Ultrafine Asymmetric Soft/Stiff Nanohybrids with Tunable Patchiness via a Dynamic Surface-Mediated Assembly.

Asymmetric soft-stiff patch nanohybrids with small size, spatially separated organics and inorganics, controllable configuration, and appealing functionality are important in applications, while the synthesis remains a great challenge. Herein, based on polymeric single micelles (the smallest assembly subunit of mesoporous materials), we report a dynamic surface-mediated anisotropic assembly approach to fabricate a new type of small asymmetric organic/inorganic patch nanohybrid for the first time. The size of this asymmetric organic/inorganic nanohybrid is ∼20 nm, which contains dual distinct subunits of a soft organic PS-PVP-PEO single micelle nanosphere (12 nm in size and 632 MPa in Young' modulus) and stiff inorganic SiO2 nanobulge (∼8 nm, 2275 MPa). Moreover, the number of SiO2 nanobulges anchored on each micelle can be quantitatively controlled (from 1 to 6) by dynamically tuning the density (fluffy or dense state) of the surface cap organic groups. This small asymmetric patch nanohybrid also exhibits a dramatically enhanced uptake level of which the total amount of intracellular endocytosis is about three times higher than that of the conventional nanohybrids.

Electron-Donating Conjugation Effect Modulated Zn2+ Reduction Reaction for Separator-Free Aqueous Zinc Batteries.

Zinc-based aqueous batteries (ZABs) are attracting extensive attention due to the low cost, high capacity, and environmental benignity of the zinc anode. However, their application is still hindered by the undesired zinc dendrites. Despite Zn-surface modification being promising in relieving dendrites, a thick separator (i.e. glass fiber, 250-700 µm) is still required to resist the dendrite puncture, which limits volumetric energy density of battery. Here, we pivot from the traditional interphase plus extra separator categories, proposing an all-in-one ligand buffer layer (ca. 20 µm) to effectively modulate the Zn2+ transfer and deposition behaviors proved by in situ electrochemical digital holography. Experimental characterizations and density functional theory simulations further reveal that the catechol groups in the buffer layer can accelerate the Zn2+ reduction reaction (ZRR) through the electron-donating p-π conjugation effect, decreasing the negative charge in the coordination environment. Without extra separators, the elaborated system endows low polarization below 28.2 mV, long lifespan of 4950 h at 5 mA cm-2 in symmetric batteries, and an unprecedented volumetric energy density of 99.2 Wh L-1 based on the whole pouch cells. The concomitantly "separator-free" and "dendrite-free" conjugation effect with an accelerated ZRR process could foster the progression of metallic anodes and benefit energetic aqueous batteries.

Implanting Colloidal Nanoparticles into Single-Crystalline Zeolites for Catalytic Dehydration.

The encapsulation of functional colloidal nanoparticles (100 nm) into single-crystalline ZSM-5 zeolites, aiming to create uniform core-shell structures, is a highly sought-after yet formidable objective due to significant lattice mismatch and distinct crystallization properties. In this study, we demonstrate the fabrication of a core-shell structured single-crystal zeolite encompassing an Fe3O4 colloidal core via a novel confinement stepwise crystallization methodology. By engineering a confined nanocavity, anchoring nucleation sites, and executing stepwise crystallization, we have successfully encapsulated colloidal nanoparticles (CN) within single-crystal zeolites. These grafted sites, alongside the controlled crystallization process, compel the zeolite seed to nucleate and expand along the Fe3O4 colloidal nanoparticle surface, within a meticulously defined volume (1.5×107≤V≤1.3×108 nm3). Our strategy exhibits versatility and adaptability to an array of zeolites, including but not restricted to ZSM-5, NaA, ZSM-11, and TS-1 with polycrystalline zeolite shell. We highlight the uniformly structured magnetic-nucleus single-crystalline zeolite, which displays pronounced superparamagnetism (14 emu/g) and robust acidity (~0.83 mmol/g). This innovative material has been effectively utilized in a magnetically stabilized bed (MSB) reactor for the dehydration of ethanol, delivering an exceptional conversion rate (98 %), supreme ethylene selectivity (98 %), and superior catalytic endurance (in excess of 100 hours).

Reviving Zn0 Dendrites to Electroactive Zn2+ by Mesoporous MXene with Active Edge Sites.

Zinc metal-based aqueous batteries (ZABs) offer a sustainable, affordable, and safe energy storage alternative to lithium, yet inevitable dendrite formation impedes their wide use, especially under long-term and high-rate cycles. How the battery can survive after dendrite formation remains an open question. Here, we pivot from conventional Zn dendrite growth suppression strategies, introducing proactive dendrite-digesting chemistry via a mesoporous Ti3C2 MXene (MesoTi3C2)-wrapped polypropylene separator. Spectroscopic characterizations and electrochemical evaluation demonstrate that MesoTi3C2, acting as an oxidant, can revive the formed dead Zn0 dendrites into electroactive Zn2+ ions through a spontaneous redox process. Density functional theory reveals that the abundant edge-Ti-O sites in our MesoTi3C2 facilitate high oxidizability and electron transfer from Zn0 dendrites compared to their in-plane counterparts. The resultant asymmetrical cell demonstrates remarkable ultralong cycle life of 2200 h at a practical current of 5 mA cm-2 with a low overpotential (<50 mV). The study reveals the unexpected edge effect of mesoporous MXenes and uncovers a new proactive dendrite-digesting chemistry to survive ZABs, albeit with inevitable dendrite formation.

Constructing Unique Mesoporous Carbon Superstructures via Monomicelle Interface Confined Assembly.

Constructing hierarchical three-dimensional (3D) mesostructures with unique pore structure, controllable morphology, highly accessible surface area, and appealing functionality remains a great challenge in materials science. Here, we report a monomicelle interface confined assembly approach to fabricate an unprecedented type of 3D mesoporous N-doped carbon superstructure for the first time. In this hierarchical structure, a large hollow locates in the center (∼300 nm in diameter), and an ultrathin monolayer of spherical mesopores (∼22 nm) uniformly distributes on the hollow shells. Meanwhile, a small hole (4.0-4.5 nm) is also created on the interior surface of each small spherical mesopore, enabling the superstructure to be totally interconnected. Vitally, such interconnected porous supraparticles exhibit ultrahigh accessible surface area (685 m2 g-1) and good underwater aerophilicity due to the abundant spherical mesopores. Additionally, the number (70-150) of spherical mesopores, particle size (22 and 42 nm), and shell thickness (4.0-26 nm) of the supraparticles can all be accurately manipulated. Besides this spherical morphology, other configurations involving 3D hollow nanovesicles and 2D nanosheets were also obtained. Finally, we manifest the mesoporous carbon superstructure as an advanced electrocatalytic material with a half-wave potential of 0.82 V (vs RHE), equivalent to the value of the commercial Pt/C electrode, and notable durability for oxygen reduction reaction (ORR).

Synthesis of Mesoporous Yolk-Shell Magnetic Prussian Blue Particles for Multi-Functional Nanomedicine.

Mesoporous magnetic Prussian Blue (PB) particles are good condidates for theragnostic nanomedicine. However, there are lack of efficient methods for fabrication of such materials. Here, we reported the synthesis of the mesoporous yolk-shell Fe3O4@PB particles by one-pot coordination replication and etching. Time-dependent transmission electron microscopy illustrated that the PB crystals nucleated and grew on the surface of Fe3O4 spheres by coordination replication with the help of protons. The extra protons in the reaction medium further disassociated the Fe3O4 and PB, leading to mesoporous particles. The mesoporous yolk-shell Fe3O4@PB particles showed enhanced efficacy for loading cisplatin. The release of the drug molecules could be facilitated by increasing temperature. Both photo irradiation and alternating magnetic fields could trigger the release of heat from the composite. The obtained materials could delivery cisplatin to kill cancer cell intracellularly.

Rational Synthesis of Hollow Prussian Blue Analogue Through Coordination Replication and Controlled-Etching for Cs-Ion Removal.

Radioactive cesium pollution have received considerable attention due to the increasing risks in development of the nuclear power plants in the world. Although various functional porous materials are utilized to adsorb Cs+ ions in water, Prussian blue analogues (PBAs) are an impressive class of candidates because of their super affinity of Cs+ ions. The adsorption ability of the PBAs strongly relate to the mesostructure and interstitial sites. To design a hollow PBA with large number of interstitial sites, the traditional hollowing methods are not suitable owing to the difficulty in processing the specific PBAs with large number of interstitial sites. In this work, we empolyed a rational strategy which was to form a "metal oxide"@"PBA" core-shell structure via coordination replication at first, then utilized a mild etching to remove the metal oxide core, led to hollow PBA finally. The obtained hollow PBAs were of high crystallinity and large number of interstitial sites, showing a super adsorption performance for Cs+ ions (221.6 mg/g) within a short period (10 min).

Solution Synthesis of Semiconducting Two-Dimensional Polymer via Trimerization of Carbonitrile.

The synthesis of crystalline two-dimensional polymers (2DPs) with proper bandgaps and well-defined repeating units presents a great challenge to synthetic chemists. Here we report the first solution synthesis of a single-layer/few-layer triazine-based 2DP via trimerization of carbonitrile at the interface of dichloromethane and trifluoromethanesulfonic acid. The processable triazine-based 2DP can be assembled into mechanically strong layered free-standing films with a high specific surface area via filtration. Moreover, the highly crystalline triazine-based 2DP can function as the active semiconducting layer in a field-effect transistor via drop coating and exhibits slightly bipolar behavior with a high on/off ratio of 103 and a remarkable mobility of 0.15 cm2 V-1 s-1.

One Versatile Route to Three-Dimensional Graphene Wrapped Metal Cyanide Aerogels for Enhanced Sodium Ion Storage.

Facile and controllable integration of metal cyanides (MCs) into three-dimensional graphene (3DG) with advantageous structures is of fundamental importance for the development of superior MC-based electrode materials for electrochemical energy storage and catalysis. Here a facile and versatile spatially-confined Ostwald ripening strategy was developed to synthesize a series of 3DG wrapped MC aerogels with different compositions, size, and structure based on the chemical instability of MC in the reaction system. Remarkably, the integration of Prussian blue (PB) into 3DG, with such unique architecture, largely improves the rate performance and long-term cycling stability of PB as a cathode material for sodium ion batteries.

The Rise of Xene Hybrids.

Xenes, mono-elemental atomic sheets, exhibit Dirac/Dirac-like quantum behavior. When interfaced with other 2D materials such as boron nitride, transition metal dichalcogenides, and metal carbides/nitrides/carbonitrides, it enables them with unique physicochemical properties, including structural stability, desirable bandgap, efficient charge carrier injection, flexibility/breaking stress, thermal conductivity, chemical reactivity, catalytic efficiency, molecular adsorption, and wettability. For example, BN acts as an anti-oxidative shield, MoS2 injects electrons upon laser excitation, and MXene provides mechanical flexibility. Beyond precise compositional modulations, stacking sequences, and inter-layer coupling controlled by parameters, achieving scalability and reproducibility in hybridization is crucial for implementing these quantum materials in consumer applications. However, realizing the full potential of these hybrid materials faces challenges such as air gaps, uneven interfaces, and the formation of defects and functional groups. Advanced synthesis techniques, a deep understanding of quantum behaviors, precise control over interfacial interactions, and awareness of cross-correlations among these factors are essential. Xene-based hybrids show immense promise for groundbreaking applications in quantum computing, flexible electronics, energy storage, and catalysis. In this timely perspective, recent discoveries of novel Xenes and their hybrids are highlighted, emphasizing correlations among synthetic parameters, structure, properties, and applications. It is anticipated that these insights will revolutionize diverse industries and technologies.

Ordered mesoporous nanofibers mimicking vascular bundles for lithium metal batteries.

Hierarchical self-assembly with long-range order above centimeters widely exists in nature. Mimicking similar structures to promote reaction kinetics of electrochemical energy devices is of immense interest, yet remains challenging. Here, we report a bottom-up self-assembly approach to constructing ordered mesoporous nanofibers with a structure resembling vascular bundles via electrospinning. The synthesis involves self-assembling polystyrene (PS) homopolymer, amphiphilic diblock copolymer, and precursors into supramolecular micelles. Elongational dynamics of viscoelastic micelle solution together with fast solvent evaporation during electrospinning cause simultaneous close packing and uniaxial stretching of micelles, consequently producing polymer nanofibers consisting of oriented micelles. The method is versatile for the fabrication of large-scale ordered mesoporous nanofibers with adjustable pore diameter and various compositions such as carbon, SiO2, TiO2 and WO3. The aligned longitudinal mesopores connected side-by-side by tiny pores offer highly exposed active sites and expedite electron/ion transport. The assembled electrodes deliver outstanding performance for lithium metal batteries.

Rheological studies of cellulose nanocrystal/dimethyl sulfoxide organogels.

Cellulose nanocrystals (CNCs)/H2O gels have received significant interest in various applications for the past decades. And yet CNCs organogels, which are important to their wider application, are less explored. In this work, CNCs/Dimethyl sulfoxide (DMSO) organogels are carefully investigated by rheological methods. It is found that metal ions also can facilitate the organogel formation as in hydrogel. Charge screening and coordination effects play vital roles in the organogel formation and their mechanical strength. CNCs/DMSO gels with different cations display similar mechanical strength, while CNCs/H2O gels show increasing mechanical strength with the increasing valence of cations. It seems that the coordination between cations and DMSO alleviate the influence of valence on gel mechanical strength. Due to weak, fast and reversible electrostatic interactions among CNCs particles, both CNCs/DMSO and CNCs/H2O gels show instant thixotropic behavior, which may find some interesting applications in the field of drug delivery. The morphological changes observed in polarized optical microscope appear to be consistent with rheological results.

Ultra-Uniform and Functionalized Nano-Ion Divider for Regulating Ion Distribution toward Dendrite-Free Lithium-Metal Batteries.

Ionic dividers with uniform pores and functionalized surfaces display significant potential for solving Li-dendrite issues in Li-metal batteries. In this study, single metal and nitrogen co-doped carbon-sandwiched MXene (M-NC@MXene) nanosheets are designed and fabricated, which possess highly ordered nanochannels with a diameter of ≈10 nm. The experiments and computational calculations verified that the M-NC@MXene nanosheets eliminate Li dendrites in several ways: (1) redistributing the Li-ion flux via the highly ordered ion channels, (2) selectively conducting Li ions and anchoring anions by heteroatom doping to extend the nucleation time for Li dendrites, and (3) tightly staggering on a routine polypropylene (PP) separator to obstruct the growth path of Li dendrites. With a Zn-NC@MXene-coated PP divider, the assembled Li||Li symmetric battery shows an ultralow overpotential of ≈25 mV and a cycle life of 1500 h at a high current density of 3 mA cm-2 and high capacity of 3 mAh cm-2 . Remarkably, the life of a Li||Ni83 pouch cell with an energy density of 305 Wh kg-1 is improved by fivefold. Moreover, the remarkable performance of Li||Li, Li||LiFePO4 , and Li||sulfur batteries reveal the significant potential of the well-designed multifunctional ion divider for further practical applications.

Prioritizing Hetero-Metallic Interfaces via Thermodynamics Inertia and Kinetics Zincophilia Metrics for Tough Zn-Based Aqueous Batteries.

Poor thermodynamic stability and sluggish electrochemical kinetics of metallic Zn anode in aqueous solution greatly hamper its practical application. To solve such problems, to date, various zincophilic surface modification strategies are developed, which can facilitate reversible Zn plating/stripping behavior. However, there is still a lack of systematic and fundamental understanding regarding the metrics of thermodynamics inertia and kinetics zincophilia in selecting zincophilic sites. Herein, hetero-metallic interfaces are prioritized for the first time via optimizing different hetero metals (Fe, Co, Ni, Sn, Bi, Cu, Zn, etc.) and synthetic solvents (ethanol, ethylene glycol, n-propanol, etc.). Specifically, both theoretical simulations and experimental results suggest that this Bi@Zn interface can exhibit high efficiency owing to the thermodynamics inertia and kinetics zincophilia. A best practice for prioritizing zincophilic sites in a more practical metric is also proposed. As a proof of concept, the Bi@Zn anode delivers ultralow overpotential of ≈55 mV at a high rate of 10 mA cm-2 and stable cycle life over 4700 cycles. The elaborated "thermodynamics inertia and kinetics metalphilia" metrics for hetero-metallic interfaces can benchmark the success of other metal-based batteries.

Activating sulfur oxidation reaction via six-electron redox mesocrystal NiS2 for sulfur-based aqueous batteries.

Sulfur-based aqueous batteries (SABs) are deemed promising candidates for safe, low-cost, and high-capacity energy storage. However, despite their high theoretical capacity, achieving high reversible value remains a great challenge due to the thermodynamic and kinetics problems of elemental sulfur. Here, the reversible six-electron redox electrochemistry is constructed by activating the sulfur oxidation reaction (SOR) process of the elaborate mesocrystal NiS2 (M-NiS2). Through the unique 6e- solid-to-solid conversion mechanism, SOR efficiency can reach an unprecedented degree of ca. 96.0%. The SOR efficiency is further revealed to be closely associated with the kinetics feasibility and thermodynamic stability of the M-NiS2 intermedium in the formation of elemental sulfur. Benefiting from the boosted SOR, compared with the bulk electrode, the M-NiS2 electrode exhibits a high reversible capacity (1258 mAh g-1), ultrafast reaction kinetics (932 mAh g-1 at 12 A g-1), and long-term cyclability (2000 cycles at 20 A g-1). As a proof of concept, a new M-NiS2‖Zn hybrid aqueous battery exhibits an output voltage of 1.60 V and an energy density of 722.4 Wh kgcath-1, which opens a new opportunity for the development of high-energy aqueous batteries.

Modular super-assembly of hierarchical superstructures from monomicelle building blocks.

Manipulating the super-assembly of polymeric building blocks still remains a great challenge due to their thermodynamic instability. Here, we report on a type of three-dimensional hierarchical core-satellite SiO2@monomicelle spherical superstructures via a previously unexplored monomicelle interfacial super-assembly route. Notably, in this superstructure, an ultrathin single layer of monomicelle subunits (~18 nm) appears in a typically hexagon-like regular discontinuous distribution (adjacent micelle distance of ~30 nm) on solid spherical interfaces (SiO2), which is difficult to achieve by conventional super-assembled methods. Besides, the number of the monomicelles on colloidal SiO2 interfaces can be quantitatively controlled (from 76 to 180). This quantitative control can be precisely manipulated by tuning the interparticle electrostatic interactions (the intermicellar electrostatic repulsion and electrostatic attractions between the monomicelle units and the SiO2 substrate). This monomicelle interfacial super-assembly strategy will enable a controllable way for building multiscale hierarchical regular micro- and/or macroscale materials and devices.

Imparting multi-functionality to covalent organic framework nanoparticles by the dual-ligand assistant encapsulation strategy.

The potential applications of covalent organic frameworks (COFs) can be further developed by encapsulating functional nanoparticles within the frameworks. However, the synthesis of monodispersed core@shell structured COF nanocomposites without agglomeration remains a significant challenge. Herein, we present a versatile dual-ligand assistant strategy for interfacial growth of COFs on the functional nanoparticles with abundant physicochemical properties. Regardless of the composition, geometry or surface properties of the core, the obtained core@shell structured nanocomposites with controllable shell-thickness are very uniform without agglomeration. The derived bowl-shape, yolk@shell, core@satellites@shell nanostructures can also be fabricated delicately. As a promising type of photosensitizer for photodynamic therapy (PDT), the porphyrin-based COFs were grown onto upconversion nanoparticles (UCNPs). With the assistance of the near-infrared (NIR) to visible optical property of UCNPs core and the intrinsic porosity of COF shell, the core@shell nanocomposites can be applied as a nanoplatform for NIR-activated PDT with deep tissue penetration and chemotherapeutic drug delivery.

Monodisperse Ultrahigh Nitrogen-Containing Mesoporous Carbon Nanospheres from Melamine-Formaldehyde Resin.

An aqueous emulsion polymerization self-assembly approach is demonstrated for the first time to synthesize ultrahigh nitrogen containing mesoporous polymer nanospheres, using melamine-formaldehyde resin oligomers as precursors. In the synthesis, change from alkaline to acidic conditions is critical for the formation of monodisperse mesostructured polymer nanospheres. Owing to unique structure of triazine stabilized in the covalent polymeric networks during the pyrolysis process, the derived mesoporous carbon nanospheres possess an ultrahigh nitrogen content (up to 15.6 wt%) even after pyrolysis at 800 °C, which is the highest nitrogen content among mesoporous carbon nanospheres. Furthermore, these monodisperse mesoporous carbon nanospheres possess a high surface area (≈883 m2 g-1 ) and large pore size (≈8.1 nm). As an anode for sodium-ion batteries, the ultrahigh nitrogen-containing mesoporous carbon nanospheres exhibit superior rate capability (117 mAh g-1 at a high current density of 3 A g-1 ) and high reversible capacity (373 mAh g-1 at 0.06 A g-1 ), indicating a promising material for energy storage.

Double-Holey-Heterostructure Frameworks Enable Fast, Stable, and Simultaneous Ultrahigh Gravimetric, Areal, and Volumetric Lithium Storage.

Deliberate design of advantageous nanostructures holds great promise for developing high-performance electrode materials for electrochemical energy storage. However, it remains a tremendous challenge to simultaneously gain high gravimetric, areal, and volumetric capacities as well as high rate performance and cyclability to meet practical requirements mainly due to the intractable insufficient ion diffusion and limited active sites for dense electrodes with high areal mass loadings. Herein we report a double-holey-heterostructure framework, in which holey Fe2O3 nanosheets (H-Fe2O3) are tightly and conformably grown on the holey reduced graphene oxide (H-RGO). This hierarchical nanostructure allows for rapid ion and electron transport and sufficient utilization of active sites throughout a highly compact and thick electrode. Therefore, the free-standing flexible H-Fe2O3/H-RGO heterostructure anode can simultaneously deliver ultrahigh gravimetric, areal, and volumetric capacities of 1524 mAh g-1, 4.72 mAh cm-2, and 2621 mAh cm-3, respectively, at 0.2 A g-1 after 120 cycles, and extraordinary rate performance with a capacity of 487 mAh g-1 (1.51 mAh cm-2) at a high current density of 30 A g-1 (93 mA cm-2) as well as excellent cycling stability with a capacity retention of 96.3% after 1600 cycles, which has rarely been achieved before.

Sub-5 nm Ultrasmall Metal-Organic Framework Nanocrystals for Highly Efficient Electrochemical Energy Storage.

Synthesis of ultrasmall metal-organic framework (MOF) nanoparticles has been widely recognized as a promising route to greatly enhance their properties but remains a considerable challenge. Herein, we report one facile and effective spatially confined thermal pulverization strategy to successfully transform bulk Co-MOF particles into sub-5 nm nanocrystals encapsulated within N-doped carbon/graphene (NC/G) by using conducting polymer coated Co-MOFs/graphene oxide as precursors. This strategy involves a feasible mechanism: calcination of Co-MOFs at proper temperature in air induces the partial thermal collapse/distortion of the framework, while the uniform coating of a conducting polymer can significantly improve the decomposition temperature and maintain the component stability of Co-MOFs, thus leading to the pulverization of bulk Co-MOF particles into ultrasmall nanocrystals without oxidation. The pulverization of Co-MOFs significantly increases the contact area between Co-MOFs with electrolyte and shortens the electron and ion transport pathway. Therefore, the sub-5 nm ultrasmall MOF nanocrystals-based composites deliver an ultrahigh reversible capacity (1301 mAh g-1 at 0.1 A g-1), extraordinary rate performance (494 mAh g-1 at 40 A g-1), and outstanding cycling stability (98.6% capacity retention at 10 A g-1 after 2000 cycles), which is the best performance achieved in all reported MOF-based anodes for lithium-ion batteries.