage due to its high gas storage capacity achieved with only structured water molecules.Nucleation is the critical controlling step in gas hydrate formatio...Gas hydrate is a promising alternative for gas capture and storage due to its high gas storage capacity achieved with only structured water molecules.Nucleation is the critical controlling step in gas hydrate formation.Adding an alien solid surface is an effective approach to regulate gas hydrate nucleation.However,how the solid surface compositions control the gas hydrate nucleation remains unclear.Benefiting from the fact that the surface compositions of graphene oxide(GO)can be finely tuned,we report the effect of functional groups of size-selected GO flakes on methane hydrate nucleation.The carbonyl and carboxyl of GO flakes showed a more prominent promotion for methane hydrate nucleation than the hydroxyl of GO flakes.Surface energy,zeta potential,Raman spectra,and molecular dynamics simulation analysis were used to reveal the regulation mechanism of the functional groups of size-selected GO flakes on methane hydrate nucleation.The GO flakes with abundant carbonyl and carboxyl exhibited higher charge density than those enriched in hydroxyl.The negatively charged GO flakes can induce water molecules to form an ordered hydrogen-bonded arrangement via charge-dipole interactions.Therefore,the water molecules surrounding the carboxyl and carbonyl showed a more ordered hydrogen-bonded structure than those around the hydroxyl of GO flakes.The ordered water arrangement,similar to methane hydrate cages,significantly accelerated methane hydrate nucleation.Our study shows how the surface chemistry of solids control gas hydrate nucleation and sheds light on the design of effective heterogeneous nucleators for gas hydrate.展开更多
Hydrogen-bonded organic frameworks(HOFs)are an emerging class of porous materials that hold promise for the adsorptive separation of industrially relevant gas mixtures.However,developing HOFs with high thermal stabili...Hydrogen-bonded organic frameworks(HOFs)are an emerging class of porous materials that hold promise for the adsorptive separation of industrially relevant gas mixtures.However,developing HOFs with high thermal stability and resistance to water remains a daunting challenge.We report here a microporous HOF(HIAM-103)assembled from a hexacarboxylate linker(2,4,6-trimethylbenzene-1,3,5-triylisophthalic acid,H6TMBTI).The compound crystallizes in the trigonal crystal system,and its structure is a four-fold interpenetrated network.Upon thermal activation,the single crystals remain intact,allowing for precise determination of the activated structure.HIAM-103 exhibits remarkable thermal and hydrothermal stability.Its microporous channels demonstrate selective adsorption of C_(2)H_(6)over C_(2)H_(4)and Xe over Kr,and its separation capability toward mixed gases has been validated by column breakthrough experiments under dry and humid conditions.The preferential gas adsorption sites and separation mechanisms have been uncovered through DFT analysis,which suggests that the methyl group decorated 1D channels are the primary reason for the selective adsorption.展开更多
The development of heterogeneous molecule-based catalysts for red light-mediated photocatalysis is still challenging due to the improper light absorption for most materials and the photoactivity deactivation for solid...The development of heterogeneous molecule-based catalysts for red light-mediated photocatalysis is still challenging due to the improper light absorption for most materials and the photoactivity deactivation for solid assembly.Herein,red light photocatalysis with a hydrogen-bonded organic framework(HOF)is established.This HOF,named HOF-66,is formed from the self-assembly of guanine-decorated naphthalenediimide(NDI)molecule through hydrogen-bonded guanine-quadruplex nodes,showing square grid supramolecular layers confirmed by powder X-ray diffraction analysis.In contrast to unsubstituted NDI HOF,introduction of ethylamino groups to NDI core in HOF-66 tunes strong electronic maximum absorption peak to 619 nm,allowing red light photocatalysis of singlet oxygen evolution proved by 1,3-diphenylisobenzofuran degradation and electron spin resonance determination.Particularly,under the same conditions,the sulfide oxidation rate in the presence of HOF-66 was 28 times higher compared to its unsubstituted analogue.This work integrates the molecular design and aggregation effect towards the application of HOFs,opening a new gate for red light photocatalysts.展开更多
基金This work was supported by the National Natural Science Foundation of China(Nos.11904326,21601159,61604132,and 51602288)the National Science Fund for Distinguished Young Scholars(No.61425021)Key Science and Technology Project of Henan Province(No.171100210600).
文摘Room temperature phosphorescence(RTP)materials show potential applications in information security and optoelectronic devices,but it is still a challenge to achieve RTP in organic materials under water ambient due to the unstable property of triplet states.Herein,water-induced RTP has been demonstrated in the organic microrod(OMR).Noting that the RTP intensity of the as-prepared OMR is greatly enhanced when water is introduced,and the reason for the enhancement can be attributed to the formation of hydrogen-bonded networks inside the OMR.The hydrogen-bonded networks can confine the molecular motion effectively,leading to the stability of triplet states;thus the lifetime of the OMR can reach 1.64 s after introducing water.By virtue of the long lifetime of the OMR in the presence of water,multilevel data encryption based on the OMR has been demonstrated.
基金supported by the National Natural Science Foundation of China (22071246 and 22272178)CAS youth interdisciplinary team (JCTD-2022-12)+1 种基金CAS-Iranian Vice presidency for science and technology joint research project (121835KYSB20200034)China Postdoctoral Science Foundation (2023M733499)。
基金Supported by the National Natural Science Foundation of China (Grants Nos.20573049 and 20633050)the research fund of the Educational Department of Liaoning Province (2004C019, 20060469)
文摘A new method is proposed to quick predict the strength of intermolecular hydrogen bonds.The method is employed to produce the hydrogen-bonding potential energy curves of twenty-nine hydro-gen-bonded dimers.The calculation results show that the hydrogen-bonding potential energy curves obtained from this method are in good agreement with those obtained from MP2/6-31+G calculations by including the BSSE correction,which demonstrate that the method proposed in this work can be used to calculate the hydrogen-bonding interactions in peptides.
基金KAKENHI(JP21H01919,JP21K18961,JP22H05461,and JP23H04029)from MEXT/JSPS,JapanI.H.thanks the Iketani Science and Technology Foundation and the Hoansha Foundation for their financial support.I.H.thanks the Multidisciplinary Research Laboratory System for Future Developments(MRL),Graduate School of Engineering Science,Osaka UniversityWe thank Ms.R.Miyake for HR−MS analysis.X-ray diffraction data were collected at BL40XU in SPring-8 with approval of JASRI(proposal nos.2021A1080,2022B1151,and 2023A1264).
文摘To develop porous organic frameworks,precise control of the stacking manner of two-dimensional porous motifs and structural characterization of the resultant framework are important.From these points of view,porous molecular crystals formed through reversible intermolecular hydrogen bonds,such as;hydrogen-bonded organic frameworks(HOFs),can provide deep insight because of their high crystallinity,affording single-crystalline X-ray diffraction analysis.In this study,we demonstrate that the stacking manner of hydrogen-bonded hexagonal network(HexNet)sheets can be controlled by synchronizing a homological triangular macrocyclic tecton and a hydrogen-bonded cyclic supramolecular synthon called the phenylene triangle.A structure of the resultant HOF was crystallographically characterized and revealed to have a large channel aperture of 2.4 nm.The HOF also shows thermal stability up to 290°C,which is higher than that of the conventional HexNet frameworks.
基金supported by the National Natural Science Foundation of China(grant nos.22271046,21971038,and 21975044)the Fujian Provincial Department of Science and Technology(grant no.2019L3004).
文摘Flexible-robust hydrogen-bonded organic frameworks(HOFs)are attracting increasing interest due to their excellent separation performance for important industrial gases,but the construction remains challenging.Herein,a sticked-layer strategy is first proposed to construct a flexible-robust HOF,HOFFJU-8,from a donor(D)–π–acceptor(A)molecule 4,4′,4″,4‴-(pyrrolo[3,2-b]pyrrole-1,2,4,5-tetrayl)tetrabenzonitrile(DP-4CN).HOF-FJU-8 is amicroporous three-dimensional framework composed of two kinds of DP-4CN molecules,one acting as building units for the two-dimensional layer via C≡N···H–C hydrogen bond dimers and another as the sticks to link the layers along channels through D–Aπ···πinteractions.The activated framework HOF-FJU-8a possesses flexible-robust pore characteristics,as determined by the gas adsorption and in situ gas-loaded powder X-ray diffraction.HOF-FJU-8a exhibits adaptive adsorption and stronger binding affinity to C_(2)H_(2)rather than CO_(2)due to the flexible-robust nature,which can effectively separate acetylene and carbon dioxide mixtures.
基金Chinese Academy of Sciences(No.JCTD-2022-12 CAS youth interdisciplinary team)Y.Y.L.acknowledges the support from the National Science Foundation(No.HRD-2112554).
文摘Hydrogen-bonded organic frameworks(HOFs)are a recent class of porous materials that have garnered considerable research interest owing to their distinctive characteristics.HOFs can be constructed through judicious selection of H-bonding motifs,which are further enforced by other weak intermolecular interactions such asπ–πstacking,van der Waals forces,and framework interpenetration.Taking advantage of these interactions,we can expand the functional field of HOFs by introducing active molecules.Recently,researchers have made substantial advancements in using HOFs for chemical sensing,catalysis,proton conduction,biological applications,and others.The low bonding energy of H-bonds allows for precise control over the concentration of ligands in solvents,forming diverse HOF structures.These varied structures offer significant advantages for producing HOFs with photo-responsive and electro-responsive properties.However,the presence of H-bonds in HOFs results in their inherent lower stability compared to metal-organic frameworks(MOFs)and covalent-organic frameworks(COFs)formed via coordination and covalent bonds,respectively.As a result,the pursuit of stable and innovative HOF materials with novel functional sites remains an ongoing challenge.This review provides an overview of recent research progress in the development of new strategies for stable HOF synthesis and applications of HOFs with stimuli-responsive properties.We first classified all synthetic methods reported to date and discussed the stable HOFs synthesized,as well as their unique properties and applications.In addition,we summarized the applications of HOFs utilizing their synergistic responses to external stimuli,including photo,electrical,pressure,and chemical stimuli.We systematically reviewed stable HOF synthesis and applications,which may lead to a deeper understanding of the structure–activity relationship for these materials and guide future HOF design.
基金supported by the National Key Research and Development Program of China(No.2022YFA1504100)the National Natural Science Foundation of China(Nos.22005215,22279089,and 22178251).
文摘Nickel-rich layered oxide cathode(LiNi_(x)Co_(y)Mn_(1−x−y)O_(2),x>0.5,NCM)shows substantial potential for applications in longer-range electrical vehicles.However,the rapid capacity decay and serious safety concerns impede its practical viability.This work provides a hydrogen-bonded organic framework(HOF)modification strategy to simultaneously improve the electrochemical performance,thermal stability and incombustibility of separator.Melamine cyanurate(MCA),as a low-cost and reliable flame-retardant HOF,was implemented in the separator modification layer,which can prevent the battery short circuit even at a high temperature.In addition,the supermolecule properties of MCA provide unique physical and chemical microenvironment for regulating ion-transport behavior in electrolyte.The MCA coating layer enabled the nickel-rich layered oxide cathode with a high-capacity retention of 90.3%after 300 cycles at 1.0 C.Collectively,the usage of MCA in lithium-ion batteries(LIBs)affords a simple,low-cost and efficient strategy to improve the security and service life of nickel-rich layered cathodes.
基金supported by the National Natural Science Foundation of China(22171210,21771139,U20A20141,U23A20119)CAS Project for Young Scientists in Basic Research(YSBR-039)+1 种基金Tianjin Research Innovation Project for Postgraduate Students(2022BKY200)C?EM,School of Physical Sciences and Technology,Shanghai Tech University(#EM02161943)for the scientific and financial support of EM facilities。
文摘The development of hydrogen-bonded organic frameworks(HOFs)faces significant constraints,primarily attributed to their fragile architectures and limited functionalization capabilities.To overcome these limitations,this work presents a new polymeron-HOF strategy by covalently tethering armor-like polymers onto the surface of HOFs.The application of this approach not only bolsters the stability of HOFs,but also facilitates the customization of their functional expansion in radionuclide sequestration.The optimized HOF-polymer materials display extraordinary ability in radionuclide sequestration,achieving uptake of I^(-)(0.699 g g^(-1)),IO_(3)^(-)(0.285 g g^(-1))and ReO_(4)^(-)(1.616 g g^(-1),setting a world record),fast adsorption kinetics(~100% removal within 45 s),and exceptional regeneration capability(>30 cycles)under continuous flow conditions.These outstanding performances benefit from the internal porous channels and surface imidazolium polymer coatings of HOFs,as proved by density functional theory calculation and molecular dynamics simulations.This work paves the way for the rational design of HOF-based hybrid materials tailored to versatile applications.
基金support from National Key Research and Development Program of China(No.2021YFB3802200)National Natural Science Foundation of China(No.U20B2023,22208238,U1732120)+1 种基金the Haihe Laboratory of Sustainable Chemical TransformationsNingbo Natural Science Foundation(No.2021J004).
文摘Hydrogen-bonded organic frameworks(HOFs)have emerged as a new class of crystalline porous materials,and their application in membrane technology needs to be explored.Herein,for the first time,we demonstrated the utilization of HOF-based mixed-matrix membrane for CO_(2) separation.HOF-21,a unique metallo-hydrogen-bonded organic framework material,was designed and processed into nanofillers via amine modulator,uniformly dispersing with Pebax polymer.Featured with the mix-bonded framework,HOF-21 possessed moderate pore size of 0.35 nm and displayed excellent stability under humid feed gas.The chemical functions of multiple binding sites and continuous hydrogen-bonded network jointly facilitated the mass transport of CO_(2).The resulting HOF-21 mixed-matrix membrane exhibited a permeability above 750 Barrer,a selectivity of~40 for CO_(2)/CH_(4) and~60 for CO_(2)/N_(2),surpassing the 2008 Robeson upper bound.This work enlarges the family of mixed-matrix membranes and lays the foundation for HOF membrane development.
基金supported by the National Natural Science Foundation of China(No.22376117)the Tsinghua University Initiative Scientific Research Program.
文摘Safe confinement of fission iodine isotopes for long-term radioactive waste disposal remains a formidable challenge,as conventional sorbents provide inherently weak iodine-host interactions.We report here a novel halogen bond(X-bond)directed strategy to sequester volatile iodine in hydrogen-bonded(H-bonded)frameworks with unprecedented stability.Charge-assisted Hbonded frameworks bearing open halide sites are developed,showing distinctive iodine encapsulation behaviors without compromising the crystallinity.Direct crystallographic evidence indicates the formation of X-bonds,i.e.,I–I···Cl^(−) and I–I···Br^(−),within the confined pore channels.Unusual polyhalogen anions,i.e.,[I_(2)Cl_(2)]^(2−)and[I_(2)Br_(2)]^(2−),sustained in H-bonded frameworks are identified for the first time.The X-bond reinforced host-guest interaction affords robust iodine trapping without leaking out even at elevated temperatures up to 180℃.By integrating the halogen-bond chemistry with H-bonded frameworks,this study offers fresh concepts for developing effective host reservoirs to secure fission iodine isotopes from spent fuel reprocessing off-gases.
基金the MICINN (Spain)(Projects PID2019-104778GB-I00, PID2020-115100GB-I00Excellence Unit “Maria de Maeztu” CEX2019-000919-M)+5 种基金the Royal Society of Chemistryfunded by Generalitat Valenciana(PROMETEU/2021/054 and SEJI/2020/034)the “Ramón y Cajal” program (RYC2019-027940-I)the Royal Society (RGSR1221390)Royal Society of Chemistry (R21-5119312833) for the funding.
文摘Porous organic molecular materials(POMMs)are an emergent class of molecular-based materials characterized by the formation of extended porous frameworks,mainly held by non-covalent interactions.POMMs represent a variety of chemical families,such as hydrogen-bonded organic frameworks,porous organic salts,porous organic cages,C-H···πmicroporous crystals,supramolecular organic frameworks,π-organic frameworks,halogen-bonded organic framework,and intrinsically porous molecular materials.In some porous materials such as zeolites and metal organic frameworks,the integration of multiscale has been adopted to build materials with multifunctionality and optimized properties.Therefore,considering the significant role of hierarchy in porous materials and the growing importance of POMMs in the realm of synthetic porous materials,we consider it appropriate to dedicate for the first time a critical review covering both topics.Herein,we will provide a summary of literature examples showcasing hierarchical POMMs,with a focus on their main synthetic approaches,applications,and the advantages brought forth by introducing hierarchy.
基金supported by the National Natural Science Foundation of China (22001154, 22271211)the Central Government Funding for Talent Promotion (231545023)+1 种基金the Youth Fund from the Department of Science and Technology of Shanxi Province (201901D211148)the Science and Technology Innovation Planning Project in Universities and Colleges of Shanxi Province (2019L0063)。
文摘By tactically integrating two different kinds of proton donors and acceptors into one supramolecular tecton, a new crystalline hydrogen-bonded organic framework(HOF-SXU-1) has been developed. HOF-SXU-1 features a remarkable proton conductivity as high as 6.32 mS cm^(-1) and an extremely low activation energy of 0.16 eV at 160℃ under anhydrous N_(2) conditions.By contrast, under identical conditions, the organic precursors of HOF-SXU-1 only exhibit negligible proton conduction performance, demonstrating that the formation of HOF is crucial for excellent proton conduction performance.
基金We acknowledge support from the Chinese Academy of Sciences and University of Science and Technology of China,the National Key Research and Development Program of China(No.2021YFA1500402)the National Natural Science Foundation of China(Nos.21571167,51502282,and 22075266)the Fundamental Research Funds for the Central Universities(Nos.WK2060190053 and WK2060190100).
文摘Elasticity,as an emerging phenomenon of crystals,endows the newfangled properties on crystals owing to the altered local crystallinity in the deformed state,and hence attracts increasing research endeavors.However,only a few molecular crystals and a limited number of one-dimensional coordination polymer crystals have exhibited such fantastic elastic response under mechanical stress.Herein,we report the first example of elastic hydrogen-bonded ionic framework(HIF)of{(CN_(3)H_(6))_(2)[Ti(μ_(2)-O)(SO_(4))_(2)]}n,assembled from one-dimensional negatively charged inorganic[Ti(μ_(2)-O)(SO_(4))_(2)]n 2n-chains and positively charged organic guanidinium cations via hydrogen bonds and electrostatic interactions.The slender prismatic single crystal exhibits remarkable elasticity with an optimal elastic bending strain(ε)of 2.5%.Impressively,the crystals give rise to two-dimensional elasticity owing to the equivalent crystallographic planes of the exposed faces and an unusual elastic response at liquid nitrogen temperature.The in-depth crystallographic analyses reveal hydrogen bonds and electrostatic interactions between anion chains and cations function like adhesive glue and account for such specific elastic properties,owing to the flexible and dynamic attributes of hydrogen bonds as they can work in a range of distance and orientation.And the channel in HIF provides space for bending with reduced strain.Incorporating these factors into low-dimensional crystals could be a general guidance for designing elastic crystals.Elasticity ganged with other intrinsic properties of HIF materials could inspire their newfangled applications in the near future.
基金supported by the National Natural Science Foundation of China (20973088)the Educational Department of Liaoning Province (2007T091, 2008T106)
文摘Understanding the mechanisms underlying the assembly of nucleobases is a great challenge. The ability to deeply understand how nucleobases interact with themselves as well as with other molecules will allow us to gain valuable insights into how we might be able to harness these interesting biological molecules to construct complex nanostructures and materials. Uracil and thymine derivatives have been reported for use in biological applications and in self-assembling triple hydrogen bonded systems. Either uracil or thymine possesses three binding sites （Site 1, Site 2, and Site 3） that can induce strong directional N-H...O=C hydrogen bonding interaction. In this paper, theoretical calculations are carded out on the structural features and binding energies of hydrogen-bonded dimers and trimers formed by uracil and thymine bases. We find that the hydrogen bonds formed through Site 1 are the strongest, those formed through Site 3 are next, while those formed through Site 2 are the weakest. The atoms in molecules analysis show that the electron densities at the bond critical points and the corresponding Laplacians have greater values for those hydrogen bonds formed through Site 1 than through Site 2. All these results indicate that a uracil （or thymine） would interact with another uracil or thymine most likely through Site 1 and least likely through Site 2. We also find that a simple summation rule roughly exists for the binding energies in these dimers and trimers.
基金financially supported by the National Natural Science Foundation of China(Nos.51973029 and 52273020)Ministry of Education(No.8091B022141).
文摘Hydrogen-bonded polymer complex fiber of poly(ethylene oxide)(PEO)and poly(acrylic acid)(PAA)shows rubber elasticity in ambient environment,but the fiber has relatively low strength and weak stability.We apply the catechol chemistry and metal coordination to stabilize and strengthen the PEO/PAA fiber.PAA is grafted with dopamine(Dopa),and then combines with PEO to prepare fiber.PAA-Dopa in the fiber is crosslinked through oxidation induced dismutation and the metal ions are introduced through coordination.The cross-linking and coordination greatly improve the stability of the fiber against the erosion of alkaline water.Among four different metal coordination fibers,PEO/PAA-Dopa/Cu fiber keeps the excellent extensibility(~1000%)and presents much higher initial modulus(~7 MPa),ultimate strength(~20 MPa),and toughness(~60 MJ/m^(3))than its precursor PEO/PAA fiber.In addition,PEO/PAA-Dopa/Cu fiber shows quick recovery and large energy dissipation ratio compared with the PEO/PAA fiber.The distinct mechanical properties enhancement of the hydrogen-bonded complex fiber is attributed to the synergy of hydrogen bonds,coordination and covalent bond cross-linking.
基金financial support from the National Key R&D Program of China(Grant 2022YFA1504000)the National Natural Science Foundation of China(Grants 22125205,22002166,22272176,22072146 and 22002158)+2 种基金the Fundamental Research Funds for the Central Universities(20720220008)the Dalian National Laboratory for Clean Energy(DNL202007,DNL201923)the financial support from the CAS Youth Innovation Promotion(Grant Y201938)。
文摘Hydrogen-bonded organic frameworks(HOFs),an emerging porous macrocyclic materials linked by hydrogen-bond,hold potential for gas separation and storage,sensors,optical,and electrocatalysts.Here,HOF-based electrocatalysts are rationally developed for nitrates reduction to ammonia,allowing not only to regulate wastewater pollution but also to accomplish carbon-neutral ammonia(NH_(3))synthesis.We preform high-throughput computational screening of thirty-six HOFs with various metals as active sites,denoted as HOF-M1,for nitrate reduction reaction(NO_(3)RR)toward NH_(3).We have implemented a hierarchical four-step screening strategy,and ultimately,HOF-Ti1 was selected based on its exceptional catalytic activity and selectivity in the NO_(3)RR process.Through additional analysis,we discovered that the d band center of the active metal sites serves as an effective parameter for designing and predicting the performance of HOFs in NO_(3)RR.This research not only showcases the immense potential of electrocatalysis in transforming NO_(3)RR into NH_(3)but also provides researchers with a compelling incentive to undertake further experimental investigations.
基金Natural Science Foundation of Jilin Province,Grant/Award Number:20230101052JCNatural Science Foundation of Shandong Province,Grant/Award Numbers:ZR2020QB111,ZR2022QB018National Natural Science Foundation of China,Grant/Award Number:22178187。
文摘Developing smart room-temperature phosphorescence(RTP)materials with facile and efficient strategies have attracted increasing attention.Herein,tunable RTP materials with two phosphorescent sources and stepwise enhanced phosphorescence in water are obtained through an in-situ self-assembly strategy based on the sensitization of phosphors by trimesic acid(TMA)through simple doping and the rigidification of phosphors by hydrogen-bonded organic frameworks(HOFs).As expected,doped TMA+phosphors simultaneously promote the RTP emission of phosphors and maintain TMA phosphorescence.In-situ assembled HOF(MATMA)@phosphors facilitate smart RTP emission in water due to the coexistence of phosphorescent HOF(MA-TMA)host and phosphors guest.Additionally,such RTP materials with good processability demonstrate the application potential in information security,benefitting from their varied afterglow lifetimes and easy luminous recognition in the darkness.This work will inspire the design of dual phosphorescent source RTP systems and provide new strategies for the development of smart RTP materials in water.
基金financially supported by the National Natural Science Foundation of China(52020105007 and 51606027)the Fundamental Research Funds for the Central Universities(DUT22LAB112)+1 种基金the Liaoning Provincial Natural Science Foundation of China(2020-MS-119)supported by the Xinghai Talent funding and the Dalian High-Level Talent Innovation Program(2021RQ035)。
文摘Gas hydrate is a promising alternative for gas capture and storage due to its high gas storage capacity achieved with only structured water molecules.Nucleation is the critical controlling step in gas hydrate formation.Adding an alien solid surface is an effective approach to regulate gas hydrate nucleation.However,how the solid surface compositions control the gas hydrate nucleation remains unclear.Benefiting from the fact that the surface compositions of graphene oxide(GO)can be finely tuned,we report the effect of functional groups of size-selected GO flakes on methane hydrate nucleation.The carbonyl and carboxyl of GO flakes showed a more prominent promotion for methane hydrate nucleation than the hydroxyl of GO flakes.Surface energy,zeta potential,Raman spectra,and molecular dynamics simulation analysis were used to reveal the regulation mechanism of the functional groups of size-selected GO flakes on methane hydrate nucleation.The GO flakes with abundant carbonyl and carboxyl exhibited higher charge density than those enriched in hydroxyl.The negatively charged GO flakes can induce water molecules to form an ordered hydrogen-bonded arrangement via charge-dipole interactions.Therefore,the water molecules surrounding the carboxyl and carbonyl showed a more ordered hydrogen-bonded structure than those around the hydroxyl of GO flakes.The ordered water arrangement,similar to methane hydrate cages,significantly accelerated methane hydrate nucleation.Our study shows how the surface chemistry of solids control gas hydrate nucleation and sheds light on the design of effective heterogeneous nucleators for gas hydrate.
基金Shenzhen Science and Technology Program(No.RCYX20200714114539243,KCXFZ20211020163818026)the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences,under Award No.DE-SC0019902.
文摘Hydrogen-bonded organic frameworks(HOFs)are an emerging class of porous materials that hold promise for the adsorptive separation of industrially relevant gas mixtures.However,developing HOFs with high thermal stability and resistance to water remains a daunting challenge.We report here a microporous HOF(HIAM-103)assembled from a hexacarboxylate linker(2,4,6-trimethylbenzene-1,3,5-triylisophthalic acid,H6TMBTI).The compound crystallizes in the trigonal crystal system,and its structure is a four-fold interpenetrated network.Upon thermal activation,the single crystals remain intact,allowing for precise determination of the activated structure.HIAM-103 exhibits remarkable thermal and hydrothermal stability.Its microporous channels demonstrate selective adsorption of C_(2)H_(6)over C_(2)H_(4)and Xe over Kr,and its separation capability toward mixed gases has been validated by column breakthrough experiments under dry and humid conditions.The preferential gas adsorption sites and separation mechanisms have been uncovered through DFT analysis,which suggests that the methyl group decorated 1D channels are the primary reason for the selective adsorption.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22011540002 and 22131005)Xiaomi Young Scholar Program,the Fundamental Research Funds for the Central Universities,the Advanced Talents Incubation Program of Hebei University,and University of Science and Technology Beijing and Hebei University are gratefully acknowledged.
文摘The development of heterogeneous molecule-based catalysts for red light-mediated photocatalysis is still challenging due to the improper light absorption for most materials and the photoactivity deactivation for solid assembly.Herein,red light photocatalysis with a hydrogen-bonded organic framework(HOF)is established.This HOF,named HOF-66,is formed from the self-assembly of guanine-decorated naphthalenediimide(NDI)molecule through hydrogen-bonded guanine-quadruplex nodes,showing square grid supramolecular layers confirmed by powder X-ray diffraction analysis.In contrast to unsubstituted NDI HOF,introduction of ethylamino groups to NDI core in HOF-66 tunes strong electronic maximum absorption peak to 619 nm,allowing red light photocatalysis of singlet oxygen evolution proved by 1,3-diphenylisobenzofuran degradation and electron spin resonance determination.Particularly,under the same conditions,the sulfide oxidation rate in the presence of HOF-66 was 28 times higher compared to its unsubstituted analogue.This work integrates the molecular design and aggregation effect towards the application of HOFs,opening a new gate for red light photocatalysts.
