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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 sp 2 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., Competing Interests: The authors declare no conflict of interest.

Molybdenum disulfide (MoS 2 ) is the second two-dimensional material after graphene that received a lot of attention from the research community. Strong S-Mo-S bonds make the sandwich-like layer mechanically and chemically stable, while the abundance of precursors and several developed synthesis methods allow obtaining various MoS 2 architectures, including those in combinations with a carbon component. Doping of MoS 2 with heteroatom substituents can occur by replacing Mo and S with other cations and anions. This creates active sites on the basal plane, which is important for the adsorption of reactive species. Adsorption is a key step in the gas detection and electrochemical energy storage processes discussed in this review. The literature data were analyzed in the light of the influence of a substitutional heteroatom on the interaction of MoS 2 with gas molecules and electrolyte ions. Theory predicts that the binding energy of molecules to a MoS 2 surface increases in the presence of heteroatoms, and experiments showed that such surfaces are more sensitive to certain gases. The best electrochemical performance of MoS 2 -based nanomaterials is usually achieved by including foreign metals. Heteroatoms improve the electrical conductivity of MoS 2 , which is a semiconductor in a thermodynamically stable hexagonal form, increase the distance between layers, and cause lattice deformation and electronic density redistribution. An analysis of literature data showed that co-doping with various elements is most attractive for improving the performance of MoS 2 in sensor and electrochemical applications. This is the first comprehensive review on the influence of foreign elements inserted into MoS 2 lattice on the performance of a nanomaterial in chemiresistive gas sensors, lithium-, sodium-, and potassium-ion batteries, and supercapacitors. The collected data can serve as a guide to determine which elements and combinations of elements can be used to obtain a MoS 2 -based nanomaterial with the properties required for a particular application.

Ni supported on N-doped carbon is rarely studied in traditional catalytic reactions. To fill this gap, we compared the structure of 1 and 6 wt% Ni species on porous N-free and N-doped carbon and their efficiency in hydrogen generation from gaseous formic acid. On the N-free carbon support, Ni formed nanoparticles with a mean size of 3.2 nm. N-doped carbon support contained Ni single-atoms stabilized by four pyridinic N atoms (N 4 -site) and sub-nanosized Ni clusters. Density functional theory calculations confirmed the clustering of Ni when the N 4 -sites were fully occupied. Kinetic studies revealed the same specific Ni mass-based reaction rate for single-atoms and clusters. The N-doped catalyst with 6 wt% of Ni showed higher selectivity in hydrogen production and did not lose activity as compared to the N-free 6 wt% Ni catalyst. The presented results can be used to develop stable Ni catalysts supported on N-doped carbon for various reactions.

Single-walled carbon nanotubes (SWCNTs) with their high surface area, electrical conductivity, mechanical strength and elasticity are an ideal component for the development of composite electrode materials for batteries. Red phosphorus has a very high theoretical capacity with respect to lithium, but has poor conductivity and expends considerably as a result of the reaction with lithium ions. In this work, we compare the electrochemical performance of commercial SWCNTs with red phosphorus deposited on the outer surface of nanotubes and/or encapsulated in internal channels of nanotubes in lithium-ion batteries. External phosphorus, condensed from vapors, is easily oxidized upon contact with the environment and only the un-oxidized phosphorus cores participate in electrochemical reactions. The support of the SWCNT network ensures a stable long-term cycling for these phosphorus particles. The tubular space inside the SWCNTs stimulate the formation of chain phosphorus structures. The chains reversibly interact with lithium ions and provide a specific capacity of 1545 mAh·g -1 (calculated on the mass of phosphorus in the sample) at a current density of 0.1 A·g -1 . As compared to the sample containing external phosphorus, SWCNTs with encapsulated phosphorus demonstrate higher reaction rates and a slight loss of initial capacity (~7%) on the 1000th cycle at 5 A·g -1 .

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 N 2 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 CF 0.3 and CF 0.5 is changed to CF 0.10 and GF 0.17 , 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 CF x matrix. The obtained results evaluate the radiation damage of the acetonitrile-intercalated fluorinated graphites and the opportunities to synthesize nitrogen-doped graphene materials.

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 BrF 3 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 H 2 SO 4 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.

Carbon nanohorns (CNHs) are attractive for various applications, where a high specific surface area and long dispersion stability in water are important. In the present work, we study these parameters of CNHs prepared by arc evaporation of graphite depending on the conditions of the synthesis and subsequent oxidation in air. It is shown that the addition of toluene in the reactor during the arcing allows obtaining CNHs functionalized with -CH x groups. Heating of CNHs in air at 400 °C leads to substitution of -CH x groups for oxygen-containing groups. Moreover, the CNH endcaps are opened at 500 °C, and as a result, the specific surface area of CNHs increases 4 times. Aqueous suspensions with a concentration of oxidized CNHs of 100 µg/mL are stable for 8 months.

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 H 2 SO 4 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., Competing Interests: The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

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.