Mendoza, David

Diels-Alder Chemistry of Graphene

CHE 392 Fall 12

INTRODUCTION Graphene is one of the most promising and versatile materials ever discovered.1 Although graphene is nothing more than a layer of graphite, it has spawned a fury of speculation and research in the past 8 years. Scientific journals like Graphene and Chemistry of the Graphene are wholly devoted to it. According to Geoff Brumfiel, a science journalist for Nature, physicists are in the grips of graphene madness.2 Physicists are not alone; biologists, engineers, and chemists are also racing to flesh out this crystals potential. In 2011, Santanu Sarkar, Elena Bekyarova, Sandip Niyogi, and Robert C. Haddon3chemists at the University of California, Riversidedemonstrated that graphene undergoes organic chemical functionalization through the powerful Diels-Alder (DA) reaction, uniquely as both a diene and dienophile. They argued that one of the distinctive electrical properties of grapheneits zero-band-gap electronic structure, in which its conduction and valence bands touch at the Fermi energy level (the Dirac point)gives it this special reactivity to the DA reaction. Although graphenes zero-band-gap makes graphene a good conductor, it is a major obstacle in its development as a semiconductor in field-effect transistors, i.e., integrated circuits. In order for chemists to develop graphene as the next generation of semiconductor material, they must find a way to reverse engineer a bandgap into its electronic structure. Sarkar et al.3 propose that the Diels-Alder reaction offers a simple and efficient approach for achieving this purposepreparing graphene for future electronic and optical applications. What is Graphene? Graphene is an allotrope of carbonlike graphite, diamond, fullerene, and carbon nanotubes. In fact, the only difference between these allotropes lies in their dimensional layouts. Graphene, as the two-dimensional (2D) form of sp2- hybridized carbon, is the basic building block for these other important allotropes. As a graphene sheet, carbon can be wrapped into 0D ball-like fullerenes, rolled to form 1D nanotubes, or stacked to form 3D graphite.4 Specifically, graphene is carbon as a film of crystals, one-atom in thicknessa 2D plane of carbon atoms.1 above In fact, it introduces scientists to experimentation in a new dimension as the first twodimensional substance of any kind to ever be isolated. History of Graphene Even though carbon in the form of graphene is currently stirring up intense excitement, it is a familiar atom, and the properties of sp2- hybridized carbon have been exploited for nearly 500 years through the use of abundant and naturally-occurring graphite. The layered morphology and weak dispersion forces between adjacent carbon sheets in graphite were utilized to make marking instruments as early as the Middle Ages. Today, these same properties are utilized in graphite pencils, as well as electrodes, heating elements, and other industrial tools.4 Despite graphites ubiquity and utility, researchers struggled to isolate graphene from it for almost 150 years. This work began in Germany in the mid-1800s by Schafhaeutl, who experimented with the intercalation of graphite. Intercalation involves inserting small-molecule species, like an acid or an alkali metal, between layers of graphite. It results in sufficient decoupling to exhibit intriguing superconductivity effects (results that foreshadowed graphenes superlative properties).5 However, this technique and those that followed continuously fell short of achieving single-layer graphene.

Mendoza, David

Diels-Alder Chemistry of Graphene

CHE 392 Fall 12

Actually, many scientists during the 20th century argued that graphene could not exist on its ownthat its structure was thermodynamically unstable. Their logic was founded in the 60 years of theoretical graphene research that preceded its eventual discovery. For example, in the 1930s, Landau and Peierls argued that thermal fluctuations in low-dimensional crystal lattices lead to such large atom displacements that they become comparable to interatomic distances. A great omnibus of experimental documentation supported this theory. For example, the melting temperature of thin films was generally found to rapidly decrease with decreasing thickness, making them unstable the thinner they became. Thus, attempts to isolate 2D structures (without a 3D base, as in intercalation) failed when thickness decreased to dozens of atomic layers. As such, many presumed that graphene could not exist in its free state and relegated it for consideration only as an academic materialan ideal substance with no ultimate real-world application.6 Obviously, these theories were disproven when Andre Geim and Konstantin Novoselov at the University of Manchester published a practical method for isolating and producing graphene in October of 2004. Their method was not only the most successful up to that point, but also the simplest. Essentially, the Geim group applied the peeling method to a graphite flakeutilizing common celluphene tape (sticky tape) to successively remove layers from it. This process was done repeatedly. The researchers then carefully applied a van der Waals attraction through another compound to delaminate the substrate. When they lifted the tape away, they were left with an impressive result: the very first single layers of graphene flakes.4 Thereafter, interest in graphene skyrocketed. The significance of their discovery was such that Geim and Novoselov were awarded the Nobel Prize in Physics in 2010only 6 years after publishing their method. A Miracle Material As described by Andre Geim, graphene is remarkable because it is stronger and stiffer than diamond, yet can be stretched by a quarter of its length, like rubber. Its surface area is the largest known for its weight.1 Naturally, having a thickness of only one carbon atom, graphene is the thinnest material in the world.7 More surprising though, is that it is also the worlds strongest material. In 2008, researchers used atomic force microscopy to measure the strength of free-standing monolayer graphene membranes by nanoindentation. They found that graphenes force-displacement behavior exhibits a strength that is about 300 times stronger than that of steelthe greatest strength ever measured.8 GRAPHENE, THE NEXT SEMICONDUCTOR Conductivity of Graphene Graphenes electrical properties are by far more impressive than any other of its superlative properties and even more commercially thrilling. To this effect, material scientists and engineers are feverishly searching for ways to build circuits with graphenewhich would be smaller and faster than any circuit built with silicon.1 Naturally, graphene circuits would be smaller due to a combination of their extreme thinness and their six-membered carbon ringswhose molecular radii are smaller than those of any other semiconductor (e.g., silicon-based semiconductors). Moreover, graphene circuits enable the creation of a new generation of high-speed electronics. Extremely high carrier mobility in graphene had long been predicted in theoretical models before actual experimentation

Mendoza, David

Diels-Alder Chemistry of Graphene

CHE 392 Fall 12

had begun. Generally, conduction varies in large part due to both the thermal motion of nuclei in conductors and the impurities in both conductors and semiconductors, which act to scatter electrons as they move through a material. The structure of graphene works to greatly increase conduction in three distinct ways: 1) it presents a flat two-dimensional surface free of obstacles, such as nuclei, for charge carriers (electrons and oppositely charged holes) to travel over; 2) it features a polyaromatic crystal lattice of carbon atoms that practically locks these atoms in place with sp2-hybridized bondslimiting the thermal motion of these atoms; and, most important, 3) its crystal lattice is of remarkably high quality, i.e., it exhibits an unusually low density of defectswhich normally serve as scattering centers that inhibit charge transport. Together these factors essentially connote ballistic conductance on the submicron-scale to a graphene sheet even at room temperature. Ballistic conductance is a remarkable property: it describes the state in which charge carriers can be transported through a material with negligible electrical resistivity. In 2008, researchers at Columbia University measured a charge carrier mobility in excess of 200,000 cm2/ (V s) for a single layer of mechanically exfoliated graphene suspended between gold contacts.4 In fact, charge carriers move so fast over graphene that traditional condensed matter physics, which accurately describes such movement in other conductors and semiconductors, is insufficient. Conductivity in traditional condensed matter relies on quantum mechanics; wherein the Schrodinger equation is employed to predict their electronic properties. However, because conduction in graphene is so great, charge carriers begin to mimic relativistic particles. The Dirac equation from another model of physics, quantum electrodynamics, which incorporates both quantum mechanics and special relativity, is better suited in this case. Indeed, the movement of electrons under an electric field around the carbon atoms of graphenes honeycomb lattice gives rise to new quasiparticles, called massless Dirac fermions, with a speed of v 106 a small but noteworthy fraction of the speed of light.6 This departure from traditional conductivity proves to be significant in terms of the chemistry of graphene and its potential as a semiconductor. Band Theory of Solids Band theory describes how the energy of quasiparticles in a solid depends on their momentum. Of course, the energy level of a quasiparticle, e.g., an electron, determines its ability to move and conduct electricity. In all materials, as atoms move closer together, their wave functions begin to overlap to initiate bonding. Eventually, the two wave functions combine to form a composite wave function. However, because each of the wave functions can be of positive spin or negative spin, when they combine there are two possible composite wave functions that can be assumed. As a result, there are two possible states of the two-atom systemconnoting the creation of two distinct energy levels for this system. Of course, when a large number of atoms are brought together, all their individual wave functions merge in multiple combinationseach combination corresponding to a different energy. Given that there are on the order of 1023 atoms per cubic centimeter in a solid, when these atoms come together their wave functions combine to form a number of energy levels of varying energy so closely spaced that they may be regarded as a continuous band of energy levels. These bands are specific to the orbitals of the combining atoms: 1s orbitals combine to form 1s bands, 2s orbitals combine to form 2s orbitals, and so on. The key detail that band theory offers to explain conductivity in solids, including graphene, is in the gaps between these orbital energy levels.9

Mendoza, David

Diels-Alder Chemistry of Graphene

CHE 392 Fall 12

With respect to reactivity and conductivity, a substances two most important bands are its two outermost bands. The lower band, called the valence band, is the last to contain electrons; the upper band, known as the conduction band, is unfilled at 0 K. The separation between these two bands, the energy gap (Eg), determines the capacity that charge carriers have to move in a substance. This is because conduction occurs when a charge carrier is displaced from the valence band to the conduction band. In between these two bands exists the Fermi energy levelthe level of potential energy calculating using Fermi-Dirac statistics at which there is 50% probability of finding an electron. In a good electrical conductor, like a metal, charge carriers are free to move in response to an applied electric field. This is possible because the conduction and valence bands actually overlap in these substances. Therefore, under a potential difference, electrons that are near the Fermi energy require only a small amount of additional energy from the applied electric field to reach nearby empty energy states (above the Fermi energy). The Zero-band Gap Graphene is unique because it exhibits a zero-band gap. This significant property of graphene was being studied long before graphene was ever isolated. In fact, the Canadian scientist, P. R. Wallace first fleshed out the structure of graphenes electronic energy bands in 1947.10 His calculations produced graphs of the conduction and valence bands (the dispersion relations) that were shaped like smooth-sided cones that meet at a point. This point is called the Dirac point. As such, graphenes conduction and valence bands do not overlap nor do they exhibit a gap between them. They exhibit an unusual property that connotes the label gapless semi-metal for graphene. Actually, the conical shape of the dispersion relation is the analog of the dispersion relation of a photon.11 In this way, the massless Dirac fermions that arise in graphene as it conducts electricity (which, as mentioned previously, travel with a Fermi velocity significantly close to the speed of light) can be explained by band theory. Concordantly, band theory also explains graphenes ballistic conductance. Columbia University scientist, Zhiqiang Li, describes the final valence electron in graphene as sort of free.12 The other three valence electrons are tied up in sp2-hybridized bonding, but the unbound fourth electrons are in orbitals extending vertically above and below [graphenes two-dimensional] plane, and the hybridization of these spreads across the whole graphene sheet. The hybridized electrons interact with the periodic field of the hexagonal crystal lattice and form Dirac fermions, described by cone-like energy bands.12 Thus, graphenes zeroband gap gives rise to unprecedented charge carrier mobility, and on this basis graphene has become a very promising candidate for future electronic applications. Band Gaps in Semiconductors However, as its name implies, the key to an efficient semiconductor is the combination of its conduction and insulating capacities. Although graphene is exemplary as a conductor, by itself it lacks the conduction-limiting insulating properties of a semiconductor. Insulators exhibit a large energy band gap; on the order of 5 eV, for example. At room temperature, 300 K, only about 0.025 eV of thermal energy is available to excite electrons above the valence bandnot nearly enough to overcome an insulators energy gap. Therefore, at such temperatures, the Fermi-Dirac distribution predicts that very few electrons are thermally excited into the conduction band. Although an insulator has many vacant states in its conduction band that can accept electrons, there are no available states that lie close in energy above the valence band and

Mendoza, David

Diels-Alder Chemistry of Graphene

CHE 392 Fall 12

into which electrons can move upward to account for the extra kinetic energy associated with motion through the material in response to an electric field. For this reason, electrons do not move in substances with large band gaps.9 Semiconductors have the same type of band structure as an insulator, but their energy band gaps are much smalleron the order of 1 eV. Because this energy gap separation between the conduction and valence bands is small at sufficient temperatures and the Fermi energy level is located near the middle of the gapappreciable numbers of electrons are thermally excited from the valence band to the conduction band. A small applied electric field is all that is required to excite a substantial number of these charge carriers to selectively produce a moderate current.9 The field-effect transistor, the cornerstone of the integrated circuita multitrillion-dollar industry that produces popular devices like MP3 players and computersdepends on this semiconducting property.9 Under a given voltage, half of a transistor may be able to conduct electricity, while the other half may be depleted of charge carriers; yet, under a different voltage, the halves can switch roles. Transistors do not only conduct electricity; they selectively respond to varying voltages to propagate, terminate, or more commonly, amplify, a potential difference. The lack of an energy gap, albeit minor, presents an obstacle for graphenes application for use in electronics. In order for graphene to achieve its marketable potential, scientists must reverse engineer an energy gap into it. Indeed, other forms of carbon have been demonstrated to be affected in this way after chemical transformation. For example, metallic single-walled carbon nanotubes (structurally very similar to single-layer graphene) were shown to react by covalent bond formation with dichlorocarbene, to effectively open their energy band gap, and change their electrical properties from metal to semiconductor.13 Scientists are searching for a method to affect this change in graphene. Otherwise, graphenes extraordinary conductivity cannot be selectively controlled or harnessed. CHEMICAL REACTIVITY OF GRAPHENE The Band Gap as an Index of Chemical Reactivity The energy band gap is doubly important in this discussion of graphene because, according to frontier molecular orbital (FMO) theory, it also determines the chemical reactivity of a substance. From an FMO theory standpoint, the conduction and valence bands are known as the HOMO (highest occupied molecular orbital) and the LUMO (lowest unoccupied molecular orbital). Both of these orbitals comprise the frontier molecular orbitals. The HOMO energy level predicts the ionization potential (IP) of a molecule; inversely, the LUMO predicts its electron affinity (EA).14 Moreover, both theoretical and experimental studies have revealed that the energy gap between the HOMO and LUMO is an important stability index, in which: a large gap connotes high stability and a small gap connotes low stability. It follows that high stability indicates low reactivity and low stability indicates high reactivity. Indeed, as stated by Ghosh and Jana,15 scientists have observed that: the energy and symmetry types of such frontier orbitals are also found to be a principal factor for determining the occurrence and non-occurrence of chemical reactions and the stereo-selective path in intra- and inter-molecular processes. Therefore, the frontier orbitals of a molecule and the energy gap between them, determine not only its chemical reactivity but also the mechanisms by which their reactions proceed. Mathematically, this idea is supported by second-order perturbation theory, which describes complicated quantum systems. The model defines the energy change of a reaction

Mendoza, David

Diels-Alder Chemistry of Graphene

CHE 392 Fall 12

(E) by dividing the matrix elements describing the overlap and symmetry of the FMOs of two reactant molecules by the difference between the orbital energies of the FMOs: E = [H(HOMO-reactant A), (LUMO-reactant B)]2 + [H(HOMO-reactant B), (LUMO-reactant A)]2 HOMO-reactant A - LUMO-reactant B HOMO-reactant B - LUMO-reactant A (1)

The values of HOMO and LUMO represent ionization potential and electron affinity, as stated previously. Of course, as their difference (H-L) decreases in magnitude, E increases. In this way, FMO theory suggests that the energy gap between the reactant FMOs is an excellent inverse of chemical reactivity.14 For these reasons, graphene is predicted to exhibit significant chemical reactivity. This is in spite of the fact that graphene is the thermodynamic reference for carbon and the prototypical stable benzenoid hydrocarbon. After all, graphene is aromatic, and aromatic molecules do not usually participate in ground-state reactions.3 However, graphenes casein which the HOMO and LUMO have energy levels that cross at a single point at the Fermi level, the Dirac point (W 4.6 eV)is very different from a normal molecular system. Its HOMO is exceptionally lowlying and its LUMO is exceptionally high-lying.14 Therefore, according to FMO theory, graphene should be an extremely reactive macromolecule. DIELS-ALDER CHEMISTRY OF GRAPHENE Part of the wave of graphene research that has passed over the global scientific community has been devoted to exploring graphenes chemical reactivity. Indeed, the key to altering graphene to make it suitable for semiconductor application may be through organic chemical functionalization. To this effect, Santanu Sarkar, Elena Bekyarova, Sandip Niyogi, and Robert Haddon3 explored graphenes reactivity in the powerful Diels-Alder reaction at the University of California, Riverside, in 2011. The Diels-Alder Reaction The Diels-Alder reaction is a cycloaddition that is extremely useful in organic synthesis because it forms two carbon-carbon bonds in a single step and is one of the few general methods available for making cyclic molecules. This reaction is considered one of the most powerful and elegant reactions in organic chemistry. It is neither polar nor radical. It is a pericyclic process in which there is a cyclic redistribution of bonding electrons that takes place in a single step (in a concerted fashion). Additionally, because it is a pericyclic, the Diels-Alder reaction can take place only if the symmetries of the reactant molecular orbitals (MOs) are the same as the symmetries of the product MOs. That is, the signs of the wave functions of the lobes of the reactant MOs must be of matching algebraic sign for bonding to occur in the transition state leading to the product. When these symmetries match, the reaction is said to be symmetryallowed.16 Thus, the Diels-Alder reaction can be analyzed from the standpoint of orbital symmetry and correlation diagrams together with the FMOs of the reactants and their relative energies. For example, the classic Diels-Alder reaction is illustrated between the diene, butadiene, and the dienophile, ethylene. It should be noted that although there are only two HOMO-LUMO pairs interacting in this reaction, it is sufficient to consider only one pair in this discussions experiments because FMO theory focuses on the energy band gap between the interacting

Mendoza, David

Diels-Alder Chemistry of Graphene

CHE 392 Fall 12

orbitals. The FMO analysis describing the Diels-Alder reaction between butadiene and ethylene is shown in Figure 1.14 The diagram shows how the antisymmetric LUMO of ethylene interacts with the antisymmetric HOMO of butadiene to produce a symmetry-allowed bond formation that results in cyclohexene. In a more general sense, this FMO analysis shows a charge transfer between reactants: electron density is transferred from an occupied orbital (HOMO) of one reactant to the unoccupied orbital (LUMO).14 Diels-Alder reactivity can be explained and predicted using this model. When Sarkar et al.3 applied it to graphene, they demonstrated not only that the 2D crystal lattice exhibited facile reactivity in the Diels-Alder reaction, but that it could serve independently as either a diene or dienophile. The theoretical resonance forms that result in this dual reactivity are illustrated in Scheme 1.3 FMO Theory Justification of Graphenes Figure 1. Diels-Alder orbital symmetry correlation diagram for the reaction of ethylene with butadiene, together with Dual Diels-Alder Reactivity frontier molecular orbital (FMO) interactions. The orbitals FMO theory usually predicts that one 14 are classified as either symmetric (S) or antisymmetric (A). molecule in a chemical reaction presents a donor orbital while the other molecule presents an acceptor orbital. In graphene, the energies for both frontier orbitals are the same; this means that both its ionization potential and electron affinity values are the same. Intuitively speaking, graphene is as likely to accept an electron in a chemical reaction as it is to donate one.14 As such, graphene presents a unique case. By analysis with the second-order perturbation theory, graphene should exhibit extreme reactivity as a Diels-Alder partner in both respects. The fastest reaction rate for the Diels-Alder reaction is known to be between diene, 9,10dimethylanthracene (DMA, IP = 7.1 eV) and dienophile, tetracyanoethylene (TCNE, EA = 2.9 eV). The difference between HOMO and LUMO (H-L) for these two reactants is 4.2 eV. In contrast, H-L in the case of graphene and DMA is 2.5 Scheme 1. Resonance forms of graphene: Graphene as Diene (1) 3 and Dienophile (2) eV; in the case of graphene and TCNE, H-L is 1.7 eV. These values are significantly lower than the 4.2 eV H-L value in the fastest Diels-Alder reaction. Therefore, by consideration of FMO energy levels, graphene should have an extremely high reactivity as both a diene and dienophile in the Diels-Alder reaction.14

Mendoza, David

Diels-Alder Chemistry of Graphene

CHE 392 Fall 12

Of course, neither reaction can proceed if the orbital symmetries do not match. An analysis of the orbital symmetry correlation diagram is presented in Figure 2.14 In fact, it shows that because graphenes HOMO and LUMO meet at the Dirac point, there is a choice in its electronic configuration. Thus, graphene can accommodate an electron pair in either the antisymmetric (Figure 2a) or the symmetric (Figure 2b) orbitalmaking it capable to function as both donor and acceptor within FMO theory by matching the orbital symmetries of its DielsAlder partner. As a diene reacting with ethylene, the antisymmetric graphene orbital donates electron density to ethylene, whereas the symmetric orbital of graphene functions as an acceptor (Figure 2a). Similarly, as a dienophile reacting with butadiene, the antisymmetric graphene orbital accepts electron density from butadiene, whereas the symmetric orbital of graphene functions as a donor (Figure 2b). As such, Sarkar, Bekyarova, and Haddon14 show that graphene can theoretically function as diene or dienophile with equal ease according to FMO theory. Methods These researchers tested this hypothesis with four common Diels-Alder partnerstwo dienophiles (tetracyanoethylene (TCNE) and maleic anhydride (MA)) and two dienes (9methylanthracene (9-MeA) and 2,3-dimethoxy1,3-butadiene (DMBD). In each case, graphenes facile Diels-Alder reactivity was demonstrated. Three different forms of graphene were used in each experiment: (1) highly oriented pyrolytic graphite (HOPG), which consists of oriented crystallites of graphene with a dimension of approximately 1 m; (2) single layer (SLG) and few layer graphenes (FLG) on a silicon dioxide substrate, acquired from exfoliation of natural graphite that were available in two forms, as flakes (XGsol) or flakes (XGflake); and, (3) epitaxial graphene (EG), which is grown on SiC by thermal desorption of Si or in an inert gas environment.14 The researchers used Raman spectroscopy to analyze the Diels-Alder reactants and products in each experiment. This technique allowed them to follow the progress of these reactions through its sensitivity to the degree of defect sites introduced into the periodic graphene lattice as well as the -electron distribution. Indeed, Raman spectroscopy has been shown to be an especially sensitive method for monitoring basalplace covalent chemical reactions in different forms graphene.3
Figure 2. Orbital symmetry correlation diagram for the Diels-Alder reaction of ethylene and butadiene with graphene (FMOs taken from the bad structure of graphene at the Dirac point) where the signs of the lobes of the p orbitals above the plan are given by open and solid 14 circles.

Experiment: Graphene as a Diene All three forms of graphene were found to react with dienophile TCNE in anhydrous dichloromethane at room temperature. Raman spectroscopy, following the progress of the reaction in each functionalization of graphene with TCNE, showed D, D', and D+D' peaks in the spectra of the products. The researchers attribute the appearance of the D band to the A1g breathing vibrations of six-membered sp2 carbon rings and becomes Raman-active after the symmetry of the nearby lattice is reduced by the introduction of defects or functionality in

Mendoza, David

Diels-Alder Chemistry of Graphene

CHE 392 Fall 12

graphitic materials.3 The defects to the graphene lattice they referred to are the Diels-Alder adducts appearing after successful reactions. Graphene was also demonstrated to react as a diene with MA. However, it was found to be sensitive to the type of the graphene sample and the temperature of the reaction. The optimum reaction temperatures for the three graphene samples with MA were: HOPG, 120 C; XGsol, 130 C; and EG, 70 C. Because of the thermal instability of DA adducts, further increases in temperature led to products with a decreased amount of functionality.3 These results are supported by FMO theory in that the H-L value for the Diels-Alder reaction between graphene and TCNE (1.7 eV) is lower than that between graphene and MA (3.4 eV). These H-L values suggest that graphene is theoretically more reactive with TCNE and graphene. The experiment supported this finding because the reaction with TCNE proceeded at room temperature whereas functionalization with MA required a reaction temperature of 120 C.14 Experiment: Graphene as a Dienophile Sarkar et al.3 were also successful in their efforts to demonstrate that graphene could react as a dienophile, once again with all three graphene samples. The two dienes that were used were 9-MeA and DMBD. They found that 9-MeA cycloadducts could be obtained in high yield by treating HOPG or XGsol with a p-xylene solution of 9-MeA at 130 C. With DMBD, they achieved their best result with EG at the relatively low temperature of 50 C under an argon atmosphere. The four reactions that show the dual nature of graphene as Diels-Alder partner are displayed in Scheme 2.14

Scheme 2. Dual nature of reactivity of Graphene in Diels-Alder chemistry.

14

Reverse Engineering a Band Gap in Graphene through Diels-Alder Chemistry As mentioned previously, graphene cannot fulfill its potential as the semiconductor of the future, unless it is modified in some way to overcome its zero-band gap. With its zero-band gap, graphene exhibits conductivity that is too high to function as a semiconductor. However, functionalization through the Diels-Alder reaction potentially offers a method for altering its electrical properties and its zero-band gap. By demonstrating that graphene can react by Diels-Alder chemistry, Sarkar et al.3 also showed that a pair of neighboring sp2 carbons in the graphene honeycomb lattice can be

Mendoza, David

Diels-Alder Chemistry of Graphene

CHE 392 Fall 12

transformed into sp3 hybridized centers. These centers represent defects in the otherwise highlypure 2D crystal plane that reduce graphenes metallic character, and thus, potentially open a band gap. Although the researchers did not definitively demonstrate the loss of the zero-band gap, they did provide evidence that one modified graphene sample, the DMBD-EG adduct, had undergone a change in electrical properties. They compared the four-point resistances of pristine EG and the DMBD-EG adduct and observed two changes: (1) the room-temperature resistance of the functionalized sample was 60% larger than that of unmodified EG, and (2) the resistance of the functionalized sample exhibited an increased temperature dependence (like a semiconductor). As mentioned, a semiconductors resistance decreases with increasing temperature because additional kinetic energy promotes electrons from its valence band to its conduction band. Like a metal, EGs resistance decreases with decreasing temperatures below 110 K; it increases only slightly beyond this temperature. However, the DMBD-EG adduct shows nonmetallic behavior over the whole temperature range, characteristic of weak localization and similar to a semiconductor.3 CONCLUSION Graphene is one of the most promising and versatile materials ever discovered.17 As engineers reach the limits of silicons semiconducting capacity, many are looking to graphene to replace it. If graphene can be successfully modified, smaller and faster integrated circuits can be builtamong a host of other electronics. It is on the roadmap of new semiconductors, but a graphene chip is not yet within reach. Santanu Sarkar, Elena Bekyarova, Sandip Niyogi, and Robert C. Haddon3chemists at the University of California, Riversidedemonstrated that graphene undergoes organic chemical functionalization through the powerful Diels-Alder (DA) reaction, uniquely as both a diene and dienophile. These scientists propose that the Diels-Alder reaction offers a simple and efficient approach for reverse engineering a band gap into the 2D crystalpreparing graphene for future electronic and optical applications.
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Carmody, T. Why graphene won scientists the nobel prize. Wired 2010. http://www.wired.com/gadgetlab/2010/10/graphene/ (December 6, 2012). 2 Brumflel, G. Graphene gets ready for the big time. Nature 2009, 458, 390-391. 3 Sarkar, S.; Bekyarova, E.; Niyogi, S.; Haddon, R. C. Diels-Alder chemistry of graphite and graphene: Graphene as diene dienophile. J. Am. Chem. Soc. 2011, 133, 3324-3327. 4 Allen, M. J.; Tung, V. C.; Kaner, R. B. Honeycomb carbon: A review of graphene. Chem. Rev. 2010, 110, 132-145. 5 Dreyer, D. R.; Ruoff, R. S.; Bielawski, C. W. From conception to realization: An historical account of graphene and some perspectives for its future. Angew. Chem. Int. Ed. 2010, 49, 9336-9345. 6 Geim, A. K.; Novoselov, K. S. The rise of graphene. Nature Matur. 2007, 6, 183-191. 7 Overbye, D. Physics Nobel honors work on ultra-thin carbon. New York Times 2010. http://www.nytimes.com/2010/10/06/science/06nobel.html (December 6, 2012). 8 Lee, C.; Wei, X.; Kysar, J. W.; Hone, J. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 2008, 321, 385-388. 9 Serway, R. A.; Jewett, Jr., J. W. Physics for scientists and engineers with modern physics, 8th. ed.; Brooks/Cole: New York, 2010; 1313-1320. 10 Wallace, P. R. The band theory of graphite. Phys. Rev. 1947, 71, 622-634. 11 Stander, N. Graphene - The missing link. 2007. http://large.stanford.edu/courses/2007/ap272/stander1/ (December 6, 2012). 12 Preuss, P. Surprising graphene: Honing in on graphene electronics with infrared synchrotron radiation . 2008. http://www.lbl.gov/Science-Articles/Archive/ALS-graphene.html (December 6, 2012).

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Kamaras, K.; Itkis, M. E.; Hu, H.; Zhao, B.; Haddon, R. C. Covalent bond formation to a carbon nanotube metal. Science 2003, 301, 1501. 14 Sarkar, S.; Bekrayova, E.; Haddon, R. C. Chemistry at the Dirac point: Diels-Alder reactivity of graphene. Acc. Chem. Res. 2012, 45, 673-682. 15 Ghosh, D. C.; Jana, J. A study of correlation of the order of chemical reactivity of a sequence of binary compounds of nitrogen and oxygen in terms of frontier orbital theory. 1998. http://www.iisc.ernet.in/currsci/feb25/articles23.htm (December 6, 2012). 16 McMurry, J. Organic chemistry, 6th. ed.; Thomson Learning: Belmont, CA, 2004; 1134-1142. 17 Carmody, T. Why graphene won scientists the nobel prize. Wired 2010. http://www.wired.com/gadgetlab/2010/10/graphene/ (December 6, 2012).