Versatile synthesis of uniform mesoporous superparticles from stable monomicelle units.

Superstructures with architectural complexity and unique functionalities are promising for a variety of practical applications in many fields, including mechanics, sensing, photonics, catalysis, drug delivery and energy storage/conversion. In the past five years, a number of attempts have been made to build superparticles based on amphiphilic polymeric micelle units, but most have failed owing to their inherent poor stability. Determining how to stabilize micelles and control their superassembly is critical to obtaining the desired mesoporous superparticles.

Enabling Interfacial Lattice Matching by Selective Epitaxial Growth of CuS Crystals on BiWO Nanosheets for Efficient CO Photoreduction into Solar Fuels.

Photocatalytic CO reduction serves as an important technology for value-added solar fuel production, however, it is generally limited by interfacial charge transport. To address this limitation, a two-dimensional/two-dimensional (2D/2D) p-n heterojunction CuS-BiWO (CS-BWO) with highly connected and matched interfacial lattices was designed in this work via a two-step hydrothermal tandem synthesis strategy. The integration of CuS with BWO created a robust interface electric field and provided fast charge transfer channels due to the work function difference, as well as highly connected and matched interfacial lattices.

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 SiO nanobulge (∼8 nm, 2275 MPa).

Selective CO Photoreduction into CH Triggered by the Synergy between Oxygen Vacancy and Ru Substitution under Near-Infrared Light Irradiation.

Near-infrared (NIR) light powdered CO photoreduction reaction is generally restricted to the separation efficiency of photogenerated carriers and the supply of active hydrogen (*H). Herein, the study reports a retrofitting hydrogenated MoO (H-MoO) nanosheet photocatalysts with Ru single atom substitution (Ru@H-MoO) fabricated by one-step solvothermal method. Experiments together with theoretical calculations demonstrate that the synergistic effect of Ru substitution and oxygen vacancy can not only inhibit the recombination of photogenerated carriers, but also facilitate the CO adsorption/activation as well as the supply of *H.

Unipolar Ionic Diode Nanofluidic Membranes Enabled by Stepped Mesochannels for Enhanced Salinity Gradient Energy Harvesting.

Developing ionic diode membranes featuring asymmetric structures is in high demand for salinity gradient energy harvesting. These membranes offer benefits in mitigating ion concentration polarization, thereby promoting ion permeability. However, most reported works focus on the role of heterogeneous charge-based bipolar ionic diode membranes for ion concentration polarization suppression, with comparatively less attention given to maintaining ion selectivity.

Hydrogen-Bonded Mesoporous Frameworks with Tunable Pore Sizes and Architectures from Nanocluster Assembly Units.

Construction of mesoporous frameworks by noncovalent bonding still remains a great challenge. Here, we report a micelle-directed nanocluster modular self-assembly approach to synthesize a novel type of two-dimensional (2-D) hydrogen-bonded mesoporous frameworks (HMFs) for the first time based on nanoscale cluster units (1.0-3.

Ultrasmall Inorganic Mesoporous Nanoparticles: Preparation, Functionalization, and Application.

Ultrasmall mesoporous nanoparticles (<50 nm), a unique porous nanomaterial, have been widely studied in many fields in the last decade owing to the abundant advantages, involving rich mesopores, low density, high surface area, numerous reaction sites, large cavity space, ultrasmall size, etc. This paper presents a review of recent advances in the preparation, functionalization, and applications of ultrasmall inorganic mesoporous nanoparticles for the first time. The soft monomicelles-directed method, in contrast to the hard-template and template-free methods, is more flexible in the synthesis of mesoporous nanoparticles.

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 FeO 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.

Tandem Chemistry with Janus Mesopores Accelerator for Efficient Aqueous Batteries.

A reliable solid electrolyte interphase (SEI) on the metallic Zn anode is imperative for stable Zn-based aqueous batteries. However, the incompatible Zn-ion reduction processes, scilicet simultaneous adsorption (capture) and desolvation (repulsion) of Zn(HO), raise kinetics and stability challenges for the design of SEI. Here, we demonstrate a tandem chemistry strategy to decouple and accelerate the concurrent adsorption and desolvation processes of the Zn cluster at the inner Helmholtz layer.

Mesoporous TiO Single-Crystal Particles from Controlled Crystallization-Driven Mono-Micelle Assembly as an Efficient Photocatalyst.

Mesoporous materials with crystalline frameworks have been widely explored in many fields due to their unique structure and crystalline feature, but accurate manipulations over crystalline scaffolds, mainly composed of uncontrolled polymorphs, are still lacking. Herein, we explored a controlled crystallization-driven monomicelle assembly approach to construct a type of uniform mesoporous TiO particles with atomically aligned single-crystal frameworks. The resultant mesoporous TiO single-crystal particles possess an angular shape ∼80 nm in diameter, good mesoporosity (a high surface area of 112 m g and a mean pore size at 8.

Asymmetric Monolayer Mesoporous Nanosheets of Regularly Arranged Semi-Opened Pores via a Dual-Emulsion-Directed Micelle Assembly.

Constructing asymmetric two-dimensional (2D) mesoporous nanomaterials with new pore structure, tunable monolayer architectures, and especially anisotropic surfaces remains a great challenge in materials science. Here, we report a dual-emulsion directed micelle assembly approach to fabricate a novel type of asymmetric monolayer mesoporous organosilica nanosheet for the first time. In this asymmetric 2D structure, numerous quasi-spherical semiopened mesopores (∼20 nm in diameter, 24 nm in opening size) were regularly arranged on a plane, endowing the porous nanosheets (several micrometers in size) with a typical surface anisotropy on two sides.

Boosted Oxygen Kinetics of Hierarchically Mesoporous MoC/C for High-current-density Zn-air Battery.

The high-current-density Zn-air battery shows big prospects in next-generation energy technologies, while sluggish O reaction and diffusion kinetics barricade the applications. Herein, the sequential assembly is innovatively demonstrated for hierarchically mesoporous molybdenum carbides/carbon microspheres with a tunable thickness of mesoporous carbon layers (Meso-MoC/C-x, where x represents the thickness). The optimum Meso-MoC/C-14 composites (≈2 µm in diameter) are composed of mesoporous nanosheets (≈38 nm in thickness), which possess bilateral mesoporous carbon layers (≈14 nm in thickness), inner MoC/C layers (≈8 nm in thickness) with orthorhombic MoC nanoparticles (≈2 nm in diameter), a high surface area of ≈426 m g, and open mesopores (≈6.

Activating sulfur oxidation reaction six-electron redox mesocrystal NiS 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 NiS (M-NiS).

High-Energy Sn-Ni and Sn-Air Aqueous Batteries via Stannite-Ion Electrochemistry.

Tin is promising for aqueous batteries (ABs) due to its multiple electrons' reactions, high corrosion resistance, large hydrogen overpotential, and excellent environmental compatibility. However, restricted to the high thermodynamic barrier and the poor electrochemical kinetics, efficient alkaline Sn plating/stripping at facile conditions has not yet been realized. Here, for the first time, we demonstrate a highly reversible stannite-ion electrochemistry and construct a novel paradigm of high-energy Sn-based ABs.

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.

Sub-10 nm Corrugated TiO Nanowire Arrays by Monomicelle-Directed Assembly for Efficient Hole Extraction.

Precise synthesis of well-ordered ultrathin nanowire arrays with tunable active surface, though attractive in optoelectronics, remains challenging to date. Herein, well-aligned sub-10 nm TiO nanowire arrays with controllable corrugated structure have been synthesized by a unique monomicelle-directed assembly method. The nanowires with an exceptionally small diameter of ∼8 nm abreast grow with an identical adjacent distance of ∼10 nm, forming vertically aligned arrays (∼800 nm thickness) with a large surface area of ∼102 m g.

Synthesis of Fully Exposed Single-Atom-Layer Metal Clusters on 2D Ordered Mesoporous TiO Nanosheets.

A sulfhydryl monomicelles interfacial assembly strategy is presented for the synthesis of fully exposed single-atom-layer Pt clusters on 2D mesoporous TiO (SAL-Pt@mTiO ) nanosheets. This synthesis features the introduction of the sulfhydryl group in monomicelles to finely realize the controllable co-assembly process of Pt precursors within ordered mesostructures. The resultant SAL-Pt@mTiO shows uniform SAL Pt clusters (≈1.

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.

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 SiO@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 (SiO), which is difficult to achieve by conventional super-assembled methods.

Gradient Hierarchically Porous Structure for Rapid Capillary-Assisted Catalysis.

Synthesis of hierarchically porous structures with uniform spatial gradient and structure reinforcement effect still remains a great challenge. Herein, we report the synthesis of zeolite@mesoporous silica core-shell nanospheres (ZeoA@MesoS) with a gradient porous structure through a micellar dynamic assembly strategy. In this case, we find that the size of composite micelles can be dynamically changed with the increase of swelling agents, which act as the building blocks for the modular assembly of gradient mesostructures.

Enzyme-Based Mesoporous Nanomotors with Near-Infrared Optical Brakes.

As one of the most important parameters of the nanomotors' motion, precise speed control of enzyme-based nanomotors is highly desirable in many bioapplications. However, owing to the stable physiological environment, it is still very difficult to in situ manipulate the motion of the enzyme-based nanomotors. Herein, inspired by the brakes on vehicles, the near-infrared (NIR) "optical brakes" are introduced in the glucose-driven enzyme-based mesoporous nanomotors to realize remote speed regulation for the first time.

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.

Spiral self-assembly of lamellar micelles into multi-shelled hollow nanospheres with unique chiral architecture.

Functional carbon nanospheres are exceptionally useful, yet controllable synthesis of them with well-defined porosity and complex multi-shelled nanostructure remains challenging. Here, we report a lamellar micelle spiral self-assembly strategy to synthesize multi-shelled mesoporous carbon nanospheres with unique chirality. This synthesis features the introduction of shearing flow to drive the spiral self-assembly, which is different from conventional chiral templating methods.