Effects of Photochemical Oxidation of the Carbonaceous Additives on Li-S Cell Performance.

We introduce a simple and easy way to functionalize the surface of various carbonaceous materials through the ultraviolet light/ozone (UV/O3) plasma where we utilize the zero-, one-, and two-dimensional carbon frameworks. In a general manner, the lamps of a UV/O3 generator create two different wavelengths (λ = 185 and 254 nm); the shorter wavelength (λ = 185 nm) dissociates the oxygen (O2) in air and the longer wavelength (λ = 254 nm) dissociates the O3 and creates the reactive and monoatomic oxygen radical, which tends to incorporate onto the defects of the carbons. By tailoring the association and dissociation of the oxygen with various forms, carbon black, carbon nanofibers, and graphite flakes, chosen as representative models for the zero-, one-, and two-dimensional carbon frameworks, their structure can be oxidized, respectively, which is known as photochemical oxidation. Various carbons have their own distinctive morphology and electron transport properties, which are applicable for the lithium-sulfur (Li-S) cell. We, here, report on the improvement of electrochemical performance of the lithium/sulfur cell through such an efficient functionalization approach.

Graphene Quantum Dots from Carbonized Coffee Bean Wastes for Biomedical Applications.

Recent studies concerning graphene quantum dots (GQDs) focus extensively on their application in biomedicine, exploiting their modifiable optical properties and ability to complex with various molecules via π-π or covalent interactions. Among these nascent findings, the potential therapeutic efficacy of GQDs was reported against Parkinson's disease, which has to date remained incurable. Herein, we present an environmentally friendly approach for synthesizing GQDs through a waste-to-treasure method, specifically from coffee waste to nanodrug. Consistent with the previous findings with carbon fiber-derived GQDs, the inhibitory effects of coffee bean-derived GQDs demonstrated similar effectiveness against abnormal α-synuclein fibrillation and the protection of neurons from relevant subcellular damages. The fact that a GQDs-based nanodrug can be prepared from a non-reusable yet edible source illustrates a potential approach to convert such waste materials into novel therapeutic agents with minimal psychological rejection by patients.

Sub-micro droplet reactors for green synthesis of Li3VO4 anode materials in lithium ion batteries.

The conventional solid-state reaction suffers from low diffusivity, high energy consumption, and uncontrolled morphology. These limitations are competed by the presence of water in solution route reaction. Herein, based on concept of combining above methods, we report a facile solid-state reaction conducted in water vapor at low temperature along with calcium doping for modifying lithium vanadate as anode material for lithium-ion batteries. The optimized material, delivers a superior specific capacity of 543.1, 477.1, and 337.2 mAh g-1 after 200 and 1000 cycles at current densities of 100, 1000 and 4000 mA g-1, respectively, which is attributed to the contribution of pseudocapacitance. In this work, we also use experimental and theoretical calculation to demonstrate that the enhancement of doped lithium vanadate is attributed to particles confinement of droplets in water vapor along with the surface and structure variation of calcium doping effect.

Tailored Graphene Micropatterns by Wafer-Scale Direct Transfer for Flexible Chemical Sensor Platform.

2D materials, such as graphene, exhibit great potential as functional materials for numerous novel applications due to their excellent properties. The grafting of conventional micropatterning techniques on new types of electronic devices is required to fully utilize the unique nature of graphene. However, the conventional lithography and polymer-supported transfer methods often induce the contamination and damage of the graphene surface due to polymer residues and harsh wet-transfer conditions. Herein, a novel strategy to obtain micropatterned graphene on polymer substrates using a direct curing process is demonstrated. Employing this method, entirely flexible, transparent, well-defined self-activated graphene sensor arrays, capable of gas discrimination without external heating, are fabricated on 4 in. wafer-scale substrates. Finite element method simulations show the potential of this patterning technique to maximize the performance of the sensor devices when the active channels of the 2D material are suspended and nanoscaled. This study contributes considerably to the development of flexible functional electronic devices based on 2D materials.

Hierarchical carbon-silicon nanowire heterostructures for the hydrogen evolution reaction.

Silicon nanowires (SiNWs) opened up exciting possibilities in a variety of research fields due to their unique anisotropic morphologies, facile tuning capabilities, and accessible fabrication methods. The SiNW-based photoelectrochemical (PEC) conversion has recently been known to provide an efficiency superior to that of various photo-responsive semiconductor heterostructures. However, a challenge still remains in designing optimum structures to minimize photo-oxidation and photo-corrosion of the Si surface in a liquid electrolyte. Here, we report a simple method to synthesize hierarchically branched carbon nanowires (CNWs) on SiNWs utilizing copper vapor as the catalyst in a chemical vapor deposition (CVD) process, which exhibits outstanding photocatalytic activities for hydrogen generation along with excellent chemical stability against oxidation and corrosion. Thus, we believe that the CNW-SiNW photoelectrodes would provide a new route to developing high-performing cost-effective catalysts essential for advanced energy conversion and storage technologies.

Smart Contact Lenses with Graphene Coating for Electromagnetic Interference Shielding and Dehydration Protection.

Recently, smart contact lenses with electronic circuits have been proposed for various sensor and display applications where the use of flexible and biologically stable electrode materials is essential. Graphene is an atomically thin carbon material with a two-dimensional hexagonal lattice that shows outstanding electrical and mechanical properties as well as excellent biocompatibility. In addition, graphene is capable of protecting eyes from electromagnectic (EM) waves that may cause eye diseases such as cataracts. Here, we report a graphene-based highly conducting contact lens platform that reduces the exposure to EM waves and dehydration. The sheet resistance of the graphene on the contact lens is as low as 593 Ω/sq (±9.3%), which persists in an wet environment. The EM wave shielding function of the graphene-coated contact lens was tested on egg whites exposed to strong EM waves inside a microwave oven. The results show that the EM energy is absorbed by graphene and dissipated in the form of thermal radiation so that the damage on the egg whites can be minimized. We also demonstrated the enhanced dehydration protection effect of the graphene-coated lens by monitoring the change in water evaporation rate from the vial capped with the contact lens. Thus, we believe that the graphene-coated contact lens would provide a healthcare and bionic platform for wearable technologies in the future.

Double-Layer Graphene Outperforming Monolayer as Catalyst on Silicon Photocathode for Hydrogen Production.

Photoelectrochemical cells are used to split hydrogen and oxygen from water molecules to generate chemical fuels to satisfy our ever-increasing energy demands. However, it is a major challenge to design efficient catalysts to use in the photoelectochemical process. Recently, research has focused on carbon-based catalysts, as they are nonprecious and environmentally benign. Interesting advances have also been made in controlling nanostructure interfaces and in introducing new materials as catalysts in the photoelectrochemical cell. However, these catalysts have as yet unresolved issues involving kinetics and light-transmittance. In this work, we introduce high-transmittance graphene onto a planar p-Si photocathode to produce a hydrogen evolution reaction to dramatically enhance photon-to-current efficiency. Interestingly, double-layer graphene/Si exhibits noticeably improved photon-to-current efficiency and modifies the band structure of the graphene/Si photocathode. On the basis of in-depth electrochemical and electrical analyses, the band structure of graphene/Si was shown to result in a much lower work function than Si, accelerating the electron-to-hydrogen production potential. Specifically, plasma-treated double-layer graphene exhibited the best performance and the lowest work function. We electrochemically analyzed the mechanism at work in the graphene-assisted photoelectrode. Atomistic calculations based on the density functional theory were also carried out to more fully understand our experimental observations. We believe that investigation of the underlying mechanism in this high-performance electrode is an important contribution to efforts to develop high-efficiency metal-free carbon-based catalysts for photoelectrochemical cell hydrogen production.

Strain Relaxation of Graphene Layers by Cu Surface Roughening.

The surface morphology of copper (Cu) often changes after the synthesis of graphene by chemical vapor deposition (CVD) on a Cu foil, which affects the electrical properties of graphene, as the Cu step bunches induce the periodic ripples on graphene that significantly disturb electrical conduction. However, the origin of the Cu surface reconstruction has not been completely understood yet. Here, we show that the compressive strain on graphene induced by the mismatch of thermal expansion coefficient with Cu surface can be released by forming periodic Cu step bunching that depends on graphene layers. Atomic force microscopy (AFM) images and the Raman analysis show the noticeably longer and higher step bunching of Cu surface under multilayer graphene and the weaker biaxial compressive strain on multilayer graphene compared to monolayer. We found that the surface areas of Cu step bunches under multilayer and monolayer graphene are increased by ∼1.41% and ∼0.77% compared to a flat surface, respectively, indicating that the compressive strain on multilayer graphene can be more effectively released by forming the Cu step bunching with larger area and longer periodicity. We believe that our finding on the strain relaxation of graphene layers by Cu step bunching formation would provide a crucial idea to enhance the electrical performance of graphene electrodes by controlling the ripple density of graphene.

Stable n-type doping of graphene via high-molecular-weight ethylene amines.

We demonstrate a stable and strong n-type doping method to tune the electrical properties of graphene via vapor phase chemical doping with various high-molecular-weight ethylene amines. The resulting carrier concentration after doping with pentaethylenehexamine (PEHA) is as high as -1.01 × 10(13) cm(-2), which reduces the sheet resistance of graphene by up to ∼400% compared to pristine graphene. Our study suggests that the branched structure of the dopant molecules is another important factor that determines the actual doping degree of graphene.

An electrochemical approach to graphene oxide coated sulfur for long cycle life.

Owing to the possibilities of achieving high theoretical energy density and gravimetric capacity, sulfur has been considered as a promising cathode material for rechargeable lithium batteries. However, sulfur shows rapid capacity fading due to the irreversible loss of soluble polysulfides and the decrease in active sites needed for conducting agents. Furthermore, the low electrical conductivity of sulfur hampers the full utilization of active materials. Here we report that graphene oxide coated sulfur composites (GO-S/CB) exhibit improved electrochemical stability as well as enhanced rate performance, evidenced by various electrochemical analyses. The cyclic voltammetry and the galvanostatic cycling analysis revealed that the GO plays key roles in homogenizing the nanocomposite structures of the electrodes, in improving the electrochemical contact, and in minimizing the loss of soluble polysulfide intermediates. An electrochemical impedance spectroscopy analysis also confirms the enhanced structural stability of the GO-S/CB composites after battery operation. As a result, the GO-S/CB exhibited excellent cycle stability and specific capacity as high as ∼723.7 mA h g(-1) even after 100 cycles at 0.5 C.

One-step synthesis of N-doped graphene quantum sheets from monolayer graphene by nitrogen plasma.

High-quality N-doped graphene quantum sheets are successfully fabricated from as-grown monolayer graphene on Cu using nitrogen plasma, which can be transferred as a film-like layer or easily dispersed in an organic solvent for further optoelectronic or photoelectrochemical applications.