Ningbo Institute of Industrial Technology

A facile approach for preparation of photoluminescent (PL) carbon dots (CDs) is reported. The three resulting CDs emit bright and stable red, green and blue (RGB) colors of luminescence, under a single ultraviolet-light excitation. Alterations of PL emission of these CDs are tentatively proposed to result from the difference in their particle size and nitrogen content. Interestingly, up-conversion (UC)PL of these CDs is also observed. Moreover, flexible full-color emissive PVA films can be achieved through mixing two or three CDs in the appropriate ratios. These CDs also show low cytotoxicity and excellent cellular imaging capability. The facile preparation and unique optical features make these CDs potentially useful in numerous applications such as light-emitting diodes, full-color displays, and multiplexed (UC)PL bioimaging.

Nanolaminated materials are important because of their exceptional properties and wide range of applications. Here, we demonstrate a general approach to synthesizing a series of Zn-based MAX phases and Cl-terminated MXenes originating from the replacement reaction between the MAX phase and the late transition-metal halides. The approach is a top-down route that enables the late transitional element atom (Zn in the present case) to occupy the A site in the pre-existing MAX phase structure. Using this replacement reaction between the Zn element from molten ZnCl2 and the Al element in MAX phase precursors (Ti3AlC2, Ti2AlC, Ti2AlN, and V2AlC), novel MAX phases Ti3ZnC2, Ti2ZnC, Ti2ZnN, and V2ZnC were synthesized. When employing excess ZnCl2, Cl-terminated MXenes (such as Ti3C2Cl2 and Ti2CCl2) were derived by a subsequent exfoliation of Ti3ZnC2 and Ti2ZnC due to the strong Lewis acidity of molten ZnCl2. These results indicate that A-site element replacement in traditional MAX phases by late transition-metal halides opens the door to explore MAX phases that are not thermodynamically stable at high temperature and would be difficult to synthesize through the commonly employed powder metallurgy approach. In addition, this is the first time that exclusively Cl-terminated MXenes were obtained, and the etching effect of Lewis acid in molten salts provides a green and viable route to preparing MXenes through an HF-free chemical approach.

A new aqueous zinc-ion battery based on a zinc anode and a zinc hexacyanoferrate cathode is demonstrated. It relies on two reversible electrochemical reactions: zinc deposition/dissolution at the anode side and Zn2+ intercalation/extraction at the cathode side. Its average operating voltage is as high as 1.7 V.

Functional polymethylmethacrylate (PMMA)/graphene nanocomposite microcellular foams were prepared by blending of PMMA with graphene sheets followed by foaming with subcritical CO(2) as an environmentally benign foaming agent. The addition of graphene sheets endows the insulating PMMA foams with high electrical conductivity and improved electromagnetic interference (EMI) shielding efficiency with microwave absorption as the dominant EMI shielding mechanism. Interestingly, because of the presence of the numerous microcellular cells, the graphene-PMMA foam exhibits greatly improved ductility and tensile toughness compared to its bulk counterpart. This work provides a promising methodology to fabricate tough and lightweight graphene-PMMA nanocomposite microcellular foams with superior electrical and EMI shielding properties by simultaneously combining the functionality and reinforcement of the graphene sheets and the toughening effect of the microcellular cells.

A key challenge in environmental remediation is the design of adsorbents bearing an abundance of accessible chelating sites with high affinity, to achieve both rapid uptake and high capacity for the contaminants. Herein, we demonstrate how two-dimensional covalent organic frameworks (COFs) with well-defined mesopore structures display the right combination of properties to serve as a scaffold for decorating coordination sites to create ideal adsorbents. The proof-of-concept design is illustrated by modifying sulfur derivatives on a newly designed vinyl-functionalized mesoporous COF (COF-V) via thiol–ene “click” reaction. Representatively, the material (COF-S-SH) synthesized by treating COF-V with 1,2-ethanedithiol exhibits high efficiency in removing mercury from aqueous solutions and the air, affording Hg2+ and Hg0 capacities of 1350 and 863 mg g–1, respectively, surpassing all those of thiol and thioether functionalized materials reported thus far. More significantly, COF-S-SH demonstrates an ultrahigh distribution coefficient value (Kd) of 2.3 × 109 mL g–1, which allows it to rapidly reduce the Hg2+ concentration from 5 ppm to less than 0.1 ppb, well below the acceptable limit in drinking water (2 ppb). We attribute the impressive performance to the synergistic effects arising from densely populated chelating groups with a strong binding ability within ordered mesopores that allow rapid diffusion of mercury species throughout the material. X-ray absorption fine structure (XAFS) spectroscopic studies revealed that each Hg is bound exclusively by two S via intramolecular cooperativity in COF-S-SH, further interpreting its excellent affinity. The results presented here thus reveal the exceptional potential of COFs for high-performance environmental remediation.

Substantial effort has been devoted to both scientific and technological developments of wearable, flexible, semitransparent, and sensing electronics (e.g., organic/perovskite photovoltaics, organic thin-film transistors, and medical sensors) in the past decade. The key to realizing those functionalities is essentially the fabrication of conductive electrodes with desirable mechanical properties. Conductive polymers (CPs) of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) have emerged to be the most promising flexible electrode materials over rigid metallic oxides and play a critical role in these unprecedented devices as transparent electrodes, hole transport layers, interconnectors, electroactive layers, or motion-sensing conductors. Here, the current status of research on PEDOT:PSS is summarized including various approaches to boosting the electrical conductivity and mechanical compliance and stability, directly linked to the underlying mechanism of the performance enhancements. Along with the basic principles, the most cutting edge-progresses in devices with PEDOT:PSS are highlighted. Meanwhile, the advantages and plausible problems of the CPs and as-fabricated devices are pointed out. Finally, new perspectives are given for CP modifications and device fabrications. This work stresses the importance of developing CP films and reveals their critical role in the evolution of these next-generation devices featuring wearable, deformable, printable, ultrathin, and see-through characteristics.

The fabrication of photoluminescent Ti3C2 MXene quantum dots (MQDs) by a facile hydrothermal method is reported, which may greatly extend the applications of MXene-based materials. Interestingly, the as-prepared MQDs show excitation-dependent photoluminescence spectra with quantum yields of up to ≈10% due to strong quantum confinement. The applications of MQDs as biocompatible multicolor cellular imaging probes and zinc ion sensors are demonstrated. 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.

As the portable device hardware has been increasing at a noticeable rate, ultrathin thermal conducting materials (TCMs) with the combination of high thermal conductivity and excellent electromagnetic interface (EMI) shielding performance, which are used to efficiently dissipate heat and minimize EMI problems generated from electronic components (such as high speed processors), are urgently needed. In this work, graphene oxide (GO) films are fabricated by direct evaporation of GO suspension under mild heating, and ultrathin graphite‐like graphene films are produced by graphitizing GO films. Further investigation demonstrates that the resulting graphene film with only ≈8.4 μm in thickness not only possesses excellent EMI shielding effectiveness of ≈20 dB and high in‐plane thermal conductivity of ≈1100 W m ‐1 K ‐1 , but also shows excellent mechanical flexibility and structure integrity during bending, indicating that the graphitization of GO film could be considered as a new alternative way to produce excellent TCMs with efficient EMI shielding.

Abstract The discovery of stable and noble‐metal‐free catalysts toward efficient electrochemical reduction of nitrogen (N 2 ) to ammonia (NH 3 ) is highly desired and significantly critical for the earth nitrogen cycle. Here, based on the theoretical predictions, MoS 2 is first utilized to catalyze the N 2 reduction reaction (NRR) under room temperature and atmospheric pressure. Electrochemical tests reveal that such catalyst achieves a high Faradaic efficiency (1.17%) and NH 3 yield (8.08 × 10 −11 mol s −1 cm −1 ) at −0.5 V versus reversible hydrogen electrode in 0.1 m Na 2 SO 4 . Even in acidic conditions, where strong hydrogen evolution reaction occurs, MoS 2 is still active for the NRR. This work represents an important addition to the growing family of transition‐metal‐based catalysts with advanced performance in NRR.

A stable perovskite heterojunction was constructed for inverted solar cells through surface sulfidation of lead (Pb)-rich perovskite films. The formed lead-sulfur (Pb-S) bonds upshifted the Fermi level at the perovskite interface and induced an extra back-surface field for electron extraction. The resulting inverted devices exhibited a power conversion efficiency (PCE) >24% with a high open-circuit voltage of 1.19 volts, corresponding to a low voltage loss of 0.36 volts. The strong Pb-S bonds could stabilize perovskite heterojunctions and strengthen underlying perovskite structures that have a similar crystal lattice. Devices with surface sulfidation retained more than 90% of the initial PCE after aging at 85°C for 2200 hours or operating at the maximum power point under continuous illumination for 1000 hours at 55° ± 5°C.

Titanium dioxide is a promising photocatalyst for water splitting, but it suffers from low visible light activity due to its wide band gap. Doping can narrow the band gap of titanium dioxide; however, new charge-carrier recombination centres may be introduced. Here we report the design of sub-10 nm rutile titanium dioxide nanoparticles, with an increased amount of surface/sub-surface defects to overcome the negative effects from bulk defects. Abundant defects can not only shift the top of the valence band of rutile titanium dioxide upwards for band-gap narrowing but also promote charge-carrier separation. The role of titanium(III) is to enhance, rather than initiate, the visible-light-driven water splitting. The sub-10 nm rutile nanoparticles exhibit the state-of-the-art activity among titanium dioxide-based semiconductors for visible-light-driven water splitting and the concept of ultra-small nanoparticles with abundant defects may be extended to the design of other robust semiconductor photocatalysts.

Photoluminescence (PL), up-conversion PL (UCPL), and phosphorescence are three kinds of phenomena common to light-emitting materials, but it is very difficult to observe all of them simultaneously when they are derived from a single material at room temperature. For the first time, triple-mode emission (that is, PL, UCPL, and room temperature phosphorescence (RTP)) is reported, which relies on a composite of the luminescent carbon dots (CDs) prepared from m-phenylenediamine and poly(vinyl alcohol) (PVA). Moreover, the CDs-PVA aqueous dispersion is nearly colorless and demonstrates promise as a triple-mode emission ink in the field of advanced anti-counterfeiting.

Abstract The sluggish kinetics of Oxygen Reduction Reaction (ORR) at the cathode in proton exchange membrane fuel cells or metal-air batteries requires highly effective and stable electrocatalysts to boost the reaction. The low abundance and high price of Pt-based electrocatalysts hamper the widespread application of proton exchange membrane fuel cells and metal-air batteries. As promising alternatives, metal-free carbon materials, especially upon doping heteroatoms or creating defects demonstrated excellent ORR activity, which is as efficient as or even superior to commercial platinum on carbon. Significant progress on the development of advanced carbon materials as highly stable and durable catalysts has been achieved, but the catalytic mechanisms of these materials still remain undistinguished. In present review, we summarized the up-to-date progress in the studies of carbon materials, and emphasized on the combination of experiment and theory to clarify the underlying mechanisms of these materials. At last, we proposed the perspectives on the proper strategies of elucidating the mechanisms of carbon materials as electrocatalysts towards ORR.

All-solid-state lithium batteries (ASSLBs) are considered as the next generation electrochemical energy storage devices because of their high safety and energy density, simple packaging, and wide operable temperature range. The critical component in ASSLBs is the solid-state electrolyte. Among all solid-state electrolytes, the sulfide electrolytes have the highest ionic conductivity and favorable interface compatibility with sulfur-based cathodes. The ionic conductivity of sulfide electrolytes is comparable with or even higher than that of the commercial organic liquid electrolytes. However, several critical challenges for sulfide electrolytes still remain to be solved, including their narrow electrochemical stability window, the unstable interface between the electrolyte and the electrodes, as well as lithium dendrite formation in the electrolytes. Herein, the emerging sulfide electrolytes and preparation methods are reviewed. In particular, the required properties of the sulfide electrolytes, such as the electrochemical stabilities of the electrolytes and the compatible electrode/electrolyte interfaces are highlighted. The opportunities for sulfide-based ASSLBs are also discussed.

We report a facile approach to produce lightweight microcellular polyetherimide (PEI)/graphene nanocomposite foams with a density of about 0.3 g/cm3 by a phase separation process. It was observed that the strong extensional flow generated during cell growth induced the enrichment and orientation of graphene on cell walls. This action decreased the electrical conductivity percolation from 0.21 vol % for PEI/graphene nanocomposite to 0.18 vol % for PEI/graphene foam. Furthermore, the foaming process significantly increased the specific electromagnetic interference (EMI) shielding effectiveness from 17 to 44 dB/(g/cm3). In addition, PEI/graphene nanocomposite foams possessed low thermal conductivity of 0.065-0.037 W/m·K even at 200 °C and high Young's modulus of 180-290 MPa.

Ferroptosis, a new form of regulated cell death that is iron- and reactive oxygen species dependent, has attracted much attention in the research communities of biochemistry, oncology, and especially material sciences. Since the first demonstration in 2012, a series of strategies have been developed to induce ferroptosis of cancer cells, including the use of nanomaterials, clinical drugs, experimental compounds, and genes. A plethora of research work has outlined the blueprint of ferroptosis as a new option for cancer therapy. However, the published ferroptosis-related reviews have mainly focused on the mechanisms and pathways of ferroptosis, which motivated this contribution to bridge the gap between biological significance and material design. Therefore, it is timely to summarize the previous efforts on the emerging strategies for inducing ferroptosis and shed light on future directions for using such a tool to fight against cancer. Here, the current strategies of cancer therapy based on ferroptosis will be elaborated, the design considerations and the advantages and limitations are highlighted, and finally a future perspective on this emerging field is given.

Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas-solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g(-1) with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g(-1) still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.

Abstract Broadband near-infrared (NIR)-emitting phosphors are key for next-generation smart NIR light sources based on blue LEDs. To achieve excellent NIR phosphors, we propose a strategy of enhancing the crystallinity, modifying the micromorphology, and maintaining the valence state of Cr 3+ in Ca 3 Sc 2 Si 3 O 12 garnet (CSSG). By adding fluxes and sintering in a reducing atmosphere, the internal quantum efficiency (IQE) is greatly enhanced to 92.3%. The optimized CSSG:6%Cr 3+ exhibits excellent thermal stability. At 150 °C, 97.4% of the NIR emission at room temperature can be maintained. The fabricated NIR-LED device emits a high optical power of 109.9 mW at 520 mA. The performances of both the achieved phosphor and the NIR-LED are almost the best results until now. The mechanism for the optimization is investigated. An application of the NIR-LED light source is demonstrated.

Though polypyrrole (PPy) is widely used in flexible supercapacitors owing to its high electrochemical activity and intrinsic flexibility, limited capacitance and cycling stability of freestanding PPy films greatly reduce their practicality in real‐world applications. Herein, we report a new approach to enhance PPy's capacitance and cycling stability by forming a freestanding and conductive hybrid film through intercalating PPy into layered Ti 3 C 2 (l‐Ti 3 C 2 , a MXene material). The capacitance increases from 150 (300) to 203 mF cm −2 (406 F cm −3 ). Moreover, almost 100% capacitance retention is achieved, even after 20 000 charging/discharging cycles. The analyses reveal that l‐Ti 3 C 2 effectively prevents dense PPy stacking, benefiting the electrolyte infiltration. Furthermore, strong bonds, formed between the PPy backbones and surfaces of l‐Ti 3 C 2 , not only ensure good conductivity and provide precise pathways for charge‐carrier transport but also improve the structural stability of PPy backbones. The freestanding PPy/l‐Ti 3 C 2 film is further used to fabricate an ultra‐thin all‐solid‐state supercapacitor, which shows an excellent capacitance (35 mF cm −2 ), stable performance at any bending state and during 10 000 charging/discharging cycles. This novel strategy provides a new way to design conductive polymer‐based freestanding flexible electrodes with greatly improved electrochemical performances.

Abstract The development of active, acid-stable and low-cost electrocatalysts for oxygen evolution reaction is urgent and challenging. Herein we report an Iridium-free and low ruthenium-content oxide material (Cr 0.6 Ru 0.4 O 2 ) derived from metal-organic framework with remarkable oxygen evolution reaction performance in acidic condition. It shows a record low overpotential of 178 mV at 10 mA cm −2 and maintains the excellent performance throughout the 10 h chronopotentiometry test at a constant current of 10 mA cm −2 in 0.5 M H 2 SO 4 solution. Density functional theory calculations further revealed the intrinsic mechanism for the exceptional oxygen evolution reaction performance, highlighting the influence of chromium promoter on the enhancement in both activity and stability.