Universal Route Research Articles

Design of a bifunctional prepolymer for simultaneously facile preparation and highly efficient electrodialysis of anion exchange membranes

A facile fabrication process for separation membranes is crucial to decrease the production cost, while the photo-polymerization approach can be conducted at ambient conditions with short processing time and low energy consumption. Herein, this work designs a bifunctional prepolymer for simultaneously facile preparation and highly efficient electrodialysis of poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) anion exchange membranes. PPO is selected as the main skeleton of prepolymer because of the excellent mechanical and thermal stability. The dimethylaminoethyl methacrylate (DMAEMA) is grafted with brominated PPO by quaternization, where it contains cationic groups, i.e. quaternary ammonium, and photopolymerized groups, i.e. methacrylate C = C. This resulting prepolymer can be fast polymerized under UV irradiation via C = C from DMAEMA. This structure is synergistically regulated by the amounts of crosslinker DMAEMA and modifier N-bromosuccinimide. The optimized membrane exhibits an excellent ion exchange capacity of 2.19 mmol g−1, a water uptake of 38.17 %, and a tensile strength of 4.8 MPa. Meanwhile, its electrolyzer cell performance achieves a density of 580 mA cm−2 at an adjusted voltage of 2.1 V, and the desalination rate of seawater during electrodialysis reaches 98.34 %. This work provides a universal and facile fabrication route for high-performance AEMs.

Direct Exfoliation of Nanoribbons from Bulk van der Waals Crystals.

Confinement of monolayers into quasi-1D atomically thin nanoribbons could lead to novel quantum phenomena beyond those achieved in their bulk and monolayer counterparts. However, current experimental availability of nanoribbon species beyond graphene is limited to bottom-up synthesis or lithographic patterning. In this study, a versatile and direct approach is introduced to exfoliate bulk van der Waals crystals as nanoribbons. Akin to the Scotch tape exfoliation method for producing monolayers, this technique provides convenient access to a wide range of nanoribbons derived from their corresponding bulk crystals, including MoS2, WS2, MoSe2, WSe2, MoTe2, WTe2, ReS2, and hBN. The nanoribbons are predominantly monolayer, single-crystalline, parallel-aligned, flat, andexhibit high aspect ratios. The role of confinement, strain, and edge configuration of these nanoribbons is observed in their electrical, magnetic, and optical properties. This versatile exfoliation technique provides a universal route for producing a variety of nanoribbon materials and supports the study of their fundamental properties and potential applications.

3D porous PEDOT/MXene scaffold toward high-performance supercapacitors

3D architectures of conductive polymer, especially PEDOT hold great promise in energy storage and conversion fields. However, the facile construction of 3D PEDOT and its functionalization have still been challenges due to its poor processability. Herein, the fabrication of 3D porous PEDOT:PSS and its functionalization with MXene are realized synchronously through a simple and low-cost self-assembly process. The prominent capacitive performance of MXene, excellent chemical stability of PEDOT:PSS and 3D porous architecture with inhibited aggregation of MXene nanosheets, large amount of active sites, and electrolyte storage chamber endow the PEDOT/MXene-based porous structure with superior capacitive performance than individual PEDOT:PSS or MXene porous and flat structures. Furthermore, the PEDOT/MXene-based porous structure can be applied as a flexible scaffold for the deposition of conductive polymer to construct excellent electrodes for supercapacitors (SCs). When polypyrrole (PPy) is deposited, the prepared porous PEDOT:PSS/MXene/PPy electrode exhibits a high gravimetric specific capacitance of 345 F g−1 at a current density of 0.5 A g−1 and a remarkable capacitance retention of 89 % over 5000 cycles. Based on it, an asymmetric supercapacitor (ASC) with a high energy density of 56.34 Wh kg−1 at the power density of 120 W kg−1, and a capacitance retention of 75 % after 5000 cycles is developed. Besides, the porous PEDOT:PSS/MXene/PPy can be constructed on various substrates in any pattern with high design freedom, thus enabling customizable electrochemical performance. When constructing on a flexible substrate, excellent deformation-tolerant performance is shown. This work provides a high-performance electrode for SCs, as well as a universal route for the construction and functionalization of 3D PEDOT-based structures.

Tailoring Coherent Microwave Emission from a Solid-State Hybrid System for Room-Temperature Microwave Quantum Electronics.

Quantum electronics operating in the microwave domain are burgeoning and becoming essential building blocks of quantum computers, sensors, and communication devices. However, the field of microwave quantum electronics has long been dominated by the need for cryogenic conditions to maintain delicate quantum characteristics. Here, a solid-state hybrid system, constituted by a photo-excited pentacene triplet spin ensemble coupled to a dielectric resonator, is reported for the first time capable of both coherent microwave quantum amplification and oscillation at X band via the masing process at room temperature. By incorporating external driving and active dissipation control into the hybrid system, efficient tuning of the maser emission characteristics at ≈9.4GHz is achieved, which is key to optimizing the performance of the maser device. The work not only pushes the boundaries of the operating frequency and functionality of the existing pentacene masers but also demonstrates a universal route for controlling the masing process at room temperature, highlighting opportunities for optimizing emerging solid-state masers for quantum information processing and communication.

The effect of thermoelectric augmentation dramatically increased the specific capacity for electrochemical energy storage

Conventional methods to enhance the performance of electrode materials include morphological modification and defect engineering, but the limited number of active sites for the electrode remains a huge obstacle to achieving high-performance supercapacitors. In this work, we proposed a strategy to improve the electrode performance under the condition of limited active sites through the thermoelectric effect, and designed thermoelectric electrodes of the p-type Fe0.3Co0.7Sb3 cathode and the n-type Cu0.3Ag1.7Se anode for supercapacitors, respectively. In particular, the charge carriers generated by the thermoelectric effect accelerate the electrochemical reaction process at the interface between the thermoelectric electrode and the electrolyte under the temperature difference (ΔT) condition, thus increasing the specific capacity of the electrode. The p-Type Fe0.3Co0.7Sb3 cathode and the n-Type Cu0.3Ag1.7Se anode exhibit a 150% and 208% increase in the specific capacity, respectively. Furthermore, electrodes with different conduction types and various thermoelectric properties, such as n/p-type bismuth telluride and n/p-type half-Heusler thermoelectric materials are also studied, confirming the universality of the above phenomenon in thermoelectric electrodes. This work provides a universal route for the thermoelectric effect to promote the energy density of supercapacitors used in high temperature difference environments.

Laser Precise Synthesis of Oxidation-Free High-Entropy Alloy Nanoparticle Libraries.

High-entropy alloy nanoparticles (HEA-NPs) show exceptional properties and great potential as a new generation of functional materials, yet a universal and facile synthetic strategy in air toward nonoxidized and precisely controlled composition remains a huge challenge. Here we provide a laser scribing method to prepare single-phase solid solution HEA-NPs libraries in air with tunable composition at the atomic level, taking advantage of the laser-induced metastable thermodynamics and substrate-assisted confinement effect. The three-dimensional porous graphene substrate functions as a microreactor during the fast heating/cooling process, which is conductive to the generation of the pure alloy phase by effectively blocking the binding of oxygen and metals, but is also beneficial for realizing accurate composition control via microstructure confinement-endowed favorable vapor pressure. Furthermore, by combining an active learning approach based on an adaptive design strategy, we discover an optimal composition of quinary HEA-NP catalysts with an ultralow overpotential for Li-CO2 batteries. This method provides a simple, fast, and universal in-air route toward the controllable synthesis of HEA-NPs, potentially integrated with machine learning to accelerate the research on HEAs.

An Organic-Inorganic Hydrogel with Exceptional Mechanical Properties via Anion-Induced Synergistic Toughening for Accelerating Osteogenic Differentiation.

Mineralized bio-tissues achieve exceptional mechanical properties through the assembly of rigid inorganic minerals and soft organic matrices, providing abundant inspiration for synthetic materials. Hydrogels, serving as an ideal candidate to mimic the organic matrix in bio-tissues, can be strengthened by the direct introduction of minerals. However, this enhancement often comes at the expense of toughness due to interfacial mismatch. This study reveals that extreme toughening of hydrogels can be realized through simultaneous in situ mineralization and salting-out, without the need for special chemical modification or additional reinforcements. The key to this strategy lies in harnessing the kosmotropic and precipitation behavior of specific anions as they penetrate a hydrogel system containing both anion-sensitive polymers and multivalent cations. The resulting mineralized hydrogels demonstrate significant improvements in fracture stress, fracture energy, and fatigue threshold due to a multiscale energy dissipation mechanism, with optimal values reaching 12MPa, 49kJm-2, and 2.98kJm-2. This simple strategy also proves to be generalizable to other anions, resulting in tough hydrogels with osteoconductivity for promoting in vitro mineralization of human adipose-derived mesenchymal stem cells. This work introduces a universal route to toughen hydrogels without compromising other parameters, holding promise for biological applications demanding integrated mechanical properties.

Enhancing X‐Ray Excited Persistent Luminescence in Lanthanide‐Doped Fluoride Nanoparticles via a Versatile Acid Pickling Strategy

AbstractX‐ray excited persistent luminescence (XEPL) of lanthanide‐doped fluoride nanoparticles (NPs) holds promise for applications in back‐ground free bio‐medicine and flexible 3D imaging. However, it remains a daunting challenge to develop a universal and convenient route to greatly improve the XEPL performance of most fluoride nanosystems. Herein, for the first time, a versatile acid pickling strategy is proposed to greatly enhance the XEPL intensity of lanthanide‐doped fluoride NPs with different chemical compositions and activator types. Especially, after treatment with diluted HCl, the XEPL intensity of the NaYF4: Tb NPs with a mean particle size of ≈ 7 nm is enhanced ≈17.4 times. Mechanistic studies indicate the trap density in the NPs upon X‐ray irradiation is greatly enhanced after HCl treatment, contributing to the enhanced XEPL intensity. By integrating the HCl‐treated NPs into a scintillation film, the X‐ray image resolution is significantly increased from 6.3 to 11 lp mm−1, and the quality of delayed X‐ray images improved, particularly at low‐dose irradiation rates. These findings are expected to advance the development of high‐performance X‐ray‐activated persistent fluoride NPs and their applications for low‐dose high‐resolution X‐ray imaging.

SCbots: Stomatocyte-like colloidosomes as versatile microrobots fabricated by one-step self-assembly

Building microrobots with asymmetric shapes is crucial to generate net driving forces, whereas often suffer from complex fabrication processes and limited availability of materials. Additionally, integrating diverse components into a single microscopic device for multifunctional microrobots is more challenging; however, if achieved, it offers promise for advanced microrobots with significantly expanded capabilities. Our group pioneered the fabrication of stomatocyte-like colloidosomes (SCs) as motherships, on which different functional components could be conveniently loaded to construct versatile microrobots (SCbots) via one-step self-assembly. It is the first time for self-assembly of enzyme powered microrobots via colloidosomes, the mechanism governing the formation of the target SCbots possessing asymmetrical narrow-opening stomatocyte shape is demonstrated. An additional benefit of SCbots is that their speed can be easily adjusted by changing the size of the shell-forming particles have been shown. As a proof of concept, like self-assembling macroscopic LEGO bricks, the proposed bottom-up strategy is used to access distinct versatile SCbots, including magnetically guided micro-carriers constructed from Fe3O4 nanoparticles and a “chemistry-on-the-fly” platform for CO2 sequestration constructed from carbonic anhydrase (CA). We report a flexible and universal route to create versatile SCbots with adjustable speeds and navigation capacities, which are in high demand for microrobots in various real applications.

Enzyme‐Immobilized Surface‐Catalyzed Cross‐Linking: Creating Multifunctional Double Network Hydrogel Coatings on Diverse Substrates

AbstractHydrogel coatings, with natural tissue‐like mechanical and biological compatibility, demonstrate promise for bulk material applications. However, existing coating methods lack efficiency and control, especially when dealing with complex geometries, diverse substrate materials, and varying sizes. In this study, an enzyme‐immobilized surface‐catalyzed cross‐link approach is proposed for the growth of hydrogel coatings on multiple substrates, accommodating various materials and shapes. The hydrogel coating is formed through the catalytic action of interface‐immobilized enzymes, which induce the crosslinking of hyaluronic acid, and its mechanical properties are further enhanced by introducing a secondary polyacrylamide network. This approach enables the controlled growth of conformal double network hydrogel coatings with a desired thickness on a wide range of substrate surfaces and devices. Notably, the hydrogel coating exhibits remarkable lubricity and anti‐thrombotic properties, especially desire for medical intervention devices. This advancement offers a universal route to impart biocompatible soft interfaces to bulk materials or devices.

A universal polymer-assisted route to fabricate Zr-doped TiO2 nanocomposite: boosting reactive desulfurization

A universal polymer-assisted route to fabricate Zr-doped TiO2 nanocomposite: boosting reactive desulfurization

Interface-engineering-enhanced energy storage performance of (Na0.8K0.2)0.5Bi4.5Ti4O15/Bi4LaTi3.5Mg0.5O15 multilayer film capacitors

Dielectric capacitors are vital components in advanced electrical power systems due to their high power density. However, how to improve their comparatively low energy density is still a major challenge. In this work, we designed a dielectric capacitor with a multilayer structure by inserting different numbers of ferroelectric (Na0.8K0.2)0.5Bi4.5Ti4O15 (NKBT) layers into relaxor ferroelectric Bi4LaTi3.5Mg0.5O15 (BLTM). Through the regulation of interface engineering, that is, the joint effects of electrical field amplifying, interlayer coupling, and block layer at the interface, enhancing the energy storage density and breakdown field in (NKBT/BLTM)N capacitors. A giant energy density (Wrec) of 81.2 J/cm3 and a high breakdown electric field of 4074 kV/cm are achieved in capacitors with N = 4. Consequently, interface engineering can be promoted as a universal route to optimize the energy storage performance of dielectric capacitors.

Effective Bidirectional Mott-Schottky Catalysts Derived from Spent LiFePO4 Cathodes for Robust Lithium-Sulfur Batteries.

It is deemed as a tough yet profound project to comprehensively cope with a range of detrimental problems of lithium-sulfur batteries (LSBs), mainly pertaining to the shuttle effect of lithium polysulfides (LiPSs) and sluggish sulfur conversion. Herein, a Co2P-Fe2P@N-doped carbon (Co2P-Fe2P@NC) Mott-Schottky catalyst is introduced to enable bidirectionally stimulated sulfur conversion. This catalyst is prepared by simple carbothermal reduction of spent LiFePO4 cathode and LiCoO2. The experimental and theoretical calculation results indicate that thanks to unique surface/interface properties derived from the Mott-Schottky effect, full anchoring of LiPSs, mediated Li2S nucleation/dissolution, and bidirectionally expedited "solid⇌liquid⇌solid" kinetics can be harvested. Consequently, the S/Co2P-Fe2P@NC manifests high reversible capacity (1569.9mAhg-1), superb rate response (808.9mAhg-1 at 3C), and stable cycling (a low decay rate of 0.06% within 600 cycles at 3C). Moreover, desirable capacity (5.35mAhcm-2) and cycle stability are still available under high sulfur loadings (4-5mgcm-2) and lean electrolyte (8µLmg-1) conditions. Furthermore, the as-proposed universal synthetic route can be extended to the preparation of other catalysts such as Mn2P-Fe2P@NC from spent LiFePO4 and MnO2. This work unlocks the potential of carbothermal reduction phosphating to synthesize bidirectional catalysts for robust LSBs.

Unprecedented Spatial Manipulation and Transformation of Dynamic Thermal Radiation Based on Vanadium Dioxide.

Reconfigurable infrared (IR) materials have widespread applications in thermal management and smart IR concealment. Although various reconfigurable IR materials can be customized by positive or negative differential VO2-based resonators, their insightful mechanism remains unknown. Here, we comprehensively investigate the fundamental design rule of reconfigurable thermal radiation between positive and negative differential thermal radiation properties for the first time. Importantly, the skin depth of VO2 film in the metal state is investigated to clarify the transformation from positive to negative differential thermal radiation properties, and the critical thickness is further derived, providing important guidance in designing the reconfigurable thermal radiation regulator. Furthermore, the reconfigurable multistate thermal images had been presented into one plate. The resulting emittance variation (△ε8-14μm) of the VO2-based resonator can change from 0.61 to -0.53, which consummates the ability for diverse demands such as infrared concealment, thermal illusion, and thermal management. This work constitutes a promising and universal route toward designing whole smart devices and may create new scientific and technological opportunities for platforms that can benefit from reconfigurable electromagnetic manipulation.

Growth-Coupled Evolutionary Pressure Improving Epimerases for D-Allulose Biosynthesis Using a Biosensor-Assisted In Vivo Selection Platform.

Fast screening strategies that enable high-throughput evaluation and identification of desired variants from diversified enzyme libraries are crucial to tailoring biocatalysts for the synthesis of D-allulose, which is currently limited by the poor catalytic performance of ketose 3-epimerases (KEases). Here, the study designs a minimally equipment-dependent, high-throughput, and growth-coupled in vivo screening platform founded on a redesigned D-allulose-dependent biosensor system. The genetic elements modulating regulator PsiR expression levels undergo systematic optimization to improve the growth-responsive dynamic range of the biosensor, which presents ≈30-fold facilitated growth optical density with a high signal-to-noise ratio (1.52 to 0.05) toward D-allulose concentrations from 0 to 100mm. Structural analysisand evolutionary conservation analysis of Agrobacterium sp. SUL3 D-allulose 3-epimerase (ADAE) reveal a highly conserved catalytic active site and variable hydrophobic pocket, which together regulate substrate recognition. Structure-guided rational design and directed evolution are implemented using the growth-coupled in vivo screening platform to reprogram ADAE, in which a mutant M42 (P38N/V102A/Y201L/S207N/I251R) is identified with a 6.28-fold enhancement of catalytic activity and significantly improved thermostability with a 2.5-fold increase of the half-life at 60 °C. The research demonstrates that biosensor-assisted growth-coupled evolutionary pressure combined with structure-guided rational design provides a universal route for engineering KEases.

Ultrafine PtCo alloy by pyrolysis etching-confined pyrolysis for enhanced hydrogen evolution

Zeolitic imidazolate framework-67 (ZIF-67) has been widely used as a precursor to developing efficient PtCo alloy catalysts for hydrogen evolution reaction (HER). However, traditional in-situ pyrolysis strategies involve complicated interface structure modulating processes between ZIF-67 and Pt precursors, challenging large-scale synthesis. Herein, a “pyrolysis etching-confined pyrolysis” approach is developed to design confined PtCo alloy in porous frameworks of onion carbon derived from ZIF-67. The confined PtCo alloy with Pt content of only 5.39 wt% exhibits a distinct HER activity in both acid (η10: 5 mV and Tafel: 9 mV dec−1) and basic (η10: 33 mV and Tafel: 51 mV dec−1) media and a drastic enhancement in stability. Density functional theory calculations reveal that the strong electronic interaction between Pt and Co allows favorable electron redistribution, which affords a favorable hydrogen spillover on PtCo alloy compared with that of pristine Pt(111). Operational electrochemical impedance spectroscopy demonstrates that the Faraday reaction process is facilitated under acidic conditions, while the transfer of intermediates through the electric double-layer region under alkaline conditions is accelerated. This work not only offers a universal route for high-performance Pt-based alloy catalysts with metal–organic framework (MOF) precursors but also provides experimental evidence for the role of the electric double layer in electrocatalysis reactions.

Liquid-Metal Molecular Scissors.

Molecules are the smallest units of matter that can exist independently, relatively stable, maintaining their physical and chemical activities. The key factors that dominate the structures and properties of molecules include atomic species, alignment commands, and chemical bonds. Herein, we reported a generalized effect in which liquid metals can directly cut off oxygen-containing groups in molecular matter at room temperature, allowing the remaining groups to recombine to form functional materials. Thus, we propose basic liquid-metal scissors for molecular directional clipping and functional transformations. As a proof of concept, we demonstrate the capabilities of liquid-metal scissors and reveal that the gallium on the surface of liquid metals directly extracts oxygen atoms from H2O or CH3OH molecules to form oxides. After clipping, the remaining hydrogen atoms from the H2O molecules recombine to form H2, while the remaining fragments of CH3OH produce H2, carbon materials, and carboxylates. This finding refreshes our basic understanding of chemistry and should lead to the development of straightforward molecular weaving techniques, which can help to overcome the limitations of molecular substances with single purposes. It also opens a universal route for realizing future innovations in molecular chemical engineering, life sciences, energy and environment research, and biomedicine.

A universal route to graft highly dispersed cobalt phthalocyanine on porous carbon for efficient CO2 electroreduction

A promising catalyst for dispersing CoPc on three-dimensional porous carbon was prepared and showed impressive performance for CO2 electroreduction to CO.

Direct in situ photolithography of ultra-stable CsPbBr3 quantum dot arrays based on crosslinking polymerization.

CsPbX3 (X = Br, Cl, I) perovskite quantum dots (PQDs) are the rising star for various display applications owing to their excellent opto-electrical properties, such as an adjustable spectrum, narrow emission linewidth and high quantum yield. However, these PQDs are well known to suffer from intrinsic instability under atmospheric conditions. In this work, a novel photosensitive ligand, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (XBPO), was employed as a dual-functional reagent for PQD surface engineering. The XBPO ligand could cleave to produce phenylphosphinyl radicals and trimethylbenzoyl radicals under UV light irradiation. The phenylphosphinyl radicals with PO bonds could effectively passivate the PQD surface defects, leading to quantum yield improvement. The CsPbBr3 and CsPbI3 PQDs with XBPO modification could achieve a photoluminescence quantum yield (PLQY) of near unity and 92%, respectively. Additionally, the in situ encapsulation of the PQDs was achieved by the subsequent crosslinking polymerization, which significantly improved the stability of the PQDs against solvents and the environment. By combining a standard photolithography procedure, we demonstrated a micro-pattern of CsPbBr3 PQDs. These results establish a universal route for PQD patterning, compatible with the existing photolithography processes, which could facilitate the application of PQDs in next-generation display technology.

Reprogrammable Metamaterial Processors for Soft Machines.

Soft metamaterials have attracted extensive attention due to their remarkable properties. These materials hold the potential to program and control the morphing behavior of soft machines, however, their combination is limited by the poor reprogrammability of metamaterials and incompatible communication between them. Here, printable and recyclable soft metamaterials possessing reprogrammable embedded intelligence to regulate the morphing of soft machines are introduced. These metamaterials are constructed from interconnected and periodically arranged logic unit cells that are able to perform compound logic operations coupling multiplication and negation. The scalable computation capacity of the unit cell empowers it to simultaneously process multiple fluidic signals with different types and magnitudes, thereby allowing the execution of sophisticated and high-level control operations. By establishing the laws of physical Boolean algebra and formulating a universal design route, soft metamaterials capable of diverse logic operations can be readily created and reprogrammed. Besides, the metamaterials' potential of directly serving as fluidic processors for soft machines is validated by constructing a soft latched demultiplexer, soft controllers capable of universal and customizable morphing programming, and a reprogrammable processor without reconnection. This work provides a facile way to create reprogrammable soft fluidic control systems to meet on-demand requirements in dynamic situations.