Jaemyung Kim

Graphene Oxide Sheets at Interfaces

Graphite oxide sheet, now called graphene oxide (GO), is the product of chemical exfoliation of graphite and has been known for more than a century. GO has been largely viewed as hydrophilic, presumably due to its excellent colloidal stability in water. Here we report that GO is an amphiphile with hydrophilic edges and a more hydrophobic basal plane. GO can act like a surfactant, as measured by its ability to adsorb on interfaces and lower the surface or interfacial tension. Since the degree of ionization of the edge -COOH groups is affected by pH, GOs amphiphilicity can be tuned by pH. In addition, size-dependent amphiphilicity of GO sheets is observed. Since each GO sheet is a single molecule as well as a colloidal particle, the molecule-colloid duality makes it behave like both a molecular and a colloidal surfactant. For example, GO is capable of creating highly stable Pickering emulsions of organic solvents like solid particles. It can also act as a molecular dispersing agent to process insoluble materials such as graphite and carbon nanotubes in water. The ease of its conversion to chemically modified graphene could enable new opportunities in solution processing of functional materials.

Visualizing graphene based sheets by fluorescence quenching microscopy.

Graphene based sheets have stimulated great interest due to their superior mechanical, electrical, and thermal properties. A general visualization method that allows quick observation of these single atomic layers would be highly desirable as it can greatly facilitate sample evaluation and manipulation, and provide immediate feedback to improve synthesis and processing strategies. Here we report that graphene based sheets can be made highly visible under a fluorescence microscope by quenching the emission from a dye coating, which can be conveniently removed afterward by rinsing without disrupting the sheets. Current imaging techniques for graphene based sheets rely on the use of special substrates. In contrast, the fluorescence quenching mechanism is no longer limited by the type of substrate. Graphene, reduced graphene oxide, or even graphene oxide sheets deposited on arbitrary substrates can now be readily visualized with good contrast for layer counting. Direct observation of suspended sheets in solution was also demonstrated. The fluorescence quenching microscopy offers unprecedented imaging flexibility and could become a general tool for characterizing graphene based materials.

Two Dimensional Soft Material: New Faces of Graphene Oxide

Graphite oxide sheets, now called graphene oxide (GO), can be made from chemical exfoliation of graphite by reactions that have been known for 150 years. Because GO is a promising solution-processable precursor for the bulk production of graphene, interest in this old material has resurged. The reactions to produce GO add oxygenated functional groups to the graphene sheets on their basal plane and edges, and this derivatization breaks the π-conjugated network, resulting in electrically insulating but highly water-dispersible sheets. Apart from making graphene, GO itself has many intriguing properties. Like graphene, GO is a two-dimensional (2D) sheet with feature sizes at two abruptly different length scales. The apparent thickness of the functionalized carbon sheet is approximately 1 nm, but the lateral dimensions can range from a few nanometers to hundreds of micrometers. Therefore, researchers can think of GO as either a single molecule or a particle, depending on which length scale is of greater interest. At the same time, GO can be viewed as an unconventional soft material, such as a 2D polymer, highly anisotropic colloid, membrane, liquid crystal, or amphiphile. In this Account, we highlight the soft material characteristics of GO. GO consists of nanographitic patches surrounded by largely disordered, oxygenated domains. Such structural characteristics effectively make GO a 2D amphiphile with a hydrophilic periphery and largely hydrophobic center. This insight has led to better understanding of the solution properties of GO for making thin films and new applications of GO as a surfactant. Changes in pH and sheet size can tune the amphiphilicity of GO, leading to intriguing interfacial activities. In addition, new all-carbon composites made of only graphitic nanostructures using GO as a dispersing agent have potential applications in photovoltaics and energy storage. On the other hand, GO can function as a 2D random diblock copolymer, one block graphitic and the other heavily hydroxylated. Therefore, GO can guide material assembly through π-π stacking and hydrogen bonding. Additionally, the selective etching of the more reactive sp(3) blocks produces a porous GO network, which greatly enhances interactions with gas molecules in chemical sensors. With their high aspect ratio, GO colloids can readily align to form liquid crystalline phases at high concentration. As single-atomic, water-dispersible, soft carbon sheets that can be easily converted to a conductive form, this 2D material should continue to inspire many curiosity-driven discoveries and applications at the interfaces of chemistry, materials science, and other disciplines.

Chemically exfoliated MoS2 as near-infrared photothermal agents.

The near-infrared (NIR) window refers to a range of wavelengths (700–1300 nm) in which biological tissues are highly transparent.[1] Consequently, biological imaging and therapy modalities employ light at these wavelengths for the monitoring[1] and triggering[2] of biological events in vitro and in vivo. For instance, photothermal ablation takes advantage of NIR absorbing materials for transducing light into heat.[2] The resultant thermal energy can be used for a number of applications, such as tissue ablation and drug release. Despite the intense interest in NIR photothermal agents, their development has suffered from considerable challenges. In particular, few nanomaterials display the requisite absorption profiles required for NIR photothermal transduction.

Graphene oxide as surfactant sheets

Graphite oxide sheet, now referred to as graphene oxide (GO), is the product of chemical oxidation and exfoliation of graphite powders that was first synthesized over a century ago. Interest in this old material has resurged in recent years, especially after the discovery of graphene, as GO is considered a promising precursor for the bulk production of graphene-based materials. GO sheets are single atomic layers that can readily extend up to tens of microns in lateral dimension. Therefore, their structure bridges the typical length scales of both chemistry and materials science. GO can be viewed as an unconventional type of soft material as it carries the characteristics of polymers, colloids, membranes, and as highlighted in this review, amphiphiles. GO has long been considered hydrophilic due to its excellent water dispersity, however, our recent work revealed that GO sheets are actually amphiphilic with an edge-to-center distribution of hydrophilic and hydrophobic domains. Thus, GO can adhere to interfaces and lower interfacial energy, acting as surfactant. This new property insight helps to better understand GO’s solution properties which can inspire novel material assembly and processing methods such as for fabricating thin films with controllable microstructures and separating GO sheets of different sizes. In addition, GO can be used as a surfactant sheet to emulsify organic solvents with water and disperse insoluble materials such as graphite and carbon nanotubes (CNTs) in water, which opens up opportunities for creating functional hybrid materials of graphene and other π-conjugated systems.

Ligand Conjugation of Chemically Exfoliated MoS2

MoS2 is a two-dimensional material that is gaining prominence due to its unique electronic and chemical properties. Here, we demonstrate ligand conjugation of chemically exfoliated MoS2 using thiol chemistry. With this method, we modulate the ζ-potential and colloidal stability of MoS2 sheets through ligand designs, thus enabling its usage as a selective artificial protein receptor for β-galactosidase. The facile thiol functionalization route opens the door for surface modifications of solution processable MoS2 sheets.

Enhanced Electrocatalytic Properties of Transition-Metal Dichalcogenides Sheets by Spontaneous Gold Nanoparticle Decoration

Here, we report that transition-metal dichalcogenides such as MoS2 and WS2 can be decorated with gold nanoparticles by a spontaneous redox reaction with hexachloroauric acid in water. The resulting gold nanoparticles tend to grow at defective sites, and therefore, selective decorations at the edges and the line defects in the basal planes of bulk single crystals were observed. The lithium intercalation-exfoliation process makes the basal planes of chemically exfoliated MoS2 and WS2 sheets much more defective than their single-crystalline counterparts, leading to a more uniform and higher-density deposition of gold nanoparticles. Due to the greatly improved charge transport between adjacent sheets, the resulting MoS2/Au and WS2/Au hybrids show significantly enhanced electrocatalytic performance toward hydrogen evolution reactions.

Surfactant-free water-processable photoconductive all-carbon composite.

Heterojunctions between different graphitic nanostructures, including fullerenes, carbon nanotubes and graphene-based sheets, have attracted significant interest for light to electrical energy conversion. Because of their poor solubility, fabrication of such all-carbon nanocomposites typically involves covalently linking the individual constituents or the extensive surface functionalization to improve their solvent processability for mixing. However, such strategies often deteriorate or contaminate the functional carbon surfaces. Here we report that fullerenes, pristine single walled carbon nanotubes, and graphene oxide sheets can be conveniently coassembled in water to yield a stable colloidal dispersion for thin film processing. After thermal reduction of graphene oxide, a solvent-resistant photoconductive hybrid of fullerene-nanotube-graphene was obtained with on-off ratio of nearly 6 orders of magnitude. Photovoltaic devices made with the all-carbon hybrid as the active layer and an additional fullerene block layer showed unprecedented photovoltaic responses among all known all-carbon-based materials with an open circuit voltage of 0.59 V and a power conversion efficiency of 0.21%. The ease of making such surfactant-free, water-processed, carbon thin films could lead to their wide applications in organic optoelectronic devices.

Sticky Interconnect for Solution-Processed Tandem Solar Cells

Graphene oxide (GO) can be viewed as a two-dimensional, random diblock copolymer with distributed nanosize graphitic patches and highly oxidized domains, thus capable of guiding the assembly of other materials through both π-π stacking and hydrogen bonding. Upon mixing GO and conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) in water, a dispersion with dramatically increased viscosity is obtained, which turns into sticky thin films upon casting. Surprisingly, the insulating GO makes PEDOT much more conductive by altering its chain conformation and morphology. The GO/PEDOT gel can function as a metal-free solder for creating mechanical and electrical connections in organic optoelectronic devices. As a proof-of-concept, polymer tandem solar cells have been fabricated by a direct adhesive lamination process enabled by the sticky GO/PEDOT film. The sticky interconnect can greatly simplify the fabrication of organic tandem architectures, which has been quite challenging via solution processing. Thus, it could facilitate the construction of high-efficiency tandem solar cells with different combinations of solution-processable materials.

Tunable assembly of graphene oxide surfactant sheets: wrinkles, overlaps and impacts on thin film properties

Graphene oxide (GO) sheets are a unique type of soft building block for creating functional graphene based materials and devices. Rapid progress has been made in the chemistry and applications of GO. However, there is a pressing need for rational assembly strategies of these two-dimensional (2D) sheets, which is crucial for determining the microstructures and thus final properties of bulk GO or graphene materials. For example, wrinkles and overlaps are the two fundamental morphologies between flexible, interacting sheets that are usually convoluted in solution-processed thin films. Based on the recent discovery of the surfactant-like property of GO sheets and their pH dependent amphiphilicity, now we are able to control the tiling of such 2D sheets to obtain thin films with either a wrinkled or overlapped type of microstructure, thus allowing us to deconvolute how these two basic microstructures affect the electrical and optical properties of the final thin films. The work here provides a well-defined example of the materials science paradigm, the microstructure-properties relationship, for this new soft material.