Synthesis of graphite/rGO-modified fungal hyphae for chromium (VI) bioremediation process.

Bioremediation is a promising technology that can eliminate the drawbacks of conventional treatment methods in removing harmful toxic metals including chromium(VI). Therefore, in this study, fungal hyphae modified with graphite and reduced graphene oxide were synthesized and assessed for their potential to bioremediate heavy metals for the first time in the literature. The effects of the carbon-based materials on microbial structure were characterized using scanning electron microscopy analysis. Thermogravimetric, RAMAN, X-ray diffraction, and enzymatic analyzes were performed to determine the role of functional groups. In addition, batch adsorption experiments utilizing response surface methodology were conducted to optimize operating parameters such as time (1-11 h), chromium (10-50 mg/L), and graphite/reduced graphene oxide (0.1-1 g/L). The maximum adsorption capacity with the graphene fungal hyphae was determined to be 568 mg.g-1, which is 9.7 times that of the crude fungal hyphae. The Cr(VI) removal for fungal hyphae-graphite and fungal hyphae-reduced graphene oxide biocomposites was 98.25% and 98.49%, respectively. The isothermal and kinetic results perfectly matched the 2nd order pseudo-model and Langmuir model in terms of the nature of the adsorption process. The laboratory scale test results indicate that fungal hyphae modified with graphite and reduced graphene oxide have a high adsorption capacity, suitable for the removal of chromium (VI) from wastewater.

Symmetry of diffraction patterns of two-dimensional crystal structures.

Conventionally, theoretical considerations in electron microscopy employ the weak phase approximation (WPA), which is only valid for weak scattering atomic elements (C, B, N) but not for transition metal dichalcogenide (TMD) materials. This leads to many exciting phenomena being overlooked. The present theoretical study goes beyond the weak phase approximation and thus the obtained results can be applied for two-dimensional (2D) crystals made of weakly as well of strongly scattering atoms, including the TMD materials. We show that the symmetry of an electron diffraction pattern, characterized by the Friedel's pairs, is governed by the symmetry of the exit wave distribution. For an infinite periodic crystal, the exit wave is an infinite and periodic 2D distribution which can be assigned an exit wave unit cell. The latter is determined by both the chemical composition of the crystallographic unit cell and the distance between the atomic layers. For 2D crystals of identical atoms, such as graphene, the exit wave unit cell is symmetrical and, thus, a symmetrical diffraction pattern is expected. For TMD materials, the exit wave unit cell is not symmetrical and a non-symmetrical diffraction pattern is expected for both monolayer and bilayer. Conventionally asymmetry in diffraction patterns has been explained by presence of dynamical (multiple) scattering effects. Our study shows that the asymmetry of a diffraction pattern can be explained solely by the asymmetry of the exit wave unit cell. The exit wave unit cell can be asymmetrical even in kinematic (single) scattering model. Therefore, conclusions about dynamical (multiple) scattering effects in 2D materials cannot be made based solely on asymmetry of a diffraction pattern. We also show that for hexagonally arranged atoms the second-order diffraction peaks show perfectly symmetrical intensities independently on the symmetry of the exit wave unit cell distribution.

Simultaneous synergistic effects of graphite addition and co-digestion of food waste and cow manure: Biogas production and microbial community.

The effects of graphite on the anaerobic digestion of food waste (FW), cow manure (CM) and its mixture (FW/CM) via batch experiments under mesophilic conditions have been investigated in this study. Maximum biogas production with graphite addition for FW + 1 g/L, CM + 1.5 g/L and FW/CM + 0.75 g/L are 1128.46, 829.6 and 1471.1 mL/gVS respectively. Additionally, this study investigates the link between microbial community structure and biogas production when graphite addition of anaerobic digester was conducted. Based on 16S rRNA gene amplicon sequencing results, Aminiphilus (13-14%), Actinobaculum (13-15%) and Clostridium (12-18%) were the predominant bacterial genera in graphite-added FW, CM and FW/CM reactors, respectively. Comparatively higher biogas production of FW/CM synergistically affected by abundances of Clostridium as well as co-digestion in this anaerobic digestion setup. Methanosaeta was the most abundant methanogen in the graphite added digesters; however, the relative abundance of these genera was different.

Local Plasmon Engineering in Doped Graphene.

Single-atom B or N substitutional doping in single-layer suspended graphene, realized by low-energy ion implantation, is shown to induce a dampening or enhancement of the characteristic interband π plasmon of graphene through a high-resolution electron energy loss spectroscopy study using scanning transmission electron microscopy. A relative 16% decrease or 20% increase in the π plasmon quality factor is attributed to the presence of a single substitutional B or N atom dopant, respectively. This modification is in both cases shown to be relatively localized, with data suggesting the plasmonic response tailoring can no longer be detected within experimental uncertainties beyond a distance of approximately 1 nm from the dopant. Ab initio calculations confirm the trends observed experimentally. Our results directly confirm the possibility of tailoring the plasmonic properties of graphene in the ultraviolet waveband at the atomic scale, a crucial step in the quest for utilizing graphene's properties toward the development of plasmonic and optoelectronic devices operating at ultraviolet frequencies.

Electronic Structure Modification of Ion Implanted Graphene: The Spectroscopic Signatures of p- and n-Type Doping.

A combination of scanning transmission electron microscopy, electron energy loss spectroscopy, and ab initio calculations is used to describe the electronic structure modifications incurred by free-standing graphene through two types of single-atom doping. The N K and C K electron energy loss transitions show the presence of π* bonding states, which are highly localized around the N dopant. In contrast, the B K transition of a single B dopant atom shows an unusual broad asymmetric peak which is the result of delocalized π* states away from the B dopant. The asymmetry of the B K toward higher energies is attributed to highly localized σ* antibonding states. These experimental observations are then interpreted as direct fingerprints of the expected p- and n-type behavior of graphene doped in this fashion, through careful comparison with density functional theory calculations.

Atomically resolved imaging of highly ordered alternating fluorinated graphene.

One of the most desirable goals of graphene research is to produce ordered two-dimensional (2D) chemical derivatives of suitable quality for monolayer device fabrication. Here we reveal, by focal series exit wave reconstruction (EWR), that C2F chair is a stable graphene derivative and demonstrates pristine long-range order limited only by the size of a functionalized domain. Focal series of images of graphene and C2F chair formed by reaction with XeF2 were obtained at 80 kV in an aberration-corrected transmission electron microscope. EWR images reveal that single carbon atoms and carbon-fluorine pairs in C2F chair alternate strictly over domain sizes of at least 150 nm(2) with electron diffraction indicating ordered domains ≥ 0.16 µm(2). Our results also indicate that, within an ordered domain, functionalization occurs on one side only as theory predicts. In addition, we show that electron diffraction provides a quick and easy method for distinguishing between graphene, C2F chair and fully fluorinated stoichiometric CF 2D phases.

Silicon-carbon bond inversions driven by 60-keV electrons in graphene.

We demonstrate that 60-keV electron irradiation drives the diffusion of threefold-coordinated Si dopants in graphene by one lattice site at a time. First principles simulations reveal that each step is caused by an electron impact on a C atom next to the dopant. Although the atomic motion happens below our experimental time resolution, stochastic analysis of 38 such lattice jumps reveals a probability for their occurrence in a good agreement with the simulations. Conversions from three- to fourfold coordinated dopant structures and the subsequent reverse process are significantly less likely than the direct bond inversion. Our results thus provide a model of nondestructive and atomically precise structural modification and detection for two-dimensional materials.

Control of radiation damage in MoS(2) by graphene encapsulation.

Recent dramatic progress in studying various two-dimensional (2D) atomic crystals and their heterostructures calls for better and more detailed understanding of their crystallography, reconstruction, stacking order, etc. For this, direct imaging and identification of each and every atom is essential. Transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) are ideal and perhaps the only tools for such studies. However, the electron beam can in some cases induce dramatic structure changes, and radiation damage becomes an obstacle in obtaining the desired information in imaging and chemical analysis in the (S)TEM. This is the case of 2D materials such as molybdenum disulfide MoS2, but also of many biological specimens, molecules, and proteins. Thus, minimizing damage to the specimen is essential for optimum microscopic analysis. In this article we demonstrate, on the example of MoS2, that encapsulation of such crystals between two layers of graphene allows for a dramatic improvement in stability of the studied 2D crystal and permits careful control over the defect nature and formation in it. We present STEM data collected from single-layer MoS2 samples prepared for observation in the microscope through three distinct procedures. The fabricated single-layer MoS2 samples were either left bare (pristine), placed atop a single-layer of graphene, or finally encapsulated between single graphene layers. Their behavior under the electron beam is carefully compared, and we show that the MoS2 sample "sandwiched" between the graphene layers has the highest durability and lowest defect formation rate compared to the other two samples, for very similar experimental conditions.

Probing the bonding and electronic structure of single atom dopants in graphene with electron energy loss spectroscopy.

A combination of scanning transmission electron microscopy, electron energy loss spectroscopy, and ab initio calculations reveal striking electronic structure differences between two distinct single substitutional Si defect geometries in graphene. Optimised acquisition conditions allow for exceptional signal-to-noise levels in the spectroscopic data. The near-edge fine structure can be compared with great accuracy to simulations and reveal either an sp(3)-like configuration for a trivalent Si or a more complicated hybridized structure for a tetravalent Si impurity.

Graphene reknits its holes.

Nanoholes, etched under an electron beam at room temperature in single-layer graphene sheets as a result of their interaction with metal impurities, are shown to heal spontaneously by filling up with either nonhexagon, graphene-like, or perfect hexagon 2D structures. Scanning transmission electron microscopy was employed to capture the healing process and study atom-by-atom the regrown structure. A combination of these nanoscale etching and reknitting processes could lead to new graphene tailoring approaches.

Scanning tunnelling microscopy of suspended graphene.

Suspended graphene has been studied by STM for the first time. Atomic resolution on mono- and bi-layer graphene samples has been obtained after ridding the graphene surface of contamination via high-temperature annealing. Static local corrugations (ripples) have been observed on both types of structures.

Direct experimental evidence of metal-mediated etching of suspended graphene.

Atomic resolution high angle annular dark field imaging of suspended, single-layer graphene, onto which the metals Cr, Ti, Pd, Ni, Al, and Au atoms had been deposited, was carried out in an aberration-corrected scanning transmission electron microscope. In combination with electron energy loss spectroscopy, employed to identify individual impurity atoms, it was shown that nanoscale holes were etched into graphene, initiated at sites where single atoms of all the metal species except for gold come into close contact with the graphene. The e-beam scanning process is instrumental in promoting metal atoms from clusters formed during the original metal deposition process onto the clean graphene surface, where they initiate the hole-forming process. Our observations are discussed in the light of calculations in the literature, predicting a much lowered vacancy formation in graphene when metal ad-atoms are present. The requirement and importance of oxygen atoms in this process, although not predicted by such previous calculations, is also discussed, following our observations of hole formation in pristine graphene in the presence of Si-impurity atoms, supported by new calculations which predict a dramatic decrease of the vacancy formation energy, when SiO(x) molecules are present.

Interaction of Metals with Suspended Graphene Observed by Transmission Electron Microscopy.

In this Perspective, we present an overview of how different metals interface with suspended graphene, providing a closer look into the metal-graphene interaction by employing high-resolution transmission electron microscopy, especially using high-angle dark field imaging. All studied metals favor sites on the omnipresent hydrocarbon surface contamination rather than on the clean graphene surface and present nonuniform distributions, which never result in continuous films but instead in clusters or nanocrystals, indicating a weak interaction between the metal and graphene. This behavior can be altered to some degree by surface pretreatment (hydrogenation) and high-temperature vacuum annealing. Graphene etching is observed in a scanning transmission electron microscope (STEM) under high vacuum and 60 kV electron beam acceleration voltage conditions for all metals, except for Au. This unusual metal-mediated etching sheds new light on the metal-graphene interaction; it might explain the observed higher frequency of cluster nucleation for certain transition metals and might have implications regarding controlled nanomanipulation, that is, for self-assembly and sculpturing of future graphene-based devices.

Metal-graphene interaction studied via atomic resolution scanning transmission electron microscopy.

Distributions and atomic sites of transition metals and gold on suspended graphene were investigated via high-resolution scanning transmission electron microscopy, especially using atomic resolution high angle dark field imaging. All metals, albeit as singular atoms or atom aggregates, reside in the omni-present hydrocarbon surface contamination; they do not form continuous films, but clusters or nanocrystals. No interaction was found between Au atoms and clean single-layer graphene surfaces, i.e., no Au atoms are retained on such surfaces. Au and also Fe atoms do, however, bond to clean few-layer graphene surfaces, where they assume T and B sites, respectively. Cr atoms were found to interact more strongly with clean monolayer graphene, they are possibly incorporated at graphene lattice imperfections and have been observed to catalyze dissociation of C-C bonds. This behavior might explain the observed high frequency of Cr-cluster nucleation, and the usefulness as wetting layer, for depositing electrical contacts on graphene.