Selective-area fluorination of graphene with fluoropolymer and laser irradiation

We have devised a method to selectively fluorinate graphene by irradiating fluoropolymer-covered graphene with a laser. This fluoropolymer produces active fluorine radicals under laser irradiation that react with graphene but only in the laser-irradiated region. The kinetics of C-F bond formation is dependent on both the laser power and fluoropolymer thickness, proving that fluorination occurs by the decomposition of the fluoropolymer. Fluorination leads to a dramatic increase in the resistance of the graphene while the basic skeletal structure of the carbon bonding network is maintained. Considering the simplicity of the fluorination process and that it allows patterning with a nontoxic fluoropolymer as a solid source, this method could find application to generate fluorinated graphene in graphene-based electronic devices such as for the electrical isolation of graphene.     

Fluorinated Phosphorene: Electrochemical Synthesis,Atomistic Fluorination,and Enhanced Stability

Phosphorene has attracted great interest due to its unique electronic and optoelectronic properties owing to its tunable direct and moderate band‐gap in association with high carrier mobility. However, its intrinsic instability in air seriously hinders its practical applications, and problems of technical complexity and in‐process degradation exist in currently proposed stabilization strategies. A facile pathway in obtaining and stabilizing phosphorene through a one‐step, ionic liquid‐assisted electrochemical exfoliation and synchronous fluorination process is reported in this study. This strategy enables fluorinated phosphorene (FP) to be discovered and large‐scale, highly selective few‐layer FP (3?6 atomic layers) to be obtained. The synthesized FP is found to exhibit unique morphological and optical characteristics. Possible atomistic fluorination configurations of FP are revealed by core‐level binding energy shift calculations in combination with spectroscopic measurements, and the results indicate that electrolyte concentration significantly modulates the fluorination configurations. Furthermore, FP is found to exhibit enhanced air stability thanks to the antioxidation and antihydration effects of the introduced fluorine adatoms, and demonstrate excellent photothermal stability during a week of air exposure. These findings pave the way toward real applications of phosphorene‐based nanophotonics.     

The safer and scalable mechanochemical synthesis of edge-chlorinated and fluorinated few-layer graphenes

Halogen functionalization of the edges of the graphene sheets can improve processability, add new properties, and enhance its interactions with other materials. Through functionalization, improved materials can be realized. Typically, halogenated graphenes are produced from pure or reactive halogen sources. Current approaches present significant safety challenges. By generating reactive dichlorine monoxide (Cl₂O) in situ, a chlorinated graphene with the nominal composition C₁₇Cl₂OH can be realized safely and scalably. Chlorinated graphene can be used as a precursor for an array of functionalized materials by mechanically driven solid-state metathesis reactions. For example, nearly 75% of the chlorine in chlorinated graphene can be exchanged with fluorine by using the safer fluorine-containing compound ammonium fluoride (NH₄F) as a reagent. A material with the composition C₃₄Cl₃F(OH)₂ is realized. Preliminary work shows that F–graphene has oxygen reduction properties and Cl–graphene can improve existing zinc–air fuel cells. A scalable production of chlorinated and fluorinated graphenes and graphites will accelerate their adoption in fuel cells, batteries, polymer composites, and catalysts.     

One‐Step Formation of a Single Atomic‐Layer Transistor by the Selective Fluorination of a Graphene Film

In this study, the scalable and one‐step fabrication of single atomic‐layer transistors is demonstrated by the selective fluorination of graphene using a low‐damage CF₄ plasma treatment, where the generated F‐radicals preferentially fluorinated the graphene at low temperature (<200 °C) while defect formation was suppressed by screening out the effect of ion damage. The chemical structure of the C–F bonds is well correlated with their optical and electrical properties in fluorinated graphene, as determined by X‐ray photoelectron spectroscopy, Raman spectroscopy, and optical and electrical characterizations. The electrical conductivity of the resultant fluorinated graphene (F‐graphene) was demonstrated to be in the range between 1.6 kΩ/sq and 1 MΩ/sq by adjusting the stoichiometric ratio of C/F in the range between 27.4 and 5.6, respectively. Moreover, a unique heterojunction structure of semi‐metal/semiconductor/insulator can be directly formed in a single layer of graphene using a one‐step fluorination process by introducing a Au thin‐film as a buffer layer. With this heterojunction structure, it would be possible to fabricate transistors in a single graphene film via a one‐step fluorination process, in which pristine graphene, partial F‐graphene, and highly F‐graphene serve as the source/drain contacts, the channel, and the channel isolation in a transistor, respectively. The demonstrated graphene transistor exhibits an on‐off ratio above 10, which is 3‐fold higher than that of devices made from pristine graphene. This efficient transistor fabrication method produces electrical heterojunctions of graphene over a large area and with selective patterning, providing the potential for the integration of electronics down to the single atomic‐layer scale.     

Modeling of epitaxial graphene functionalization

A new model for graphene epitaxially grown on silicon carbide is proposed. Density functional theory modeling of epitaxial graphene functionalization by hydrogen, fluorine, methyl and phenyl groups has been performed, with hydrogen and fluorine showing a high probability of cluster formation in high adatom concentration. It has also been shown that the clusterization of fluorine adatoms provides midgap states in formation, due to significant flat distortion of graphene. The functionalization of epitaxial graphene using larger species (methyl and phenyl groups) renders cluster formation impossible, due to the steric effect, and results in uniform coverage with the energy gap opening.     

Preparation of non-covalently functionalized graphene using 9-anthracene carboxylic acid

A simple way of achieving stable aqueous dispersion of graphene by non-covalent functionalization using 9-anthracene carboxylic acid has been successfully accomplished. Unlike in chemically reduced graphene, the C-sp(2) network of the graphene remains undistorted and therefore of superior quality. The non-covalent functionalization facilitates the exfoliation of graphite layers in a polarity controlled combination of media. A detailed exfoliation mechanism is proposed based on the controlled experiment and is supported by the data from UV-vis spectroscopy, transmission electron microscopy, and x-ray diffraction studies. Formation of monolayer graphene has been confirmed from Raman spectroscopy. The graphene based ultracapacitor shows a high value of specific capacitance (148 F g(-1)).     

橡胶材料表面氟化改性的研究

用ＸｅＦ２与橡胶表面发生反应,在不同条件下,得到氟化改性的结果,其表面致密光滑,表面含有一定量的氟,在高分子链上发生氟原子取代氢原子,形成碳氟键,并且氟化程度随时间增长而进一步加深,橡胶的性能明显提高。     

Graphene-based materials: synthesis, characterization, properties, and applications

Graphene, a two-dimensional, single-layer sheet of sp(2) hybridized carbon atoms, has attracted tremendous attention and research interest, owing to its exceptional physical properties, such as high electronic conductivity, good thermal stability, and excellent mechanical strength. Other forms of graphene-related materials, including graphene oxide, reduced graphene oxide, and exfoliated graphite, have been reliably produced in large scale. The promising properties together with the ease of processibility and functionalization make graphene-based materials ideal candidates for incorporation into a variety of functional materials. Importantly, graphene and its derivatives have been explored in a wide range of applications, such as electronic and photonic devices, clean energy, and sensors. In this review, after a general introduction to graphene and its derivatives, the synthesis, characterization, properties, and applications of graphene-based materials are discussed.     

氟化石墨烯结构表征及接枝增强芳纶Ⅲ薄膜的力学性能

首先对自制的氟化石墨烯(FG)进行结构与性能表征。然后采用拥有优异耐热性和分散性的FG对芳纶Ⅲ(PA)薄膜进行共混改性,提高其力学性能。PA分子链的咪唑环上的氮原子因弱碱性而具备亲核反应能力,有望取代氟化石墨烯的氟原子形成C-N键,进而有效增强聚合物基体。然而,研究发现,PA胶液中的HCl会与咪唑环络合,降低咪唑环的反应活性。吡啶的加入中和了HCl的同时也能够催化反应,促进C-N的生成。红外光谱结果表明,加入吡啶的FG-PA复合体系能够形成基体与填料间的C-N共价键接。同时,加入吡啶所制得的FG-PA共混薄膜相比未加入吡啶的拉伸强度增加了25.6%。     

Series of Halogen Engineered Ni(OH)2 Nanosheet for Pseudocapacitive Energy Storage with High Energy Density

Ni(OH)₂ nanosheet, acting as a potential active material for supercapacitors, commonly suffers from sluggish reaction kinetics and low intrinsic conductivity, which results in suboptimal energy density and long cycle life. Herein, a convenient electrochemical halogen functionalization strategy is applied for the preparation of mono/bihalogen engineered Ni(OH)₂ electrode materials. The theoretical calculations and experimental results found that thanks to the extraordinarily high electronegativity, optimal reversibility, electronic conductivity, and reaction kinetics could be achieved through F functionalization  . However, benefiting from the largest ionic radius, I Ni(OH)₂ contributes the best specific capacity and morphology transformation, which is a new finding that distinguishes it from previous reports in the literature. The exploration of the interaction effect of halogens (F, I Ni(OH)₂, F, Br Ni(OH)₂, and Cl, I Ni(OH)₂) manifests that F, I Ni(OH)₂ delivers a higher specific capacity of 200.6 mAh g⁻¹ and an excellent rate capability of 58.2% due to the weaker electrostatic repulsion, abundant defect structure, and large layer spacing. Moreover, the F, I Ni(OH)₂//FeOOH@NrGO device achieves a high energy density of 97.4 Wh kg⁻¹ and an extremely high power density of 32426.7 W kg⁻¹, as well as good cycling stability. This work develops a pioneering tactic for designing energy storage materials to meet various demands.     

Initiating Fluorine Chemistry in Polycyclic Aromatic Hydrocarbon-Derived Carbon for New Cluster-Mode Na Storage with Superhigh Capacity

Carbon materials are widely accepted as promising candidates for sodium-ion batteries (SIBs) anodes due to their chemical stability and conductivity, while the capacity is still unsatisfactory. Here, this work reports the superhigh capacity Na storage through initiating fluorine chemistry (C F bonds) in carbon synthesized by the dehydrogenation and fluorination of polycyclic aromatic hydrocarbon such as pitch. Experimental and theoretical investigations uncover that C F bonds exist at the form of dangling bonds (C F_x), which generates the coexistence of graphitic and defective nanodomains. It delivers a superhigh capacity of 450 mAh g⁻¹, far surpassing most of current SIBs carbon anodes. Theoretical calculation attributes this performance to a new Na storage mechanism that Na can be accommodated in the form of cluster rather than a single ion at each host site with F-doping. This work highlights the significance of carbon material chemistry in establishing the novel ion storage manner in SIBs and other batteries.     

Patterning nanoroads and quantum dots on fluorinated graphene

Using ab initio methods we have investigated the fluorination of graphene and find that different stoichiometric phases can be formed without a nucleation barrier, with the complete “2D-Teflon” CF phase being thermodynamically most stable. The fluorinated graphene is an insulator and turns out to be a perfect matrix-host for patterning nanoroads and quantum dots of pristine graphene. The electronic and magnetic properties of the nanoroads can be tuned by varying the edge orientation and width. The energy gaps between the highest occupied and lowest unoccupied molecular orbitals (HOMO-LUMO) of quantum dots are size-dependent and show a confinement typical of Dirac fermions. Furthermore, we study the effect of different basic coverage of F on graphene (with stoichiometries CF and C₄F) on the band gaps, and show the suitability of these materials to host quantum dots of graphene with unique electronic properties.     

Peptide-functionalized colloidal graphene via interdigited bilayer coating and fluorescence turn-on detection of enzyme

Synthesis of colloidal functional graphene is challenging because graphene is water-insoluble and its relatively inert surface made the functionalization a difficult task. Here we report interdigited bilayer type coating that provide both colloidal stability and functionalization option for graphene. Colloidal graphene oxide is first converted into interdigited bilayer coated graphene oxide and next they are transformed into colloidal graphene by hydrazine reduction. These coated graphenes can be further transformed into colloidal functional graphene using covalent conjugation chemistry. Functional graphene has been synthesized for optical detection of enzyme where a fluorescent dye is covalently linked through a peptide so that the dye fluorescence is quenched by graphene but switches on once enzymes cleave the peptide bond. The interdigited bilayer coating reported here is unique as it provides coating thickness <3 nm, offering optically responsive graphene-fluorophore substrate with high colloidal stability.     

Ozonolysis of functionalized single-walled carbon nanotubes

Room temperature ozonolysis of fluorinated SWNT and phenyl-sulfonated SWNT have been studied in perfluoropolyether (PFPE) solvents. Etching at the end caps (approximately 70 nm/hour for fluorinated SWNT/PFPE suspension with 1 g/l concentration) has been demonstrated to be the dominating effect during the ozonolysis of fluorinated SWNT. Base on characterization by AFM analysis, X-ray Photoelectron Spectroscopy (XPS) and Raman Spectroscopy, fluorination along the SWNT sidewalls protects F-SWNT from extensive functionalization by ozonolysis. An ozone reaction with fluorinated SWNT has been found to improve its solubility in 96% sulfuric acid. This allows oxidative cutting by ammonium peroxydisulfate without defluorination. In comparison to fluorinated SWNT, phenyl-sulfonated SWNT was found to be effectively and homogeneous cut by ozonolysis in a water suspension.     

Controlled release of drug from folate-decorated and graphene mediated drug delivery system: Synthesis,loading efficiency,and drug release response

A novel folate-decorated and graphene mediated drug delivery system was prepared that involves uniquely combining graphene oxide (GO) with anticancer drug for controlled drug release. The nanocarrier system was synthesized by attaching doxorubicin (DOX) to graphene oxide via strong π–π stacking interaction, followed by encapsulation of graphene oxide with folic acid conjugated chitosan. The π–π stacking interaction, simplified as a non-covalent type of functionalization, enables high drug loading and subsequent controlled release of the drug. The encapsulated graphene oxide enhanced the stability of the nanocarrier system in aqueous medium because of the hydrophilicity and cationic nature of chitosan. The loading and release of DOX indicated strong pH dependence and imply hydrogen-bonding interaction between graphene oxide and DOX. The proposed strategy is advantageous in terms of targeted drug delivery and has high potential to address the current challenges in drug delivery. Thus, the prepared nanohybrid system offers a novel formulation that combines the unique properties of a biodegradable material, chitosan, and graphene oxide for biomedical applications.     

High‐Performance All‐Polymer Solar Cells Enabled by an n‐Type Polymer Based on a Fluorinated Imide‐Functionalized Arene

A novel imide‐functionalized arene, di(fluorothienyl)thienothiophene diimide (f‐FBTI2), featuring a fused backbone functionalized with electron‐withdrawing F atoms, is designed, and the synthetic challenges associated with highly electron‐deficient fluorinated imide are overcome. The incorporation of f‐FBTI2 into polymer affords a high‐performance n‐type semiconductor f‐FBTI2‐T, which shows a reduced bandgap and lower‐lying lowest unoccupied molecular orbital (LUMO) energy level than the polymer analog without F or with F‐functionalization on the donor moiety. These optoelectronic properties reflect the distinctive advantages of fluorination of electron‐deficient acceptors, yielding “stronger acceptors,” which are desirable for n‐type polymers. When used as a polymer acceptor in all‐polymer solar cells, an excellent power conversion efficiency of 8.1% is achieved without any solvent additive or thermal treatment, which is the highest value reported for all‐polymer solar cells except well‐studied naphthalene diimide and perylene diimide‐based n‐type polymers. In addition, the solar cells show an energy loss of 0.53 eV, the smallest value reported to date for all‐polymer solar cells with efficiency > 8%. These results demonstrate that fluorination of imide‐functionalized arenes offers an effective approach for developing new electron‐deficient building blocks with improved optoelectronic properties, and the emergence of f‐FBTI2 will change the scenario in terms of developing n‐type polymers for high‐performance all‐polymer solar cells.     

Dichlorocarbene‐Functionalized Fluorographene: Synthesis and Reaction Mechanism

Halogen functionalization of graphene is an important branch of graphene research as it provides opportunities to tailor the band gap and catalytic properties of graphene. Monovalent C–X bond obviates pitfalls of functionalization with atoms of groups 13, 15, and 16, which can introduce various poorly defined groups. Here, the preparation of functionalized graphene containing both fluorine and chlorine atoms is shown. The starting material, fluorographite, undergoes a reaction with dichlorocarbene to provide dichlorocarbene‐functionalized fluorographene (DCC‐FG). The material is characterized by X‐ray photoelectron spectroscopy, Raman spectroscopy, and high‐resolution transmission electron microscopy with X‐ray dispersive spectroscopy. It is found that the chlorine atoms in DCC‐FG are distributed homogeneously over the entire area of the fluorographene sheet. Further density functional theory calculations show that the mechanism of dichlorocarbene attack on fluorographene sheet is a two‐step process. Dichlorocarbene detaches fluorine atoms from fluorographene sheet and subsequently adds to the newly formed sp² carbons. Halogenated graphene consisting of two (or eventually three) types of halogen atoms is envisioned to find its way as new graphene materials with tailored properties.     

Photo-induced liquid crystal alignment of poly(vinyl cinnamate) and fluorinated polyimide blends

Liquid crystal(LC) alignment properties were mainly affected by surface properties of alignment layers. In our previous work, we prepared poly(vinyl cinnamate) (PVCi) and polyimide blend alignment layer for thermally stable LC alignment. In this work, we utilized fluorinated polyimide for blend alignment layers in order to modify surface properties of alignment layers. For this purpose, polyimides containing fluorine unit were synthesized and used for the blend alignment layers. Fluorine containing diamine, 4,4′-bis[2-(4-aminophenyl)hexafluoropropyl]-diphenyl ether(BDAF), is used for the polyimide synthesis. We prepared the fluorinated polyimide and PVCi blend alignment layers and investigated the effect of fluorine on the LC alignment properties and pretilt angle of LC.     

氟代有机光电功能小分子材料的研究

有机电致发光材料是有机电致发光器件的基本与核心,发展新型有机光电材料也是国际上此领域的热点。在过去的几十年里,氟化通过降低能级被用来增强小分子或者聚合物的稳定性、电子传输和双极传输性能,尤其是在有机发光二极管中,特别是C-H…F相互作用（类似氢键）在固态堆积时具有重要的作用,能引起典型的π-堆积排列方式,从而增强电荷迁移率。作者研究团队系统地研究了不同位置和数目取代的氟或三氟甲基等吸电子基团对不同材料体系吸收与发射光谱、HOMO／LUMO能级、热性质以及材料的空穴传输和发光性能的影响,同时运用量化计算进行了相应的理论分析,最终发展了一系列新型空穴传输材料、双极性的主体材料以及深蓝光的荧光客体材料。     

Comparison of flash-memory elements using materials based on graphene

Charge capture on flash-memory test structures with floating gates made of graphene (few-layer graphene) and its compounds (graphene oxide and partially fluorinated graphene) is investigated. A comparison of the memory window for different structures has shown the potential of using reduced graphene oxide, graphene with only a few layers, and fluorographene. For the first time, partially fluorinated graphene has been employed as a floating gate in flash-memory structures. Graphene-based materials are promising for 2D printing technologies and flexible electronics.