Noncovalent sidewall functionalization of singlewalled carbon nanotubes alexander star, yi liu, kevin grant, ludek ridvan, j. Functionalization of graphene for efficient energy. The resulting graphene nanoplatelets were readily dispersible and displayed high conductivity and electrochemical biosensing properties for organophosphates. Ruoff, and junhong chen1 1 department of mechanical engineering, university of wisconsinmilwaukee, 3200 n. In this account, i summarize some of our new ideas and strategies for the controlled functionalization of graphene for the. Noncovalent functionalization of boron nitride nanotubes. Introduction to the physical properties of graphene. The desired functionalization route is most plausibly followed by a reaction between the generated radical species figure 7, step c, which is based on the addition of aryl radicals to the graphene sheet. Controlled functionalization of graphene oxide with sodium azide. Improved properties of chemically modified graphenepoly. Tuning the electronic structure and transport properties. Figure 5li bacteria surface adhesion probed with fluorescence microscopy. Nonspecific binding on nanotubes, a phenomenon found with a.
Graphene, the twodimensional parent structural unit of threedimensional graphite and onedimensional carbon nanotubes 1, 2, has been treated theoretically since decades, with suggestions of numerous applications that would benefit from the predicted unusual electron transport properties of a defectfree extended delocalized aromatic carbon system. Films of this molecule act as adhesion layers to produce long ribbons of exfoliated graphene 7,8,9. The prospective twodimensional graphene nanosheets. Surface properties of extremely thin graphite lamellae pdf. Chemical functionalization of graphene enables this material to be processed by solventassisted techniques, such as layerbylayer assembly, spincoating, and filtration. The reaction sequence that we have developed for the first wet chemical bulk functionalization of graphene is depicted in fig. Graphene sheets were stably dispersed in water by functionalization with sulfonated polyaniline spani, and the composite film of spanifunctionalized graphene showed improved electrochemical stability and enhanced electrocatalytic activity.
This study reports the synthesis and characterizations of a new kind of functionalized graphene. Noncovalent chiral functionalization of graphene with. Apr 29, 2003 novel nanomaterials for bioassay applications represent a rapidly progressing field of nanotechnology and nanobiotechnology. Functionalization an overview sciencedirect topics. The two main methods of cnt functionalization are covalent and noncovalent modifications. Interlayer interactions in graphite and carbon nanotubes. Covalent bulk functionalization of graphene nature chemistry.
These onedimensional nanostructures reveal exceptional thermal, electrical, mechanical and optical properties, which make them promising candidates for potential applications in various fields. Compared to noncovalent functionalization, covalent strategies lead to go conjugates with a higher stability in biological fluids. Characterization, direct electrochemistry, and amperometric biosensing of graphene by noncovalent functionalization with picket. In this work, graphene oxide go was covalently functionalized with dmannose mango using mannosylated ethylenediamine. The complexity of go makes the derivatization of the oxygenated groups difficult to control. Heatinitiated chemical functionalization of graphene.
The noncovalent functionalization of graphene by small molecule aromatic adsorbates, phenanthrenequinone pq, is investigated systematically by combining electrochemical characterization, highresolution interfacial xray scattering, and ab initio density functional theory calculations. The covalent functionalization of graphene represents a main topic in the growing field of. All set to become the standard reference on the topic, this book covers the most important procedures for chemical functionalization, making it an indispensable resource for all chemists, physicists, materials scientists and engineers entering or already working in the field. Functionalization of graphene with nitrile groups by. One common approach is to conduct such a functionalization in an organic solvent and to use amyl or isoamyl nitrite to generate the. By contrast, however, the theoretical work on the subject has been distinctly biased towards understanding the. Graphene is twodimensional monolayers of carbon atoms that arranged in a honeycombed network, and have diverse applications in various field such as nanoelectronics sensors, composite materials, and energy technology. Good solvents and nonsolvents for the dried reduced graphene.
Covalent functionalization can enhance graphenes properties including opening its band gap, tuning conductivity, and improving solubility and stability. Covalent bulk functionalization of graphene article pdf available in nature chemistry 34. Abstract graphene is a 2d sheet of sp2 bonded carbon atoms and tends to aggregate together, due to the strong. Decades ago, they were important in conferring cationexchange properties to coal and coalderived chars. Here, we demonstrate that the energy st 2014 journal of materials chemistry a hot articles. The pyrenepcbm moiety was synthesized via a facile esterification reaction, and pyrene was used as an anchoring bridge to link rgo and pcbm. Carboxyl groups are ubiquitous in graphene based materials. The properties of gqds are different from bulk graphene due to the quantum. Functionalization of graphene nanosheets affects the totalfree energy of mixture systems, which consists of enthalpic and entropic contributions. This method offers a larger number of amino functionalities on the surface of cnts and gs so that large number of biological and drug molecules can be attached. Noncovalent functionalization of carbon nanotubes for. Recently, significant efforts have focused on surface functionalization of graphene to achieve specific properties for various practical applications.
It also prevents the agglomeration of single layer graphene during reduction and maintains the inherent properties of graphene. Noncovalent functionalization of graphene and graphene. Facile, noncovalent decoration of graphene oxide sheets with. Noncovalent functionalization of graphene request pdf. Covalent functionalization takes place through a classical chemical reaction as well as by introducing a new chemical function into the graphene monolayer by grafting new functional groups. Pdf noncovalent functionalization of graphene with a ni. An efficient methodology to make stable aqueous solutions of single. Facile, noncovalent decoration of graphene oxide sheets with nanocrystals ganhua lu 1, shun mao, sungjin park 2, rodney s. Graphene based materials gbms, with graphene, their most known member, at the head, constitute a large family of materials which has aroused the interest of scientists working in different research fields such as chemistry, physics, or materials science, to mention a few, arguably as no other material befo graphene chemistry. T1 noncovalent functionalization of singlewalled carbon nanotubes. Here we describe a tripodal motif that binds multivalently to graphene. In this way, a new member of the growing family of 2d materials, named phosphorene,1,2 the all pcounterpart of graphene, was isolated. While xps results confirmed the functionalization of graphene with organosilane, fig. Functionalization of graphene oxide by tetrazine derivatives.
Xps c1s and n1s confirmed the functionalization of go through the binding energies at 288. Noncovalent and reversible functionalization of carbon. Properties of graphene with impurities materials research. Noncovalent functionalization of graphene attaching 6,6. Functionalization of graphene through selfassembly of a hydrophobic backbone of nafion has been reported by choi et al. An investigation into noncovalent functionalization of a.
However, only a few double covalent functionalization approaches have been developed so far. Chemical functionalization of lowdimensional materials such as nanotubes, nanowires and graphene leads to profound changes in their properties and is essential for solubilizing them in common. Cnts have found applications in nanotechnology, electronics, sensors and biosensors, catalysis, energy conversion storage devices, the delivery field, and in the polymer field to. A new graphene fullerene composite rgopyrenepcbm, in which 6,6phenylc61butyric acid methyl ester pcbm was attached onto reduced graphene oxide rgo via the noncovalent functionalization approach, was reported.
Noncovalent functionalization of singlewalled carbon nanotubes. Carbon nanotube chemistry involves chemical reactions, which are used to modify the properties of carbon nanotubes cnts. Singlelayer graphene is a newly available conductive material ideally suited for forming welldefined interfaces with electroactive compounds. Natural polymers lignin and cellulose derivatives are adsorbed on the graphene surfaceby. Surface functionalization of graphene with polymers for enhanced. Noncovalent functionalization of single wall carbon. Related content improving gas sensing properties of graphene by introducing dopants and. In interpreting these numbers, one must, however, consider that several publications on graphene appeared before 2006, e.
The covalent functionalization of graphene on substrates. An aqueous dispersion of reduced graphene was prepared by chemical reduction of graphene oxide in aqueous media and was vacuum filtered to generate reduced graphene sheets. The initial step is the reduction of graphite with solvated electrons. The rollup direction is theoretically represented by a pair of defined indices n, m. Pdf selective organic functionalization of graphene bulk. The pyrenepcbm moiety was synthesized via a facile esterification reaction, and pyrene was used as an anchoring bridge to link rgo and pcbm components. At this moment, the name graphene was not commonly used. Noncovalent functionalization of carbon nanotubes for highly. Single and fewlayer bp 2d bp have been obtained by either micromechanical cleavage scotch tape method3 or liquid. The assemblies, in suspension and after deposition on solid supports, were characterized by nmr, absorption, and fluorescence spectroscopy and by transmission electron microscopy, where the welldefined shape and size of an appended 60fulleropyrrolidine. Cnts can be functionalized to attain desired properties that can be used in a wide variety of applications. Noncovalent functionalization of graphene and graphene oxide for energy materials, biosensing, catalytic, and biomedical applications vasilios georgakilas, jitendra n.
Covalent functionalization of graphene oxide with dmannose. Graphene, a material made exclusively of sp2 carbon atoms with its. Functionalization of graphene can be done by two different methods. Noncovalent functionalization of graphene oxide and.
Synthesis and electrical properties of covalent organic. Noncovalent sidewall functionalization of singlewalled. The functionalization evidence is highlighted using xray photoemission spectroscopy xps, scanning tunneling microscopy stm, scanning xray photoelectron microscopy spem or angle resolved photoemission spectroscopy arpes. To investigate chemical functionalization of graphene nanoribbons section 5 zigzag stripes with widths of 22 and 66.
Generally speaking, functionalization of graphene with polymers can be achieved via either covalent or noncovalent interactions. Yonghui zhang et al 2010 nanotechnology 21 065201 view the article online for updates and enhancements. Novel nanomaterials for bioassay applications represent a rapidly progressing field of nanotechnology and nanobiotechnology. Selective organic functionalization of graphene bulk or graphene edges. Noncovalent functionalization of graphene in suspension. Graphene for biosensing in the past 2 years, there have been a significant number of publications reporting graphenebased biosensors, 4,914,27,3542 mainly utilizing the unique chemical. Graphene has got considerable attention in both experimental and theoretical fields for its extraordinary properties.
Electrical properties of covalently functionalized graphene. Noncovalent functionalization generally has little e. Here we describe a tripodal motif that binds multivalently to graphene through three. Department of chemistry, massachusetts institute of technology, cambridge, massachusetts 029, united states s supporting information s igni. Surface functionalization of graphene graphene materials. Edge functionalization of graphene and 2d ccops although graphene has been demonstrated as an attractive candidate for energy applications due to its special structure and unique properties, it is rare for graphene based materials with desirable bulk properties to also possess the necessary surface. To date, the mixing of graphene and functionalized graphene with polymers covers the. Englert 1, christoph dotzer 1, guang yang 2, martin schmid 3,christianpapp 3, j. Theoretical models of graphene can be built up using simple aromatic molecules. Binderfree, monolithic, high surface area graphene macroassemblies gmas are promising materials for supercapacitor electrodes, but, like all graphitic carbon based supercapacitor electrodes, still lack sufficient energy density for demanding practical applications. Functionalized single or multiwalled carbon nanotubes are spin coated on copper. Noncovalent functionalization of boron nitride nanotubes in.
Covalent bonding to graphene a great deal of interest in covalent functionalization of graphene cfgr was generated when. Covalent polymer functionalization of graphene nanosheets and. This chapter deals with the theoretical and experimental aspects of noncovalent functionalization of graphene. Suspensions of graphene, prepared from graphite foil by sonochemical exfoliation, have been treated with new nonpolar pyrenebutyric amides. Chemical functionalization of graphene and its applications. Number of manuscripts with graphene in the title posted on the preprint server. Decoration of exfoliated black phosphorus with nickel. Covalent functionalization of graphene with organosilane and. Pdf stable aqueous dispersion of graphene nanosheets. Large surface area, chemical stability, and good biocompatibility are features that make graphene base materials appropriate for use. Dec 21, 20 despite its great promise, chemical functionalization of go is still in early stage, and novel chemical tools for the modification of go are demanded. An investigation into noncovalent functionalization of a singlewalled carbon nanotube and a graphene sheet with protein g. Noncovalent functionalization is a simple and economic approach to introduce specific functionalities to the graphene surface.
Furthermore, the functionalization of graphene is always based on the graphene from previously prepared go, which has multiple oxygencontaining functionalities, such as hydroxyl and carboxyl groups. Surface functionalization of graphene with polymers for. Noncovalent chiral functionalization of graphene with optically active helical polymers chonglei ren state key laboratory of chemical resource engineering, college of materials science and engineering, beijing university of chemical technology, beijing, 29 china. Understanding defectstabilized noncovalent functionalization. Highly selective covalent organic functionalization of. Here, we present an exploration of singlewalled carbon nanotubes as a platform for investigating surfaceprotein and proteinprotein binding and developing highly specific electronic biomolecule detectors. Synthesis and electrical properties of covalent organic frameworks with heavy chalcogens selma duhovicand mircea dinca. Covalent functionalization of monolayered transition metal. The functionalization or doping of graphene aims at tuning its electronic properties by opening a energy gap, main challenge for possible electronic applications. Stable dispersion of reduced graphene in various organic solvents was achieved via noncovalent functionalization with amineterminated polymers.
Analysis of the bulk material was carried out by scanning raman. Tuning the electronic structure and transport properties of. The present work reports the noncovalent functionalization of carbon nanomaterials e. Fence porphyrin wenwen tu moe key laboratory of analytical chemistry for life science, school of chemistry and chemical engineering, nanjing university, nanjing 210093 p. Noncovalent functionalization of graphene with a niii tetraaza14annulene complex royal society of chemistry guidelines to referees research works. Graphene oxide quantum dots covalently functionalized pvdf membrane with significantlyenhanced bactericidal and antibiofouling performances.
Noncovalent functionalization of graphene sheets by. Functionalization of graphene by electrophilic alkylation of reduced. Wet functionalization of graphene and its applications in. Covalent functionalization of graphene with reactive. Graphene functionalization with organics is expected to be an important step for the development of graphene based materials with tailored electronic properties. Covalent functionalization is an efficient strategy to render graphene additional properties and overcome its shortcomings such as zero band gap and nondispersibility in solvents. The assemblies, in suspension and after deposition on solid supports, were characterized by nmr, absorption, and fluorescence spectroscopy and by transmission electron microscopy, where the welldefined shape and size. A versatile approach toward covalent bridges between graphene sheets yuan li, valerie alainrizzo, laurent galmiche, pierre audebert, fabien miomandre, guy louarn, michael bozlar, michael a. N2 singlewalled carbon nanotubes swnts have attracted much attention on account of their potential to be transformed into new materials that can be employed to address a wide range of applications.
Graphene is a novel twodimensional carbon material nobel prize, 2010, which holds the technological promise of replacing or at least supplementing traditional silicon. Introduction noncovalent functionalization of graphene covalent functionalization of graphene graphene nanoparticles conclusion. The utilization of grown or deposited graphene on solid substrates offers key benefits for functionalization processes, but especially to attain structures with a high level of control for electronics and smart materials. Chemical functionalization and characterization of graphene.