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block copolymer Supported Gold Nanoparticles Assemblies with Exposed Gold Surface

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Chemical Research in Chinese Universities 2022年第4期38卷 1118-1122页

作者： ZONG Chen LIU Guangnan XU Wenhao CHEN Jie TANG Yun Department of Chemistry Laboratory of Advanced MaterialsShanghai Key Laboratory of Molecular CatalysisCollaborative Innovation Center of Chemistry for Energy MaterialsFudan UniversityShanghai200438P.R.China

Polymer-involved nanoparticles or nanoparticle assemblies are now facing a crossroad,where the exposure of nanoparticle and multiple nanoparticles cannot be obtained at the same ***,a new series of nanoparticle clusters is synthesized,where multiple gold nanoparticles assemble with amphiphilic block copolymers supporting *** exposure of gold nanoparticles of the structure is confirmed and increases the reduction rate of 4-nitrophenol by 60%.The assemblies can also be used as surface enhanced Raman scattering(SERS)probes with an enhancement factor(EF)as high as 3×10^(3).

关键词： Gold nanoparticle block copolymer co-Assembly

Ordered Bicontinuous Network Structures Regulated by Orientational Interactions in a Rod-Coil block copolymer

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Chinese Journal of Polymer Science 2024年第5期42卷 636-642,I0008页

作者： Xiao-Lin Lyu Shi-Chu Yang An-Qi Xiao Ping-Ping Hou Wei Zhang Hong-Bing Pan Zhi-Hao Shen Xing-He Fan Qi-Feng Zhou Beijing National Laboratory for Molecular Sciences Key Laboratory of Polymer Chemistry and Physics of Ministry of EducationCollege of Chemistry and Molecular EngineeringPeking UniversityBeijing100871China Key Laboratory of Advanced Materials Technologies International(HongKong Macao and Taiwan)Joint Laboratory on Advanced Materials TechnologiesCollege of Materials Science and EngineeringFuzhou UniversityFuzhou350108China

The rich phase behavior of block copolymers(BCPs)has drawn great attention in recent ***,the double diamond(DD)phase is rarely obtained because of the competition between the minimization of interfacial energy and packing ***,a rod-coil BCP containing mesogen-jacketed liquid crystalline polymer is designed to acquire ordered bicontinuous network *** reduction of internal energy originating from the orientational interaction among the rod blocks can compensate for the free energy penalty of packing frustration to stabilize the DD *** resulting BCP can also experience lamellae-to-DD and double gyroid-to-lamellae transitions by changing the annealing *** results make the rod-coil BCP an excellent candidate for the self-assembly of ordered network structures,demonstrating great potential in nanopatterning and metamaterials.

关键词： block copolymer Rod-coil Ordered bicontinuous phase Double diamond Double gyroid

Temperature/pH dual-responsive reversible morphology evolution of block copolymer microparticles under three-dimensional confinement

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Science China Chemistry 2023年第12期66卷 3587-3593页

作者： Mengmeng Zhang Zaiyan Hou Simeng Liu Guoqiang Han Meirong Tian Jintao Zhu Jiangping Xu Key Laboratory of Materials Chemistry for Energy Conversion and Storage of Ministry of Education School of Chemistry and Chemical EngineeringHuazhong University of Science and TechnologyWuhan 430074China

Development of block copolymer(BCP)microparticles with switchable morphology in response to external stimuli is important for exploiting new intelligent *** this work,thermo/p H dual-responsive nanoparticles(NPs)were employed as a cosurfactant to modulate the self-assembly morphology of polystyrene-b-poly(2-vinylpyridine)(PS-b-P2VP)microparticles within confined emulsion *** co-surfactant was synthesized by grafting poly(acrylic acid)-b-poly(N-isopropylacrylamide)onto the surface of *** introduction of the dual-responsive co-surfactant enabled thermo/p H dual-responsive reversible morphology transition of the PS-b-P2VP microparticles by tailoring the hydrophobicity and interfacial affinity of the *** using this strategy,the thermo-inert PS-b-P2VP self-assembled into pupa-like microparticles at T=10℃ and p H7.5,which could transform into tulip-like microparticles when T was increased to 50℃.When the p H value was increased to 11,the pupa-like particles turned into onion-like microparticles although the PS-b-P2VP was inert to ***,the pupa-like microparticles remained unchanged when both T and p H were simultaneously *** PAA-b-PNIPAM-grafted Fe3O4NP surfactants showed obvious advantages over the linear PAA-b-PNIPAM surfactants in modulating the morphology transition,since the linear PAA-b-PNIPAM could not induce the reversible shape transition of *** work provides an efficient strategy to achieve reversible shape transformation of BCP microparticles while the internal phase structure is preserved,which may be utilized to switch the structural color properties of BCP microparticles.

关键词： block copolymer self-assembly stimuli-responsiveness lower critical solution temperature microparticle

Asymmetric Mesoporous Carbon Microparticles by 3D-Confined Self-Assembly of block copolymer/Homopolymer Blends and Selective Carbonization

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Chinese Journal of Polymer Science 2023年第5期41卷 787-793,I0010页

作者： Jing-Ye Liu Hao-Rui Song Mian Wang Shao-Hong Jin Zheng Liang Xi Mao Wang Li Ren-Hua Deng Jin-Tao Zhu State Key Laboratory of Materials Processing and Die&Mould Technology Key Laboratory of Material Chemistry for Energy Conversion and Storage of Ministry of EducationSchool of Chemistry and Chemical EngineeringHuazhong University of Science and TechnologyWuhan 430074China

Shape control of mesoporous carbon microparticles(MCMPs)is of critical importance;in particular,asymmetric shapes that can yield unique properties have attracted significant ***,the tailored synthesis of asymmetric MCMPs with ordered structures remains ***,we report a facile route to prepare asymmetric MCMPs by dynamic neutral interface-guided 3D-confined self-assembly(3D-CSA)of block copolymer/homopolymer(BCP/hP)blends,followed by a self-templated selective direct carbonization ***/h P Janus microparticles with ordered hierarchical mesostructures were prepared with emulsion solvent evaporation-induced *** continuous phase of BCP domains was then *** asymmetric MCMPs are successfully generated after selective carbonization of the crosslinked continuous *** method allows tuning the shape of MCMPs easily by varying the blending ratio of BCP/h *** composite asymmetric MCMPs combine the advantages of asymmetric shape,ordered structure,high specific surface area,chemical inertness and thermal stability and could provide great possibilities for applications in catalysis,drug delivery,energy conversion and storage.

关键词： 3D-confined self-assembly block copolymer Phase separation Mesoporous carbon spheres Janus

An Efficient Algorithm for Self-consistent Field Theory Calculations of Complex Self-assembled Structures of block copolymer Melts

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Chinese Journal of Polymer Science 2018年第4期36卷 488-496页

作者： Jun-Qing Song Yi-Xin Liu Hong-Dong Zhang State Key Laboratory of Molecular Engineering of Polymers Department of Macromolecular Science Fudan University

Self-consistent field theory（SCFT）, as a state-of-the-art technique for studying the self-assembly of block copolymers, is attracting continuous efforts to improve its accuracy and efficiency. Here we present a fourth-order exponential time differencing Runge-Kutta algorithm（ETDRK4） to solve the modified diffusion equation（MDE） which is the most time-consuming part of a SCFT calculation. By making a careful comparison with currently most efficient and popular algorithms, we demonstrate that the ETDRK4 algorithm significantly reduces the number of chain contour steps in solving the MDE, resulting in a boost of the overall computation efficiency, while it shares the same spatial accuracy with other algorithms. In addition, to demonstrate the power of our ETDRK4 algorithm, we apply it to compute the phase boundaries of the bicontinuous gyroid phase in the strong segregation regime and to verify the existence of the triple point of the O70 phase, the lamellar phase and the cylindrical phase.

关键词： block copolymer Self-consistent field theory Algorithm Pseudo-spectral Phase structure

Two-dimensional Nitrogen-doped Mesoporous Carbon/Graphene Nanocomposites from the Self-assembly of block copolymer Micelles in Solution

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Chinese Journal of Polymer Science 2018年第3期36卷 266-272页

作者： Nan Wang Hao Tian Shu-Yan Zhu De-Yue Yan Yi-Yong Mai School of Chemistry and Chemical Engineering Shanghai Key Laboratory of Electrical Insulation and Thermal AgeingShanghai Jiao Tong University Shanghai 200240China

The self-assembly of block copolymer in solution has proven to be an effective strategy for building up a wide range of nanomaterials with diverse structures and *** paper reports a facile self-assembly approach towards two-dimensional(2D)sandwich-like mesoporous nitrogen-doped carbon/reduced graphene oxide nanocomposites(denoted as mNC/rGO)with well-defined large *** strategy involves the synergistic self-assembly ofpolystyrene-block-poly(ethylene oxide)(PS-b-PEO)spherical micelles,m-phenylenediamine(mPD)monomers and GO in solution and the subsequent carbonization at 900~*** resultant mNC/rGO nanosheets have an average pore size of 19 nm,a high specific surface of 812 m^(2)'g^(-1)and a nitrogen content of 2.2 wt%.As an oxygen reduction reaction(ORR)catalyst,the unique structural features render the metal-free nanosheets excellent electrocatalytic *** a 0.1 mol.L-~KOH alkaline medium,mNC/rGO exhibits a four-electron transfer pathway with a high half-wave-potential(El/2)of+0.77 V versus reversible hydrogen electrode(RHE)and a limiting current density(JL)of 5.2 mA'cm^(-2),which are well comparable with those of the commercial Pt/C catalysts.

关键词： block copolymer Self-assembly 2D materials Mesoporous carbon ORR

CRYSTALLIZATION OF BLENDS OF AN ASYMMETRIC POLY(OXYETHYLENE)-b-POLY(OXYBUTYLENE) block copolymer WITH POLY(OXYBUTYLENE)

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Chinese Journal of Polymer Science 2004年第5期22卷 477-483页

作者：徐君庭 Guo-dongLiang Shao-minMai A.J.Ryan DepartmentofPolymerScience＆Engineering ZhejiangUm＇versity.Hangzhou310027China ChemistryDepartment TheUniversityofSheffieldSheffieldS37HFUK DepartmentofPolymerScience＆Engineering ZhejiangUm＇versity.Hangzhou310027China

An oxyethylene/oxybutylene block copolymer with asymmetric volume fraction (E115B105) was blended with oxybutylene homopolymer (Bh) at different volume fractions of the block Crystallization behavior of the blends was studied and was compared with that of the blends from a symmetric block copolymer (E114B56). It was found that the crystallization temperature of E115B103/B28 blend is lower than that of the blends from symmetric block copolymer. For the blend with = 0.30 breakout crystallization with an Avrami exponent n 3.0 is observed. At = 0.22 the blend exhibits a variable crystallization behavior: confined crystallization with n 1.0 at lower crystallization temperatures but breakout crystallization at high crystallization temperatures. For the blend with = 0.14 and sphere morphology confined crystallization occurs at all crystallization temperatures studied. When compared with the blends from symmetric block copolymer, confined crystallization occurs more easily in the E115B103/B28 blends. The SAXS results agree with the isothermal crystallization kinetics. Deformation of the confined crystalline block is observed in the blend with =0.14 and mixed lamellar and cylinder morphologies in the blend with = 0.22.

关键词： Crystallization block copolymer Blend Confinement

Double diamond structured bicontinuous mesoporous titania templated by a block copolymer for anode material of lithium-ion battery

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Nano Research 2021年第4期14卷 992-997页

作者： Qingqing Sheng Qian Li Luoxing Xiang Tao Huang Yiyong Mai Lu Han School of Chemistry and Chemical Engineering Frontiers Science Center for Transformative MoleculesShanghai Key Laboratory of Electrical Insulation and Thermal AgeingShanghai Jiao Tong Universityy 800 Dongchuan RoadShanghai 200240China School of Chemical Science and Engineering Tongji UniversityShanghai 200092China

Titania has received considerable attention as a promising anode material of Li-ion battery(LIB).Controlling the structure and morphology of titania nanostructures is crucial to govern their ***,we report a mesoporous titania scaffold with a bicontinuous shifted double diamond(SDD)structure for anode material of *** titania scaffold was synthesized by the cooperative self-assembly of a block copolymer poly(ethylene oxide)-block-polystyrene template and titanium diisopropoxide bis(acetylacetonate)as the inorganic precursor in a mixture solvent of tetrahydrofuran and HCl/*** structure shows tetragonal symmetry(space group I4_(1)/amd)comprising two sets of diamond networks adjoining each other with the unit cell parameter of a=90 nm and c=127 nm,which affords the porous titania a specific surface area(SSA)of 42 m^(2)·g^(-1)with a mean pore diameter of 38 *** as an anode material of LIB,the bicontinuous titania scaffold exhibits a high specific capacity of 254 mAh·g^(-1)at the current density of 1 A·g^(-1)and an alluring self-improving feature upon charge/discharge over 1,000 *** study overcomes the difficulty in building up ordered bicontinuous functional materials and demonstrates their potential in energy storage application.

关键词： bicontinuous structure block copolymer lithium-ion battery mesoporous titania self-assembly

Dependence of Size and Morphology on Shear Flow for PS-based Amphiphilic block copolymer Micelles in Aqueous Solution

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Chinese Journal of Polymer Science 2017年第5期35卷 641-648页

作者： Zhi-da Wang Chang-feng Yan Ying Huang Li-qi Yi Key Laboratory of Renewable Energy Guangzhou Institute of Energy ConversionChinese Academy of Sciences Guangdong Key Laboratory of New and Renewable Energy Research and Development University of Chinese Academy of Sciences

This contribution focuses on the impact of shear flow on size and nanostructure of PS-based amphiphilic block copolymer （BC） micelles by varying the stirring rate and copolymer composition. The results show that the vesicles formed from diblock copolymer （di-BC） of PS-b-PAA remain with vesicular morphology, although the average size decreases, with the increase of stirring rate. However, the multi-compartment micelles （MCMs） formed from tri-block copolymer （tri-BC） of PS-b-P2VP-b-PEO are quite intricate, in which the copolymer first self-assembles into spheres, then to clusters, to large compound micelles （LCMs）, and finally back to spheres, as stirring rate increases from 100 r/min to 2200 r/min. Formation mechanism studies manifest that vesicles form simultaneously as water is added to the di-BC solution, termed as direct- assembly, and remain with vesicular structure in the flowing process. While for the PS-b-P2VP-b-PEO copolymer, spherical micelles at initial stage can further assemble into clusters and LCMs, termed as second-assembly, due to the speeding-up- aggregation of the favorable stirring. As a result, an invert V-relationship between tri-BC micelle dimension and stirring rate is observed in contrast to the non-linear decreasing curve of di-BC vesicles. It is by investigating these various amphiphilic BCs that the understanding of shear dependence of size and morphology of micelles is improved from self-assembly to second-assembly process.

关键词： Self-assembly Shear Size Nanostructure block copolymer