A Generalized Strategy for the Synthesis of Large‐Size Ultrathin Two‐Dimensional Metal Oxide Nanosheets

Two‐dimensional (2D) nanomaterials show unique electrical, mechanical, and catalytic performance owing to their ultrahigh surface‐to‐volume ratio and quantum confinement effects. However, ways to simply synthesize 2D metal oxide nanosheets through a general and facile method is still a big challenge. Herein, we report a generalized and facile strategy to synthesize large‐size ultrathin 2D metal oxide nanosheets by using graphene oxide (GO) as a template in a wet‐chemical system. Notably, the novel strategy mainly relies on accurately controlling the balance between heterogeneous growth and nucleation of metal oxides on the surface of GO, which is independent on the individual character of the metal elements. Therefore, ultrathin nanosheets of various metal oxides, including those from both main‐group and transition elements, can be synthesized with large size. The ultrathin 2D metal oxide nanosheets also show controllable thickness and unique surface chemical state.     

Robust Superhydrophobic/Superoleophilic Wrinkled Microspherical MOF@rGO Composites for Efficient Oil–Water Separation

Graphene/MOF‐based composite materials in three‐dimensional (3D) architectures are promising for the treatment of oil‐containing wastewater by absorption owing to their intrinsic properties of graphene and metal‐organic frameworks (MOFs), such as high porosity, ultralow density, and facilely tailored superwettability. In this study, novel wrinkled 3D microspherical MOF@rGO composites with both superhydrophobic and superoleophilic properties were developed by embedding MOF nanoparticles between graphene oxide (GO) nanosheets, followed by high‐temperature reduction self‐assembly. The microspherical composites feature a unique micro/nano hierarchy consisting of crumpled reduced GO (rGO) nanosheets intercalated with well‐dispersed MOF nanoparticles. Combined with the superwettability and abundant meso/microporosity, the peculiar architectures of wrinkled ZIF‐8@rGO microspheres show very fast absorption rates and high sorption selectivity for organic solvents and oils from water.     

A Molecular Pillar Approach To Grow Vertical Covalent Organic Framework Nanosheets on Graphene: Hybrid Materials for Energy Storage

Hybrid 2D–2D materials composed of perpendicularly oriented covalent organic frameworks (COFs) and graphene were prepared and tested for energy storage applications. Diboronic acid molecules covalently attached to graphene oxide (GO) were used as nucleation sites for directing vertical growth of COF‐1 nanosheets (v‐COF‐GO). The hybrid material has a forest of COF‐1 nanosheets with a thickness of 3 to 15 nm in edge‐on orientation relative to GO. The reaction performed without molecular pillars resulted in uncontrollable growth of thick COF‐1 platelets parallel to the surface of GO. The v‐COF‐GO was converted into a conductive carbon material preserving the nanostructure of precursor with ultrathin porous carbon nanosheets grafted to graphene in edge‐on orientation. It was demonstrated as a high‐performance electrode material for supercapacitors. The molecular pillar approach can be used for preparation of many other 2D‐2D materials with control of their relative orientation.     

An efficient way to functionalize graphene sheets with presynthesized polymer via ATNRC chemistry

Graphene nanosheets offer intriguing electronic, thermal and mechanical properties and are expected to find a variety of applications in high‐performance nanocomposite materials. The great challenge of exfoliating and dispersing pristine graphite or graphene sheets in various solvents or matrices can be achieved by facilely and properly chemical functionalization of the carbon nanosheets. Here we reported an efficient way to functionalize graphene sheets with presynthesized polymer via a combination of atom transfer nitroxide radical coupling chemistry with the grafting‐onto strategy, which enable us to functionalize graphene sheets with well‐defined polymer synthesized via living radical polymerization. A radical scavenger species, 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO), was firstly anchored onto ? COOH groups on graphene oxide (GO) to afford TEMPO‐functionalized graphene sheets (GS‐TEMPO), meanwhile, the GO sheets were thermally reduced. Next, GS‐TEMPO reacted with Br‐terminated well‐defined poly(N‐isopropylacrylamide) (PNIPAM) homopolymer, which was presynthesized by SET‐LRP, in the presence of CuBr/N,N,N′,N′,N″‐pentamethyldiethylenetriamine to form PNIPAM‐graphene sheets (GS‐PNIPAM) nanocomposite in which the polymers were covalently linked onto the graphene via the alkoxyamine conjunction points. The PNIPAM‐modified graphene sheets are easily dispersible in organic solvents and water, and a temperature‐induced phase transition was founded in the water suspension of GS‐PNIPAM. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Self‐(Un)rolling Biopolymer Microstructures: Rings,Tubules, and Helical Tubules from the Same Material

We have demonstrated the facile formation of reversible and fast self‐rolling biopolymer microstructures from sandwiched active–passive, silk‐on‐silk materials. Both experimental and modeling results confirmed that the shape of individual sheets effectively controls biaxial stresses within these sheets, which can self‐roll into distinct 3D structures including microscopic rings, tubules, and helical tubules. This is a unique example of tailoring self‐rolled 3D geometries through shape design without changing the inner morphology of active bimorph biomaterials. In contrast to traditional organic‐soluble synthetic materials, we utilized a biocompatible and biodegradable biopolymer that underwent a facile aqueous layer‐by‐layer (LbL) assembly process for the fabrication of 2D films. The resulting films can undergo reversible pH‐triggered rolling/unrolling, with a variety of 3D structures forming from biopolymer structures that have identical morphology and composition.     

Self‐(Un)rolling Biopolymer Microstructures: Rings,Tubules, and Helical Tubules from the Same Material

We have demonstrated the facile formation of reversible and fast self‐rolling biopolymer microstructures from sandwiched active–passive, silk‐on‐silk materials. Both experimental and modeling results confirmed that the shape of individual sheets effectively controls biaxial stresses within these sheets, which can self‐roll into distinct 3D structures including microscopic rings, tubules, and helical tubules. This is a unique example of tailoring self‐rolled 3D geometries through shape design without changing the inner morphology of active bimorph biomaterials. In contrast to traditional organic‐soluble synthetic materials, we utilized a biocompatible and biodegradable biopolymer that underwent a facile aqueous layer‐by‐layer (LbL) assembly process for the fabrication of 2D films. The resulting films can undergo reversible pH‐triggered rolling/unrolling, with a variety of 3D structures forming from biopolymer structures that have identical morphology and composition.     

A Direct Hybridization between Isocharged Nanosheets of Layered Metal Oxide and Graphene through a Surface‐Modification Assembly Process

An efficient and universal method to directly hybridize isocharged nanosheets of layered metal oxide and reduced graphene oxide (rGO) is developed on the basis of the surface modification and an electrostatically driven assembly process. On the basis of this synthetic method, the CoO₂–rGO nanocomposite can be synthesized with exfoliated CoO₂ and rGO nanosheets, and transformed into CoO–CoO₂–rGO nanocomposites with excellent electrode performance for lithium‐ion batteries. Also, this surface‐modification assembly route is successfully applied for the synthesis of another mesoporous TiO₂–rGO nanocomposite. This result provides clear evidence for the usefulness of the present method as a universal way of hybridizing isocharged anionic nanosheets of inorganic solids and graphene.     

Covalent polymeric modification of graphene nanosheets via surface‐initiated single‐electron‐transfer living radical polymerization

Graphene nanosheets offer intriguing electronic, thermal, and mechanical properties and are expected to find a variety of applications in high‐performance nanocomposite materials. Dispersal of graphene nanosheets in polymer hosts and precise interface control are challenging due to their strong interlayer cohesive energy and surface inertia. Here, an efficient strategy is presented for growing polymers directly from the surface of reduced graphene oxide (GO). This method involves the covalent attachment of Br‐containing initiating groups onto the surface of hydrazine hydrate reduced GO via a diazonium addition and the succeeding linking of poly(tert‐butyl methacrylate) (PtBMA) chains (71.7 wt % grafting efficiency) via surface‐initiated single‐electron‐transfer living radical polymerization (SET‐LRP) to graphene nanosheets. The resulting materials were characterized by using a range of testing techniques and it was proved that polymer chains were successfully introduced to the surface of exfoliated graphene sheets. After grafting with PtBMA, the modified graphene sheets still maintained the separated single layers, and the dispersibility was improved significantly. The method is believed to offer possibilities for optimizing the processing properties and interface structure of graphene–polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Nanocrystalline cellulose acetate (NCCA)/graphene oxide (GO) nanocomposites with enhanced mechanical properties and barrier against water vapor

Highly flexible nanocomposite films of nanocrystalline cellulose acetate (NCCA) and graphene oxide (GO) were synthesized by combining NCCA and GO sheets in a well-controlled manner. By adjusting the GO content, various NCCA/GO nanocomposites with 0.3–1 wt% GO were obtained. Films of these nanocomposites were prepared using the solvent casting method. Microscopic and X-ray diffraction (XRD) measurements demonstrated that the GO nanosheets were uniformly dispersed in the NCCA matrix. Mechanical properties of the composite films were also studied. The best GO composition of the samples tested was 0.8 wt%, giving tensile strength of 157.49 MPa, which represents a 61.92 % enhancement compared with NCCA. On the other hand, the composite films showed improved barrier properties against water vapor. This simple process for preparation of NCCA/GO films is attractive for potential development of high-performance films for electrical and electrochemical applications.     

Functionalization of graphene oxide towards thermo‐sensitive nanocomposites via moderate in situ SET‐LRP

A mild and efficient strategy is presented for growing thermo‐sensitive polymers directly from the surface of exfoliated graphene oxide (GO). This method involves the covalent attachment of Br‐containing initiating groups onto the surface of GO sheets followed by in situ growing poly[poly(ethylene glycol) ethyl ether methacrylate] (PPEGEEMA) via single‐electron‐transfer living radical polymerization (SET‐LRP). Considering the lack of reactive functional groups on the surface of GO, exfoliated GO sheets were subjected to an epoxide ring opening reaction with tris(hydroxymethyl) aminomethane (TRIS) at room temperature. The initiating groups were grafted onto TRIS‐GO sheets by treating hydroxyls with 2‐bromo‐2‐methylpropionyl bromide at room temperature. PPEGEEMA chains were synthesized by in situ SET‐LRP using CuBr/Me₆TREN as catalytic system at 40 °C in H₂O/THF. The resulting materials were characterized using a range of testing techniques and it was proved that polymer chains were successfully introduced to the surface of GO sheets. After grafting with PPEGEEMA, the modified GO sheets still maintained the separated single layers and the dispersibility was significantly improved. This TRIS‐GO‐PPEGEEMA hybrid material shows reversible self‐assembly and deassembly in water by switching temperature at about 34 °C. Such smart graphene‐based materials promise important potential applications in thermally responsive nanodevices and microfluidic switches. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Grafting polymerization of single‐handed helical poly(phenyl isocyanide)s on graphene oxide and their application in enantioselective separation

We herein report a “grafting from” strategy to immobilize optically active helical poly(phenyl isocyanide)s onto graphene oxide (GO) nanosheets. After covalently bounding alkyne‐Pd(II) initiator onto GO nanosheets, the designed GO/polymer composites P1 @GO and P1 ‐b‐ P2 @GO featuring single‐handed helical poly(phenyl isocyanide)s growing from GO nanosheets were prepared by sequential addition of the chiral and achiral isocyanide monomers. Post‐synthetic hydrolysis rendered P1 ‐b‐ P3 @GO to improve the hydrophilicity. The successful covalent bonding of poly(phenyl isocyanide)s chains onto GO nanosheets was certified by several cross evidences including scan emission microscopy, atomic force microscopy, Raman spectroscopy, X‐ray photoelectron spectroscopy, and thermogravimetric analysis. Circular dichroism spectra proved that the chiral information was introduced through the grafted single‐handed helical polymer chains successfully. In addition, the resulting GO/polymer composites were explored as a chiral additive to induce enantioselective crystallization of racemic organic molecules. Preferential formation of rod‐like L‐alanine crystals was induced by composites bearing right‐handed helical poly(phenyl isocyanide)s. The enantiomeric excess value of the induced crystals reached 76%, displaying the potential in future applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2092–2103     

Layer-by-layer engineered Co-Al hydroxide nanosheets/graphene multilayer films as flexible electrode for supercapacitor

Multilayer films of Co-Al layered double hydroxide nanosheets (Co-Al LDH-NS) and graphene oxide (GO) were fabricated through layer-by-layer (LBL) assembly. By using a three-electrode system, the electrochemical performances of the films were investigated to evaluate their potential as electrode materials to be used in flexible supercapacitor devices. The Co-Al LDH-NS/GO multilayer films exhibited a high specific capacitance of 880 F/g and area capacitance of 70 F/m(2) under the scan rate of 5 mV/s. And the film exhibited good cycle stability over 2000 cycles. After treating the films at 200 °C in H(2) atmosphere, the specific capacitance and area capacitance were largely increased up to 1204 F/g and 90 F/m(2) due to partial reduction of GO. A flexible electrode by depositing Co-Al LDH-NS/GO multilayer film onto PET substrate was prepared to show the potential of Co-Al LDH-NS/GO films for flexible energy storage.     

A Generalized Strategy for the Synthesis of Large-Size Ultrathin Two-Dimensional Metal Oxide Nanosheets

Two-dimensional (2D) nanomaterials show unique electrical, mechanical, and catalytic performance owing to their ultrahigh surface-to-volume ratio and quantum confinement effects. However, ways to simply synthesize 2D metal oxide nanosheets through a general and facile method is still a big challenge. Herein, we report a generalized and facile strategy to synthesize large-size ultrathin 2D metal oxide nanosheets by using graphene oxide (GO) as a template in a wet-chemical system. Notably, the novel strategy mainly relies on accurately controlling the balance between heterogeneous growth and nucleation of metal oxides on the surface of GO, which is independent on the individual character of the metal elements. Therefore, ultrathin nanosheets of various metal oxides, including those from both main-group and transition elements, can be synthesized with large size. The ultrathin 2D metal oxide nanosheets also show controllable thickness and unique surface chemical state.     

One‐Step Electrodeposition to Layer‐by‐Layer Graphene–Conducting‐Polymer Hybrid Films

One‐step fabrication of graphene–polyaniline (graphene–PANI) hybrid film was facilely achieved by cyclic voltammetric electrolysis of a bath containing both graphene oxide (GO) and aniline, where graphene is obtained by electrochemical reduction of GO and PANI is simultaneously obtained by aniline electropolymerization. As there is no strong attraction between aniline and GO under the electrodeposition conditions, the independent depositions of PANI and reduced GO nanosheets at their greatly differed potentials led to alternate layered graphene–PANI films, with the topmost layer being PANI particles or graphene sheets just by changing the initial scan directions. The two kinds of graphene–PANI hybrid films present excellent but different electrical and electrochemical behaviors.     

Ultrathin Hexagonal Hybrid Nanosheets Synthesized by Graphene Oxide‐Assisted Exfoliation of β‐Co(OH)2 Mesocrystals

In the present study, we report the synthesis of a high‐quality, single‐crystal hexagonal β‐Co(OH)₂ nanosheet, exhibiting a thickness down to ten atomic layers and an aspect ratio exceeding 900, by using graphene oxide (GO) as an exfoliant of β‐Co(OH)₂ nanoflowers. Unlike conventional approaches using ionic precursors in which morphological control is realized by structure‐directing molecules, the β‐Co(OH)₂ flower‐like superstructures were first grown by a nanoparticle‐mediated crystallization process, which results in large 3D superstructure consisting of ultrathin nanosheets interspaced by polydimethoxyaniline (PDMA). Thereafter, β‐Co(OH)₂ nanoflowers were chemically exfoliated by surface‐active GO under hydrothermal conditions into unilamellar single‐crystal nanosheets. In this reaction, GO acts as a two‐dimensional (2D) amphiphile to facilitate the exfoliation process through tailored interactions between organic and inorganic molecules. Meanwhile, the on‐site conjugation of GO and Co(OH)₂ promotes the thermodynamic stability of freestanding ultrathin nanosheets and restrains further growth through Oswald ripening. The unique 2D structure combined with functionalities of the hybrid ultrathin Co(OH)₂ nanosheets on rGO resulted in a remarkably enhanced lithium‐ion storage performance as anode materials, maintaining a reversible capacity of 860 mA h g^?1 for as many as 30 cycles. Since mesocrystals are ubiquitous and rich in morphological diversity, the strategy of the GO‐assisted exfoliation of mesocrystals developed here provides an opportunity for the synthesis of new functional nanostructures that could bear importance in clean renewable energy, catalysis, photoelectronics, and photonics.     

Nanostructured Three‐Dimensional (3D) Assembly of 2D MoS2 and Graphene Directly Build From Acidic Graphite Oxide

A 3D highly interconnected macroporous network of reduced GO having finely dispersed few‐layered 2D MoS₂ nanosheets was constructed through direct use of acidic graphite oxide (GO) for the first time. This facile and technologically scalable process can afford efficient hydrodesulfurization electrocatalysts as potential anode materials at lower cost, and can circumvent the poor thermal stability and recyclability of the material. The strategy provided here can be the basis to design and develop practical processes to address the ultimate goal of large‐scale manufacturing of hybrids composed of 2D materials for various energy and catalysis applications.     

Fluorescence Turn‐on Synthetic Lipid Rafts on Supramolecular Sheets and Hierarchical Concanavalin A Assembly

Here we report fluorescence turn‐on synthetic lipid rafts by self‐assembly of a cationic distyrylanthracene derivative on a negatively‐charged sheet in an aqueous solution. First, the negatively‐charged 2D membrane structure is formed by lateral associations of aromatic rods with carboxylate groups. Then, the synthetic rafts are floated on the surface of the negatively‐charged sheets through electrostatic interactions. The fluorescence of the synthetic rafts is turned on due to the aggregation of the positively‐charged AIE dye on the sheets, facilitating monitoring of the formation of rafts. Concanavalin A (Con A) protein can load hierarchically onto the synthetic rafts at neutral pH to provide discrete Con A aggregates with a uniform size of ≈12 nm. The uniform aggregates of Con A on the synthetic rafts can stimulate Jurkat cells with enhanced efficiency, as compared with random‐sized aggregates of Con A.     

Synthesis of polystyrene nanoparticles “armoured” with nanodimensional graphene oxide sheets by miniemulsion polymerization

Polystyrene particles “armoured” with nanosized graphene oxide (GO) sheets have been prepared by aqueous miniemulsion polymerization of styrene, exploiting the amphiphilic properties of GO in the absence of conventional surfactants. The nanoscale GO sheets were prepared from graphite nanofibers of diameter approximately 100 nm based on a novel procedure, thus effectively ensuring the absence of larger sheets. Polymerization proceeded to high conversion with minor coagulation, with final number‐average particle diameters of approximately 500 nm, but relatively broad particle size distributions. Scanning electron microscopy analysis revealed particles with a textured surface, consistent with the expected morphology. Interestingly, analysis of GO sheets recovered from the polymerization revealed that the GO sheets are partially reduced during the polymerization—approximately 50% of the initial carboxyl groups of the GO were lost, consistent with some loss in colloidal stability at high conversion. The overall approach offers a convenient and attractive synthetic route to novel graphene‐based polymeric nanostructures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Surface‐Coated Thermally Expandable Microspheres with a Composite of Polydisperse Graphene Oxide Sheets

Surface‐modified thermally expandable microcapsules (TEMs) hold potential for applications in various fields. In this work, we discussed the possible surface coating mechanism and reported the properties of TEMs coated with polyaniline (PANI) and polydisperse graphene oxide sheets (ionic liquid‐graphene oxide hybrid nanomaterial (ILs‐GO)). The surface coating of PANI/ ILs‐GO increased the corresponding particle size and its distribution range. The morphologies analyzed by scanning electron microscopy indicated that no interfacial gap was observed between the microspheres ink and substrate layer during the substrate application. The thermal properties were determined by thermogravimetric and differential thermal analyses. The addition of ILs‐GO to the polyaniline coating significantly improved the thermal expansion and thermal conductivity of the microcapsules. The evaporation of hexane present in the core of TEMs was not prevented by the coating of PANI/ ILs‐GO. The printing application of TEMs showed excellent adaptability to various flexible substrates with great 3D appearance. By incorporating a flame retardant agent into TEMs coated by PANI/ILs‐GO, finally, these TEMs also demonstrated a great flame retardant ability. We expect that these TEM‐coated PANI/ ILs‐GO are likely to have the potential to improve the functional properties for various applications.     

Synthesis of layered double hydroxides/graphene oxide nanocomposite as a novel high-temperature CO_2 adsorbent

In this contribution, a novel high-temperature CO2 adsorbent consisting of Mg-Al layered double hydroxide(LDH) and graphene oxide(GO)nanosheets was prepared and evaluated. The nanocomposite-type adsorbent was synthesized based on the electrostatically driven self-assembly between positively charged Mg-Al LDH single sheet and negatively charged GO monolayer. The characteristics of this novel adsorbent were investigated using XRD, FE-SEM, HRTEM, FT-IR, BET and TGA. The results showed that both the CO2 adsorption capacity and the multicycle stability of LDH were increased with the addition of GO owing to the enhanced particle dispersion and stabilization. In particular, the absolute CO2 capture capacity of LDH was increased by more than twice by adding 6.54 wt% GO as support. GO appeared to be especially effective for supporting LDH sheets. Moreover, the CO2 capture capacity of the adsorbent could be further increased by doping with 15 wt%K2CO3. This work demonstrated a new approach for the preparation of LDH-based hybrid-type adsorbents for CO2 capture.