X-ray Spectroscopy Study of Defect Contribution to Lithium Adsorption on Porous Carbon.

Lithium adsorption on high-surface-area porous carbon (PC) nanomaterials provides superior electrochemical energy storage performance dominated by capacitive behavior. In this study, we demonstrate the influence of structural defects in the graphene lattice on the bonding character of adsorbed lithium. Thermally evaporated lithium was deposited in vacuum on the surface of as-grown graphene-like PC and PC annealed at 400 °C. Changes in the electronic states of carbon were studied experimentally using surface-sensitive X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. NEXAFS data in combination with density functional theory calculations revealed the dative interactions between lithium sp2 hybridized states and carbon π*-type orbitals. Corrugated defective layers of graphene provide lithium with new bonding configurations, shorter distances, and stronger orbital overlapping, resulting in significant charge transfer between carbon and lithium. PC annealing heals defects, and as a result, the amount of lithium on the surface decreases. This conclusion was supported by electrochemical studies of as-grown and annealed PC in lithium-ion batteries. The former nanomaterial showed higher capacity values at all applied current densities. The results demonstrate that the lithium storage in carbon-based electrodes can be improved by introducing defects into the graphene layers.

Tuning humidity sensing properties via grafting fluorine and nitrogen-containing species on single-walled carbon nanotubes.

The effect of humidity on the electrical conductivity of single-walled carbon nanotube (SWCNT) films depends on both the conductivity of individual nanotubes and the electrical contacts between them. Here, we study these factors by comparing the sensor response of nanotubes with fluorine- and nitrogen-containing groups attached to the sidewalls. Experiments carried out in a wide range of relative humidity (RH) at room and elevated temperatures showed that the conductivity of non-functionalized SWCNTs and contacts between them decreases upon the adsorption of water molecules. Covalent fluorination reduces the conductivity of SWCNTs and significantly increases the sensitivity of the film to low concentrations of water vapor. The response at high RH decreases due to the large number of water molecules adsorbed on the conductive regions of the nanotubes. As a result of substitutional reactions of fluorinated SWCNTs with dimethylformamide and ethylenediamine, nitrogen-containing groups are added, the amount of which, however, is much less than the amount of fluorine. This modification of the SWCNTs improves intertube contacts in the film and increases the surface area for water adsorption. Our results show that an increase in the number of functional groups on the SWCNT surface enhances the sensitivity of the sensor to low water concentrations and worsens the response at high RH. SWCNTs modified with ethylenediamine have the highest sensitivity over the entire range of RH.

A ferromagnetic Eu-Pt surface compound grown below hexagonal boron nitride.

One of the fundamental applications for monolayer-thick 2D materials is their use as protective layers of metal surfaces and in situ intercalated reactive materials in ambient conditions. Here we investigate the structural, electronic, and magnetic properties, as well as the chemical stability in air of a very reactive metal, Europium, after intercalation between a hexagonal boron nitride (hBN) layer and a Pt substrate. We demonstrate that Eu intercalation leads to a hBN-covered ferromagnetic EuPt2 surface alloy with divalent Eu2+ atoms at the interface. We expose the system to ambient conditions and find a partial conservation of the di-valent signal and hence the Eu-Pt interface. The use of a curved Pt substrate allows us to explore the changes in the Eu valence state and the ambient pressure protection at different substrate planes. The interfacial EuPt2 surface alloy formation remains the same, but the resistance of the protecting hBN layer to ambient conditions is reduced, likely due to a rougher surface and a more discontinuous hBN coating.

Doping of Carbon Nanotubes with Encapsulated Phosphorus Chains.

Single-walled carbon nanotubes (SWCNTs) are a perfect host for the formation of one-dimensional phosphorus structures and to obtain hybrid materials with a large P-C ratio. This work presents a procedure for high-yield phosphorus filling of commercial Tuball SWCNTs and efficient removal of phosphorus deposits from the external nanotube surface. We probed white and red phosphorus as precursors, varied the synthesis temperature and the ampoule shape, and tested three solvents for sample purification. High-resolution transmission electron microscopy and Raman spectroscopy indicated crystallization of interior phosphorus in a form resembling fibrous red phosphorus. An aqueous sodium hydroxide solution allowed removing the majority of external phosphorus particles. Thermogravimetric analysis of the product determined ∼23 wt % (∼10 atom %) of phosphorus, and the X-ray photoelectron spectroscopy (XPS) data showed that ca. 80% of it is in the form of elemental phosphorus. Externally purified SWCNTs filled with phosphorus were used to study the interaction between the components. Raman spectroscopy and core-level XPS revealed p-type SWCNT doping. Valence-band XPS data and density functional theory calculations confirmed the transfer of the SWCNT electron density to the encapsulated phosphorus.

High-Quality Graphene Using Boudouard Reaction.

Following the game-changing high-pressure CO (HiPco) process that established the first facile route toward large-scale production of single-walled carbon nanotubes, CO synthesis of cm-sized graphene crystals of ultra-high purity grown during tens of minutes is proposed. The Boudouard reaction serves for the first time to produce individual monolayer structures on the surface of a metal catalyst, thereby providing a chemical vapor deposition technique free from molecular and atomic hydrogen as well as vacuum conditions. This approach facilitates inhibition of the graphene nucleation from the CO/CO2 mixture and maintains a high growth rate of graphene seeds reaching large-scale monocrystals. Unique features of the Boudouard reaction coupled with CO-driven catalyst engineering ensure not only suppression of the second layer growth but also provide a simple and reliable technique for surface cleaning. Aside from being a novel carbon source, carbon monoxide ensures peculiar modification of catalyst and in general opens avenues for breakthrough graphene-catalyst composite production.

Photolysis of Fluorinated Graphites with Embedded Acetonitrile Using a White-Beam Synchrotron Radiation.

Fluorinated graphitic layers with good mechanical and chemical stability, polar C-F bonds, and tunable bandgap are attractive for a variety of applications. In this work, we investigated the photolysis of fluorinated graphites with interlayer embedded acetonitrile, which is the simplest representative of the acetonitrile-containing photosensitizing family. The samples were continuously illuminated in situ with high-brightness non-monochromatized synchrotron radiation. Changes in the compositions of the samples were monitored using X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NEXAFS N K-edge spectra showed that acetonitrile dissociates to form HCN and N2 molecules after exposure to the white beam for 2 s, and the latter molecules completely disappear after exposure for 200 s. The original composition of fluorinated matrices CF0.3 and CF0.5 is changed to CF0.10 and GF0.17, respectively. The highly fluorinated layers lose fluorine atoms together with carbon neighbors, creating atomic vacancies. The edges of vacancies are terminated with the nitrogen atoms and form pyridinic and pyrrolic units. Our in situ studies show that the photolysis products of acetonitrile depend on the photon irradiation duration and composition of the initial CFx matrix. The obtained results evaluate the radiation damage of the acetonitrile-intercalated fluorinated graphites and the opportunities to synthesize nitrogen-doped graphene materials.

Laser Patterning of Aligned Carbon Nanotubes Arrays: Morphology, Surface Structure, and Interaction with Terahertz Radiation.

The patterning of arrays of aligned multi-walled carbon nanotubes (MWCNTs) allows creating metastructures for terahertz (THz) applications. Here, the strips and columns from MWCNTs vertically grown on silicon substrates are prepared using CO2 laser treatment. The tops of the patterned arrays are flat when the laser power is between 15 and 22 W, and craters appear there with increasing power. Laser treatment does not destroy the alignment of MWCNTs while removing their poorly ordered external layers. The products of oxidative destruction of these layers deposit on the surfaces of newly produced arrays. The oxygen groups resulting from the CO2 laser treatment improve the wettability of nanotube arrays with an epoxy resin. We show that the patterned MWCNT arrays absorb the THz radiation more strongly than the as-synthesized arrays. Moreover, the pattern influences the frequency behavior of the absorbance.

Atomically-Precise Texturing of Hexagonal Boron Nitride Nanostripes.

Monolayer hexagonal boron nitride (hBN) is attracting considerable attention because of its potential applications in areas such as nano- and opto-electronics, quantum optics and nanomagnetism. However, the implementation of such functional hBN demands precise lateral nanostructuration and integration with other two-dimensional materials, and hence, novel routes of synthesis beyond exfoliation. Here, a disruptive approach is demonstrated, namely, imprinting the lateral pattern of an atomically stepped one-dimensional template into a hBN monolayer. Specifically, hBN is epitaxially grown on vicinal Rhodium (Rh) surfaces using a Rh curved crystal for a systematic exploration, which produces a periodically textured, nanostriped hBN carpet that coats Rh(111)-oriented terraces and lattice-matched Rh(337) facets with tunable width. The electronic structure reveals a nanoscale periodic modulation of the hBN atomic potential that leads to an effective lateral semiconductor multi-stripe. The potential of such atomically thin hBN heterostructure for future applications is discussed.

Extreme Biomimetics: Designing of the First Nanostructured 3D Spongin-Atacamite Composite and its Application.

The design of new composite materials using extreme biomimetics is of crucial importance for bioinspired materials science. Further progress in research and application of these new materials is impossible without understanding the mechanisms of formation, as well as structural features at the molecular and nano-level. It presents a challenge to obtain a holistic understanding of the mechanisms underlying the interaction of organic and inorganic phases under conditions of harsh chemical reactions for biopolymers. Yet, an understanding of these mechanisms can lead to the development of unusual-but functional-hybrid materials. In this work, a key way of designing centimeter-scale macroporous 3D composites, using renewable marine biopolymer spongin and a model industrial solution that simulates the highly toxic copper-containing waste generated in the production of printed circuit boards worldwide, is proposed. A new spongin-atacamite composite material is developed and its structure is confirmed using neutron diffraction, X-ray diffraction, high-resolution transmission electron microscopy/selected-area electron diffraction, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and electron paramagnetic resonance spectroscopy. The formation mechanism for this material is also proposed. This study provides experimental evidence suggesting multifunctional applicability of the designed composite in the development of 3D constructed sensors, catalysts, and antibacterial filter systems.

Enhancement of Volumetric Capacitance of Binder-Free Single-Walled Carbon Nanotube Film via Fluorination.

Robust electrode materials without the addition of binders allow increasing efficiency of electrical storage devices. We demonstrate the fabrication of binder-free electrodes from modified single-walled carbon nanotubes (SWCNTs) for electrochemical double-layer capacitors (EDLCs). Modification of SWCNTs included a sonication in 1,2-dichlorobenzene and/or fluorination with gaseous BrF3 at room temperature. The sonication caused the shortening of SWCNTs and the splitting of their bundles. As a result, the film prepared from such SWCNTs had a higher density and attached a larger amount of fluorine as compared to the film from non-sonicated SWCNTs. In EDLCs with 1M H2SO4 electrolyte, the fluorinated films were gradually defluorinated, which lead to an increase of the specific capacitance by 2.5-4 times in comparison with the initial values. Although the highest gravimetric capacitance (29 F g-1 at 100 mV s-1) was observed for the binder-free film from non-modified SWCNT, the fluorinated film from the sonicated SWCNTs had an enhanced volumetric capacitance (44 F cm-3 at 100 mV s-1). Initial SWCNT films and defluorinated films showed stable work in EDLCs during several thousand cycles.

Hydrothermal Activation of Porous Nitrogen-Doped Carbon Materials for Electrochemical Capacitors and Sodium-Ion Batteries.

Highly porous nitrogen-doped carbon nanomaterials have distinct advantages in energy storage and conversion technologies. In the present work, hydrothermal treatments in water or ammonia solution were used for modification of mesoporous nitrogen-doped graphitic carbon, synthesized by deposition of acetonitrile vapors on the pyrolysis products of calcium tartrate. Morphology, composition, and textural characteristics of the original and activated materials were studied by transmission electron microscopy, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, infrared spectroscopy, and nitrogen gas adsorption method. Both treatments resulted in a slight increase in specific surface area and volume of micropores and small mesopores due to the etching of carbon surface. Compared to the solely aqueous medium, activation with ammonia led to stronger destruction of the graphitic shells, the formation of larger micropores (1.4 nm vs 0.6 nm), a higher concentration of carbonyl groups, and the addition of nitrogen-containing groups. The tests of nitrogen-doped carbon materials as electrodes in 1M H2SO4 electrolyte and sodium-ion batteries showed improvement of electrochemical performance after hydrothermal treatments especially when ammonia was used. The activation method developed in this work is hopeful to open up a new route of designing porous nitrogen-doped carbon materials for electrochemical applications.

2D/3D Metallic Nano-objects Self-Organized in an Organic Molecular Thin Film.

We present the fabrication and investigation of the properties of nanocomposite structures consisting of two-dimensional (2D) and three-dimensional (3D) metallic nano-objects self-organized on the surface and inside of organic molecular thin-film copper tetrafluorophthalocyanine (CuPcF4). Metallic atoms, deposited under ultrahigh vacuum (UHV) conditions onto the organic ultrathin film, diffuse along the surface and self-assemble into a system of 2D metallic overlayers. At the same time, the majority of the metal atoms diffuse into the organic matrix and self-organize into 3D nanoparticles (NPs) in a well-defined manner. The evolution of the morphology and electronic properties of such structures as a function of nominal metal content is studied under UHV conditions using transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), and photoelectron spectroscopy (PES) techniques. Using HR-TEM, we have observed the periodicity of atomic planes of individual silver NPs. The steady formation of agglomerates from individual single nanocrystallites with intercrystallite boundaries is observed as well. PES reveals generally weak chemical interactions between silver and the organic matrix and n-doping of CuPcF4 at the initial stages of silver deposition, which is associated with charge transfer from the 2D wetting layer on the basis of core-level spectra shift analysis.

Light-Induced Sulfur Transport inside Single-Walled Carbon Nanotubes.

Filling of single-walled carbon nanotubes (SWCNTs) and extraction of the encapsulated species from their cavities are perspective treatments for tuning the functional properties of SWCNT-based materials. Here, we have investigated sulfur-modified SWCNTs synthesized by the ampoule method. The morphology and chemical states of carbon and sulfur were analyzed by transmission electron microscopy, Raman scattering, thermogravimetric analysis, X-ray photoelectron and near-edge X-ray absorption fine structure spectroscopies. Successful encapsulation of sulfur inside SWCNTs cavities was demonstrated. The peculiarities of interactions of SWCNTs with encapsulated and external sulfur species were analyzed in details. In particular, the donor-acceptor interaction between encapsulated sulfur and host SWCNT is experimentally demonstrated. The sulfur-filled SWCNTs were continuously irradiated in situ with polychromatic photon beam of high intensity. Comparison of X-ray spectra of the samples before and after the treatment revealed sulfur transport from the interior to the surface of SWCNTs bundles, in particular extraction of sulfur from the SWCNT cavity. These results show that the moderate heating of filled nanotubes could be used to de-encapsulate the guest species tuning the local composition, and hence, the functional properties of SWCNT-based materials.

Oxidation of h-BN on strongly and weakly interacting metal surfaces.

We used x-ray photoemission and absorption spectroscopies to study the influence of thermal molecular oxygen exposure on the h-BN/Co(0001) and h-BN/Au/Co(0001) systems. The spectral analysis was supported by density functional theory calculations. It is shown that oxygen can intercalate h-BN on Co(0001) and also be embedded into its lattice, replacing the nitrogen atoms. Upon substitution, the structures containing one (BN2O) and three (BO3) oxygen atoms in the boron atom environment are formed predominantly. In the case of gold-intercalated h-BN, only the (BN2O) structures are formed; the long-lasting oxygen exposures lead to etching of the h-BN layer.

DNA with Ionic, Atomic, and Clustered Silver: An XPS Study.

The rapidly developing field of bionanotechnology requires detailed knowledge of the mechanisms of interaction between inorganic matter and biomolecules. Under conditions different from those in an aqueous solution, however, the chemistry of these systems is elusive and may differ dramatically from their interactions in vitro and in vivo. Here, we report for the first time a photoemission study of a metal silver-DNA interface, formed in vacuo, in comparison with DNA-Ag+ and fluorescent DNA-Ag complexes formed in solution. The high-resolution photoelectron spectra reveal that in vacuo silver atoms interact mainly with oxygen atoms of the phosphodiester bond and deoxyribose in DNA, in contrast to the behavior of silver ions, which interact preferentially with the nitrogen atoms of the bases. This offers new insight into the mechanism of DNA metallization, which is of importance in creating metal-bio interfaces for nanotechnology applications.

A curious interplay in the films of N-heterocyclic carbene Pt(II) complexes upon deposition of alkali metals.

The recently synthesized series of Pt(II) complexes containing cyclometallating (phenylpyridine or benzoquinoline) and N-heterocyclic carbene ligands possess intriguing structures, topologies, and light emitting properties. Here, we report curious physicochemical interactions between in situ PVD-grown films of a typical representative of the aforementioned Pt(II) complex compounds and Li, Na, K and Cs atoms. Based on a combination of detailed core-level photoelectron spectroscopy and quantum-chemical calculations at the density functional theory level, we found that the deposition of alkali atoms onto the molecular film leads to unusual redistribution of electron density: essential modification of nitrogen sites, reduction of the coordination Pt(II) centre to Pt(0) and decrease of electron density on the bromine atoms. A possible explanation for this is formation of a supramolecular system "Pt complex-alkali metal ion"; the latter is supported by restoration of the system to the initial state upon subsequent oxygen treatment. The discovered properties highlight a considerable potential of the Pt(II) complexes for a variety of biomedical, sensing, chemical, and electronic applications.

Insight into bio-metal interface formation in vacuo: interplay of S-layer protein with copper and iron.

The mechanisms of interaction between inorganic matter and biomolecules, as well as properties of resulting hybrids, are receiving growing interest due to the rapidly developing field of bionanotechnology. The majority of potential applications for metal-biohybrid structures require stability of these systems under vacuum conditions, where their chemistry is elusive, and may differ dramatically from the interaction between biomolecules and metal ions in vivo. Here we report for the first time a photoemission and X-ray absorption study of the formation of a hybrid metal-protein system, tracing step-by-step the chemical interactions between the protein and metals (Cu and Fe) in vacuo. Our experiments reveal stabilization of the enol form of peptide bonds as the result of protein-metal interactions for both metals. The resulting complex with copper appears to be rather stable. In contrast, the system with iron decomposes to form inorganic species like oxide, carbide, nitride, and cyanide.