Construction of Hierarchical Films via Layer-by-Layer Assembly of Exfoliated Unilamellar Zeolite Nanosheets.

Zeolites have been widely applied as versatile catalysts, sorbents, and ion exchangers with unique porous structures showing molecular sieving capability. In these years, it is reported that some layered zeolites can be delaminated into molecularly thin 2-dimensional (2D) nanosheets characterized by inherent porous structures and highly exposed active sites. In the present study, two types of zeolite nanosheets with distinct porous structures with MWW topology (denoted mww) and ferrierite-related structure (denoted bifer) are deposited on a substrate through the solution process via electrostatic self-assembly. Alternate deposition of zeolite nanosheets with polycation under optimized conditions allows the layer-by-layer growth of their multilayer films with a stacking distance of 2-3 nm. Furthermore, various hierarchical structures defined at the unit-cell dimensions can be constructed simply by conducting the deposition of mww and bifer nanosheets in a designed sequence. Adsorption of a dye, Rhodamine B, in these films, is examined to show that adsorption is dependent on constituent zeolite nanosheets and their assembled nanostructures. This work has provided fundamental advancements in the fabrication of artificial zeolite-related hierarchical structures, which may be extended to other zeolite nanosheets, broadening their functionalities, applications, and benefits.

Crystal Structure Regulation of CoSe2 Induced by Fe Dopant for Promoted Surface Reconstitution toward Energetic Oxygen Evolution Reaction.

Most nonoxide catalysts based on transition metal elements will inevitably change their primitive phases under anodic oxidation conditions in alkaline media. Establishing a relationship between the bulk phase and surface evolution is imperative to reveal the intrinsic catalytic active sites. In this work, it is demonstrated that the introduction of Fe facilitates the phase transition of orthorhombic CoSe2 into its cubic counterpart and then accelerates the Co-Fe hydroxide layer generation on the surface during electrocatalytic oxygen evolution reaction (OER). As a result, the Fe-doped cubic CoSe2 catalyst exhibits a significantly enhanced activity with a considerable overpotential decrease of 79.9 and 66.9 mV to deliver 10 mA·cm-2 accompanied by a Tafel slope of 48.0 mV·dec-1 toward OER when compared to orthorhombic CoSe2 and Fe-doped orthorhombic CoSe2, respectively. Density functional theory (DFT) calculations reveal that the introduction of Fe on the surface hydroxide layers will tune electron density around Co atoms and raise the d-band center. These findings will provide deep insights into the surface reconstitution of the OER electrocatalysts based on transition metal elements.

Mild selective photochemical oxidation of an organic sulfide using OxP-polyimide porous polymers as singlet oxygen generators.

A series of porous organic polymers based on a singlet oxygen generating oxoporphyinogen ('OxP') has been successfully prepared from a pseudotetrahedral OxP-tetraamine precursor (OxP(4-NH2Bn)4) by its reaction with tetracarboxylic acid dianhydrides under suitable conditions. Of the compounds studied, those containing naphthalene (OxP-N) and perylene (OxP-P) spacers, respectively, have large surface areas (~530 m2 g-1). On the other hand, the derivative with a simple benzene spacer (OxP-B) exhibits the best 1O2 generating capability. Although the starting OxP-tetraamine precursor is a poor 1O2 generator, its incorporation into OxP POPs leads to a significant enhancement of 1O2 productivity, which is largely due to the transformation of NH2 groups to electron-withdrawing diimides. Overall 1O2 production efficacy of OxP-POPs under irradiation by visible light is significantly improved over the common reference material PCN-222. All the materials OxP-B, OxP-N and OxP-P promote oxidation of thioanisole involving conversion of ambient triplet state oxygen to singlet oxygen under visible light irradiation and its reaction with the sulfide. Although the reaction rate of the oxidation promoted by OxP POPs is generally lower than for conventional materials (such as PCN-222) or previously studied OxP derivatives, undesired overoxidation of the substrate to methyl phenyl sulfone is suppressed. For organic sulfides, selectivity of oxidation is especially important for detoxification of mustard gas (bis(2-chloroethyl)sulfide) or similarly toxic compounds since controlled oxidation leads to the low toxicity bis(2-chloroethyl)sulfoxide while overoxidation leads to intoxification (since bis(2-chloroethyl)sulfone presents greater toxicity to humans than the sulfide substrate). Therefore, OxP POPs capable of promoting selective oxidation of sulfides to sulfoxides have excellent potential to be used as mild and selective detoxification agents.

Oxoporphyrinogen (OxP) is a unique chromophore compound in that it is intrinsically de-aggregated allowing large quantum yields of singlet oxygen generation. Due to its structure, OxP is also an ideal building block for porous systems. In this work, we describe the first incorporation of OxP in highly stable microporous polymers strongly enhanced singlet oxygen generation for selective oxidation of organic sulfides to sulfoxides (as a model reaction) under heterogeneous conditions. The novelty of this work lies in the high stability and easy recovery of the materials, the synergetic enhancement of singlet oxygen generation in the polymers over the starting OxP, and the excellent selectivity for the oxidation reaction.

Porous and Partially Dehydrogenated Fe2+ -Containing Iron Oxyhydroxide Nanosheets for Efficient Electrochemical Nitrogen Reduction Reaction (ENRR).

The design and development of efficient catalysts for electrochemical nitrogen reduction reaction (ENRR) under ambient conditions are critical for the alternative ammonia (NH3 ) synthesis from N2 and H2 O, wherein iron-based electrocatalysts exhibit outstanding NH3 formation rate and Faradaic efficiency (FE). Here, the synthesis of porous and positively charged iron oxyhydroxide nanosheets by using layered ferrous hydroxide as a starting precursor, which undergoes topochemical oxidation, partial dehydrogenated reaction, and final delamination, is reported. As the electrocatalyst of ENRR, the obtained nanosheets with a monolayer thickness and 10-nm mesopores display exceptional NH3 yield rate (28.5 µg h-1 mgcat. -1 ) and FE (13.2%) at a potential of -0.4 V versus RHE in a phosphate buffered saline (PBS) electrolyte. The values are much higher than those of the undelaminated bulk iron oxyhydroxide. The larger specific surface area and positive charge of the nanosheets are beneficial for providing more exposed reactive sites as well as retarding hydrogen evolution reaction. This study highlights the rational control on the electronic structure and morphology of porous iron oxyhydroxide nanosheets, expanding the scope of developing non-precious iron-based highly efficient ENRR electrocatalysts.

Reversible Ammonium Ion Intercalation/de-intercalation with Crystal Water Promotion Effect in Layered VOPO4 ⋠2 H2 O.

The non-metal NH4 + carrier has attracted tremendous interests for aqueous energy storage owing to its light molar mass and fast diffusion in aqueous electrolytes. Previous study inferred that NH4 + ion storage in layered VOPO4 ⋅2 H2 O is impossible due to the removal of NH4 + from NH4 VOPO4 leads to a phase change inevitably. Herein, we update this cognition and demonstrated highly reversible intercalation/de-intercalation behavior of NH4 + in layered VOPO4 ⋅2 H2 O host. Satisfactory specific capacity of 154.6 mAh g-1 at 0.1 A g-1 and very stable discharge potential plateau at 0.4 V based on reference electrode was achieved in VOPO4 ⋅2 H2 O. A rocking-chair ammonium-ion full cell with the VOPO4 ⋅2 H2 O//2.0 M NH4 OTf//PTCDI configuration exhibited a specific capacity of 55 mAh g-1 , an average operating voltage of about 1.0 V and excellent long-term cycling stability over 500 cycles with a coulombic efficiency of ≈99 %. Theoretical DFT calculations suggest a unique crystal water substitution process by ammonium ion during the intercalation process. Our results provide new insight into the intercalation/de-intercalation of NH4 + ions in layered hydrated phosphates through crystal water enhancement effect.

Aprotic Lithium-Carbon Dioxide Batteries: Reaction Mechanism and Catalyst Design.

In recent years, the combustion of fossil fuels leads to the release of a large amount of CO2 gas, which induces the greenhouse effect and the energy crisis. To solve these problems, researchers have turned their focus to a novel Li-CO2 battery (LCB). LCB has received much attention because of its high theoretical energy density and reversible CO2 reduction/evolution process. So far, the emerging LCB still faces many challenges derived from the slow reaction kinetics of discharge products. In this review, the latest status and progress of LCB, especially the influence of the structure design of cathode catalysts on the battery performance, are systematically elaborated. This review summarizes in detail the existing issues and possible solutions of LCB, which is of high research value for further promoting the development of Li-Air battery.

Exfoliated Ferrierite-Related Unilamellar Nanosheets in Solution and Their Use for Preparation of Mixed Zeolite Hierarchical Structures.

Direct exfoliation of layered zeolites into solutions of monolayers has remained unresolved since the 1990s. Recently, zeolite MCM-56 with the MWW topology (layers denoted mww) has been exfoliated directly in high yield by soft-chemical treatment with tetrabutylammonium hydroxide (TBAOH). This has enabled preparation of zeolite-based hierarchical materials and intimate composites with other active species that are unimaginable via the conventional solid-state routes. The extension to other frameworks, which provides broader benefits, diversified activity, and functionality, is not routine and requires finding suitable synthesis formulations, viz. compositions and conditions, of the layered zeolites themselves. This article reports exfoliation and characterization of layers with ferrierite-related structure, denoted bifer, having rectangular lattice constants like those of the FER and CDO zeolites, and thickness of approximately 2 nm, which is twice that of the so-called fer layer. Several techniques were combined to prove the exfoliation, supported by simulations: AFM; in-plane, in situ, and powder X-ray diffraction; TEM; and SAED. The results confirmed (i) the structure and crystallinity of the layers without unequivocal differentiation between the FER and CDO topologies and (ii) uniform thickness in solution (monodispersity), ruling out significant multilayered particles and other impurities. The bifer layers are zeolitic with Brønsted acid sites, demonstrated catalytic activity in the alkylation of mesitylene with benzyl alcohol, and intralayer pores visible in TEM. The practical benefits are demonstrated by the preparation of unprecedented intimately mixed zeolite composites with the mww, with activity greater than the sum of the components despite high content of inert silica as pillars.

Two-Dimensional Molecular Sheets of Transition Metal Oxides toward Wearable Energy Storage.

Flexible and wearable electronics have recently sparked intense interest in both academia and industry because they can greatly revolutionize human lives by impacting every aspect of our daily routine. Therefore, developing compatible energy storage devices has become one of the most important research frontiers in this field. Particularly, the development of flexible electrodes is of great significance when considering their essential role in the performance of these devices. Although there is no doubt that transition metal oxide nanomaterials are suitable for providing electrochemical energy storage, individual oxides generally cannot be developed into freestanding electrodes because of their intrinsically low mechanical strength.Two-dimensional sheets with genuine unilamellar thickness are perfect units for the assembly of freestanding and mechanically flexible devices, as they have the advantages of low thickness and good flexibility. Therefore, the development of metal oxide materials into a two-dimensional sheet morphology analogous to graphene is expected to solve the above-mentioned problems. In this Account, we summarize the recent progress on two-dimensional molecular sheets of transition metal oxides for wearable energy storage applications. We start with our understanding of the principle of producing two-dimensional metal oxides from their bulk-layered counterparts. The unique layered structure of the precursors inspired the exploration of their interlayer chemistry, which helps us to understand the processes of swelling and delamination. Rational methods for tuning the chemical composition, size/thickness, and surface chemistry of the obtained nanosheets and how physicochemical properties of the nanosheets can be modulated are then briefly introduced. Subsequently, the orientational alignment of the anisotropic sheets and the origins of their liquid-crystalline characteristics are discussed, which are of vital importance for their subsequent macroscopic assembly. Finally, macroscopic electrodes with geometric diversity ranging from one-dimensional macroscopic fibers to two-dimensional films/papers and three-dimensional monolithic foams are summarized. The intrinsically low mechanical stiffness of metal oxide sheets can be effectively overcome by wisely designing the assembly mode and sheet interfaces to obtain decent mechanical properties integrated with superior electrochemical performance, thereby providing critical advantages for the fabrication of wearable energy storage devices.We expect that this Account will stimulate further efforts toward fundamental research on interface engineering in metal oxide sheet assembly and facilitate wide applications of their designed assemblies in future new-concept energy conversion devices and beyond. In the foreseeable future, we believe that there will be a big explosion in the application of transition metal oxide sheets in flexible electronics.

Metal-Organic Framework Hexagonal Nanoplates: Bottom-up Synthesis, Topotactic Transformation, and Efficient Oxygen Evolution Reaction.

Rational design and bottom-up synthesis based on the structural topology is a promising way to obtain two-dimensional metal-organic frameworks (2D MOFs) in well-defined geometric morphology. Herein, a topology-guided bottom-up synthesis of a novel hexagonal 2D MOF nanoplate is realized. The hexagonal channels constructed via the distorted (3,4)-connected Ni2(BDC)2(DABCO) (BDC = 1,4-benzenedicarboxylic acid, DABCO = 1,4-diazabicyclo[2.2.2]octane) framework serve as the template for the specifically designed morphology. Under the inhibition and modulation of pyridine through a substitution-suppression process, the morphology can be modified from hexagonal nanorods to nanodisks and to nanoplates with controllable thickness tuned by the dosage of pyridine. Subsequent pyrolysis treatment converts the nanoplates into a N-doped Ni@carbon electrocatalyst, which exhibits a small overpotential as low as 307 mV at a current density of 10 mA cm-2 in the oxygen evolution reaction.

Interface Modulation of Two-Dimensional Superlattices for Efficient Overall Water Splitting.

Molecular-scale modulation of interfaces between different unilamellar nanosheets in superlattices is promising for efficient catalytic activities. Here, three kinds of superlattices from alternate restacking of any two of the three unilamellar nanosheets of MoS2, NiFe-layered double hydroxide (NiFe-LDH), and graphene are systematically investigated for electrocatalytic water splitting. The MoS2/NiFe-LDH superlattice exhibits a low overpotential of 210 and 110 mV at 10 mA cm-2 for oxygen evolution reaction (OER) and alkaline hydrogen evolution reaction (HER), respectively, superior than MoS2/graphene and NiFe-LDH/graphene superlattices. High activity and stability toward the overall water splitting are also demonstrated on the MoS2/NiFe-LDH superlattice bifunctional electrocatalyst, outperforming the commercial Pt/C-RuO2 couple. This outstanding performance can be attributed to optimal adsorption energies of both HER and OER intermediates on the MoS2/NiFe-LDH superlattice, which originates from a strong electronic coupling effect at the heterointerfaces. These results herald the interface modulation of superlattices providing a promising approach for designing advanced electrocatalysts.

2D Free-Standing Nitrogen-Doped Ni-Ni3 S2 @Carbon Nanoplates Derived from Metal-Organic Frameworks for Enhanced Oxygen Evolution Reaction.

2D metal-organic frameworks (2D MOFs) are promising templates for the fabrication of carbon supported 2D metal/metal sulfide nanocomposites. Herein, controllable synthesis of a newly developed 2D Ni-based MOF nanoplates in well-defined rectangle morphology is first realized via a pyridine-assisted bottom-up solvothermal treatment of NiSO4 and 4,4'-bipyridine. The thickness of the MOF nanoplates can be controlled to below 20 nm, while the lateral size can be tuned in a wide range with different amounts of pyridine. Subsequent pyrolysis treatment converts the MOF nanoplates into 2D free-standing nitrogen-doped Ni-Ni3 S2 @carbon nanoplates. The obtained Ni-Ni3 S2 nanoparticles encapsulated in the N-doped carbon matrix exhibits high electrocatalytic activity in oxygen evolution reaction. A low overpotential of 284.7 mV at a current density of 10 mA cm-2 is achieved in alkaline solution, which is among the best reported performance of substrate-free nickel sulfides based nanomaterials.

Size-Independent Fast Ion Intercalation in Two-Dimensional Titania Nanosheets for Alkali-Metal-Ion Batteries.

Compared to lithium ions, the fast redox intercalation of large-radius sodium or potassium ions into a solid lattice in non-aqueous electrolytes is an elusive goal. Herein, by regulating the interlayer structure of stacked titania sheets through weakened layer-to-layer interactions and a robustly pillared gallery space, the two-dimensional channel between neighboring sheets was completely open to guest intercalation, allowing fast intercalation that was practically irrespective of the carrier-ion sizes. Regardless of employing regular Li or large-radius Na and K ions, the material manifested zero strain-like behavior with no significant change in both host structure and interlayer space, enabling comparable capacities for all tested ions along with excellent rate behaviors and extraordinarily long lifetimes, even with 80-µm-thick electrodes. The result highlights the importance of interlayer structural features for unlocking the electrochemical activity of a layered material.

Serpentine Ni3 Ge2 O5 (OH)4 Nanosheets with Tailored Layers and Size for Efficient Oxygen Evolution Reactions.

Layered serpentine Ni3 Ge2 O5 (OH)4 is compositionally active and structurally favorable for adsorption and diffusion of reactants in oxygen evolution reactions (OER). However, one of the major problems for these materials is limited active sites and low efficiency for OER. In this regard, a new catalyst consisting of layered serpentine Ni3 Ge2 O5 (OH)4 nanosheets is introduced via a controlled one-step synthetic process where the morphology, size, and layers are well tailored. The theoretical calculations indicate that decreased layers and increased exposure of (100) facets in serpentine Ni3 Ge2 O5 (OH)4 lead to much lower Gibbs free energy in adsorption of reactive intermediates. Experimentally, it is found that the reduction in number of layers with minimized particle size exhibits plenty of highly surface-active sites of (100) facets and demonstrates a much enhanced performance in OER than the corresponding multilayered nanosheets. Such a strategy of tailoring active sites of serpentine Ni3 Ge2 O5 (OH)4 nanosheets offers an effective method to design highly efficient electrocatalysts.

Flexible Lithium-Ion Fiber Battery by the Regular Stacking of Two-Dimensional Titanium Oxide Nanosheets Hybridized with Reduced Graphene Oxide.

Increasing interest has recently been devoted to developing small, rapid, and portable electronic devices; thus, it is becoming critically important to provide matching light and flexible energy-storage systems to power them. To this end, compared with the inevitable drawbacks of being bulky, heavy, and rigid for traditional planar sandwiched structures, linear fiber-shaped lithium-ion batteries (LIB) have become increasingly important owing to their combined superiorities of miniaturization, adaptability, and weavability, the progress of which being heavily dependent on the development of new fiber-shaped electrodes. Here, we report a novel fiber battery electrode based on the most widely used LIB material, titanium oxide, which is processed into two-dimensional nanosheets and assembled into a macroscopic fiber by a scalable wet-spinning process. The titania sheets are regularly stacked and conformally hybridized in situ with reduced graphene oxide (rGO), thereby serving as efficient current collectors, which endows the novel fiber electrode with excellent integrated mechanical properties combined with superior battery performances in terms of linear densities, rate capabilities, and cyclic behaviors. The present study clearly demonstrates a new material-design paradigm toward novel fiber electrodes by assembling metal oxide nanosheets into an ordered macroscopic structure, which would represent the most-promising solution to advanced flexible energy-storage systems.

Stability and Nature of Chemically Exfoliated MoS2 in Aqueous Suspensions.

We reveal that chemically exfoliated MoS2 nanosheets undergo lateral fracture and aggregation upon prolonged storage of the dispersion in ambient air, which was found to be associated with the reoxidation of the nanosheets. Such nanosheet degradation could be effectively prevented by storing the sample in an inert atmosphere to suppress the reoxidation process.

Two-dimensional oxide and hydroxide nanosheets: controllable high-quality exfoliation, molecular assembly, and exploration of functionality.

CONSPECTUS: Two-dimensional (2D) materials, represented by graphene, have attracted tremendous interest due to their ultimate structural anisotropy and fascinating resultant properties. The search for 2D material alternatives to graphene, molecularly thin with diverse composition, structure, and functionality, has become a hot research topic. A wide variety of layered metal oxides and hydroxides have been exfoliated into the form of individual host layers, that is, 2D nanosheets. This Account presents an overview of 2D oxide and hydroxide nanosheets on the following subtopics: (1) controllable preparation of high-quality nanosheets and (2) molecular assembly and the exploration of functionality of the nanosheets. High-quality exfoliation is generally achieved via a multistep soft chemical process, comprised of ion-exchange, osmotic swelling, and exfoliation. A high degree of hydration-induced swelling, typically triggered by intercalation of organo-ammonium ions, is a critical stage leading to the high-yield production of molecularly thin nanosheets. Recent studies reveal that massive swelling, an astounding ∼100 times the original size, can be induced by a range of amine solutions. The degree of swelling is controlled by the balance of osmotic pressure between the inner gallery and the outer electrolyte solution, which is strongly influenced by amine molarity. Conversely, the stability of the resultant swollen structure is dependent on the chemical nature of the amine/ammonium ions. Particular species of lower polarity and bulky size, for example, quaternary ammonium ions, are beneficial in promoting exfoliation. Rational design and tuning of the lateral dimension, chemical composition, and structure of nanosheets are vital in exploring diverse functionalities. The lateral dimension of the nanosheets can be tuned by controlling the crystal size of the parent layered compounds, as well as the kinetics of the exfoliating reaction, for example, the type of amine/ammonium ions, their concentration, and the mode of exfoliation (manual versus mechanical shaking, etc.). Employing optimum conditions enables the production of high-quality nanosheets with a lateral size as large as several tens of micrometers. A couple of examples tailoring the nanosheets have been demonstrated with a highlight on a novel class of 2D perovskite-type oxide nanosheets with a finely tuned composition and a progressively increasing thickness at a step of 0.4-0.5 nm (corresponding to the height of the MO6 octahedron). The charge-bearing nanosheets can be organized through solution-based molecular assembly techniques (e.g., electrostatic layer-by-layer deposition, Langmuir-Blodgett method) to produce highly organized nanofilms, superlattices, etc., the exploration of which holds great potential for the development of various electronic and optical applications, among others.

Organic-Base-Driven Intercalation and Delamination for the Production of Functionalized Titanium Carbide Nanosheets with Superior Photothermal Therapeutic Performance.

The delamination of titanium carbide sheets, an intriguing class of two-dimensional materials, has been critically dependent on the extraction of interlayer Al in acidic media, such as concentrated hydrofluoric acid (HF) or a mixture of hydrochloric acid (HCl) and a fluoride salt. Herein, we report an organic-base-driven intercalation and delamination of titanium carbide that takes advantage of the amphoteric nature of interlayer Al. The resulting aluminum-oxoanion-functionalized titanium carbide sheets manifested unusually strong optical absorption in the near-infrared (NIR) region with a mass extinction coefficient as high as 29.1 L g-1 cm-1 at 808 nm. Thus, the performance of this material is comparable or even superior to that of state-of-the-art photoabsorption materials, including gold-based nanostructures, carbon-based materials, and transition-metal dichalcogenides. Preliminary studies show that the titanium carbide sheets serve as efficient photothermal agents against tumor cells.

Tuning the surface charge of 2D oxide nanosheets and the bulk-scale production of superlatticelike composites.

The surface charge of various anionic unilamellar nanosheets, such as graphene oxide (GO), Ti0.87O2(0.52-), and Ca2Nb3O10(-) nanosheets, has been successfully modified to be positive by interaction with polycations while maintaining a monodispersed state. A dilute anionic nanosheet suspension was slowly added dropwise into an aqueous solution of high molecular weight polycations, which attach on the surface of the anionic nanosheets via electrostatic interaction. Surface modification and transformation to positively charged nanosheets were confirmed by various characterizations including atomic force microscopy and zeta potential measurements. Because the sizes of the polycations used are much larger than the nanosheets, the polymer chains may run off the nanosheet edges and fold to the fronts of the nanosheets, which could be a reason for the continued dispersion of the modified nanosheets in the suspension. By slowly adding a suspension of polycation-modified nanosheets and pristine anionic nanosheet dropwise into water under suitable conditions, a superlatticelike heteroassembly can be readily produced. Characterizations including transmission electron microscopy and X-ray diffraction measurements provide evidence for the formation of the alternately stacked structures. This approach enables the combination of various pairs of anionic nanosheets with different functionalities, providing a new opportunity for the creation of unique bulk-scale functional materials and their applications.

Macroscopic and Strong Ribbons of Functionality-Rich Metal Oxides from Highly Ordered Assembly of Unilamellar Sheets.

The strong interest in macroscopic graphene and/or carbon nanotube (CNT) fiber has highlighted that anisotropic nanostructured materials are ideal components for fabricating fiber assemblies. Prospectively, employing two-dimensional (2D) crystals or nanosheets of functionality-rich transition metal oxides would notably enrich the general knowledge for desirable fiber constructions and more importantly would greatly broaden the scope of functionalities. However, the fibers obtained up to now have been limited to carbon-related materials, while those made of 2D crystals of metal oxides have not been achieved, probably due to the intrinsically low mechanical stiffness of a molecular sheet of metal oxides, which is only few hundredths of that for graphene. Here, using 2D titania sheets as an illustrating example, we present the first successful fabrication of macroscopic fiber of metal oxides composed of highly aligned stacking sheets with enhanced sheet-to-sheet binding interactions. Regardless of the intrinsically weak Ti-O bond in molecular titania sheets, the optimal fiber manifested mechanical performance comparable to that documented for graphene or CNTs. This work provided important hints for devising optimized architecture in macroscopic assemblies, and the rich functionalities of titania promises fibers with limitless promise for a wealth of innovative applications.

Dendritic silica nanoparticles synthesized by a block copolymer-directed seed-regrowth approach.

A facile seed regrowth method is presented for the preparation of a new type of colloidal dendritic silica nanoparticles (DSNPs) with unique Konpeito-like morphology and high surface area (∼400 m(2) g(-1)). Growth of silica nanoprotrusions on the surfaces of colloidal silica nanoparticles proceeds by hydrolysis and polycondensation of tetraethoxysilane (TEOS) in the presence of a PEO-PPO-PEO-type block copolymer (Pluronic F127) under controlled pH conditions. The polymers adsorbed on the seed surface play a crucial role in the formation of DSNPs. DSNPs with controllable size (28-85 nm) and narrow size distributions can be obtained by using monodisperse silica nanoparticles with various sizes as seeds. The surface morphology of DSNPs is tunable by changing the concentration of TEOS. Additionally, novel dendritic silica nanochains are prepared using one-dimensionally assembled silica nanoparticles as the seeds.