Kian Ping Loh

The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets

Ultrathin two-dimensional nanosheets of layered transition metal dichalcogenides (TMDs) are fundamentally and technologically intriguing. In contrast to the graphene sheet, they are chemically versatile. Mono- or few-layered TMDs - obtained either through exfoliation of bulk materials or bottom-up syntheses - are direct-gap semiconductors whose bandgap energy, as well as carrier type (n- or p-type), varies between compounds depending on their composition, structure and dimensionality. In this Review, we describe how the tunable electronic structure of TMDs makes them attractive for a variety of applications. They have been investigated as chemically active electrocatalysts for hydrogen evolution and hydrosulfurization, as well as electrically active materials in opto-electronics. Their morphologies and properties are also useful for energy storage applications such as electrodes for Li-ion batteries and supercapacitors.

Graphene oxide as a chemically tunable platform for optical applications

Chemically derived graphene oxide (GO) is an atomically thin sheet of graphite that has traditionally served as a precursor for graphene, but is increasingly attracting chemists for its own characteristics. It is covalently decorated with oxygen-containing functional groups - either on the basal plane or at the edges - so that it contains a mixture of sp(2)- and sp(3)-hybridized carbon atoms. In particular, manipulation of the size, shape and relative fraction of the sp(2)-hybridized domains of GO by reduction chemistry provides opportunities for tailoring its optoelectronic properties. For example, as-synthesized GO is insulating but controlled deoxidation leads to an electrically and optically active material that is transparent and conducting. Furthermore, in contrast to pure graphene, GO is fluorescent over a broad range of wavelengths, owing to its heterogeneous electronic structure. In this Review, we highlight the recent advances in optical properties of chemically derived GO, as well as new physical and biological applications.

Graphene Photonics, Plasmonics, and Broadband Optoelectronic Devices

Graphene has been hailed as a wonderful material in electronics, and recently, it is the rising star in photonics, as well. The wonderful optical properties of graphene afford multiple functions of signal emitting, transmitting, modulating, and detection to be realized in one material. In this paper, the latest progress in graphene photonics, plasmonics, and broadband optoelectronic devices is reviewed. Particular emphasis is placed on the ability to integrate graphene photonics onto the silicon platform to afford broadband operation in light routing and amplification, which involves components like polarizer, modulator, and photodetector. Other functions like saturable absorber and optical limiter are also reviewed.

The chemistry of graphene

A review on the latest developments on graphene, written from the perspective of a chemist, is presented. The role of chemistry in bringing graphene research to the next level is discussed.

One-Pot Synthesis of Fluorescent Carbon Nanoribbons, Nanoparticles, and Graphene by the Exfoliation of Graphite in Ionic Liquids

In this work we demonstrate a facile means to generate fluorescent carbon nanoribbons, nanoparticles, and graphene from graphite electrode using ionic liquid-assisted electrochemical exfoliation. A time-dependence study of products exfoliated from the graphite anode allows the reconstruction of the exfoliation mechanism based on the interplay of anodic oxidation and anion intercalation. We have developed strategies to control the distribution of the exfoliated products. In addition, the fluorescence of these carbon nanomaterials can be tuned from the visible to ultraviolet region by controlling the water content in the ionic liquid electrolyte.

Molybdenum disulfide (MoS_2) as a broadband saturable absorber for ultra-fast photonics

The nonlinear optical property of few-layered MoS₂ nanoplatelets synthesized by the hydrothermal exfoliation method was investigated from the visible to the near-infrared band using lasers. Both open-aperture Z-scan and balanced-detector measurement techniques were used to demonstrate the broadband saturable absorption property of few-layered MoS₂. To explore its potential applications in ultrafast photonics, we fabricated a passive mode locker for ytterbium-doped fibre laser by depositing few-layered MoS₂ onto the end facet of optical fiber by means of an optical trapping approach. Our laser experiment shows that few-layer MoS₂-based mode locker allows for the generation of stable mode-locked laser pulse, centered at 1054.3 nm, with a 3-dB spectral bandwidth of 2.7 nm and a pulse duration of 800 ps. Our finding suggests that few-layered MoS₂ nanoplatelets can be useful nonlinear optical material for laser photonics devices, such as passive laser mode locker, Q-switcher, optical limiter, optical switcher and so on.

Origin of Enhanced Stem Cell Growth and Differentiation on Graphene and Graphene Oxide

The culture of bone marrow derived mesenchymal stem cells (MSCs), as well as the control of its differentiation toward different tissue lineage, is a very important part of tissue engineering, where cells are combined with artificial scaffold to regenerate tissues. Graphene (G) and graphene oxide (GO) sheets are soft membranes with high in-plane stiffness and can potentially serve as a biocompatible, transferable, and implantable platform for stem cell culture. While the healthy proliferation of stem cells on various carbon platforms has been demonstrated, the chemical role of G and GO, if any, in guiding uncommitted stem cells toward differentiated cells is not known. Herein, we report that the strong noncovalent binding abilities of G allow it to act as a preconcentration platform for osteogenic inducers, which accelerate MSCs growing on it toward the osteogenic lineage. The molecular origin of accelerated differentation is investigated by studying the binding abilities of G and GO toward different growth agents. Interestingly, differentiation to adipocytes is greatly suppressed on G because insulin, which is a key regulator for the synthesis of fatty acids, is denatured upon π-π adsorption on G; in contrast, GO does not interfere with adipogenesis due to electrostatic binding with insulin. The different binding interactions and their subsequent influence on stem cell growth and differentiation are ascribed to different degrees of π-π stacking and electrostatic and hydrogen bonding mediated by G and GO.

Electrocatalytically Active Graphene–Porphyrin MOF Composite for Oxygen Reduction Reaction

Pyridine-functionalized graphene (reduced graphene oxide) can be used as a building block in the assembly of metal organic framework (MOF). By reacting the pyridine-functionalized graphene with iron-porphyrin, a graphene-metalloporphyrin MOF with enhanced catalytic activity for oxygen reduction reactions (ORR) is synthesized. The structure and electrochemical property of the hybrid MOF are investigated as a function of the weight percentage of the functionalized graphene added to the iron-porphyrin framework. The results show that the addition of pyridine-functionalized graphene changes the crystallization process of iron-porphyrin in the MOF, increases its porosity, and enhances the electrochemical charge transfer rate of iron-porphyrin. The graphene-metalloporphyrin hybrid shows facile 4-electron ORR and can be used as a promising Pt-free cathode in alkaline Direct Methanol Fuel Cell.

Interface Engineering of Layer‐by‐Layer Stacked Graphene Anodes for High‐Performance Organic Solar Cells

The major efforts in solar energy research are currently directed at developing cost-effective systems for energy conversion and storage. [ 1–3 ] The high cost of materials and preparation methods that are required for the fabrication of inorganic solar cells prevent their widespread deployment. Seeking a low-cost alternative in the form of solution-processable or roll-to-roll printable organic solar cells features prominently in the energy research roadmap. The conventional anode of choice for organic solar cells has been indium tin oxide (ITO), which consumes as much as 30% of the fabrication cost in solar cells. High quality ITO is expensive due to the dwindling supplies of indium. ITO also suffers from drawbacks like brittleness, sensitivity to acids and bases during processing, and reactive interface formation with copper indium sulfi de during high-temperature sintering. Graphene fi lms have been proposed as the new generation of multifunctional, transparent, and conducting electrodes. The attractiveness of graphene arises from their low cost, transparency, high electrical conductivity, chemical robustness, and fl exibility, as opposed to the rising cost and brittleness of ITO. [ 4–6 ]

Transforming C60 molecules into graphene quantum dots

The fragmentation of fullerenes using ions, surface collisions or thermal effects is a complex process that typically leads to the formation of small carbon clusters of variable size. Here, we show that geometrically well-defined graphene quantum dots can be synthesized on a ruthenium surface using C(60) molecules as a precursor. Scanning tunnelling microscopy imaging, supported by density functional theory calculations, suggests that the structures are formed through the ruthenium-catalysed cage-opening of C(60). In this process, the strong C(60)-Ru interaction induces the formation of surface vacancies in the Ru single crystal and a subsequent embedding of C(60) molecules in the surface. The fragmentation of the embedded molecules at elevated temperatures then produces carbon clusters that undergo diffusion and aggregation to form graphene quantum dots. The equilibrium shape of the graphene can be tailored by optimizing the annealing temperature and the density of the carbon clusters.