Ingenierie des Materiaux polymeres

We show a simple, robust, chemical route to the fabrication of ultrahigh-density arrays of nanopores with high aspect ratios using the equilibrium self-assembled morphology of asymmetric diblock copolymers. The dimensions and lateral density of the array are determined by segmental interactions and the copolymer molecular weight. Through direct current electrodeposition, we fabricated vertical arrays of nanowires with densities in excess of 1.9 x 10(11) wires per square centimeter. We found markedly enhanced coercivities with ferromagnetic cobalt nanowires that point toward a route to ultrahigh-density storage media. The copolymer approach described is practical, parallel, compatible with current lithographic processes, and amenable to multilayered device fabrication.

International audience

The self-assembly of particles at fluid interfaces, driven by the reduction in interfacial energy, is well established. However, for nanoscopic particles, thermal fluctuations compete with interfacial energy and give rise to a particle-size-dependent self-assembly. Ligand-stabilized nanoparticles assembled into three-dimensional constructs at fluid-fluid interfaces, where the properties unique to the nanoparticles were preserved. The small size of the nanoparticles led to a weak confinement of the nanoparticles at the fluid interface that opens avenues to size-selective particle assembly, two-dimensional phase behavior, and functionalization. Fluid interfaces afford a rapid approach to equilibrium and easy access to nanoparticles for subsequent modification. A photoinduced transformation is described in which nanoparticles, initially soluble only in toluene, were transported across an interface into water and were dispersed in the water phase. The characteristic fluorescence emission of the nanoparticles provided a direct probe of their spatial distribution.

This review explores the features and corresponding application of ZIF-67 and its derivatives.

International audience

Interfacial layers (ILs) are prerequisites to form the selective charge transport for high-performance organic photovoltaics (OPVs) but mostly result in considerable parasitic absorption loss. Trimming the ILs down to a mono-molecular level via the self-assembled monolayer is an effective strategy to mitigate parasitic absorption loss. However, such a strategy suffers from inferior electrical contact with low surface coverage on rough surfaces and poor producibility. To address these issues, here, the self-assembled interlayer (SAI) strategy is developed, which involves a thin layer of 2-6 nm to form a full coverage on the substrate via both covalent and van der Waals bonds by using a self-assembled molecule of 2-(9H-carbazol-9-yl) (2PACz). Via the facile spin coating without further rinsing and annealing process, it not only optimizes the electrical and optical properties of OPVs, which enables a world-record efficiency of 20.17% (19.79% certified) but also simplifies the tedious processing procedure. Moreover, the SAI strategy is especially useful in improving the absorbing selectivity for semi-transparent OPVs, which enables a record light utilization efficiency of 5.34%. This work provides an effective strategy of SAI to optimize the optical and electrical properties of OPVs for high-performance and solar window applications.

Abstract Rechargeable aqueous zinc‐ion batteries (ZIBs) have been emerging as potential large‐scale energy storage devices due to their high energy density, low cost, high safety, and environmental friendliness. However, the commonly used cathode materials in ZIBs exhibit poor electrochemical performance, such as significant capacity fading during long‐term cycling and poor performance at high current rates, which significantly hinder the further development of ZIBs. Herein, a new and highly reversible Mn‐based cathode material with porous framework and N‐doping (MnO x @N‐C) is prepared through a metal–organic framework template strategy. Benefiting from the unique porous structure, conductive carbon network, and the synergetic effect of Zn 2+ and Mn 2+ in electrolyte, the MnO x @N‐C shows excellent cycling stability, good rate performance, and high reversibility for aqueous ZIBs. Specifically, it exhibits high capacity of 305 mAh g −1 after 600 cycles at 500 mA g −1 and maintains achievable capacity of 100 mAh g −1 at a quite high rate of 2000 mA g −1 with long‐term cycling of up to 1600 cycles, which are superior to most reported ZIB cathode materials. Furthermore, insight into the Zn‐storage mechanism in MnO x @N‐C is systematically studied and discussed via multiple analytical methods. This study opens new opportunities for designing low‐cost and high‐performance rechargeable aqueous ZIBs.

This Review describes the state-of-the-art of wearable electronics (smart textiles). The unique and promising advantages of smart electronic textiles are highlighted by comparing them with the conventional planar counterparts. The main kinds of smart electronic textiles based on different functionalities, namely the generation, storage, and utilization of electricity, are then discussed with an emphasis on the use of functional materials. The remaining challenges are summarized together with important new directions to provide some useful clues for the future development of smart electronic textiles.

Abstract Improving charge extraction and suppressing charge recombination are critically important to minimize the loss of absorbed photons and improve the device performance of polymer solar cells (PSCs). In this work, highly efficient PSCs are demonstrated by progressively improving the charge extraction and suppressing the charge recombination through the combination of side‐chain engineering of new nonfullerene acceptors (NFAs), adopting ternary blends, and introducing volatilizable solid additives. The 2D side chains on BTP‐Th induce a certain steric hindrance for molecular packing and phase separation, which is mitigated by fluorination of side chains on BTP‐FTh. Moreover, by introducing two highly crystalline molecules as the second acceptor and volatilizable solid additive, respectively, into the BTP‐FTh‐based host blend, the molecular crystallinity is significantly improved and the blend morphology is finely optimized. As expected, enhanced charge extraction and suppressed charge recombination are progressively realized, contributing to the largely improved fill factor (FF) of the resultant devices. Accompanied by the enhanced open‐circuit voltage ( V oc ) and short‐circuit current density ( J sc ), a record high power conversion efficiency (PCE) of 19.05% is realized finally.

Abstract A new strategy of platinum(II) complexation is developed to regulate the crystallinity and molecular packing of polynitrogen heterocyclic polymers, optimize the morphology of the active blends, and improve the efficiency of the resulting nonfullerene polymer solar cells (NF‐PSCs). The newly designed s‐tetrazine (s‐TZ)‐containing copolymer of PSFTZ (4,8‐bis(5‐((2‐butyloctyl)thio)‐4‐fluorothiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐ alt ‐3,6‐bis(4‐octylthiophen‐2‐yl)‐1,2,4,5‐tetrazine) has a strong aggregation property, which results in serious phase separation and large domains when blending with Y6 ((2,2′‐((2Z,2′Z)‐((12,13‐bis(2‐ethylhexyl)‐3,9‐diundecyl‐12,13‐dihydro‐[1,2,5]thiadiazolo[3,4‐e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2‐g]thieno[2′,3′:4,5]thieno[3,2‐b]indole‐2,10‐diyl)bis(methanylylidene))bis(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1 H ‐indene‐2,1‐diylidene))dimalononitrile)), and produces a power‐conversion efficiency (PCE) of 13.03%. By adding small amount of Pt(Ph) 2 (DMSO) 2 (Ph, phenyl and DMSO, dimethyl sulfoxide), platinum(II) complexation would occur between Pt(Ph) 2 (DMSO) 2 and PSFTZ. The bulky benzene ring on the platinum(II) complex increases the steric hindrance along the polymer main chain, inhibits the polymer aggregation strength, regulates the phase separation, optimizes the morphology, and thus improves the efficiency to 16.35% in the resulting devices. 16.35% is the highest efficiency for single‐junction PSCs reported so far.

Abstract We synthesized a series of carbon‐supported atomic metal‐N‐C catalysts (M‐SACs: M=Mn, Fe, Co, Ni, Cu) with similar structural and physicochemical properties to uncover their catalytic activity trends and mechanisms. The peroxymonosulfate (PMS) catalytic activity trends are Fe‐SAC>Co‐SAC>Mn‐SAC>Ni‐SAC>Cu‐SAC, and Fe‐SAC displays the best single‐site kinetic value (1.65×10 5 min −1 mol −1 ) compared to the other metal‐N‐C species. First‐principles calculations indicate that the most reasonable reaction pathway for 1 O 2 production is PMS→OH*→O*→ 1 O 2 ; M‐SACs that exhibit moderate and near‐average Gibbs free energies in each reaction step have a better catalytic activity, which is the key for the outstanding performance of Fe‐SACs. This study gives the atomic‐scale understanding of fundamental catalytic trends and mechanisms of PMS‐assisted reactive oxygen species production via M‐SACs, thus providing guidance for developing M‐SACs for catalytic organic pollutant degradation.

A high-performance epoxy vitrimer was facilely prepared from a renewable lignin derivative vanillin, and its carbon-fiber composites were nondestructively recycled.

The objective of the present work is to investigate, from the open literature, the recent developments in the rheology of silica and organoclay nanocomposites. In particular, this paper focuses on general trends of the linear viscoelastic behaviour of such nanocomposites. Hence, the variations of the equilibrium shear modulus and critical strain (limit of linearity), which depend on power laws of the volume fraction of particles, are discussed as filler fractal structure. In the third section, the strong nonlinearity behaviour (Payne effect) of filled polymers has been discussed in terms of filler nature. Typically two mechanisms arise to depict the linear solid-like behaviour and the Payne effect: particle–particle interactions is the dominant mechanism in fumed silica nanocomposites whereas particle–polymer interaction is the dominant one in colloidal silica nanocomposites at identical filler concentrations. However, these interactions are balanced in each nanocomposite systems by the silica surface treatments (chain grafting, silane modification) and the molecular weight of the matrix. Finally, we aim to unify the main findings of the literature on this subject, at least from a qualitative point of view. We finally report on the thixotropy and modulus recovery after a large deformation in steady and dynamic shear conditions. Following this, the nonlinear rheological properties of nanocomposite materials have been discussed. The discussion is particularly focused on the effect of flow history (transient shear experiments) on the orientation–disorientation of clay platelets. Actually, the linear and nonlinear rheological properties are consistent with a network structure of a weakly agglomerated tactoids. As far as exfoliated clay nanocomposites are concerned, the inter-particle interaction is the dominant effect in the nonlinearity effect.

As a reliable and scalable precursor of graphene, graphene oxide (GO) is of great importance. However, the environmentally hazardous heavy metals and poisonous gases, explosion risk and long reaction times involved in the current synthesis methods of GO increase the production costs and hinder its real applications. Here we report an iron-based green strategy for the production of single-layer GO in 1 h. Using the strong oxidant K2FeO4, our approach not only avoids the introduction of polluting heavy metals and toxic gases in preparation and products but also enables the recycling of sulphuric acid, eliminating pollution. Our dried GO powder is highly soluble in water, in which it forms liquid crystals capable of being processed into macroscopic graphene fibres, films and aerogels. This green, safe, highly efficient and ultralow-cost approach paves the way to large-scale commercial applications of graphene.

A light-activated hypoxia-responsive conjugated polymer-based nanocarrier is developed for efficiently producing singlet oxygen (1O2) and inducing hypoxia to promote release of its cargoes in tumor cells, leading to enhanced antitumor efficacy. This dual-responsive nanocarrier provides an innovative design guideline for enhancing traditional photodynamic therapeutic efficacy integrated with a controlled drug-release modality. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

The ever-increasing interest in the Suzuki–Miyaura cross-coupling reaction (SMR) and its applications, with more than 40 years of history, has increased exponentially in the last decade, which speaks volumes about its efficiency and effectiveness; recent improvements in terms of efficient catalysts in benign media are highlighted.

Abstract Self-healing materials integrated with excellent mechanical strength and simultaneously high healing efficiency would be of great use in many fields, however their fabrication has been proven extremely challenging. Here, inspired by biological cartilage, we present an ultrarobust self-healing material by incorporating high density noncovalent bonds at the interfaces between the dentritic tannic acid-modified tungsten disulfide nanosheets and polyurethane matrix to collectively produce a strong interfacial interaction. The resultant nanocomposite material with interwoven network shows excellent tensile strength (52.3 MPa), high toughness (282.7 MJ m ‒3 , which is 1.6 times higher than spider silk and 9.4 times higher than metallic aluminum), high stretchability (1020.8%) and excellent healing efficiency (80–100%), which overturns the previous understanding of traditional noncovalent bonding self-healing materials where high mechanical robustness and healing ability are mutually exclusive. Moreover, the interfacical supramolecular crosslinking structure enables the functional-healing ability of the resultant flexible smart actuation devices. This work opens an avenue toward the development of ultrarobust self-healing materials for various flexible functional devices.

A series of alkene-functional polymers were synthesized by controlled polymerization techniques in order to investigate and compare the efficiency and orthogonality of both photochemically and thermally initiated thiol−ene click coupling reactions. The copolymers were designed to have single or multiple alkene-functional groups along the backbone, and to evaluate the robustness of these procedures, functionalization reactions with a library of mercaptans were studied. In comparing the photoinitiated reaction to its thermal counterpart, the thiol−ene photocoupling was found to proceed with higher efficiency, require shorter reaction times for complete conversion, and displayed a higher tolerance to various backbones and functional groups. To examine the orthogonality of the thiol−ene click reaction, an asymmetric telechelic polymer based on PS was designed with alkene functionality at one end and an azide at the other. The thermally initiated thiol−ene coupling was found to be completely orthogonal with the traditional azide/alkyne click reaction allowing the individual chain ends to be quantitatively functionalized without the need for protection/deprotection strategies. From these studies, the demonstrated efficiency and orthogonality of thiol−ene chemistry shows it to be a practical addition to the family of click reactions that are suitable for polymer functionalization.

Ferroelectric polymers are the most promising electroactive materials with outstanding properties that can be integrated into a variety of flexible electronic devices. Their multifunctional capabilities, ability to bend and stretch, ease of processing, chemical stability, and the high biocompatibility of polyvinylidene fluoride (PVDF)‐based polymers make them attractive for applications in flexible memories, energy transducers, and electronic skins. Here, recent advance in the research of PVDF‐based flexible electronic devices is reviewed, including nonvolatile memories, energy‐harvesting devices, and multifunctional portable sensors.

Abstract Two novel wide‐bandgap copolymers, PBDT‐TDZ and PBDTS‐TDZ, are developed based on 1,3,4‐thiadiazole (TDZ) and benzo[1,2‐b:4,5‐b′]dithiophene (BDT) building blocks. These copolymers exhibit wide bandgaps over 2.07 eV and low‐lying highest occupied molecular orbital (HOMO) levels below −5.35 eV, which match well with the typical low‐bandgap acceptor of ITIC, resulting in a good complementary absorption from 300 to 900 nm and a low HOMO level offset (≤0.13 eV). Compared to PBDT‐TDZ, PBDTS‐TDZ with alkylthio side chains exhibits the stronger optical absorption, lower‐lying HOMO level, and higher crystallinity. By using a single green solvent of o ‐xylene, PBDTS‐TDZ:ITIC devices exhibit a large open‐circuit voltage ( V oc ) up to 1.10 eV and an extremely low energy loss ( E loss ) of 0.48 eV. At the same time, the desirable high short‐circuit current density ( J sc ) of 17.78 mA cm −2 and fill factor of 65.4% are also obtained, giving rise to a high power conversion efficiency (PCE) of 12.80% without any additive and post‐treatment. When adopting a homotandem device architecture, the PCE is further improved to 13.35% (certified as 13.19%) with a much larger V oc of 2.13 V, which is the best value for any type of homotandem organic solar cells reported so far.