Due to their environmentally friendly nature and high energy density,direct ethanol fuel cells have attracted extensive research attention in recent decades.However,the actual Faraday efficiency of the ethanol oxidati...Due to their environmentally friendly nature and high energy density,direct ethanol fuel cells have attracted extensive research attention in recent decades.However,the actual Faraday efficiency of the ethanol oxidation reaction(EOR)is much lower than its theoretical value and the reaction kinetics of the EOR is sluggish due to insufficient active sites on the electrocatalyst surface.Pt/C is recognized as one of the most promising electrocatalysts for the EOR.Thus,the microscopic interfacial reaction mechanisms of the EOR on Pt/C were systematically studied in this work.In metal hydroxide solutions,hydrated alkali cations were found to bind with OH_(ad)through noncovalent interactions to form clusters and occupy the active sites on the Pt/C electrocatalyst surface,thus resulting in low Faraday efficiency and sluggish kinetics of the EOR.To reduce the negative effect of the noncovalent interactions on the EOR,a shield was made on the electrocatalyst surface using 4-trifluoromethylphenyl,resulting in twice the EOR catalytic reactivity of Pt/C.展开更多
CONSPECTUS:Controlling self-assembled peptide nanostructures has emerged as a significant area of research,offering versatile tools for developing functional materials for various applications.This Account emphasizes ...CONSPECTUS:Controlling self-assembled peptide nanostructures has emerged as a significant area of research,offering versatile tools for developing functional materials for various applications.This Account emphasizes the essential role of noncovalent interactions,particularly in peptide-based materials.Key forces,such as aromatic stacking and hydrogen bonding,are crucial for promoting molecular aggregation and stabilizing supramolecular structures.Numerous studies demonstrate how these interactions influence the phase transitions and the morphology of self-assembled structures.Recent advances in computational methodologies,including molecular dynamics simulations and machine learning,have significantly enhanced our understanding of self-assembly processes.These tools enable researchers to predict how molecular properties,such as hydrophobicity,charge distribution,and aromaticity,affect assembly behavior.Simulations uncover the energetic landscapes governing peptide aggregation,providing insights into the kinetic pathways and thermodynamic stabilities.Meanwhile,machine learning facilitates the rapid screening of peptide libraries,identifying sequences with optimal self-assembly characteristics,and accelerating material design with tailored functionalities.Beyond their structural and physicochemical properties,self-assembled peptide nanostructures hold immense potential in biological applications due to their versatility and biocompatibility.By manipulating molecular interactions,researchers have engineered responsive systems that interact with cellular environments to elicit specific biological responses.These peptide nanostructures can mimic extracellular matrices,facilitating cell adhesion,proliferation,and differentiation.They also show promise in modulating immune responses,recruiting immune cells,and regulating signaling pathways,making them valuable tools in immunotherapy and regenerative medicine.Moreover,their ability to disrupt bacterial membranes positions them as innovative alternatives to conventional antibiotics,addressing the urgent need for solutions to antimicrobial resistance.Despite its promise,peptide self-assembly faces several challenges.The assembly process is highly sensitive to environmental conditions,such as pH,temperature,and ionic strength,leading to variability in the morphology and properties.Furthermore,peptide aggregation can result in heterogeneous and poorly defined assemblies,complicating the reproducibility and scalability.Designing peptides with predictable self-assembly behavior remains a significant hurdle.Looking ahead,integrating computational predictions with experimental validations will be crucial in discovering novel peptide sequences with tailored self-assembly properties.Machine learning,combined with high-throughput screening techniques,will enable the rapid identification of optimal peptide sequences.In situ characterization tools,such as cryoelectron microscopy and advanced spectroscopy,will provide deeper insights into assembly mechanisms,aiding the rational design of peptide materials.As research progresses,the dynamic and reversible nature of noncovalent interactions can be leveraged to create adaptive responsive to environmental stimuli.Self-assembled peptide nanostructures are poised for impactful applications in biomedicine including targeted drug delivery,tissue repair,and advanced therapeutic strategies.Ultimately,these nanostructures represent a powerful platform for addressing complex challenges in biomedicine and beyond,paving the way for transformative breakthroughs in science and technology.展开更多
The wide application of photoswitches requires control over their isomerization dynamics.Utilizing noncovalent interactions is a promising strategy as it offers active regulation in-situ.However,this control strategy ...The wide application of photoswitches requires control over their isomerization dynamics.Utilizing noncovalent interactions is a promising strategy as it offers active regulation in-situ.However,this control strategy has not yet been explored in-depth to reach its full potential.In this work,we demonstrate that by directing noncovalent interactions to the central rotating bond of indigo-based photoswitches,their thermal relaxation dynamics were altered in two opposite directions(either slowed down or sped up)allowing for modulating the relaxation half-lives across four orders of magnitude.More importantly,our work established two distinct and orthogonal working mechanisms of noncovalent control over isomerization:(1)Thermodynamic stabilization of photoisomers;and(2)Facilitating an alternative reaction pathway through Brønsted/Lewis acid catalysis.This two-directional modulation(resembling agonists and inverse agonists in biological systems)via two orthogonal working mechanisms will enable more delicate manipulation of photoswitches for advanced applications.展开更多
Intramolecular noncovalent conformational locks(NoCLs)have emerged as an important strategy for developing high-performance organic/polymeric semiconductors(OPSs)via suppressing the non-radiative decay.Despite extensi...Intramolecular noncovalent conformational locks(NoCLs)have emerged as an important strategy for developing high-performance organic/polymeric semiconductors(OPSs)via suppressing the non-radiative decay.Despite extensive investigation into the impact of NoCLs on small molecules,elucidating their influence on the physicochemical properties of conjugated polymers(CPs)remains a critical challenge.By employing a combination of theoretical and experimental methods,it is revealed that the incorporation of NoCLs increases the rigidity of the polymer chain,enhances intermolecular interactions,promotes the formation of pre-aggregates of optimal length,and improves charge transport,providing valuable insights for designing high-performance CPs.展开更多
Two palladium(II) complexes, \[Pd(bipy)(BzPhe N,O)\] and \[Pd(phen)(BzPhe N,O)\]·4H 2 O were synthesized by reactions between Pd(bipy)Cl 2 and BzPheH 2( N benzoyl β phenylalanine), Pd(phen...Two palladium(II) complexes, \[Pd(bipy)(BzPhe N,O)\] and \[Pd(phen)(BzPhe N,O)\]·4H 2 O were synthesized by reactions between Pd(bipy)Cl 2 and BzPheH 2( N benzoyl β phenylalanine), Pd(phen)Cl 2 and BzPheH 2 in water at pH～9, with their structures determined by X ray diffraction analysis. The Pd atom is coordinated by two nitrogen atoms of bipy (or phen), the deprotonated amido type nitrogen atom and one of the carboxylic oxygens of BzPhe (BzPhe= N benzoyl β phenylalaninate dianion). In the complex \[Pd(phen)(BzPhe N,O)\]·4H 2O, the side chain of phenylalanine is located above and approximately parallels to the coordination plane. Both the aromatic aromatic stacking interaction between the phenyl ring of phenylalanine and phen, and the metal ion aromatic interaction between the phenyl ring of phenylalanine and Pd(II) were observed. \[Pd(bipy)(BzPhe N,O)\] has the phenylalanyl side chain oriented outwards from the coordination plane, which is mainly due to the interaction between the carbonyl oxygen atom of the amido group and the phenyl ring of phenylalanine. The reason for the different orientation of phenylalanyl side chain in the complexes was suggested.展开更多
Although organic compounds are considered to be promising electrode materials with their remarkable characteristics such as diverse structures,design controllability,and environmental friendliness,their low charge-tra...Although organic compounds are considered to be promising electrode materials with their remarkable characteristics such as diverse structures,design controllability,and environmental friendliness,their low charge-transfer capability and limited cycling durability hinder their application in aqueous proton batteries.Herein,we prepared a noncovalent phenazine-based graphene aerogel(H/G)composite for aqueous proton storage,which is realized by redox-active Hexaazatrinaphthalene(HATN)organic compound combined with conductive reduced graphene oxide(rGO).The integration of rGO into HATN not only effectively optimizes the electronic structure of the H/G composite to enhance its electrochemical activity,but also the favorable noncovalent π-π interaction existed between HATN and rGO provides a stable structure for fast electron transportation.The obvious electron transfer in the aerogel composite promotes fast and reversible redox reactions occurred with the imino-active HATN in the composite electrode for proton uptake/removal in an aqueous acidic electrolyte,which are demonstrated by in-situ Fourier transform infrared(FTIR)investigation,theoretical calculations and experimental measurements.Therefore,it can deliver a fast,stable and efficient aqueous proton storage behavior with a large specific capacity of 274 mA·h·g^(-1) and considerable calendar life with~100%capacity retention after 3000 cycles,surpassing previously reported proton-based organic electrodes in aqueous acidic electrolytes.Furthermore,an outstanding soft-package aqueous proton(APB)has been fabricated with considerable long-term cycling stability.展开更多
Thermoelectric(TE)generators capable of converting thermal energy into applicable electricity have gained great popularity among emerging energy conversion technologies.Biopolymer-based ionic thermoelectric(i-TE)mater...Thermoelectric(TE)generators capable of converting thermal energy into applicable electricity have gained great popularity among emerging energy conversion technologies.Biopolymer-based ionic thermoelectric(i-TE)materials are promising candidates for energy conversion systems because of their wide sources,innocuity,and low manufacturing cost.However,common physically crosslinked biopolymer gels induced by single hydrogen bonding or hydrophobic interaction suffer from low differential thermal voltage and poor thermodynamic stability.Here,we develop a novel i-TE gel with supramolecular structures through multiple noncovalent interactions between ionic liquids(ILs)and gelatin molecular chains.The thermopower and thermoelectric power factor of the ionic gels are as high as 2.83 mV K-1 and 18.33μW m^(-1)K^(-2),respectively.The quasi-solid-state gelatin-[EMIM]DCA i-TE cells achieve ultrahigh 2 h output energy density(E_(2h)=9.9 mJ m^(-2))under an optimal temperature range.Meanwhile,the remarkable stability of the supramolecular structure provides the i-TE hydrogels with a thermal stability of up to 80℃.It breaks the limitation that biopolymer-based i-TE gels can only be applied in the low temperature range and enables biopolymer-based i-TE materials to pursue better performance in a higher temperature range.展开更多
Understanding the regulatory mechanism of self-assembly processes is a necessity to modulate nanostructures and their properties. Herein, we have studied the mechanism of self-assembly in the C3 symmetric 1,3,5-benzen...Understanding the regulatory mechanism of self-assembly processes is a necessity to modulate nanostructures and their properties. Herein, we have studied the mechanism of self-assembly in the C3 symmetric 1,3,5-benzentricarboxylic amino acid methyl ester enantiomers(TPE) in a mixed solvent system consisting of methanol and water. The resultant chiral structure was used for chiral recognition. The formation of chiral structures from the synergistic effect of multiple noncovalent interaction forces was confirmed by various techniques. Molecular dynamics simulations were used to characterize the time evolution of TPE structure and properties in solution. The theoretical results were consistent with the experimental results. Furthermore, the chiral structure assembled by the building blocks of TPE molecules was highly stereoselective for diamine compounds.展开更多
The interactions of complexes of XeOF_(2) and XeO_(3) with a series of different hybridization N-containing donors are studied by means of DFT and MP_(2) calculations.The aerogen bonding interaction energies range fro...The interactions of complexes of XeOF_(2) and XeO_(3) with a series of different hybridization N-containing donors are studied by means of DFT and MP_(2) calculations.The aerogen bonding interaction energies range from 6.5 kcal/mol to19.9 kcal/mol between XeO_(3) or XeOF_(2) and typical N-containing donors.The sequence of interaction for N-containing hy-bridization is sp^(3)>sp^(2)>sp,and XeO_(3)is higher than XeOF_(2).For some donors of sp^(2)and sp^(3) hybridization,the steric effect plays a minor role in the interaction with the evidence of reduced density gradient plots.The dominant stable part is the electrostatic interaction.In complex of XeO_(3),the weight of polarization is larger than dispersion,while the situation is opposite for XeOF_(2)complexes.Except for the sum of the maximum value of molecular electrostatic potential on Xe atom and minimum value of molecular electrostatic potential on N atom,the other five interaction parameters including the potential energy density at bond critical point,the equilibrium distances,interaction energies with the basis set superposition error correction,localized molecular orbital energy decomposition analysis interaction energies,and the electron charge density,show great linear correlation coefficients with each other.展开更多
Achieving seamless tiling through the self-assembly of organic species has long fascinated scientists for its potential applications across various fields.However,constructing periodic nanostructures with high-order t...Achieving seamless tiling through the self-assembly of organic species has long fascinated scientists for its potential applications across various fields.However,constructing periodic nanostructures with high-order tessellation remains challenging,particularly in achieving precise control at the supramolecular level.In this study,we present the successful creation of multiple seamless 2D tessellations on Au(111)surface using versatile hexagonal tiles derived from a singular molecular unit,namely 2,6,10-tribromotricycloquinazoline.Through scanning tunneling microscopy imaging,seven distinct 2D tessellations,ranging from regular to semiregular to k-uniform tilings,are unveiled at the molecular level.Density functional theory calculations provide a theoretical basis for the formation of these complex 2D tessellation,highlighting the important role of the variability of Br···Br/H contacts in facilitating complex seamless 2D tessellations on surface.This work opens avenues for exploring possibilities in constructing intricate tiling patterns with diverse applications.展开更多
Polymer-based thermally conductive composites have attracted tremendous interest in thermal management of electronics.However,it remains challenging to achieve high thermal conductivity partly because the difficulty t...Polymer-based thermally conductive composites have attracted tremendous interest in thermal management of electronics.However,it remains challenging to achieve high thermal conductivity partly because the difficulty to obtain favorable distribution and orientation of conductive fillers within the polymer matrix.Herein,networked boron nitride(BN)conductive pathway was realized within the poly(lactic acid)(PLA)matrix,via regenerated cellulose(RC)-assisted assembly of BN on Pickering emulsion interface based on the noncovalent interaction,followed by solvent evaporation and hot-compressing.The strong noncovalent interactions between BN and RC were found critical to enhance the wettability and stability of BN in aqueous media with a lowest mass ratio of 1:40 of RC and BN.The obtained PLA/BN composites feature a thermal conductivity of 1.06 W/(m K)at 28.4 wt%BN loading,representing an enhancement of 430%comparing to neat PLA,and the crystallinity of the composites could increase significantly from11.7%(neat PLA)to 43.7%.This simple,environmentally friendly and effective strategy could be easily extended for effective construction of thermally conductive composites.展开更多
The synthesis of cyclopolymers upon controlling the degree of macrocyclic polymerization,followed by the discovery of new properties has attracted increasing attention in supramolecular chemistry.Herein,a Schiff-base ...The synthesis of cyclopolymers upon controlling the degree of macrocyclic polymerization,followed by the discovery of new properties has attracted increasing attention in supramolecular chemistry.Herein,a Schiff-base condensation method performed at room temperature was used to control the formation of[1+1]and[2+2]macrocycles.In pure MeOH,the isomer[1+1]macrocycles were synthesized and organic particles such as dendritic,rods,and solid microspheres were directly precipitated from the reaction solution.The[1+1]macrocycles can be efficiently converted into their corresponding[2+2]macrocycles accompanied by the tunable morphology of the organic particles when n-hexane was added to the MeOH solution.Further studies showed that these organic particles have potential application toward the selective removal of Cd^(2+)ions with different adsorption ability in MeOH solution.展开更多
Developing narrow-bandgap organic semiconductors is important to facilitate the advancement of organic photovoltaics(OPVs). Herein, two near-infrared non-fused ring acceptors(NIR NFRAs), PTBFTT-F and PTBFTT-Cl have be...Developing narrow-bandgap organic semiconductors is important to facilitate the advancement of organic photovoltaics(OPVs). Herein, two near-infrared non-fused ring acceptors(NIR NFRAs), PTBFTT-F and PTBFTT-Cl have been developed with A-π_A-π_D-D-π_D-π_A-A non-fused structures. It is revealed that the introduction of electron deficient π-bridge(π_A) and multiple intramolecular noncovalent interactions effectively retained the structural planarity and intramolecular charge transfer of NFRAs, extending strong NIR photon absorption up to 950 nm. Further, the chlorinated acceptor, with the enlarged π-surface compared to the fluorinated counterpart, promoted not only molecular stacking in solid, but also the desirable photochemical stability in ambient, which are helpful to thereby improve the exciton and charge dynamics for the corresponding OPVs. Overall, this work provides valuable insights into the design of NIR organic semiconductors.展开更多
Benefitting from the development of non-fullerene acceptors(NFAs),remarkable advances have been achieved with the power conversion efficiency(PCE)exceeding 19%over the last few years.However,the major achievement come...Benefitting from the development of non-fullerene acceptors(NFAs),remarkable advances have been achieved with the power conversion efficiency(PCE)exceeding 19%over the last few years.However,the major achievement comes from fused ring electron acceptors(FREAs)with complex structures,leading to high cost.Hence,it is urgent to design new materials to resolve the cost issues concerning basic commercial requirements of organic solar cells.Recently,great progress has been made in fully non-fused ring electron acceptors(NFREAs)with only single-aromatic ring in the electron-donating core,which might achieve a fine balance between the efficiency and cost,thus accelerating the commercial application of organic solar cells.Therefore,this article summarizes the recent advances of fully NFREAs with efficiency over 10%,which may provide a guidance for developing the cost-effective solar cells.展开更多
Two novel acid-base adducts,[H2L1^2＋]（Hpbda）2（1,L1 = 1,4-di（lH-imidazol-4-yl）benzene,H2pbda = 1,4-benzenedicarboxylic acid） and[H2L2^2＋]（NO3）2（2,L2 = l,4-di（l-carboxymethyl-imidazol-4-yl）benzene）,have be...Two novel acid-base adducts,[H2L1^2＋]（Hpbda）2（1,L1 = 1,4-di（lH-imidazol-4-yl）benzene,H2pbda = 1,4-benzenedicarboxylic acid） and[H2L2^2＋]（NO3）2（2,L2 = l,4-di（l-carboxymethyl-imidazol-4-yl）benzene）,have been prepared and characterized by single-crystal X-ray diffraction,IR spectroscopy and elemental analysis.Compound 1 crystallizes in monoclinic,space group P21/n with a = 5.3525（11）,b = 9.1471（19）,c = 19.314（4） ？,β = 92.342（3）°,V= 944.8（3） A°3,Z = 2,C16H16N6O（10）,Mr = 452.35,Dc = 1.590 g/cm^3,μ = 0.135 mm^-1,S = 1.058,F（000） = 468,the final R = 0.0661 and wR = 0.1887 for 2298 observed reflections（I〉 2σ（I））.Compound 2 crystallizes in monoclinic,space group P21/c with a = 9.6923（10）,b = 17.2950（17）,c = 7.1880（7） ？,β =94.801（2）°,V= 1200.7（2）A°3,Z = 2,C（28）H（22）N4O8,Mr = 542.50,Dc = 1.501 g/cm^3,μ = 0.112 mm^-1,S= 1.060,F（000） = 564,the final R = 0.0394 and wR = 0.1017 for 2768 observed reflections（I 〉2σ（I））.In the title compounds,both of L1 and L2 ligands act as weak base to accept protons to exhibit diprotonated H2L1^2＋ and H2L2^2＋ form,which can effectively employ as hydrogen bonding donors to combine anion moieties to form binary adducts respectively.In the crystal packing diagram of two polymers,there exist extensive noncovalent interactions including charge-transfer interactions,C（N）-H…π and N-H…O,C-H…O,O-H…O hydrogen bonding interactions between co-crystal moieties which consolidate the structures of supramolecular polymers,thus generating three-dimensional（3D） frameworks.展开更多
Regioregular poly(3-hexylthio)thiopene(P3HTT) has emerged tremendous potential in organic electronic applications due to the strong noncovalent interactions from the sulfur atom linked to thiophene. However, P3HTT gen...Regioregular poly(3-hexylthio)thiopene(P3HTT) has emerged tremendous potential in organic electronic applications due to the strong noncovalent interactions from the sulfur atom linked to thiophene. However, P3HTT generally exhibits low charge mobility mostly due to poor solution processability attributed to dense arrangement of hexylthio side chain in polymer, which led to strong noncovalent interactions among sulfur atoms. To balance the nonvalent interaction and aggregation for P3HTT, herein, we systematically study the effect of hexylthio side chain content in polymer backbone on the structure and properties. A series of regioregular P3HTT-based homopolymers(P3HTT, P3HTT-50,P3HTT-33 and P3HTT-25) were prepared via Kumada catalyst transfer polycondensation method from a set of mono-, bi-, ter-and quarterthiophenes containing different contents of hexylthio side chain. The DFT calculation shows the planarity of polymers backbone could be improved through reducing the density of hexylthio side chain in polymer mainchain. And significant changes in their crystallinity, aggregation and optical properties were observed with the content of hexylthio side chain reducing. The P3HTT-33 displayed the highest field-effect transistor hole mobility of 2.83×10^(-2) cm^(2)·V^(-1)·s^(-1) resulting from a balance between the crystallinity and planarity. This study demonstrates modulating the content of hexylthio side chain in P3HTT is an effective strategy to optimize the opto-electronic properties of polymer obtaining excellent semiconductor device performance.展开更多
Ammonium dinitramide(ADN)is a new type of green energetic oxidizer with excellent energy density and low pollution combustion characteristics.However,the strong hygroscopicity has a significant impact on its practical...Ammonium dinitramide(ADN)is a new type of green energetic oxidizer with excellent energy density and low pollution combustion characteristics.However,the strong hygroscopicity has a significant impact on its practical application.To assist in the research on moisture-proof modification of ADN materials,an innovative hygroscopic modeling approach was proposed to evaluate the hygroscopicity of ADN at various temperatures and humidities.By investigating the diffusion coefficient of water molecules in molecular dynamics processes,a visual insight into the hygroscopic process of ADN was gained.Furthermore,analyzing the non-covalent interactions between ADN and water molecules,the hygroscopicity of ADN could be evaluated qualitatively and quantitatively.The energy analysis revealed that electrostatic forces play a dominant role in the process of water adsorption by ADN,whereas van der Waals forces impede it.As a whole,the simulation results show that ADN presents the following hygroscopic law:At temperatures ranging from 273 K to 373 K and relative humidity(RH)from 10%to 100%,the hygroscopicity of ADN generally shows an increasing trend with the rise in temperature and humidity based on the results of three simulations.According to the non-hygroscopic point(298 K,52%RH)of ADN obtained by experiment in the literature,a non-hygroscopic range of temperature and humidity for ADN can be depicted when the simulation results in relative hygroscopicity is less than or equal to 17%.This study can provide effective strategies for screening anti-hygroscopic modified materials of ADN.展开更多
Biomass carbon and small redox biomolecules are attractive materials for green,sustainable energy storage devices owing to their environmentally friendly,low-cost,scalable,and novel sources.However,most devices manufa...Biomass carbon and small redox biomolecules are attractive materials for green,sustainable energy storage devices owing to their environmentally friendly,low-cost,scalable,and novel sources.However,most devices manufactured using these materials have low specific capacitance,poor cycle stability,short lifetime,complexity,and low precision of device fabrication.Herein,we report the directed self-assembly of mononuclear anthraquinone(MAQ)derivatives and porous lignin-based graphene oxide(PLGO)into a renewable colloidal gel through noncovalent interactions.These self-assembled gel electrode materials exhibited high capacitance(484.8 F g^(−1) at a current density of 1 A g^(−1))and could be further printed as flexible micro-supercapacitors(FMSCs)with arbitrary patterns and a relatively high resolution on specific substrates.The FMSCs exhibited excellent areal capacitance(43.6 mF cm^(−2)),energy and power densities(6.1μWh cm^(−2) and 50μW cm^(−2),respectively),and cycle stability(>10,000 cycles).Furthermore,the printed FMSCs and integrated FMSC arrays exhibited remarkable flexibility while maintaining a stable capacitance.The proposed approach can be applied to other quinone biomolecules and biomass-based carbon materials.This study provides a basis for fabricating green and sustainable energy storage device architectures with high capacitance,long-term cycling,high scalability,and high precision.展开更多
Optimal bulk-heterojunction(BHJ)morphology is crucial for efficient charge transport and good photovoltaic performance in organic solar cells(OSCs).Yet,the correlation between chemical structures of nonfullerene accep...Optimal bulk-heterojunction(BHJ)morphology is crucial for efficient charge transport and good photovoltaic performance in organic solar cells(OSCs).Yet,the correlation between chemical structures of nonfullerene acceptors(NFAs)and molecular interaction in the BHJ blends remains opaque.Herein,we study three isomeric NFAs referred to as MQ1-x(x=β,y,or 8)that shared an asymmetric selenophene-fused heteroheptacene backbone end-capped by two monochlorinated end groups.Remarkably,miscibility between the polymer donor of PM6 and MQ1-x successively elevates as the chlorine atoms move fromβ-,to y-,to 8-position of terminals.Combined with the varied molecular crystallinity of these NFAs,diverse BHJ morphologies are observed in their blend films.As a result,the MQ1-8-based devices present the highest PCE of 12.08%owing to the efficient charge dissociation and transport induced by the compact molecular packing and optimal BHJ morphology.Our investigation provides a new insight in the material design that has a good balance in molecular packing and film morphology for high-performance OSCs.展开更多
The branching structures in natural rubber(NR) were believed to be critical for its superior mechanical properties. However, it is challenging to unravel the branching structure-function relationship of NR due to the ...The branching structures in natural rubber(NR) were believed to be critical for its superior mechanical properties. However, it is challenging to unravel the branching structure-function relationship of NR due to the complexity of the system. Herein, polyisoprene-(polyisoprene-g-polylactide)(PI-PLA) as model compound containing branching structure was designed and synthesized, which can improve the modulus, strength and viscoelasticity activation energy compared to those of the pristine polyisoprene(PI). The reason is that the branching structure contributes to the entanglement between polyisoprene chains. In order to probe the effect of branching structure on noncovalently crosslinked system, the polyisoprene block of PI-PLA was epoxidized and mixed with Fe3+ ions to introduce coordination bonds. Compared with the linear counterpart, the branching structure obviously enhanced activation energy of coordinated polyisoprenes, remarkably improving the mechanical properies of elastomer.展开更多
基金National Key R&D Program of China under Grant,Grant/Award Number:2021YFC1910601National Natural Science Foundation of China,Grant/Award Number:52104402HBIS Group Co.,Ltd Key R&D Program under Grant,Grant/Award Numbers:20210032,HG2022111。
文摘Due to their environmentally friendly nature and high energy density,direct ethanol fuel cells have attracted extensive research attention in recent decades.However,the actual Faraday efficiency of the ethanol oxidation reaction(EOR)is much lower than its theoretical value and the reaction kinetics of the EOR is sluggish due to insufficient active sites on the electrocatalyst surface.Pt/C is recognized as one of the most promising electrocatalysts for the EOR.Thus,the microscopic interfacial reaction mechanisms of the EOR on Pt/C were systematically studied in this work.In metal hydroxide solutions,hydrated alkali cations were found to bind with OH_(ad)through noncovalent interactions to form clusters and occupy the active sites on the Pt/C electrocatalyst surface,thus resulting in low Faraday efficiency and sluggish kinetics of the EOR.To reduce the negative effect of the noncovalent interactions on the EOR,a shield was made on the electrocatalyst surface using 4-trifluoromethylphenyl,resulting in twice the EOR catalytic reactivity of Pt/C.
基金supported by the National Natural Science Foundation of China(82272145)and the Foundation of Westlake University.
文摘CONSPECTUS:Controlling self-assembled peptide nanostructures has emerged as a significant area of research,offering versatile tools for developing functional materials for various applications.This Account emphasizes the essential role of noncovalent interactions,particularly in peptide-based materials.Key forces,such as aromatic stacking and hydrogen bonding,are crucial for promoting molecular aggregation and stabilizing supramolecular structures.Numerous studies demonstrate how these interactions influence the phase transitions and the morphology of self-assembled structures.Recent advances in computational methodologies,including molecular dynamics simulations and machine learning,have significantly enhanced our understanding of self-assembly processes.These tools enable researchers to predict how molecular properties,such as hydrophobicity,charge distribution,and aromaticity,affect assembly behavior.Simulations uncover the energetic landscapes governing peptide aggregation,providing insights into the kinetic pathways and thermodynamic stabilities.Meanwhile,machine learning facilitates the rapid screening of peptide libraries,identifying sequences with optimal self-assembly characteristics,and accelerating material design with tailored functionalities.Beyond their structural and physicochemical properties,self-assembled peptide nanostructures hold immense potential in biological applications due to their versatility and biocompatibility.By manipulating molecular interactions,researchers have engineered responsive systems that interact with cellular environments to elicit specific biological responses.These peptide nanostructures can mimic extracellular matrices,facilitating cell adhesion,proliferation,and differentiation.They also show promise in modulating immune responses,recruiting immune cells,and regulating signaling pathways,making them valuable tools in immunotherapy and regenerative medicine.Moreover,their ability to disrupt bacterial membranes positions them as innovative alternatives to conventional antibiotics,addressing the urgent need for solutions to antimicrobial resistance.Despite its promise,peptide self-assembly faces several challenges.The assembly process is highly sensitive to environmental conditions,such as pH,temperature,and ionic strength,leading to variability in the morphology and properties.Furthermore,peptide aggregation can result in heterogeneous and poorly defined assemblies,complicating the reproducibility and scalability.Designing peptides with predictable self-assembly behavior remains a significant hurdle.Looking ahead,integrating computational predictions with experimental validations will be crucial in discovering novel peptide sequences with tailored self-assembly properties.Machine learning,combined with high-throughput screening techniques,will enable the rapid identification of optimal peptide sequences.In situ characterization tools,such as cryoelectron microscopy and advanced spectroscopy,will provide deeper insights into assembly mechanisms,aiding the rational design of peptide materials.As research progresses,the dynamic and reversible nature of noncovalent interactions can be leveraged to create adaptive responsive to environmental stimuli.Self-assembled peptide nanostructures are poised for impactful applications in biomedicine including targeted drug delivery,tissue repair,and advanced therapeutic strategies.Ultimately,these nanostructures represent a powerful platform for addressing complex challenges in biomedicine and beyond,paving the way for transformative breakthroughs in science and technology.
文摘The wide application of photoswitches requires control over their isomerization dynamics.Utilizing noncovalent interactions is a promising strategy as it offers active regulation in-situ.However,this control strategy has not yet been explored in-depth to reach its full potential.In this work,we demonstrate that by directing noncovalent interactions to the central rotating bond of indigo-based photoswitches,their thermal relaxation dynamics were altered in two opposite directions(either slowed down or sped up)allowing for modulating the relaxation half-lives across four orders of magnitude.More importantly,our work established two distinct and orthogonal working mechanisms of noncovalent control over isomerization:(1)Thermodynamic stabilization of photoisomers;and(2)Facilitating an alternative reaction pathway through Brønsted/Lewis acid catalysis.This two-directional modulation(resembling agonists and inverse agonists in biological systems)via two orthogonal working mechanisms will enable more delicate manipulation of photoswitches for advanced applications.
基金supported by the National Natural Science Foundation of China(NSFC)(52120105006,52450063,62322115,and U24A20226)Strategic Priority Research Program of Chinese Academy of Sciences(XDB 0520103)+3 种基金National Key R&D Program of China(2024YFB3614300)Project of International Cooperation of Chinese Academy of Sciences(124GJHZ2023079MI)China Postdoctoral Science Foundation funded project(BX20240002,2024M750051)University of Chinese Academy of Sciences。
文摘Intramolecular noncovalent conformational locks(NoCLs)have emerged as an important strategy for developing high-performance organic/polymeric semiconductors(OPSs)via suppressing the non-radiative decay.Despite extensive investigation into the impact of NoCLs on small molecules,elucidating their influence on the physicochemical properties of conjugated polymers(CPs)remains a critical challenge.By employing a combination of theoretical and experimental methods,it is revealed that the incorporation of NoCLs increases the rigidity of the polymer chain,enhances intermolecular interactions,promotes the formation of pre-aggregates of optimal length,and improves charge transport,providing valuable insights for designing high-performance CPs.
基金theNaturalScienceFoundationofZhejiangProvince (No .2 980 6 8)
文摘Two palladium(II) complexes, \[Pd(bipy)(BzPhe N,O)\] and \[Pd(phen)(BzPhe N,O)\]·4H 2 O were synthesized by reactions between Pd(bipy)Cl 2 and BzPheH 2( N benzoyl β phenylalanine), Pd(phen)Cl 2 and BzPheH 2 in water at pH～9, with their structures determined by X ray diffraction analysis. The Pd atom is coordinated by two nitrogen atoms of bipy (or phen), the deprotonated amido type nitrogen atom and one of the carboxylic oxygens of BzPhe (BzPhe= N benzoyl β phenylalaninate dianion). In the complex \[Pd(phen)(BzPhe N,O)\]·4H 2O, the side chain of phenylalanine is located above and approximately parallels to the coordination plane. Both the aromatic aromatic stacking interaction between the phenyl ring of phenylalanine and phen, and the metal ion aromatic interaction between the phenyl ring of phenylalanine and Pd(II) were observed. \[Pd(bipy)(BzPhe N,O)\] has the phenylalanyl side chain oriented outwards from the coordination plane, which is mainly due to the interaction between the carbonyl oxygen atom of the amido group and the phenyl ring of phenylalanine. The reason for the different orientation of phenylalanyl side chain in the complexes was suggested.
基金financially supported by the National Natural Science Foundation of China(52002157).
文摘Although organic compounds are considered to be promising electrode materials with their remarkable characteristics such as diverse structures,design controllability,and environmental friendliness,their low charge-transfer capability and limited cycling durability hinder their application in aqueous proton batteries.Herein,we prepared a noncovalent phenazine-based graphene aerogel(H/G)composite for aqueous proton storage,which is realized by redox-active Hexaazatrinaphthalene(HATN)organic compound combined with conductive reduced graphene oxide(rGO).The integration of rGO into HATN not only effectively optimizes the electronic structure of the H/G composite to enhance its electrochemical activity,but also the favorable noncovalent π-π interaction existed between HATN and rGO provides a stable structure for fast electron transportation.The obvious electron transfer in the aerogel composite promotes fast and reversible redox reactions occurred with the imino-active HATN in the composite electrode for proton uptake/removal in an aqueous acidic electrolyte,which are demonstrated by in-situ Fourier transform infrared(FTIR)investigation,theoretical calculations and experimental measurements.Therefore,it can deliver a fast,stable and efficient aqueous proton storage behavior with a large specific capacity of 274 mA·h·g^(-1) and considerable calendar life with~100%capacity retention after 3000 cycles,surpassing previously reported proton-based organic electrodes in aqueous acidic electrolytes.Furthermore,an outstanding soft-package aqueous proton(APB)has been fabricated with considerable long-term cycling stability.
基金financially supported by the National Natural Science Foundation of China(NNSFC grants 52125301)the Fundamental Research Funds for the Central Universities
文摘Thermoelectric(TE)generators capable of converting thermal energy into applicable electricity have gained great popularity among emerging energy conversion technologies.Biopolymer-based ionic thermoelectric(i-TE)materials are promising candidates for energy conversion systems because of their wide sources,innocuity,and low manufacturing cost.However,common physically crosslinked biopolymer gels induced by single hydrogen bonding or hydrophobic interaction suffer from low differential thermal voltage and poor thermodynamic stability.Here,we develop a novel i-TE gel with supramolecular structures through multiple noncovalent interactions between ionic liquids(ILs)and gelatin molecular chains.The thermopower and thermoelectric power factor of the ionic gels are as high as 2.83 mV K-1 and 18.33μW m^(-1)K^(-2),respectively.The quasi-solid-state gelatin-[EMIM]DCA i-TE cells achieve ultrahigh 2 h output energy density(E_(2h)=9.9 mJ m^(-2))under an optimal temperature range.Meanwhile,the remarkable stability of the supramolecular structure provides the i-TE hydrogels with a thermal stability of up to 80℃.It breaks the limitation that biopolymer-based i-TE gels can only be applied in the low temperature range and enables biopolymer-based i-TE materials to pursue better performance in a higher temperature range.
基金supported by the National Natural Science Foundation of China(No.21962003)the Natural Science Foundation of Jiangsu Province(No.BK20190056)the“Fundamental Research Funds for the Central Universities”(No.021514380014)。
文摘Understanding the regulatory mechanism of self-assembly processes is a necessity to modulate nanostructures and their properties. Herein, we have studied the mechanism of self-assembly in the C3 symmetric 1,3,5-benzentricarboxylic amino acid methyl ester enantiomers(TPE) in a mixed solvent system consisting of methanol and water. The resultant chiral structure was used for chiral recognition. The formation of chiral structures from the synergistic effect of multiple noncovalent interaction forces was confirmed by various techniques. Molecular dynamics simulations were used to characterize the time evolution of TPE structure and properties in solution. The theoretical results were consistent with the experimental results. Furthermore, the chiral structure assembled by the building blocks of TPE molecules was highly stereoselective for diamine compounds.
基金financially supported by the China Postdoctoral Science Foundation(No.2020M682154)。
文摘The interactions of complexes of XeOF_(2) and XeO_(3) with a series of different hybridization N-containing donors are studied by means of DFT and MP_(2) calculations.The aerogen bonding interaction energies range from 6.5 kcal/mol to19.9 kcal/mol between XeO_(3) or XeOF_(2) and typical N-containing donors.The sequence of interaction for N-containing hy-bridization is sp^(3)>sp^(2)>sp,and XeO_(3)is higher than XeOF_(2).For some donors of sp^(2)and sp^(3) hybridization,the steric effect plays a minor role in the interaction with the evidence of reduced density gradient plots.The dominant stable part is the electrostatic interaction.In complex of XeO_(3),the weight of polarization is larger than dispersion,while the situation is opposite for XeOF_(2)complexes.Except for the sum of the maximum value of molecular electrostatic potential on Xe atom and minimum value of molecular electrostatic potential on N atom,the other five interaction parameters including the potential energy density at bond critical point,the equilibrium distances,interaction energies with the basis set superposition error correction,localized molecular orbital energy decomposition analysis interaction energies,and the electron charge density,show great linear correlation coefficients with each other.
基金supported by the Strategic Priority Research Program of CAS(No.XDB0520201)the National Natural Science Foundation of China((Nos.22132007,22372175,22202208,22372030)CAS Project for Young Scientists in Basic Research(No.YSBR-053).
文摘Achieving seamless tiling through the self-assembly of organic species has long fascinated scientists for its potential applications across various fields.However,constructing periodic nanostructures with high-order tessellation remains challenging,particularly in achieving precise control at the supramolecular level.In this study,we present the successful creation of multiple seamless 2D tessellations on Au(111)surface using versatile hexagonal tiles derived from a singular molecular unit,namely 2,6,10-tribromotricycloquinazoline.Through scanning tunneling microscopy imaging,seven distinct 2D tessellations,ranging from regular to semiregular to k-uniform tilings,are unveiled at the molecular level.Density functional theory calculations provide a theoretical basis for the formation of these complex 2D tessellation,highlighting the important role of the variability of Br···Br/H contacts in facilitating complex seamless 2D tessellations on surface.This work opens avenues for exploring possibilities in constructing intricate tiling patterns with diverse applications.
基金supported by the One Belt and One Road Innovative Talent Exchange Program for Foreign Experts[Grant No.DL20200009005]the Fundamental Research Funds for the Central Universities[Grant No.2232021G-02]Fundamental Research Funds for the Central Universities[Grant No.2232020G-04]。
文摘Polymer-based thermally conductive composites have attracted tremendous interest in thermal management of electronics.However,it remains challenging to achieve high thermal conductivity partly because the difficulty to obtain favorable distribution and orientation of conductive fillers within the polymer matrix.Herein,networked boron nitride(BN)conductive pathway was realized within the poly(lactic acid)(PLA)matrix,via regenerated cellulose(RC)-assisted assembly of BN on Pickering emulsion interface based on the noncovalent interaction,followed by solvent evaporation and hot-compressing.The strong noncovalent interactions between BN and RC were found critical to enhance the wettability and stability of BN in aqueous media with a lowest mass ratio of 1:40 of RC and BN.The obtained PLA/BN composites feature a thermal conductivity of 1.06 W/(m K)at 28.4 wt%BN loading,representing an enhancement of 430%comparing to neat PLA,and the crystallinity of the composites could increase significantly from11.7%(neat PLA)to 43.7%.This simple,environmentally friendly and effective strategy could be easily extended for effective construction of thermally conductive composites.
基金supported by the National Natural Science Foundation of China(Nos.21961007 and 21871063)the Science and Technology Foundation of Hunan Province(No.2020JJ2021).
文摘The synthesis of cyclopolymers upon controlling the degree of macrocyclic polymerization,followed by the discovery of new properties has attracted increasing attention in supramolecular chemistry.Herein,a Schiff-base condensation method performed at room temperature was used to control the formation of[1+1]and[2+2]macrocycles.In pure MeOH,the isomer[1+1]macrocycles were synthesized and organic particles such as dendritic,rods,and solid microspheres were directly precipitated from the reaction solution.The[1+1]macrocycles can be efficiently converted into their corresponding[2+2]macrocycles accompanied by the tunable morphology of the organic particles when n-hexane was added to the MeOH solution.Further studies showed that these organic particles have potential application toward the selective removal of Cd^(2+)ions with different adsorption ability in MeOH solution.
基金funded by National Natural Science Foundation of China (No.22125901)the National Key Research and Development Program of China (No.2019YFA0705900)the Fundamental Research Funds for the Central Universities (No.226–2023–00113)。
文摘Developing narrow-bandgap organic semiconductors is important to facilitate the advancement of organic photovoltaics(OPVs). Herein, two near-infrared non-fused ring acceptors(NIR NFRAs), PTBFTT-F and PTBFTT-Cl have been developed with A-π_A-π_D-D-π_D-π_A-A non-fused structures. It is revealed that the introduction of electron deficient π-bridge(π_A) and multiple intramolecular noncovalent interactions effectively retained the structural planarity and intramolecular charge transfer of NFRAs, extending strong NIR photon absorption up to 950 nm. Further, the chlorinated acceptor, with the enlarged π-surface compared to the fluorinated counterpart, promoted not only molecular stacking in solid, but also the desirable photochemical stability in ambient, which are helpful to thereby improve the exciton and charge dynamics for the corresponding OPVs. Overall, this work provides valuable insights into the design of NIR organic semiconductors.
基金The authors gratefully acknowledge the financial support from National Natural Science Foundation of China(NSFC,Nos.51973169 and 52003209)the Open Project Program of Wuhan National Laboratory for Optoelectronics(No.2020WNLOKF015)the Science Foundation of Wuhan Institute of Technology(Nos.K202023 and K202025).
文摘Benefitting from the development of non-fullerene acceptors(NFAs),remarkable advances have been achieved with the power conversion efficiency(PCE)exceeding 19%over the last few years.However,the major achievement comes from fused ring electron acceptors(FREAs)with complex structures,leading to high cost.Hence,it is urgent to design new materials to resolve the cost issues concerning basic commercial requirements of organic solar cells.Recently,great progress has been made in fully non-fused ring electron acceptors(NFREAs)with only single-aromatic ring in the electron-donating core,which might achieve a fine balance between the efficiency and cost,thus accelerating the commercial application of organic solar cells.Therefore,this article summarizes the recent advances of fully NFREAs with efficiency over 10%,which may provide a guidance for developing the cost-effective solar cells.
基金supported by the National Natural Science Foundation of China(No.21171040 and 21302019)the disguished organic project(2013JCJS01)
文摘Two novel acid-base adducts,[H2L1^2＋]（Hpbda）2（1,L1 = 1,4-di（lH-imidazol-4-yl）benzene,H2pbda = 1,4-benzenedicarboxylic acid） and[H2L2^2＋]（NO3）2（2,L2 = l,4-di（l-carboxymethyl-imidazol-4-yl）benzene）,have been prepared and characterized by single-crystal X-ray diffraction,IR spectroscopy and elemental analysis.Compound 1 crystallizes in monoclinic,space group P21/n with a = 5.3525（11）,b = 9.1471（19）,c = 19.314（4） ？,β = 92.342（3）°,V= 944.8（3） A°3,Z = 2,C16H16N6O（10）,Mr = 452.35,Dc = 1.590 g/cm^3,μ = 0.135 mm^-1,S = 1.058,F（000） = 468,the final R = 0.0661 and wR = 0.1887 for 2298 observed reflections（I〉 2σ（I））.Compound 2 crystallizes in monoclinic,space group P21/c with a = 9.6923（10）,b = 17.2950（17）,c = 7.1880（7） ？,β =94.801（2）°,V= 1200.7（2）A°3,Z = 2,C（28）H（22）N4O8,Mr = 542.50,Dc = 1.501 g/cm^3,μ = 0.112 mm^-1,S= 1.060,F（000） = 564,the final R = 0.0394 and wR = 0.1017 for 2768 observed reflections（I 〉2σ（I））.In the title compounds,both of L1 and L2 ligands act as weak base to accept protons to exhibit diprotonated H2L1^2＋ and H2L2^2＋ form,which can effectively employ as hydrogen bonding donors to combine anion moieties to form binary adducts respectively.In the crystal packing diagram of two polymers,there exist extensive noncovalent interactions including charge-transfer interactions,C（N）-H…π and N-H…O,C-H…O,O-H…O hydrogen bonding interactions between co-crystal moieties which consolidate the structures of supramolecular polymers,thus generating three-dimensional（3D） frameworks.
基金financially supported by the Science and Technology Commission of Shanghai Municipality (No.20JC1414900)the National Natural Science Foundation of China (No.52203005)the Science and Technology Commission of Shanghai Municipality (No.21ZR1401400)。
文摘Regioregular poly(3-hexylthio)thiopene(P3HTT) has emerged tremendous potential in organic electronic applications due to the strong noncovalent interactions from the sulfur atom linked to thiophene. However, P3HTT generally exhibits low charge mobility mostly due to poor solution processability attributed to dense arrangement of hexylthio side chain in polymer, which led to strong noncovalent interactions among sulfur atoms. To balance the nonvalent interaction and aggregation for P3HTT, herein, we systematically study the effect of hexylthio side chain content in polymer backbone on the structure and properties. A series of regioregular P3HTT-based homopolymers(P3HTT, P3HTT-50,P3HTT-33 and P3HTT-25) were prepared via Kumada catalyst transfer polycondensation method from a set of mono-, bi-, ter-and quarterthiophenes containing different contents of hexylthio side chain. The DFT calculation shows the planarity of polymers backbone could be improved through reducing the density of hexylthio side chain in polymer mainchain. And significant changes in their crystallinity, aggregation and optical properties were observed with the content of hexylthio side chain reducing. The P3HTT-33 displayed the highest field-effect transistor hole mobility of 2.83×10^(-2) cm^(2)·V^(-1)·s^(-1) resulting from a balance between the crystallinity and planarity. This study demonstrates modulating the content of hexylthio side chain in P3HTT is an effective strategy to optimize the opto-electronic properties of polymer obtaining excellent semiconductor device performance.
基金supported by the National Natural Science Foundation of China(Grant Nos.22375098,21805139 and 12102194)the Joint Funds of the National Natural Science Foundation of China(Grant No.U2141202)Young Elite Scientists Sponsorship Program by CAST(Grant No.2021QNRC001).
文摘Ammonium dinitramide(ADN)is a new type of green energetic oxidizer with excellent energy density and low pollution combustion characteristics.However,the strong hygroscopicity has a significant impact on its practical application.To assist in the research on moisture-proof modification of ADN materials,an innovative hygroscopic modeling approach was proposed to evaluate the hygroscopicity of ADN at various temperatures and humidities.By investigating the diffusion coefficient of water molecules in molecular dynamics processes,a visual insight into the hygroscopic process of ADN was gained.Furthermore,analyzing the non-covalent interactions between ADN and water molecules,the hygroscopicity of ADN could be evaluated qualitatively and quantitatively.The energy analysis revealed that electrostatic forces play a dominant role in the process of water adsorption by ADN,whereas van der Waals forces impede it.As a whole,the simulation results show that ADN presents the following hygroscopic law:At temperatures ranging from 273 K to 373 K and relative humidity(RH)from 10%to 100%,the hygroscopicity of ADN generally shows an increasing trend with the rise in temperature and humidity based on the results of three simulations.According to the non-hygroscopic point(298 K,52%RH)of ADN obtained by experiment in the literature,a non-hygroscopic range of temperature and humidity for ADN can be depicted when the simulation results in relative hygroscopicity is less than or equal to 17%.This study can provide effective strategies for screening anti-hygroscopic modified materials of ADN.
基金supported by the National Natural Science Foundation of China(Grant Nos.21905069 and U21A20307)the Shenzhen Science and Technology Innovation Committee(Grant Nos.ZDSYS20190902093220279,KQTD20170809110344233,GXWD20201230155427003-20200821181245001,GXWD20201230155427003-20200821181809001,and ZX20200151)+1 种基金the Department of Science and Technology of Guangdong Province(Grant No.2020A1515110879)University Stable Support Foundation of Shenzhen(Grant No.GXWD20201230155427003-20200821181809001).
文摘Biomass carbon and small redox biomolecules are attractive materials for green,sustainable energy storage devices owing to their environmentally friendly,low-cost,scalable,and novel sources.However,most devices manufactured using these materials have low specific capacitance,poor cycle stability,short lifetime,complexity,and low precision of device fabrication.Herein,we report the directed self-assembly of mononuclear anthraquinone(MAQ)derivatives and porous lignin-based graphene oxide(PLGO)into a renewable colloidal gel through noncovalent interactions.These self-assembled gel electrode materials exhibited high capacitance(484.8 F g^(−1) at a current density of 1 A g^(−1))and could be further printed as flexible micro-supercapacitors(FMSCs)with arbitrary patterns and a relatively high resolution on specific substrates.The FMSCs exhibited excellent areal capacitance(43.6 mF cm^(−2)),energy and power densities(6.1μWh cm^(−2) and 50μW cm^(−2),respectively),and cycle stability(>10,000 cycles).Furthermore,the printed FMSCs and integrated FMSC arrays exhibited remarkable flexibility while maintaining a stable capacitance.The proposed approach can be applied to other quinone biomolecules and biomass-based carbon materials.This study provides a basis for fabricating green and sustainable energy storage device architectures with high capacitance,long-term cycling,high scalability,and high precision.
基金supported by the National Natural Science Foundation of China(Nos.52130306,22075287,22101285)the Program of Youth Innovation Promotion Association CAS(No.2021299).
文摘Optimal bulk-heterojunction(BHJ)morphology is crucial for efficient charge transport and good photovoltaic performance in organic solar cells(OSCs).Yet,the correlation between chemical structures of nonfullerene acceptors(NFAs)and molecular interaction in the BHJ blends remains opaque.Herein,we study three isomeric NFAs referred to as MQ1-x(x=β,y,or 8)that shared an asymmetric selenophene-fused heteroheptacene backbone end-capped by two monochlorinated end groups.Remarkably,miscibility between the polymer donor of PM6 and MQ1-x successively elevates as the chlorine atoms move fromβ-,to y-,to 8-position of terminals.Combined with the varied molecular crystallinity of these NFAs,diverse BHJ morphologies are observed in their blend films.As a result,the MQ1-8-based devices present the highest PCE of 12.08%owing to the efficient charge dissociation and transport induced by the compact molecular packing and optimal BHJ morphology.Our investigation provides a new insight in the material design that has a good balance in molecular packing and film morphology for high-performance OSCs.
基金financially supported by the National Natural Science Foundation of China(Nos.51973126 and 51333003)。
文摘The branching structures in natural rubber(NR) were believed to be critical for its superior mechanical properties. However, it is challenging to unravel the branching structure-function relationship of NR due to the complexity of the system. Herein, polyisoprene-(polyisoprene-g-polylactide)(PI-PLA) as model compound containing branching structure was designed and synthesized, which can improve the modulus, strength and viscoelasticity activation energy compared to those of the pristine polyisoprene(PI). The reason is that the branching structure contributes to the entanglement between polyisoprene chains. In order to probe the effect of branching structure on noncovalently crosslinked system, the polyisoprene block of PI-PLA was epoxidized and mixed with Fe3+ ions to introduce coordination bonds. Compared with the linear counterpart, the branching structure obviously enhanced activation energy of coordinated polyisoprenes, remarkably improving the mechanical properies of elastomer.
