Acid Exfoliation of Imine‐linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films

Covalent organic frameworks (COFs) are highly modular porous crystalline polymers that are of interest for applications such as charge‐storage devices, nanofiltration membranes, and optoelectronic devices. COFs are typically synthesized as microcrystalline powders, which limits their performance in these applications, and their limited solubility precludes large‐scale processing into more useful morphologies and devices. We report a general, scalable method to exfoliate two‐dimensional imine‐linked COF powders by temporarily protonating their linkages. The resulting suspensions were cast into continuous crystalline COF films up to 10 cm in diameter, with thicknesses ranging from 50 nm to 20 μm depending on the suspension composition, concentration, and casting protocol. Furthermore, we demonstrate that the film fabrication process proceeds through a partial depolymerization/repolymerization mechanism, providing mechanically robust films that can be easily separated from their substrates.     

A Kinetic Model for Exfoliation Kinetics of Layered Materials

Exfoliation of two‐dimensional materials is key to obtaining high‐performance properties. We present a simple kinetic model for exfoliation that is readily solved analytically. Random and irreversible sheet separation is postulated in the presence of highly effective stabilizers. This model appears to quantitatively fit graphene exfoliation data, and it illuminates mechanistic aspects of exfoliation. Thicker sheets exfoliate much faster than trilayer and bilayer sheets. Exfoliation follows highly activated diffusion‐controlled intercalation of stabilizer into inter‐sheet galleries. Application to the most concentrated graphene exfoliation data available supports these assumptions and provides insight for practical treatment regimens.     

pH-Dependent self-assembly of water-soluble sulfonate-tetraphenylethylene with aggregation-induced emission

The fabrication of well-defined nanostructures with luminescent properties in the solid or aggregated state is of intense interest due to their applications in nano- and biotechnology. We report the synthesis of water-soluble tetraphenylethylene bearing four sulfonate groups as a sodium salt (Su-TPE), and investigations concerning its AIE characteristics by the addition of organic solvent into the aqueous solution, which is the reverse procedure to conventional AIE-active TPE derivatives. The resultant compound is weakly emissive in pure water, however, emits strongly upon addition of THF solvent (with THF fraction > 60%). The emission properties and the morphologies of the aggregates were greatly dependent upon the solution pH. Su-TPE self-assembled into variety of structures in water/THF mixture with pH control, for the first time. Well-defined uniform nanorods with a width of about 200 nm and a length of up to 10 μm were obtained at solution pH of 1. The Su-TPE showed very good mechanochromic properties were observed during the process of grounding and fuming.     

Fabrication of Boron Nitride Nanosheets by Exfoliation

Nanomaterials with layered structures, with their intriguing properties, are of great research interest nowadays. As one of the primary two‐dimensional nanomaterials, the hexagonal boron nitride nanosheet (BNNS, also called white graphene), which is an analogue of graphene, possesses various attractive properties, such as high intrinsic thermal conductivity, excellent chemical and thermal stability, and electrical insulation properties. After being discovered, it has been one of the most intensively studied two‐dimensional non‐carbon nanomaterials and has been applied in a wide range of applications. To support the exploration of applications of BNNSs, exfoliation, as one of the most promising approaches to realize large‐scale production of BNNSs, has been intensively investigated. In this review, methods to yield BNNSs by exfoliation will be summarized and compared with other potential fabrication methods of BNNSs. In addition, the future prospects of the exfoliation of h‐BN will also be discussed.     

Controlled Gas Exfoliation of Boron Nitride into Few‐Layered Nanosheets

The controlled exfoliation of hexagonal boron nitride (h‐BN) into single‐ or few‐layered nanosheets remains a grand challenge and becomes the bottleneck to essential studies and applications of h‐BN. Here, we present an efficient strategy for the scalable synthesis of few‐layered h‐BN nanosheets (BNNS) using a novel gas exfoliation of bulk h‐BN in liquid N₂ (L‐N₂). The essence of this strategy lies in the combination of a high temperature triggered expansion of bulk h‐BN and the cryogenic L ‐N₂ gasification to exfoliate the h‐BN. The produced BNNS after ten cycles (BNNS‐10) consisted primarily of fewer than five atomic layers with a high mass yield of 16–20 %. N₂ sorption and desorption isotherms show that the BNNS‐10 exhibited a much higher specific surface area of 278 m² g^?1 than that of bulk BN (10 m² g^?1). Through the investigation of the exfoliated intermediates combined with a theoretical calculation, we found that the huge temperature variation initiates the expansion and curling of the bulk h‐BN. Subseqently, the L ‐N₂ penetrates into the interlayers of h‐BN along the curling edge, followed by an immediate drastic gasification of L ‐N₂, further peeling off h‐BN. This novel gas exfoliation of high surface area BNNS not only opens up potential opportunities for wide applications, but also can be extended to produce other layered materials in high yields.     

Single‐Step Exfoliation and Covalent Functionalization of MoS2 Nanosheets by an Organosulfur Reaction

A simple approach to exfoliate and functionalize MoS₂ in a single‐step is described, which combines the dispersion of MoS₂ in polybutadiene solution and ultrasonication processes. The great advantage of this process is that a colloidal stability of MoS₂ in nonpolar solvent is achieved by chemically bonding polybutadiene on the perimeter edge sites of MoS₂ sheets. In addition, elastomeric nanocomposite has been prepared with singular mechanical properties using functionalized MoS₂ as nanofiller in a polybutadiene matrix with a subsequent vulcanization reaction.     

Enriching and Quantifying Porous Single Layer 2D Polymers by Exfoliation of Chemically Modified van der Waals Crystals

2D polymer sheets with six positively charged pyrylium groups at each pore edge in a stacked single crystal can be transformed into a 2D polymer with six pyridines per pore by exposure to gaseous ammonia. This reaction furnishes still a crystalline material with tunable protonation degree at regular nano‐sized pores promising as separation membrane. The exfoliation is compared for both 2D polymers with the latter being superior. Its liquid phase exfoliation yields nanosheet dispersions, which can be size‐selected using centrifugation cascades. Monolayer contents of ≈30 % are achieved with ≈130 nm sized sheets in mg quantities, corresponding to tens of trillions of monolayers. Quantification of nanosheet sizes, layer number and mass shows that this exfoliation is comparable to graphite. Thus, we expect that recent advances in exfoliation of graphite or inorganic crystals (e.g. scale‐up, printing etc.) can be directly applied to this 2D polymer as well as to covalent organic frameworks.     

Synthesis of Layered Hydroxide Zinc m‐Aminobenzoate Compounds and Their Exfoliation Reactions

Two types of layered hydroxide zinc m‐aminobenzoate compounds with structures of layered basic metal salt (LBMS) were prepared by the reaction of zinc hydroxide with m‐aminobenzoic acid solution in the temperature range of 40–120°C. The formation reactions, structures, chemical compositions, and exfoliation reactions of the layered compounds in alcohol solvents were investigated by XRD, TG‐DTA, SEM, and TEM. One layered phase with a basal spacing of 1.08 nm has a α‐Ni(OH)₂‐like structure, and its chemical formula can be written as Zn(OH)_0.67(m‐NH₂C₆H₄COO)_1.33. This phase has strip‐like particle morphology and cannot be exfoliated into its nanosheets in alcohol solvents. The other layered phase with a basal spacing of 2.66 nm has a zinc hydroxide‐nitrate‐like structure, and can be exfoliated in alcohol solvents.     

Synthesis of Novolac/Layered Silicate Nanocomposites by Reaction Exfoliation Using Acid‐Modified Montmorillonite

Novolac/layered silicate nanocomposites were synthesized by condensation polymerization of phenol and formaldehyde catalyzed by H‐montmorillonite (H‐MMT). Exfoliation of the clay was investigated by X‐ray diffraction and transmission electron microscopy (TEM). It turned out that the intra‐gallery condensation of phenol and formaldehyde played a predominant role in the exfoliation of MMT. Exfoliated clay plates with interlayer spacings of 10–30 nm were dispersed in the matrix uniformly as shown by the TEM micrograph.     

Electrochemical Exfoliation of Pillared‐Layer Metal–Organic Framework to Boost the Oxygen Evolution Reaction

Two‐dimensional (2D) materials and ultrathin nanosheets are advantageous for elevating the catalysis performance and elucidating the catalysis mechanism of heterogeneous catalysts, but they are mostly restricted to inorganic or organic materials based on covalent bonds. We report an electrochemical/chemical exfoliation strategy for synthesizing metal–organic 2D materials based on coordination bonds. A catechol functionalized ligand is used as the redox active pillar to construct a pillared‐layer framework. When the 3D pillared‐layer MOF serves as an electrocatalyst for water oxidation (pH 13), the pillar ligands can be oxidized in situ and removed. The remaining ultrathin (2 nm) nanosheets of the metal–organic layers are an efficient catalyst with overpotentials as low as 211 mV at 10 mA cm^?2 and a turnover frequency as high as 30 s^?1 at an overpotential of 300 mV.     

Fast Exfoliation and Functionalisation of Two‐Dimensional Crystalline Carbon Nitride by Framework Charging

Two‐dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one‐pot reductive method to produce solutions of single‐ and few‐layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High‐resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties.     

Controlled Exfoliation of Layered Silicate Heterostructures into Bilayers and Their Conversion into Giant Janus Platelets

Ordered heterostructures of layered materials where interlayers with different reactivities strictly alternate in stacks offer predetermined slippage planes that provide a precise route for the preparation of bilayer materials. We use this route for the synthesis of a novel type of reinforced layered silicate bilayer that is 15 % stiffer than the corresponding monolayer. Furthermore, we will demonstrate that triggering cleavage of bilayers by osmotic swelling gives access to a generic toolbox for an asymmetrical modification of the two vis‐à‐vis standing basal planes of monolayers. Only two simple steps applying arbitrary commercial polycations are needed to obtain such Janus‐type monolayers. The generic synthesis route will be applicable to many other layered compounds capable of osmotic swelling, rendering this approach interesting for a variety of materials and applications.     

Modulated Synthesis of Self-Standing Covalent Organic Framework Films

The weak interaction of covalent organic framework (COF) nanoparticles makes the preparation of self-standing COF films difficult. Herein, a modulated strategy for the facile synthesis of self-standing COF films with good crystallinity and tunable thickness is reported. As compared with the non-modulated approach, the modulated strategy changes the COF morphology from nanoparticles to nanofibers, enabling the facile preparation of self-standing COF films with improved mechanical properties. The Young's modulus of the self-standing COF film obtained via the modulated strategy could increase by 26 times. Moreover, self-standing LZU-8 film can be used as a membrane for efficient removal of 99 % mercury ions from aqueous solution. Our results open up a new approach to prepare self-standing COF thin films for practical applications.     

The Rapid Exfoliation and Subsequent Restacking of Layered Titanates Driven by an Acid–Base Reaction

Two‐dimensional (2D) (hydro)oxide materials, that is, nanosheets, enable the preparation of advanced 2D materials and devices. The general synthesis route of nanosheets involves exfoliating layered metal (hydro)oxide crystals. This exfoliation process is considered to be time‐consuming, hindering their industrial‐scale production. Based on in situ exfoliation studies on the protonated layered titanate H_1.07Ti_1.73O₄?H₂O (HTO), it is now shown that ion intercalation‐assisted exfoliation driven by chemical reaction provides a viable and fast route to isolated nanosheets. Contrary to the general expectation, data indicate that direct exfoliation of HTO occurs within seconds after mixing of the reactants, instead of proceeding via a swollen state as previously thought. These findings reveal that ion intercalation‐assisted exfoliation driven by chemical reaction is a promising exfoliation route for large‐scale synthesis.     

Soft‐Chemical Exfoliation Route to Layered Cobalt Oxide Monolayers and Its Application for Film Deposition and Nanoparticle Synthesis

A colloidal suspension of exfoliated, layered cobalt oxide nanosheets has been synthesized through the intercalation of quaternary tetramethylammonium ions into protonated lithium cobalt oxide. According to atomic force microscopy, exfoliated nanosheets of layered cobalt oxide show a plateau‐like height profile with nanometer‐level height, underscoring the formation of unilamellar 2D nanosheets. The exfoliation of layered cobalt oxide was cross‐confirmed by X‐ray diffraction, UV/Vis spectroscopy, and transmission electron microscopy. The maintenance of the hexagonal in‐plane structure of the cobalt oxide lattice after the exfoliation process was evidenced by selected‐area electron diffraction and Co K‐edge X‐ray absorption near‐edge structure analysis. The zeta‐potential measurements clearly demonstrated the negative surface charge of cobalt oxide nanosheets. Adopting the nanosheets of layered cobalt oxide as a precursor, we were able to prepare the monodisperse CoO nanocrystals with a particle size of ≈10 nm as well as the heterolayered film composed of cobalt oxide monolayer and polycation.     

Fabrication of Hexagonal Boron Nitride Nanosheets by Using a Simple Thermal Exfoliation Process

A simple and inexpensive method to exfoliate boron nitride powder to form boron nitride nanosheets (BNNSs) with few layers was achieved by using a physically thermal process. The obtained BNNSs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), IR spectroscopy, and Raman spectroscopy. The size distribution of the sheets and average sheet size is in the range of 80–380 nm and 200±62 nm, respectively, and the pure phase h‐BN products were confirmed. XPS result showed the B/N atomic ratio to be 0.99. In addition, the BNNSs can well disperse in aqueous solution to form a cloudy suspension and importantly, can remain suspended for 1 month without precipitate, which would have good potential in a wide range of applications.     

pH-Dependent Assembly of Hybrid Materials Based on Molybdates and Copper/imidazole Complexes

Three novel inorganic-organic hybrid materials, [Cu（imi）2（H2O）（MoO4）]n 1, [Cuz（imi）3（MoO4）E]n.nH2O 2 and [Cu3（imi）2（OH）2（MoO4）2]n 3 （imi = imidazole）, were synthesized and characterized by X-ray single-crystal structure determination. 1 crystallizes in orthorhombic, space group Pca21 with a = 13.382（4）, b = 8.527（2）, c = 9.622（3）A, V = 1098.0（5） A^3 Z = 4, C6H10CuMoN4O5, Mr = 377.66, Dc = 2.285 g/cm^3, F（000） = 740,μ（MoKa） = 3.095 mm^-1, the final R = 0.0256 and wR = 0.0722 for 1896 observed reflections with I 〉 2σ（I）. 2 crystallizes in monoclinic, space group P2t/c with a= 11.170（2）, b = 7.8244（15）, c = 22.631（4）A, β = 115.790（7）°, V = 1780.9（6）A^3 Z = 4, C9H14Cu2Mo2N6O9, Mr = 669.24, Dc= 2.496 g/cm^3, F（000）=1295,μ（MoKa） = 3.792 mm^-1, the final R = 0.0225 and wR = 0.0615 for 3838 observed reflections with I 〉 2σ（I）. 3 crystallizes in monoclinic, space group P21/c with a = 5.5599（19）, b = 23.771（8）, c = 7.3044（18）A , β = 129.356（16）°, V = 746.5（4）A^3, Z = 2, C6H10Cu3Mo2N4O10, Mr = 680.71, Dc = 3.029 g/cm^3, F（000） = 650,μ（MoKa） = 5.900 mm^-1, the final R = 0.0215 and wR = 0.0524 for 1620 observed reflections with I 〉 2σ（I）.     

Exfoliated Single Layers of Layered Cobalt Hydroxide for Ultrafine Co3O4 Nanoparticles on Graphene Nanosheets as an Efficient Electrocatalyst for Oxygen Reduction

A highly effective way to produce an oxygen reduction electrocatalyst was developed through the self-assembly of exfoliated single layers of cobalt hydroxide (Co(OH)₂) and graphene oxide (GO). These 2D materials have complete contact with one another because of their physical flexibility and the electrostatic attraction between negatively charged GO and positively charged Co(OH)₂ layers. The strong coupling induces transformation of the Co(OH)₂ single layer into a discrete nanocrystal of spinel Co₃O₄ with an average size of 8 nm on reduced GO (RGO) during calcination, which could not be obtained with bulk-layered cobalt hydroxide because of its rapid layer collapse. The ultrafine Co₃O₄/RGO hybrid exhibited not only comparable performance in the oxygen reduction reaction but also higher durability compared with the commercial 20 wt % Pt/C catalyst.     

Facile Synthesis of Ultrathin Lepidocrocite Nanosheets from Layered Precursors

Ultrathin two‐dimensional nanosheets have been widely studied because of their peculiar properties and promising applications. As a typical layered material, successful exfoliation of freestanding ultrathin lepidocrocite (γ‐FeOOH) nanosheets from the bulk material has not been reported to date. Herein, we report a facile synthetic route to prepare ultrathin lepidocrocite nanosheets with a thickness of approximately 2–3 nm from FeO_x–propanediol layered precursors through weakening of the hydrogen bonds during the crystallization process. The ultrathin morphology and single‐crystal structure of the nanosheets were confirmed by transmission electron microscopy, X‐ray diffraction, and atomic force microscopy. The formation process of these nanosheets demonstrated simultaneous exfoliation and crystallization of lepidocrocite in basic aqueous solution. The obtained ultrathin nanosheets exhibited a much lower Néel temperature (18.3 K) than bulk lepidocrocite and weak ferromagnetic behavior below this temperature.