State Key Laboratory for Modification of Chemical Fibers and Polymer Materials

Semiconductor-mediated photocatalysis has received tremendous attention as it holds great promise to address the worldwide energy and environmental issues. To overcome the serious drawbacks of fast charge recombination and the limited visible-light absorption of semiconductor photocatalysts, many strategies have been developed in the past few decades and the most widely used one is to develop photocatalytic heterojunctions. This review attempts to summarize the recent progress in the rational design and fabrication of heterojunction photocatalysts, such as the semiconductor–semiconductor heterojunction, the semiconductor–metal heterojunction, the semiconductor–carbon heterojunction and the multicomponent heterojunction. The photocatalytic properties of the four junction systems are also discussed in relation to the environmental and energy applications, such as degradation of pollutants, hydrogen generation and photocatalytic disinfection. This tutorial review ends with a summary and some perspectives on the challenges and new directions in this exciting and still emerging area of research.

Electrolytes are one of the vital constituents of electrochemical energy storage devices and their physical and chemical properties play an important role in these devices' performance, including capacity, power density, rate performance, cyclability and safety. This article reviews the current state of understanding of the electrode-electrolyte interaction in supercapacitors and battery-supercapacitor hybrid devices. The article discusses factors that affect the overall performance of the devices such as the ionic conductivity, mobility, diffusion coefficient, radius of bare and hydrated spheres, ion solvation, viscosity, dielectric constant, electrochemical stability, thermal stability and dispersion interaction. The requirements needed to design better electrolytes and the challenges that still need to be addressed for building better supercapacitive devices for the competitive energy storage market have also been highlighted.

The demand for flexible/wearable electronic devices that have aesthetic appeal and multi-functionality has stimulated the rapid development of flexible supercapacitors with enhanced electrochemical performance and mechanical flexibility. After a brief introduction to flexible supercapacitors, we summarize current progress made with graphene-based electrodes. Two recently proposed prototypes for flexible supercapacitors, known as micro-supercapacitors and fiber-type supercapacitors, are then discussed. We also present our perspective on the development of graphene-based electrodes for flexible supercapacitors.

In the past two decades, artificial skin-like materials have received increasing research interests for their broad applications in artificial intelligence, wearable devices, and soft robotics. However, profound challenges remain in terms of imitating human skin because of its unique combination of mechanical and sensory properties. In this work, a bioinspired mineral hydrogel is developed to fabricate a novel type of mechanically adaptable ionic skin sensor. Due to its unique viscoelastic properties, the hydrogel-based capacitive sensor is compliant, self-healable, and can sense subtle pressure changes, such as a gentle finger touch, human motion, or even small water droplets. It might not only show great potential in applications such as artificial intelligence, human/machine interactions, personal healthcare, and wearable devices, but also promote the development of next-generation mechanically adaptable intelligent skin-like devices.

Recent research progresses on high performance anode materials for high-energy sodium-ion batteries are comprehensively summarized.

Stretchable ionic skins are intriguing in mimicking the versatile sensations of natural skins. However, for their applications in advanced electronics, good elastic recovery, self-healing, and more importantly, skin-like nonlinear mechanoresponse (strain-stiffening) are essential but can be rarely met in one material. Here we demonstrate a robust proton-conductive ionic skin design via introducing an entropy-driven supramolecular zwitterionic reorganizable network to the hydrogen-bonded polycarboxylic acid network. The design allows two dynamic networks with distinct interacting strength to sequentially debond with stretch, and the conflict among elasticity, self-healing, and strain-stiffening can be thus defeated. The representative polyacrylic acid/betaine elastomer exhibits high stretchability (1600% elongation), immense strain-stiffening (24-fold modulus enhancement), ~100% self-healing, excellent elasticity (97.9 ± 1.1% recovery ratio, <14% hysteresis), high transparency (99.7 ± 0.1%), moisture-preserving, anti-freezing (elastic at -40 °C), water reprocessibility, as well as easy-to-peel adhesion. The combined advantages make the present ionic elastomer very promising in wearable iontronic sensors for human-machine interfacing.

Marine animals, such as leptocephalus and jellyfish, can sense external stimuli and achieve optical camouflage in the aquatic environment. Fabricating an intelligent soft sensor that can mimic the capabilities of transparent marine animals and function underwater can enable transformative applications in various novel fields. However, previously reported soft sensors struggle to meet the requirements of adhesion, self-healing ability, optical transparency, and stable conductivity in the aquatic environment. Herein, high-performance ionogels by virtue of ion-dipole and ion-ion interactions between fluorine-rich poly(ionic liquid) and ionic liquid are designed. The hydrophobic dynamic viscoelastic networks provide excellent properties for ionogels, including optical transparency, adjustable mechanical properties, underwater self-healing ability, underwater adhesiveness, conductivity, and 3D printability. A mechanically compliant and visually invisible underwater soft sensor based on ionogel is developed. This sensor can achieve optical camouflage, human-body-motion detection, and barrier-free communication in the aquatic environment. A novel contactless sensing mechanism based on changing the electron transfer pathway is proposed. Several interesting functions, such as detection of water environment changes, recognition of objects, delivery of information, and even identification of human standing posture can be realized. Importantly, the ionogel sensor can avoid fatigue and physical damage in the sensing process.

Intrinsically stretchable conductors have undergone rapid development in the past few years and a variety of strategies have been established to improve their electro-mechanical properties. However, ranging from electronically to ionically conductive materials, they are usually vulnerable either to large deformation or at high/low temperatures, mainly due to the fact that conductive domains are generally incompatible with neighboring elastic networks. This is a problem that is usually overlooked and remains challenging to address. Here, we introduce synergistic effect between conductive zwitterionic nanochannels and dynamic hydrogen-bonding networks to break the limitations. The conductor is highly transparent (>90% transmittance), ultra-stretchable (>10,000% strain), high-modulus (>2 MPa Young's modulus), self-healing, and capable of maintaining stable conductivity during large deformation and at different temperatures. Transparent integrated systems are further demonstrated via 3D printing of its precursor and could achieve diverse sensory capabilities towards strain, temperature, humidity, etc., and even recognition of different liquids.

This review highlights the most recent progress in the construction of iron oxide nanoparticle-based hybrid platforms for tumor imaging and therapy.

Cascade reactions that produce multiple chemical bonds in one synthetic operation are important in the efficient construction of complex molecules. In addition, photoredox and nickel dual catalysis opens a new and powerful avenue for transition-metal-catalyzed cross-coupling reactions. By combining these two concepts, photoredox and nickel dual-catalyzed cascade reactions have been recently established, and they provide an efficient and mild method for accessing a series of valuable organic compounds.

The catalytic dicarbofunctionalization of unsaturated π bonds represents a powerful platform for the rapid construction of complex motifs. Despite remarkable progress, novel and efficient methods for achieving such transformations under milder conditions with chemo-, regio-, and stereoselectivity still remain a significant challenge; thus, their development is highly desirable. Recently, the merging of nickel catalysis with radical chemistry offers a new and benign platform for the catalytic dicarbofunctionalization of unsaturated π bonds with unprecedented reactivity and selectivity. In this review, we summarize the recent advances in this area by underpinning the catalytic domino transformations involving radical capture by nickel to provide a clear overview of reaction designs and mechanistic scenarios.

The novel conductive polyaniline/bacterial cellulose (PANI/BC) nanocomposite membranes have been synthesized in situ by oxidative polymerization of aniline with ammonium persulfate as an oxidant and BC as a template. The resulting PANI-coated BC nanofibrils formed a uniform and flexible membrane. It was found that the PANI nanoparticles deposited on the surface of BC connected to form a continuous nanosheath by taking along the BC template, which greatly increases the thermal stability of BC. The content of PANI and the electrical conductivity of composites increased with increasing reaction time from 30 to 90 min, while the conductivity decreased because of the aggregation of PANI particles by further prolonging the reaction time. In addition, the acids remarkably improve the accessibility and reactivity of the hydroxyl groups of BC. The results indicate that the composites exhibit excellent electrical conductivity (the highest value was 5.0 × 10(-2) S/cm) and good mechanical properties (Young's modulus was 5.6 GPa and tensile strength was 95.7 MPa). Moreover, the electrical conductivity of the membrane is sensitive to the strain. This work provides a straightforward method to prepare flexible films with high conductivity and good mechanical properties, which could be applied in sensors, flexible electrodes, and flexible displays. It also opens a new field of potential applications of BC materials.

A Co@N-CNTF electrocatalyst derived from a metal–organic framework exhibits high catalytic activity in the ORR, OER and HER.

A 3D printed thermo-responsive hydrogel is designed as a novel multifunctional skin-like sensor.

A nickel-catalyzed, enantioselective, three-component fluoroalkylarylation of unactivated alkenes with aryl halides and perfluoroalkyl iodides has been described. This cross-electrophile coupling protocol utilizes a chiral nickel/BiOx system as well as a pendant chelating group to facilitate the challenging three-component, asymmetric difunctionalization of unactivated alkenes, providing direct access to valuable chiral β-fluoroalkyl arylalkanes with high efficiency and excellent enantioselectivity. The mild conditions allow for a broad substrate scope as well as good functional group toleration.

Quasi-solid-state micro-supercapacitors with cellular graphene film as the active material and polyvinyl alcohol/H₃PO₄as the gel electrolyte have been fabricated. The 3D porous graphene films not only serve as high performance supercapacitor electrodes, but also provide an abundant ion reservoir for the gel electrolyte.

Abstract Aqueous Zn‐ion batteries have aroused much attention recently, yet challenges still exist in the lack of low‐cost, highly stable electrolytes to tackle the serious side reactions at Zn anode–electrolyte interface. Herein, a ZnSO 4 ‐based low‐cost aqueous electrolyte is demonstrated with a small amount of eco‐friendly silk peptide as an efficient additive. Compared with silk sericin and fibroin, silk peptide with abundant strong polar groups (COOH and NH 2 ) suppresses the side reactions. Namely, silk peptide regulates the solvation structure of Zn 2+ to decrease coordinated active H 2 O and SO 4 2− , and tends to anchor on Zn anode surface for the isolation of contact H 2 O/SO 4 2− as well as electrostatic shielding, demonstrating synergistic solvation and interface regulating effect. Consequently, the excellent cycle life (3000 h) and Coulombic efficiency (99.7%) of Zn anodes are revealed in 2 m ZnSO 4 electrolyte with only 5 mg mL −1 of silk peptide (≈0.49 USD L −1 ), promising practical applications of reversible zinc‐ion batteries.

Abstract Producing electrolytes with high ionic conductivity has been a critical challenge in the progressive development of solid oxide fuel cells (SOFCs) for practical applications. The conventional methodology uses the ion doping method to develop electrolyte materials, e.g., samarium-doped ceria (SDC) and yttrium-stabilized zirconia (YSZ), but challenges remain. In the present work, we introduce a logical design of non-stoichiometric CeO 2-δ based on non-doped ceria with a focus on the surface properties of the particles. The CeO 2−δ reached an ionic conductivity of 0.1 S/cm and was used as the electrolyte in a fuel cell, resulting in a remarkable power output of 660 mW/cm 2 at 550 °C. Scanning transmission electron microscopy (STEM) combined with electron energy-loss spectroscopy (EELS) clearly clarified that a surface buried layer on the order of a few nanometers was composed of Ce 3+ on ceria particles to form a CeO 2−δ @CeO 2 core–shell heterostructure. The oxygen deficient layer on the surface provided ionic transport pathways. Simultaneously, band energy alignment is proposed to address the short circuiting issue. This work provides a simple and feasible methodology beyond common structural (bulk) doping to produce sufficient ionic conductivity. This work also demonstrates a new approach to progress from material fundamentals to an advanced low-temperature SOFC technology.

Rechargeable zinc-air batteries (ZABs) are currently receiving extensive attention because of their extremely high theoretical specific energy density, low manufacturing costs, and environmental friendliness. Exploring bifunctional catalysts with high activity and stability to overcome sluggish kinetics of oxygen reduction reaction and oxygen evolution reaction is critical for the development of rechargeable ZABs. Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts possessing prominent advantages of high metal atom utilization and electrocatalytic activity are promising candidates to promote oxygen electrocatalysis. In this work, general principles for designing atomically dispersed M-N-C are reviewed. Then, strategies aiming at enhancing the bifunctional catalytic activity and stability are presented. Finally, the challenges and perspectives of M-N-C bifunctional oxygen catalysts for ZABs are outlined. It is expected that this review will provide insights into the targeted optimization of atomically dispersed M-N-C catalysts in rechargeable ZABs.

ABSTRACT The research activities in the development of recyclable and reprocessable covalently crosslinked networks, and the construction of polymers from renewable resources are both stemmed from the economical and environmental problems associated with traditional thermosets. However, there is little effort in combination of these two attractive strategies in material designs. This article reported a bio‐based vitrimer constructed from isosorbide‐derived epoxy and aromatic diamines containing disulfide bonds. The resulted dynamic epoxy resins showed comparable thermomechanical properties as compared to similar epoxy networks cured by traditional curing agent. Rheological tests demonstrated the fast stress relaxation of the dynamic network due to the rapid metathesis of disulfide bonds at temperature higher than glass transition temperature. This feature permitted the recycling and reprocessing of the fragmented samples for several times by hot press. The dynamic epoxy resins also exhibited shape‐memory effect, and it is demonstrated that the shape recovery ratio could be readily adjusted by controlling the stress relaxation in the temporary state at programming temperature. Moreover, the degradability of the dynamic epoxy resins in alkaline aqueous solution was also demonstrated. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1790–1799