Evidence for Trans-Oligoene Chain Formation in Graphene Induced by Iodine.

Functionalization of pristine graphene by hydrogen and fluorine is well studied, resulting in graphane and fluorographene structures. In contrast, functionalization of pristine graphene with iodine has not been reported. Here, the functionalization of graphene with iodine using photochemical activation is presented, which is thermally reversible at 400 °C. Additional dispersive dominant Raman modes that are probed by resonance Raman spectroscopy are observed. Additionally, iodinated graphene is probed by Kelvin probe force microscopy and by transport measurements showing p-doping surpassing non-covalent iodine doping by charge transfer-complex formation. The emergent Raman modes combined with strong p-doping indicate that iodine functionalization is distinct from simple iodine doping. A reaction mechanism based on these findings is proposed, identifying the large size of iodine atoms as the probable cause governing regiochemically controlled addition due to steric hinderance of reactive sites. The modification of the electronic structure is explained by the confinement of 1D trans-oligoene chains between sp3 -defects. These results demonstrate the uniqueness of iodine reactivity toward graphene and the modification of the electronic structure of iodinated graphene, highlighting its dependence on the spatial arrangement of substituents.

Influence of Lattice Defects on Trans-Oligoene Substructure Formation in Graphene.

The photochemical reaction of iodine and graphene induces strong new Raman modes due to the formation of trans-oligoene substructures in graphene domains. This unique reactivity was demonstrated before on defect-free graphene, however leaving the influence of e. g. carbon vacancies, unexplored. Here, we investigate the photochemical reaction applied on graphene with varying average distances of lattice defects and statistically analyze the characteristic Raman modes which develop with the iodination reaction. We show that the iodination reaction does not lead to Raman-active defects and thus, the newly formed trans-oligoene substructures do not contribute to the D-mode of graphene. A statistical analysis reveals the correlation between the average distance of lattice defects and the intensity of the v1-mode. For defective graphene with average defect distances below ~1 nm no new Raman modes evolve, which is the lower limit of the substructure size probed at 532 nm and explains why this observation was not possible before using common graphene oxide as graphene source.

Experimental and theoretical inquiry into optical properties of graphene derivatives.

Graphene oxide (GO), a functional derivative of graphene, is a promising nanomaterial for a variety of optoelectronic applications as it exhibits fluorescence and maintains many of graphene's beneficial physical properties. although other graphene derivatives are chemically plausible and may serve to the benefit of the aforementioned applications, GO remains the one heavily used. the nature of optical behavior of other graphene derivatives has yet to be fully understood and studied. in this work we develop a variety of graphene derivatives and characterize their optical properties concomitantly suggesting a unified model for optical emission in graphene derivatives. in this process we examine the influence of different functional groups on the surface of graphene on its optoelectronic properties. mildly oxidized graphene (oxo-g1), nitrated graphene, arylated graphene, brominated graphene, and fluorinated graphene are obtained and characterized via TEM and EDX, FTIR and fluorescence spectroscopies with the latter indicating a potential band gap-derived fluorescence from each of the materials. this suggests that optical properties of graphene derivatives have minimal functional group dependence and are manifested by the localized environments within the flakes. this is confirmed by the hyperchem theoretical modeling of all aforementioned graphene derivatives indicating a similar electronic configuration for all, assessed by the pm3 semi-empirical approach. this work can further serve to describe and predict optical properties of similar graphene-based structures and promote graphene derivatives other than GO for utilization in research and industry.

Electric field quenching of graphene oxide photoluminescence.

With the advent of graphene, there has been an interest in utilizing this material and its derivative, graphene oxide (GO) for novel applications in nanodevices such as bio and gas sensors, solid-state supercapacitors and solar cells. Although GO exhibits lower conductivity and structural stability, it possesses an energy band gap that enables fluorescence emission in the visible/near infrared leading to a plethora of optoelectronic applications. In order to allow fine-tuning of its optical properties in the device geometry, new physical techniques are required that, unlike existing chemical approaches, yield substantial alteration of GO structure. Such a desired new technique is one that is electronically controlled and leads to reversible changes in GO optoelectronic properties. In this work, we for the first time investigate the methods to controllably alter the optical response of GO with the electric field and provide theoretical modeling of the electric field-induced changes. Field-dependent GO emission is studied in bulk GO/polyvinylpyrrolidone films with up to 6% reversible decrease under 1.6 V µm-1 electric fields. On an individual flake level, a more substantial over 50% quenching is achieved for select GO flakes in a polymeric matrix between interdigitated microelectrodes subject to two orders of magnitude higher fields. This effect is modeled on a single exciton level by utilizing Wentzel, Kremer, and Brillouin approximation for electron escape from the exciton potential well. In an aqueous suspension at low fields, GO flakes exhibit electrophoretic migration, indicating a degree of charge separation and a possibility of manipulating GO materials on a single-flake level to assemble electric field-controlled microelectronics. As a result of this work, we suggest the potential of varying the optical and electronic properties of GO via the electric field for the advancement and control over its optoelectronic device applications.

Thermal Disproportionation of Oxo-Functionalized Graphene.

Graphene production by wet chemistry is an ongoing scientific challenge. Controlled oxidation of graphite introduces oxo functional groups; this material can be processed and converted back to graphene by reductive defunctionalization. Although thermal processing yields conductive carbon, a ruptured and undefined carbon lattice is produced as a consequence of CO2 formation. This thermal process is not understood, but it is believed that graphene is not accessible. Here, we thermally process oxo-functionalized graphene (oxo-G) with a low (4-6 %) and high degree of functionalization (50-60 %) and find on the basis of Raman spectroscopy and transmission electron microscopy performed at atomic resolution (HRTEM) that thermal processing leads predominantly to an intact carbon framework with a density of lattice defects as low as 0.8 %. We attribute this finding to reorganization effects of oxo groups. This finding holds out the prospect of thermal graphene formation from oxo-G derivatives.

Graphene Oxide: A One- versus Two-Component Material.

The structure of graphene oxide (GO) is a matter of discussion. While established GO models are based on functional groups attached to the carbon framework, another frequently used model claims that GO consists of two components, a slightly oxidized graphene core and highly oxidized molecular species, oxidative debris (OD), adsorbed on it. Those adsorbents are claimed to be the origin for optical properties of GO. Here, we examine this model by preparing GO with a low degree of functionalization, combining it with OD and studying the optical properties of both components and their combination in an artificial two-component system. The analyses of absorption and emission spectra as well as lifetime measurements reveal that properties of the combined system are distinctly different from those of GO. That confirms structural models of GO as a separate oxygenated hexagonal carbon framework with optical properties governed by its internal structure rather than the presence of OD. Understanding the structure of GO allows further reliable interpretation of its optical and electronic properties and enables controlled processing of GO.

Self-Stacked Reduced Graphene Oxide Nanosheets Coated with Cobalt-Nickel Hydroxide by One-Step Electrochemical Deposition toward Flexible Electrochromic Supercapacitors.

The implementation of an optical function into supercapacitors is an innovative approach to make energy storage devices smarter and to meet the requirements of smart electronics. Here, it is reported for the first time that nickel-cobalt hydroxide on reduced graphene oxide can be utilized for flexible electrochromic supercapacitors. A new and straightforward one-step electrochemical deposition process is introduced that is capable of simultaneously reducing GO and depositing amorphous Co(1-x)Ni(x)(OH)2 on the rGO. It is shown that the rGO nanosheets are homogeneously coated with metal hydroxide and are vertically stacked. No high temperature processes are used so that flexible polymer-based substrates can be coated. The synthesized self-stacked rGO-Co(1-x)Ni(x)(OH)2 nanosheet material exhibits pseudocapacitive charge storage behavior with excellent rate capability, high Columbic efficiency, and nondiffusion limited behavior. It is shown that the electrochemical behavior of the Ni(OH)2 can be modulated, by simultaneously depositing nickel and cobalt hydroxide, into broad oxidization and reduction bands. Further, the material exhibits electrochromic property and can switch between a bleached and transparent state. Literature comparison reveals that the performance characteristics of the rGO-Co(1-x)Ni(x)(OH)2 nanosheet material, in terms of gravimetric capacitance, areal capacitance, and long-term cycling stability, are among the highest reported values of supercapacitors with electrochromic property.

Enhancement of Sodium Ion Battery Performance Enabled by Oxygen Vacancies.

The utilization of oxygen vacancies (OVs) in sodium ion batteries (SIBs) is expected to enhance performance, but as yet it has rarely been reported. Taking the MoO(3-x) nanosheet anode as an example, for the first time we demonstrate the benefits of OVs on SIB performance. Moreover, the benefits at deep-discharge conditions can be further promoted by an ultrathin Al2O3 coating. A series of measurements show that the OVs increase the electric conductivity and Na-ion diffusion coefficient, and the promotion from ultrathin coating lies in the effective reduction of cycling-induced solid-electrolyte interphase. The coated nanosheets exhibited high reversible capacity and great rate capability with the capacities of 283.9 (50 mA g(-1)) and 179.3 mAh g(-1) (1 A g(-1)) after 100 cycles. This work may not only arouse future attention on OVs for sodium energy storage, but also open up new possibilities for designing strategies to utilize defects in other energy storage systems.

Cost-effective atomic layer deposition synthesis of Pt nanotube arrays: application for high performance supercapacitor.

Due to the unique advantages of Pt, it plays an important role in fuel cells and microelectronics. Considering the fact that Pt is an expensive metal, a major challenging point nowadays is how to realize efficient utilization of Pt. In this paper, a cost-effective atomic layer deposition (ALD) process with a low N2 filling step is introduced for realizing well-defined Pt nanotube arrays in anodic alumina nano-porous templates. Compared to the conventional ALD growth of Pt, much fewer ALD cycles and a shorter precursor pulsing time are required, which originates from the low N2 filling step. To achieve similar Pt nanotubes, about half cycles and 10% Pt precursor pulsing time is needed using our ALD process. Meanwhile, the Pt nanotube array is explored as a current collector for supercapacitors based on core/shell Pt/MnO2 nanotubes. This nanotube-based electrode exhibits high gravimetric and areal specific capacitance (810 Fg(-1) and 75 mF cm(-2) at a scan rate of 5 mV s(-1) ) as well as an excellent rate capability (68% capacitance retention from 2 to 100 Ag(-1) ). Additionally, a negligible capacitance loss is observed after 8000 cycles of random charging-discharging from 2 to 100 Ag(-1) .

Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution.

Molybdenum disulfide (MoS2) has emerged as a promising electrocatalyst for catalyzing protons to hydrogen via the so-called hydrogen evolution reaction (HER). In order to enhance the HER activity, tremendous effort has been made to engineer MoS2 catalysts with either more active sites or higher conductivity. However, at present, synergistically structural and electronic modulations for HER still remain challenging. In this work, we demonstrate the successfully synergistic regulations of both structural and electronic benefits by controllable disorder engineering and simultaneous oxygen incorporation in MoS2 catalysts, leading to the dramatically enhanced HER activity. The disordered structure can offer abundant unsaturated sulfur atoms as active sites for HER, while the oxygen incorporation can effectively regulate the electronic structure and further improve the intrinsic conductivity. By means of controllable disorder engineering and oxygen incorporation, an optimized catalyst with a moderate degree of disorder was developed, exhibiting superior activity for electrocatalytic hydrogen evolution. In general, the optimized catalyst exhibits onset overpotential as low as 120 mV, accompanied by extremely large cathodic current density and excellent stability. This work will pave a new pathway for improving the electrocatalytic activity by synergistically structural and electronic modulations.

Emerging field of few-layered intercalated 2D materials.

The chemistry and physics of intercalated layered 2D materials (2DMs) are the focus of this review article. Special attention is given to intercalated bilayer and few-layer systems. Thereby, intercalated few-layers of graphene and transition metal dichalcogenides play the major role; however, also other intercalated 2DMs develop fascinating properties with thinning down. Here, we briefly introduce the historical background of intercalation and explain concepts, which become relevent with intercalating few-layers. Then, we describe various synthetic methods to yield intercalated 2DMs and focus next on current research directions, which are superconductivity, band gap tuning, magnetism, optical properties, energy storage and chemical reactions. We focus on major breakthroughs in all introduced sections and give an outlook to this emerging field of research.

Regiochemically Oxo-functionalized Graphene, Guided by Defect Sites, as Catalyst for Oxygen Reduction to Hydrogen Peroxide.

Heteroatom-doped graphene attracted tremendous attention because of advanced electrocatalytic properties, for example, for oxygen reduction. However, the role of oxygen atoms as heteroatoms in graphene should be explored more deeply. Here, we used statistical Raman spectroscopy for single-layer material analysis and found that the regiochemistry close to vacancy defects plays a decisive role. Accordingly, defects possess a guiding effect on the introduction of oxygen functional groups close to those defect-sites. After the addition of oxo-groups close to vacancy defects, the activity and hydrogen peroxide (H2O2) selectivity of the material on hydrogen peroxide production improved significantly. The selectivity of H2O2 is above 84%, which is higher than the initial oxo-functionalized graphene and electrochemically reduced graphene. The half-wave potential is 0.73 VRHE, which is more positive than the initial oxo-functionalized graphene.

Effect of friction on oxidative graphite intercalation and high-quality graphene formation.

Oxidative wet-chemical delamination of graphene from graphite is expected to become a scalable production method. However, the formation process of the intermediate stage-1 graphite sulfate by sulfuric acid intercalation and its subsequent oxidation are poorly understood and lattice defect formation must be avoided. Here, we demonstrate film formation of micrometer-sized graphene flakes with lattice defects down to 0.02% and visualize the carbon lattice by transmission electron microscopy at atomic resolution. Interestingly, we find that only well-ordered, highly crystalline graphite delaminates into oxo-functionalized graphene, whereas other graphite grades do not form a proper stage-1 intercalate and revert back to graphite upon hydrolysis. Ab initio molecular dynamics simulations show that ideal stacking and electronic oxidation of the graphite layers significantly reduce the friction of the moving sulfuric acid molecules, thereby facilitating intercalation. Furthermore, the evaluation of the stability of oxo-species in graphite sulfate supports an oxidation mechanism that obviates intercalation of the oxidant.

Highly-Ordered 3D Vertical Resistive Switching Memory Arrays with Ultralow Power Consumption and Ultrahigh Density.

Resistive switching random access memories (RRAM) have attracted great scientific and industrial attention for next generation data storage because of their advantages of nonvolatile properties, high density, low power consumption, fast writing/erasing speed, good endurance, and simple and small operation system. Here, by using a template-assisted technique, we demonstrate a three-dimensional highly ordered vertical RRAM device array with density as high as that of the nanopores of the template (10(8)-10(9) cm(-2)), which can also be fabricated in large area. The high crystallinity of the materials, the large contact area and the intimate semiconductor/electrode interface (3 nm interfacial layer) make the ultralow voltage operation (millivolt magnitude) and ultralow power consumption (picowatt) possible. Our procedure for fabrication of the nanodevice arrays in large area can be used for producing many other different materials and such three-dimensional electronic device arrays with the capability to adjust the device densities can be extended to other applications of the next generation nanodevice technology.

Self-supported metallic nanopore arrays with highly oriented nanoporous structures as ideally nanostructured electrodes for supercapacitor applications.

Self-supported metallic nanopore arrays with highly oriented nanoporous structures are fabricated and applied as ideally nanostructured electrodes for supercapacitor applications. Their large specific surface area can ensure a high capacitance, and their highly oriented and stable nanoporous structure can facilitate ion transport.

Magnetocaloric effects in a freestanding and flexible graphene-based superlattice synthesized with a spatially confined reaction.

Superlattices have attracted great interest because of their tailorable electronic properties at the interface. However, the lack of an efficient and low-cost synthetic method represents a huge challenge to implement superlattices into practical applications. Herein, we report a space-confined nanoreactor strategy to synthesize flexible freestanding graphene-based superlattice nanosheets, which consist of alternately intercalated monolayered metal-oxide frameworks and graphene. Taking vanadium oxide as an example, clear-cut evidences in extended X-ray absorption fine structure, high-resolution transmission electron microscopy and infrared spectra have confirmed that the vanadium oxide frameworks in the superlattice nanosheets show high symmetry derived from the space-confinement and electron-donor effect of graphene layers, which enable the superlattice nanosheets to show emerging magnetocaloric effect. Undoubtedly, this freestanding and flexible superlattice synthesized from a low-cost and scalable method avoids complex transferring processes from growth substrates for final applications and thus should be beneficial to a wide variety of functionalized devices.