Degradation‐Restructuring Induced Anisotropic Epitaxial Growth for Fabrication of Asymmetric Diblock and Triblock Mesoporous Nanocomposites

A novel degradation‐restructuring induced anisotropic epitaxial growth strategy is demonstrated for the synthesis of uniform 1D diblock and triblock silica mesoporous asymmetric nanorods with controllable rod length (50 nm to 2 µm) and very high surface area of 1200 m² g^?1. The asymmetric diblock mesoporous silica nanocomposites are composed of a 1D mesoporous organosilicate nanorod with highly ordered hexagonal mesostructure, and a closely connected dense SiO₂ nanosphere located only on one side of the nanorods. Furthermore, the triblock mesoporous silica nanocomposites constituted by a cubic mesostructured nanocube, a nanosphere with radial mesopores, and a hexagonal mesostructured nanorod can also be fabricated with the anisotropic growth of mesopores. Owing to the ultrahigh surface area, unique 1D mesochannels, and functionality asymmetry, the obtained match‐like asymmetric Au‐NR@SiO₂&EPMO (EPMO = ethane bridged periodic mesoporous organosilica) mesoporous nanorods can be used as an ideal nanocarrier for the near‐infrared photothermal triggered controllable releasing of drug molecules.     

Directing Gold Nanoparticles into Free‐Standing Honeycomb‐Like Ordered Mesoporous Superstructures

2D mesoporous materials fabricated via the assembly of nanoparticles (NPs) not only possess the unique properties of nanoscale building blocks but also manifest additional collective properties due to the interactions between NPs. In this work, reported is a facile and designable way to prepare free‐standing 2D mesoporous gold (Au) superstructures with a honeycomb‐like configuration. During the fabrication process, Au NPs with an average diameter of 5.0 nm are assembled into a superlattice film on a diethylene glycol substrate. Then, a subsequent thermal treatment at 180 °C induces NP attachment, forming the honeycomb‐like ordered mesoporous Au superstructures. Each individual NP connects with three neighboring NPs in the adjacent layer to form a tetrahedron‐based framework. Mesopores confined in the superstructure have a uniform size of 3.5 nm and are arranged in an ordered hexagonal array. The metallic bonding between Au NPs increases the structural stability of architected superstructures, allowing them to be easily transferred to various substrates. In addition, electron energy‐loss spectroscopy experiments and 3D finite‐difference time‐domain simulations reveal that electric field enhancement occurs at the confined mesopores when the superstructures are excited by light, showing their potential in nano‐plasmonic applications.     

Ultrathin 2D Zirconium Metal–Organic Framework Nanosheets: Preparation and Application in Photocatalysis

Synthesizing ultrathin 2D metal–organic framework nanosheets in high yields has received increasing research interest but remains a great challenge. In this work, ultrathin zirconium‐porphyrinic metal–organic framework (MOF) nanosheets with thickness down to ≈1.5 nm are synthesized through a pseudoassembly–disassembly strategy. Owing to the their unique properties originating from their ultrathin thickness and highly exposed active sites, the as‐prepared ultrathin nanosheets exhibit far superior photocatalysis performance compared to the corresponding bulk MOF. This work highlights new opportunities in designing ultrathin MOF nanosheets and paves the way to expand the potential applications of MOFs.     

Ordered, mesoporous metal phosphonate materials with microporous crystalline walls for selective separation techniques

Ordered, hexagonal, mesoporous metal (Ti, Zr, V, Al)-phosphonate materials with microporous crystalline walls are synthesized through a microwave-assisted procedure by using triblock copolymer F127 as the template. Corresponding metal chlorides and ethylene diamine tetra(methylene phosphonic acid) are chosen as the inorganic precursors and the coupling molecule, respectively. X-ray diffractometry, transmission electron microscopy, N(2) sorption, and thermogravimetry measurements confirm that the obtained metal phosphonates possess a hierarchically porous structure with pore sizes of 7.1-7.5 nm and 1.3-1.7 nm for mesopores and micropores, respectively, and the metal phosphonate materials are thermally stable up to around 450 °C with the pore structure and hybrid framework well preserved. Magic angle spinning NMR, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy analyses indicate that the phosphonate groups are homogenously incorporated into the hybrid framework of the obtained materials. For the first time, the mesoporous hybrid materials are employed as the stationary phase in open tubular capillary electrochromatography technique for the separation of various substances including acidic, basic, and neutral compounds. These materials show good selectivity and reproducibility for this application.     

Influence of Chain Architecture on Nanopore Accessibility in Polyelectrolyte Block‐Co‐Oligomer Functionalized Mesopores

Functionalized ordered mesoporous silica materials are commonly investigated for applications such as drug release, sensing, and separation processes. Although, various homopolymer functionalized responsive mesopores are reported, little focus has been put on copolymers in mesopores. Mesoporous silica films are functionalized with responsive and orthogonally charged block‐co‐oligomers. Responsive 2‐dimethylamino)ethyl methacrylate)‐block‐2‐(methacryloyloxy)ethyl phosphate (DMAEMA‐b‐MEP) block‐co‐oligomers are introduced into mesoporous films using controlled photoiniferter initiated polymerization. This approach allows a very flexible charge composition design. The obtained block‐co‐oligomer functionalized mesopores show a complex gating behavior indicating a strong interplay between the different blocks emphasizing the strong influence of charge distribution inside mesopores on ionic pore accessibility. For example, in contrast to mesopores functionalized with zwitterionic polymers, DMAEMA‐b‐MEP block‐co‐oligomer functionalized mesopores, containing two oppositely charged blocks, do not show bipolar ion exclusion, demonstrating the influence of the chain architecture on mesopore accessibility. Furthermore, ligand binding–based selective gating is strongly influenced by this chain architecture as demonstrated by an expansion of pore accessibility states for block‐co‐oligomer functionalized mesopores as compared to the individual polyelectrolyte functionalization for calcium induced gating.     

Ultrathin Amorphous Nickel Doped Cobalt Phosphates with Highly Ordered Mesoporous Structures as Efficient Electrocatalyst for Oxygen Evolution Reaction

Herein, the facile preparation of ultrathin (≈3.8 nm in thickness) 2D cobalt phosphate (CoPi) nanoflakes through an oil‐phase method is reported. The obtained nanoflakes are composed of highly ordered mesoporous (≈3.74 nm in diameter) structure and exhibit an amorphous nature. Attractively, when doped with nickel, such 2D mesoporous Ni‐doped CoPi nanoflakes display decent electrocatalytic performances in terms of intrinsic activity, and low kinetic barrier toward the oxygen evolution reaction (OER). Particularly, the optimized 10 at% Ni‐doped CoPi nanoflakes (denoted as Ni10‐CoPi) deliver a low overpotential at 10 mA cm^?2 (320 mV), small Tafel slope (44.5 mV dec^?1), and high stability for OER in 1.0 m KOH solution, which is comparable to the state‐of‐the‐art RuO₂ tested in the same condition (overpotential: 327 mV at 10 mA cm^?2, Tafel slope: 73.7 mV dec^?1). The robust framework coupled with good OER performance enables the 2D mesoporous Ni10‐CoPi nanoflakes to be a promising material for energy conversion applications.     

Highly Excavated Octahedral Nanostructures Integrated from Ultrathin Mesoporous PtCu3 Nanosheets: Construction of Three‐Dimensional Open Surfaces for Enhanced Electrocatalysis

Developing electrocatalysts with ultrathin nanostructures and high mesoporosity is a relevant high‐priority research direction toward enhancing the performance of noble metals. Herein, mesoporous, highly excavated octahedral PtCu₃ nanostructures are prepared by a facile one‐pot synthesis. The mesoporous, highly excavated octahedral PtCu₃ nanostructures are built with mutually perpendicular interlaced mesoporous nanosheets with a thickness of ≈4.5 nm. Benefiting from its mesoporous features, three‐dimensional (3D) open surfaces, ultrathin nanosheets, and a Cu‐rich surface, PtCu₃ exhibits excellent electrocatalytic performance and high antipoisoning activity toward the methanol oxidation reaction.     

Ultrasonic‐Ball Milling: A Novel Strategy to Prepare Large‐Size Ultrathin 2D Materials

Large‐size ultrathin 2D materials, with extensive applications in optics, medicine, biology, and semiconductor fields, can be prepared through an existing common physical and chemical process. However, the current exfoliation technologies still need to be improved upon with urgency. Herein, a novel and simple “ultrasonic‐ball milling” strategy is reported to effectively obtain high quality and large size ultrathin 2D materials with complete lattice structure through the introduction of moderate sapphire (Al₂O₃) abrasives in a liquid phase system. Ultimately numerous high‐quality ultrathin h‐BN, graphene, MoS₂, WS₂, and BCN nanosheets are obtained with large sizes ranging from 1–20 µm, small thickness of ≈1–3 nm and a high yield of over 20%. Utilizing shear and friction force synergistically, this strategy provides a new method and alternative for preparing and optimizing large size ultrathin 2D materials.     

In Situ Probing of the Particle‐Mediated Mechanism of WO3‐Networked Structures Grown inside Confined Mesoporous Channels

Nanocasting, using ordered mesoporous silica or carbon as a hard template, has enormous potential for preparing novel mesoporous materials with new structures and compositions. Although a variety of mesoporous materials have been synthesized in recent years, the growth mechanism of nanostructures in a confined space, such as mesoporous channels, is not well understood, which hampers the controlled synthesis and further application of mesoporous materials. Here, the nucleation and growth of WO₃‐networked mesostructures within an ordered mesoporous matrix, using an in situ transmission electron microscopy heating technique and in situ synchrotron small‐angle X‐ray scattering spectroscopy, are probed. It is found that the formation of WO₃ mesostructures involves a particle‐mediated transformation and coalescence mechanism. The liquid‐like particle‐mediated aggregation and mesoscale transformation process can occur in ≈10 nm confined mesoporous channels, which is completely unexpected. The detailed mechanistic study will be of great help for experimental design and to exploit a variety of mesoporous materials for diverse applications, such as catalysis, absorption, separation, energy storage, biomedicine, and nanooptics.     

Two‐Dimensional Self‐Organization of an Ordered Au Silicide Nanowire Network on a Si(110)‐16 × 2 Surface

A well‐ordered two‐dimensional (2D) network consisting of two crossed Au silicide nanowire (NW) arrays is self‐organized on a Si(110)‐16 × 2 surface by the direct‐current heating of ≈1.5 monolayers of Au on the surface at 1100 K. Such a highly regular crossbar nanomesh exhibits both a perfect long‐range spatial order and a high integration density over a mesoscopic area, and these two self‐ordering crossed arrays of parallel‐aligned NWs have distinctly different sizes and conductivities. NWs are fabricated with widths and pitches as small as ≈2 and ≈5 nm, respectively. The difference in the conductivities of two crossed‐NW arrays opens up the possibility for their utilization in nanodevices of crossbar architecture. Scanning tunneling microscopy/spectroscopy studies show that the 2D self‐organization of this perfect Au silicide nanomesh can be achieved through two different directional electromigrations of Au silicide NWs along different orientations of two nonorthogonal 16 × 2 domains, which are driven by the electrical field of direct‐current heating. Prospects for this Au silicide nanomesh are also discussed.     

Chemical Patterning of High‐Mobility Semiconducting 2D Bi2O2Se Crystals for Integrated Optoelectronic Devices

Patterning of high‐mobility 2D semiconducting materials with unique layered structures and superb electronic properties offers great potential for batch fabrication and integration of next‐generation electronic and optoelectronic devices. Here, a facile approach is used to achieve accurate patterning of 2D high‐mobility semiconducting Bi₂O₂Se crystals using dilute H₂O₂ and protonic mixture acid as efficient etchants. The 2D Bi₂O₂Se crystal after chemical etching maintains a high Hall mobility of over 200 cm² V^?1 s^?1 at room temperature. Centimeter‐scale well‐ordered arrays of 2D Bi₂O₂Se with tailorable configurations are readily obtained. Furthermore, integrated photodetectors based on 2D Bi₂O₂Se arrays are fabricated, exhibiting excellent air stability and high photoresponsivity of ≈2000 A W^?1 at 532 nm. These results are one step towards the practical application of ultrathin 2D integrated digital and optoelectronic circuits.     

Conformal Coating of Co/N‐Doped Carbon Layers into Mesoporous Silica for Highly Efficient Catalytic Dehydrogenation–Hydrogenation Tandem Reactions

To maximize the utilizing efficiency of cobalt (Co) and optimize its catalytic activity and stability, engineering of size and interfacial chemical properties, as well as controllable support are of ultimate importance. Here, the concept of coating uniform thin Co/N‐doped carbon layers into the mesopore surfaces of mesoporous silica is proposed for heterogeneous aqueous catalysis. To approach the target, a one‐step solvent‐free melting‐assisted coating process, i.e., heating a mixture of a cobalt salt, an amino acid (AA), and a mesoporous silica, is developed for the synthesis of mesoporous composites with thin Co/N‐doped carbon layers uniformly coated within mesoporous silica, high surface areas (250–630 m² g⁻¹), ordered mesopores (7.0–8.4 nm), and high water dispersibility. The strong silica/AA adhesive interactions and AA cohesive interactions direct the uniform coating process. The metal/N coordinating, carbon anchoring, and mesopore confining lead to the formation of tiny Co nanoclusters. The carbon intercalation and N coordination optimize the interfacial properties of Co for catalysis. The optimized catalyst exhibits excellent catalytic performance for tandem hydrogenation of nitrobenzene and dehydrogenation of NaBH₄ with well‐matched reaction kinetics, 100% conversion and selectivity, high turnover frequencies, up to ≈6.06 mol_nitrobenzene mol_Co⁻¹ min⁻¹, the highest over transition‐metal catalysts, and excellent stability and magnetic separability.     

Nonsacrificial Self‐Template Synthesis of Colloidal Magnetic Yolk–Shell Mesoporous Organosilicas for Efficient Oil/Water Interface Catalysis

Using interfacial reaction systems for biphasic catalytic reactions is attracting more and more attention due to their simple reaction process and low environmental pollution. Yolk–shell structured materials have broad applications in biomedicine, catalysis, and environmental remediation owing to their open channels and large space for guest molecules. Conventional methods to obtain yolk–shell mesoporous materials rely on costly and complex hard‐template strategies. In this study, a mild and convenient nonsacrificial self‐template strategy is developed to construct yolk–shell magnetic periodic mesoporous organosilica (YS‐mPMO) particles by using the unique swelling–deswelling property of low‐crosslinking density resorcinol formaldehyde (RF). The obtained YS‐mPMO microspheres possess an amphiphilic outer shell, high surface area (393 m² g^?1), uniform mesopores (2.58 nm), a tunable middle hollow space (50–156 nm), and high superparamagnetism (34.4–37.1 emu g^?1). By tuning the synthesis conditions, heterojunction structured yolk–shell Fe₃O₄@RF@void@PMO particles with different morphologies can be produced. Owing to the amphipathy of PMO framworks, the YS‐mPMO particles show great emulsion stabilization ability and recyclability under a magnetic field. YS‐mPMO microspheres with immobilized Au nanoparticles (≈3 nm) act as both solid emulsifier for dispersing styrene (St) in water and interface catalysts for selective conversion of St into styrene oxide with a high selectivity of 86%, and yields of over 97%.     

Synthesis, characterization, and evaluation of lubrication properties of composites of ordered mesoporous carbons and luminescent CePO4:Tb nanocrystals

Having new potential applications in forging processes in mind, composites of an ordered mesoporous carbon and luminescent metal phosphate nanocrystals were synthesized for the first time. Three kinds of CMK-3/CePO₄:Tb nanocomposites were prepared by treating a mesoporous CMK-3 host with different lanthanide phosphate precursor solutions. Characterization of the obtained nanocomposites by small-angle X-ray scattering, wide-angle X-ray diffraction, transmission electron microscopy, thermogravimetry, and nitrogen physisorption analysis showed that in two cases, the nanocrystals (ca. 2–3 nm in size) were located inside the mesopores, whereas in the third case the nanocystals (ca. 6 nm in size) merely adhered to the outer surfaces of the carbon particles. The CMK-3 and the two nanocomposites had ordered hexagonal structures (space group p6mm); all the materials possessed amorphous carbon walls. After combustion of the nanocomposites, the residues upon excitation with UV light exhibited the typical green luminescence of Tb³⁺. A preliminary evaluation of the lubrication properties of the CMK-3 and one nanocomposite material was performed. The friction factors determined by means of ring upsetting tests revealed that the carbon materials were able to lower frictional forces although they were 3–4 times less efficient than a commercial graphite-based reference lubricant.     

Multiscale Phase Separations for Hierarchically Ordered Macro/Mesostructured Metal Oxides

Porous architectures play an important role in various applications of inorganic materials. Several attempts to develop mesoporous materials with controlled macrostructures have been reported, but they usually require complicated multiple‐step procedures, which limits their versatility and suitability for mass production. Here, a simple approach for controlling the macrostructures of mesoporous materials, without templates for the macropores, is reported. The controlled solvent evaporation induces both macrophase separation via spinodal decomposition and mesophase separation via block copolymer self‐assembly, leading to the formation of hierarchically porous metal oxides with periodic macro/mesostructures. In addition, using this method, macrostructures of mesoporous metal oxides are controlled into spheres and mesoporous powders containing isolated macropores. Nanocomputed tomography, focused ion beam milling, and electron microscopy confirm well‐defined macrostructures containing mesopores. Among the various porous structures, hierarchically macro/mesoporous metal oxide is employed as an anode material in lithium‐ion batteries. The present approach could provide a broad and easily accessible platform for the manufacturing of mesoporous inorganic materials with different macrostructures.     

Ultrasmall Particle Sizes of Walnut‐Like Mesoporous Silica Nanospheres with Unique Large Pores and Tunable Acidity for Hydrogenating Reaction

The large particle sizes, inert frameworks, and small pore sizes of mesoporous silica nanoparticles greatly restrict their application in the acidic catalysis. The research reports a simple and versatile approach to synthesize walnut‐like mesoporous silica nanospheres (WMSNs) with large tunable pores and small particle sizes by assembling with Beta seeds. The as‐synthesized Beta‐WMSNs composite materials possess ultrasmall particulate sizes (70 nm), large radial mesopores (≈30 nm), and excellent acidities (221.6 mmol g^?1). Ni₂P active phase is supported on the surface of Beta‐WMSNs composite materials, and it is found that the obtained composite spherical materials can reduce the Ni₂P particle sizes from 8.4 to 4.8 nm with the increasing amount of Beta seeds, which can provide high accessibilities of reactants to the active sites. Furthermore, the unique large pores and ultrasmall particle sizes of Beta‐WMSNs samples facilitate the reduction of the diffusion resistance of reactants due to the short transporting length, thus the corresponding Ni₂P/Beta‐WMSNs composite catalysts show the excellent hydrogenating activity compared to the pure Ni₂P/WMSNs catalyst.     

A Magnetic‐Field Guided Interface Coassembly Approach to Magnetic Mesoporous Silica Nanochains for Osteoclast‐Targeted Inhibition and Heterogeneous Nanocatalysis

1D core–shell magnetic materials with mesopores in shell are highly desired for biocatalysis, magnetic bioseparation, and bioenrichment and biosensing because of their unique microstructure and morphology. In this study, 1D magnetic mesoporous silica nanochains (Fe₃O₄@nSiO₂@mSiO₂ nanochain, Magn‐MSNCs named as FDUcs‐17C) are facilely synthesized via a novel magnetic‐field‐guided interface coassembly approach in two steps. Fe₃O₄ particles are coated with nonporous silica in a magnetic field to form 1D Fe₃O₄@nSiO₂ nanochains. A further interface coassembly of cetyltrimethylammonium bromide and silica source in water/n‐hexane biliquid system leads to 1D Magn‐MSNCs with core–shell–shell structure, uniform diameter (≈310 nm), large and perpendicular mesopores (7.3 nm), high surface area (317 m² g^?1), and high magnetization (34.9 emu g^?1). Under a rotating magnetic field, the nanochains with loaded zoledronate (a medication for treating bone diseases) in the mesopores, show an interesting suppression effect of osteoclasts differentiation, due to their 1D nanostructure that provides a shearing force in dynamic magnetic field to induce sufficient and effective reactions in cells. Moreover, by loading Au nanoparticles in the mesopores, the 1D Fe₃O₄@nSiO₂@mSiO₂‐Au nanochains can service as a catalytically active magnetic nanostirrer for hydrogenation of 4‐nitrophenol with high catalytic performance and good magnetic recyclability.     

Self‐Confined Growth of Ultrathin 2D Nonlayered Wide‐Bandgap Semiconductor CuBr Flakes

2D planar structures of nonlayered wide‐bandgap semiconductors enable distinguished electronic properties, desirable short wavelength emission, and facile construction of 2D heterojunction without lattice match. However, the growth of ultrathin 2D nonlayered materials is limited by their strong covalent bonded nature. Herein, the synthesis of ultrathin 2D nonlayered CuBr nanosheets with a thickness of about 0.91 nm and an edge size of 45 µm via a controllable self‐confined chemical vapor deposition method is described. The enhanced spin‐triplet exciton (Z_f, 2.98 eV) luminescence and polarization‐enhanced second‐harmonic generation based on the 2D CuBr flakes demonstrate the potential of short‐wavelength luminescent applications. Solar‐blind and self‐driven ultraviolet (UV) photodetectors based on the as‐synthesized 2D CuBr flakes exhibit a high photoresponsivity of 3.17 A W^?1, an external quantum efficiency of 1126%, and a detectivity (D*) of 1.4 × 10¹¹ Jones, accompanied by a fast rise time of 32 ms and a decay time of 48 ms. The unique nonlayered structure and novel optical properties of the 2D CuBr flakes, together with their controllable growth, make them a highly promising candidate for future applications in short‐wavelength light‐emitting devices, nonlinear optical devices, and UV photodetectors.     

Mesoporous Silica Thin Membranes with Large Vertical Mesochannels for Nanosize‐Based Separation

Membrane separation technologies are of great interest in industrial processes such as water purification, gas separation, and materials synthesis. However, commercial filtration membranes have broad pore size distributions, leading to poor size cutoff properties. In this work, mesoporous silica thin membranes with uniform and large vertical mesochannels are synthesized via a simple biphase stratification growth method, which possess an intact structure over centimeter size, ultrathin thickness (≤50 nm), high surface areas (up to 1420 m² g^?1), and tunable pore sizes from ≈2.8 to 11.8 nm by adjusting the micelle parameters. The nanofilter devices based on the free‐standing mesoporous silica thin membranes show excellent performances in separating differently sized gold nanoparticles (>91.8%) and proteins (>93.1%) due to the uniform pore channels. This work paves a promising way to develop new membranes with well‐defined pore diameters for highly efficient nanosize‐based separation at the macroscale.     

Agglomeration Dynamics of 1D Materials: Gas‐Phase Collision Rates of Nanotubes and Nanorods

The agglomeration and self‐assembly of gas‐phase 1D materials in anthropogenic and natural systems dictate their resulting nanoscale morphology, multiscale hierarchy, and ultimate macroscale properties. Brownian motion induces collisions, upon which 1D materials often restructure to form bundles and can lead to aerogels. Herein, the first results of collision rates for 1D nanomaterials undergoing thermal transport are presented. The Langevin dynamic simulations of nanotube rotation and translation demonstrate that the collision kernels for rigid nanotubes or nanorods are ≈10 times greater than spherical systems. Resulting reduced order equations allow straightforward calculation of the physical parameters to determine the collision kernel for straight and curved 1D materials from 10² to 10⁶ nm length. The collision kernels of curved 1D structures increase ≈1.3 times for long (>10² nm), and ≈5 times for short (≈10² nm) relative to rigid materials. Applications of collision frequencies allow the first kinetic analysis of aerogel self‐assembly from gas‐phase carbon nanotubes (CNTs). The timescales for CNT collision and bundle formation (0.3–42 s) agree with empirical residence times in CNT reactors (3–15 s). These results provide insights into the CNT length, number, and timescales required for aerogel formation, which bolsters our understanding of mass‐produced 1D aerogel materials.