Nitrogen-phosphorus codoped carbon nanotube sponges for detecting volatile organic compounds: experimental and DFT calculations.

The sensing of harmful gases and vapors is of fundamental interest to control the industrial emissions and environmental contamination. Nitrogen/phosphorus codoped carbon nanotube sponges (NP-CNTSs) were used to detect ethanol, acetone, cyclohexane, isopropanol, and methanol. The NP-CNTSs were produced through the aerosol-assisted chemical vapor deposition (AACVD) method using acetonitrile and triphenylphosphine as precursors at 1020 °C. The sensors based on NP-CNTSs were tested with varying operating temperatures (25-100 °C) and gas vapor concentrations (5-50 ppm). For instance, for a gas vapor concentration of 30 ppm and an operating temperature of 65 °C, the sensors showed changes in the electrical resistance of 1.12%, 1.21%, 1.09%, 2.4%, and 1.34% for ethanol, acetone, cyclohexane, isopropanol, and methanol, respectively. We found that the response and recovery times for isopropanol gas vapor are up to 43.7 s and 95 s, respectively. The current sensor outperformed the sensors reported in the literature by at least two times in the response measurement. Additionally, we performed van der Waals density functional theory calculations to elucidate the role of nitrogen and phosphorous codoped single-walled carbon nanotubes (SWCNTs) and their interaction with the considered gas molecule. We analyzed the molecular adsorption energy, optimized structures, and the density of states and calculated the electrostatic potential surface for N-doped, P-doped, NP-codoped, and OH-functionalized NP-codoped metallic SWCNTs-(6,6) and semiconducting SWCNTs-(10,0). Adsorption energy calculations revealed that in most cases the molecules are adsorbed to carbon nanotubes via physisorption. The codoping in SWCNTs-(6,6) promoted structural changes in the surface nanotube and marked chemisorption for acetone molecules.

Amaranth calcium oxalate crystals are associated with chloroplast structures and proteins.

Calcium oxalate (CaOx) crystals in plants are formed in crystal idioblasts cells and have specific geometric shapes. Their proposed functions include calcium homeostasis and carbon source, among others. Amaranth is a plant that presents high tolerance to abiotic stresses and accumulates considerable amounts of CaOx crystals; however, few studies have focused on characterizing the crystals ultrastructure and none is related to identifying proteins bound to them. This information is of great interest to understand the mechanisms related to CaOx crystal formation and to support their proposed functions. Thus, this work aimed to characterize CaOx crystals in amaranth leaves. Crystals were purified and the proteins bound to them were isolated and identified by nLC-MS/MS. Leaf sections were analyzed by light and electron microscopy. The identified proteins were related to the chloroplast such as ATPb synthase, RuBisCO large subunit, and cell wall-related proteins, which were validated by immunohistochemistry and immunogold labeling. In addition, it was observed that CaOx crystal idioblasts were formed from parenchyma cells associated with mesophyll and veins, in which the thylakoid membranes of degraded chloroplasts turned into crystal chambers. These results significantly advance our understanding of the mechanisms of CaOx crystal formation and the potential function as an alternative carbon source in leaves.

Potential Use of Nitrogen-Doped Carbon Nanotube Sponges as Payload Carriers Against Malignant Glioma.

Glioblastoma is the most aggressive brain tumor with a low median survival of 14 months. The only Food and Drug Administration (FDA)-approved treatment for topical delivery of the cancer drug carmustine is Gliadel. However, its use has been associated with several side-effects, mainly provoked by a mass effect. Nitrogen-doped carbon nanotube sponges (N-CNSs) are a new type of nanomaterial exhibiting high biocompatibility, and they are able to load large amounts of hydrophobic drugs, reducing the amount of carriers. This study evaluated the use of N-CNSs as potential carmustine carriers using malignant glioma cell lines. N-CNSs were characterized by nanoparticle tracking analysis and transmission electron microscopy. The biocompatibility of N-CNSs was determined in glioma cell lines and in primary astrocytes. Afterward, N-CNSs were loaded with carmustine (1:10 w/w), and the drug and liberation efficiency, as well as cytotoxicity induction, were determined. N-CNSs presented a homogeneous size distribution formed by round nanotubes, without induced cytotoxicity, at concentrations below 40 µg/mL. The N-CNSs loaded with carmustine exhibited a continuous kinetic release of carmustine with a maximum release after 72 h. The cytotoxic effect of N-CNSs loaded with carmustine was similar to that of carmustine alone. The results demonstrated that N-CNSs are a biocompatible nanostructure that could be used as carriers for the tumoral load of large amounts of chemotherapeutic agents.

Nitrogen-phosphorus doped graphitic nano onion-like structures: experimental and theoretical studies.

Onion-like graphitic structures are of great importance in different fields. Pentagons, heptagons, and octagons are essential features of onion-like graphitic structures that could generate important properties for diverse applications such as anodes in Li metal batteries or the oxygen reduction reaction. These carbon nanomaterials are fullerenes organized in a nested fashion. In this work, we produced graphitic nano onion-like structures containing phosphorus and nitrogen (NP-GNOs), using the aerosol assisted chemical vapor deposition method. The NP-GNOs were grown at high temperature (1020 °C) using ferrocene, trioctylphosphine oxide, benzylamine, and tetrahydrofuran precursors. The morphology, structure, composition, and surface chemistry of NP-GNOs were characterized using different techniques. The NP-GNOs showed diameters of 110-780 nm with Fe-based nanoparticles inside. Thermogravimetric analysis showed that NP-GNOs are thermally stable with an oxidation temperature of 724 °C. The surface chemistry analysis by FTIR and XPS revealed phosphorus-nitrogen codoping, and several functionalities containing C-H, N-H, P-H, P-O, P[double bond, length as m-dash]O, C[double bond, length as m-dash]O, and C-O bonds. We show density functional theory calculations of phosphorus-nitrogen doping and functionalized C240 fullerenes. We present the optimized structures, electronic density of states, HOMO, and LUMO wave functions for P-doped and OH-functionalized fullerenes. The P[double bond, length as m-dash]O and P-O bonds attributed to phosphates or hydroxyl groups attached to phosphorus atoms doping the NP-GNOs could be useful in improving supercapacitor function.

Tailoring the structure of MoS2 using ball-milled MoO3 powders: hexagonal, triangular, and fullerene-like shapes.

Single and few-layered MoS2 materials have attracted attention due to their outstanding physicochemical properties with potential applications in optoelectronics, catalysis, and energy storage. In the past, these materials have been produced using the chemical vapor deposition (CVD) method using MoO3 films and powders as Mo precursors. In this work, we demonstrate that the size and morphology of few-layered MoS2 nanostructures can be controlled, modifying the Mo precursor mechanically. We synthesized few-layered MoS2 materials using MoO3 powders previously exposed to a high-energy ball milling treatment by the salt-assisted CVD method. The MoO3 powders milled for 30, 120, and 300 min were used to synthesize sample MoS2-30, MoS2-120, and MoS2-300, respectively. We found morphologies mainly of hexagons (MoS2-30), triangles (MoS2-120), and fullerenes (MoS2-300). The MoS2 nanostructures and MoO3 powders were characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, x-ray diffraction, and thermogravimetric analysis. It was found that MoO3 milled powders exhibit oxygen loss and decrease in crystallite size as milling time increases. Oxygen deficiency in the Mo precursor prevents the growth of large MoS2 crystals and a large number of milled MoO3-x  + NaCl promote greater nucleation sites for the formation of MoS2, achieving a high density of nanoflakes in the 2H and 3R phases, with diameter sizes in the range of ∼30-600 nm with 1-12 layers. Photoluminescence characterization at room temperature revealed a direct bandgap and exciting trends for the different MoS2 samples. We envisage that our work provides a route for modifying the structure and optical properties for future device design via precursor engineering.

Understanding the electrochemistry of armchair graphene nanoribbons containing nitrogen and oxygen functional groups: DFT calculations.

The surface and edge chemistry are vital points to assess a specific application of graphene and other carbon nanomaterials. Based on first-principles density functional theory, we investigate twenty-four chemical functional groups containing oxygen and nitrogen atoms anchored to the edges of armchair graphene nanoribbons (AGNRs). Results for the band structures, formation energy, band gaps, electronic charge deficit, oxidation energy, reduction energy, and global hydrophilicity index are analyzed. Among the oxygen functional groups, carbonyl, anhydride, quinone, lactone, phenol, ethyl-ester, carboxyl, α-ester-methyl, and methoxy act as electron-withdrawing groups and, conversely, pyrane, pyrone, and ethoxy act as electron-donating groups. In the case of nitrogen-functional groups, amine, N-p-toluidine, ethylamine, pyridine-N-oxide, pyridone, lactam, and pyridinium transfer electrons to the AGNRs. Nitro, amide, and N-ethylamine act as electron-withdrawing groups. The carbonyl and pyridinium group-AGNRs show metallic behavior. The formation energy calculations revealed that AGNRs with pyridinium, amine, pyrane, carbonyl, and phenol are the most stable structures. In terms of the global hydrophilicity index, the quinone and N-ethylamine groups showed the most significant values, suggesting that they are highly efficient in accepting electrons from other chemical species. The oxidation and reduction energies as a function of the ribbon's width are discussed for AGNRs with quinone, hydroquinone, nitro, and nitro + 2H. Besides, we discuss the effect of nitrogen-doping in AGNRs on the oxidation and reduction energies for the quinone and hydroquinone functional groups.

Oxygenated Surface of Carbon Nanotube Sponges: Electroactivity and Magnetic Studies.

We report the synthesis of nitrogen-doped carbon nanotube sponges (N-CNSs) by pyrolysis of solutions of benzylamine, ferrocene, thiophene, and isopropanol-based mixture at 1020 °C for 4 h using an aerosol-assisted chemical vapor deposition system. The precursors were transported through a quartz tube using a dynamic flow of H2/Ar. We characterized the N-CNSs by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and thermogravimetric analysis. We found that isopropanol, isopropanol-ethanol, and isopropanol-acetone as precursors promote the formation of complex-entangled carbon fibers making knots and junctions. The N-CNSs displayed an outstanding oxygen concentration reaching a value of 9.2% for those synthesized with only isopropanol. We identified oxygen and nitrogen functional groups; in particular, the carbon fibers produced using only isopropanol exhibited a high concentration of ether groups (C-O bonds). This fact suggests the presence of phenols, carboxyl, methoxy, ethoxy, epoxy, and more complex functional groups. Usually, the functionalization of graphitic materials is carried out through aggressive acid treatments; here, we offer an alternative route to produce a superoxygenated surface. The understanding of the chemical surface of these novel materials represents a huge challenge and offers an opportunity to study complex oxygen functional groups different from the conventional quinone, carboxyl, phenols, carbonyl, methoxy, ethoxy, among others. The cyclic voltammetry measurements confirmed the importance of oxygen in N-CNSs, showing that with high oxygen concentration, the highest anodic and cathodic currents are displayed. N-CNSs displayed ferromagnetic behavior with an outstanding saturation magnetization. We envisage that our sponges are promising for anodes in lithium-ion batteries and magnetic sensor devices.

Synthesis of ZnMn2O4 Nanoparticles by a Microwave-Assisted Colloidal Method and their Evaluation as a Gas Sensor of Propane and Carbon Monoxide.

Spinel-type ZnMn2O4 nanoparticles were synthesized via a simple and inexpensive microwave-assisted colloidal route. Structural studies by X-ray diffraction showed that a spinel crystal phase of ZnMn2O4 was obtained at a calcination temperature of 500 °C, which was confirmed by Raman and UV-vis characterizations. Spinel-type ZnMn2O4 nanoparticles with a size of 41 nm were identified by transmission electron microscopy. Pellet-type sensors were fabricated using ZnMn2O4 nanoparticles as sensing material. Sensing measurements were performed by exposing the sensor to different concentrations of propane or carbon monoxide at temperatures in the range from 100 to 300 °C. Measurements performed at an operating temperature of 300 °C revealed a good response to 500 ppm of propane and 300 ppm of carbon monoxide. Hence, ZnMn2O4 nanoparticles possess a promising potential in the gas sensors field.

Wrinkled Nitrogen-doped Carbon Belts.

Graphene, carbon nanotubes, and fullerenes are nanomaterials with outstanding properties such as electrical, thermal, mechanical strength, flexibility, and high surface area. These nanomaterials are used as building blocks for the construction of novel and astonishing 3D-dimensional networks. In the present work, nitrogen-doped carbon belt (N-CB) structures containing wrinkled carbon fibres as building blocks were synthesized under unstable conditions in a chemical vapour deposition experiment. N-CB structures with 0.2-3.0 microns of wide and 350 nm thick were assembled from complex individual wrinkled carbon fibres grown on Co/Cu films. These complex structures have a tubular appearance, showing holed and wrinkled graphite layers. Sulphur and copper atoms drastically affect the catalytic role of cobalt, changing the conventional growth of carbon nanotubes. Chemical functional groups, N-doping, and carbons hybridizations involved in the winkled carbon fibres are investigated. These findings provides a novel material that can be used as an excellent oxygen-reduction reaction catalyst or nano-electronics component.

Two Sprayer CVD Synthesis of Nitrogen-doped Carbon Sponge-type Nanomaterials.

Nitrogen-doped carbon sponge-type nanostructures (N-CSTNs) containing coaxial multiwalled carbon nanotubes are synthesized at 1020 °C by using a modified chemical vapor deposition (CVD) arrangement. Here, the CVD reactor is supplied by two flows coming from two independent sprayers (called sprayer A and sprayer B). The nebulized material in each sprayer is transported by two different gases with different flow velocities. The synthesis of carbon N-CSTNs is performed using different precursors: sprayer A contains a solution composed of ethanol, thiophene and ferrocene, whereas sprayer B contains a solution of benzylamine, thiophene and ferrocene. Samples are classified according to the position inside the reactor and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and thermogravimetric analysis (TGA). Samples collected at the beginning of the reactor contain curly structures with diameters of 10-100 nm. At the end of the reactor, the sample is mainly formed by one type of structure. A spongy-type material is mainly formed in the hottest zone of the tubular furnace. The N-CSTNs are highly hydrophobic with oil sorption properties, which could be used for adsorption of oil spills.

Cytotoxicity induced by carbon nanotubes in experimental malignant glioma.

Despite multiple advances in the diagnosis of brain tumors, there is no effective treatment for glioblastoma. Multiwalled carbon nanotubes (MWCNTs), which were previously used as a diagnostic and drug delivery tool, have now been explored as a possible therapy against neoplasms. However, although the toxicity profile of nanotubes is dependent on the physicochemical characteristics of specific particles, there are no studies exploring how the effectivity of the carbon nanotubes (CNTs) is affected by different methods of production. In this study, we characterize the structure and biocompatibility of four different types of MWCNTs in rat astrocytes and in RG2 glioma cells as well as the induction of cell lysis and possible additive effect of the combination of MWCNTs with temozolomide. We used undoped MWCNTs (labeled simply as MWCNTs) and nitrogen-doped MWCNTs (labeled as N-MWCNTs). The average diameter of both pristine MWCNTs and pristine N-MWCNTs was ~22 and ~35 nm, respectively. In vitro and in vivo results suggested that these CNTs can be used as adjuvant therapy along with the standard treatment to increase the survival of rats implanted with malignant glioma.

Synthesis, Characterization, and Sensor Applications of Spinel ZnCo2O4 Nanoparticles.

Spinel ZnCo2O4 nanoparticles were synthesized by means of the microwave-assisted colloidal method. A solution containing ethanol, Co-nitrate, Zn-nitrate, and dodecylamine was stirred for 24 h and evaporated by a microwave oven. The resulting solid material was dried at 200 °C and subsequently calcined at 500 °C for 5 h. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy, confirming the formation of spinel ZnCo2O4 nanoparticles with average sizes between 49 and 75 nm. It was found that the average particle size decreased when the dodecylamine concentration increased. Pellets containing ZnCo2O4 nanoparticles were fabricated and tested as sensors in carbon monoxide (CO) and propane (C3H8) gases at different concentrations and temperatures. Sensor performance tests revealed an extremely high response to 300 ppm of CO at an operating temperature of 200 °C.

Clean nanotube unzipping by abrupt thermal expansion of molecular nitrogen: graphene nanoribbons with atomically smooth edges.

We report a novel physicochemical route to produce highly crystalline nitrogen-doped graphene nanoribbons. The technique consists of an abrupt N(2) gas expansion within the hollow core of nitrogen-doped multiwalled carbon nanotubes (CN(x)-MWNTs) when exposed to a fast thermal shock. The multiwalled nanotube unzipping mechanism is rationalized using molecular dynamics and density functional theory simulations, which highlight the importance of open-ended nanotubes in promoting the efficient introduction of N(2) molecules by capillary action within tubes and surface defects, thus triggering an efficient and atomically smooth unzipping. The so-produced nanoribbons could be few-layered (from graphene bilayer onward) and could exhibit both crystalline zigzag and armchair edges. In contrast to methods developed previously, our technique presents various advantages: (1) the tubes are not heavily oxidized; (2) the method yields sharp atomic edges within the resulting nanoribbons; (3) the technique could be scaled up for the bulk production of crystalline nanoribbons from available MWNT sources; and (4) this route could eventually be used to unzip other types of carbon nanotubes or intercalated layered materials such as BN, MoS(2), WS(2), etc.

Millimeter-long carbon nanotubes: outstanding electron-emitting sources.

We are reporting the fabrication of a very efficient electron source using millimeter-long and highly crystalline carbon nanotubes. These devices start to emit electrons at fields as low as 0.17 V/µm and reach threshold emission at 0.24 V/µm. In addition, these electron sources are very stable and can achieve a peak current density of 750 mA cm(-2) at only 0.45 V/µm. In order to demonstrate intense electron beam generation, these devices were used to produce visible light by cathodoluminescence. Finally, density functional theory calculations were used to rationalize the measured electronic field emission properties in open carbon nanotubes of different lengths. The modeling establishes a clear correlation between length and field enhancement factor.

Phosphorus and phosphorus-nitrogen doped carbon nanotubes for ultrasensitive and selective molecular detection.

A first-principles approach is used to establish that substitutional phosphorus atoms within carbon nanotubes strongly modify the chemical properties of the surface, thus creating highly localized sites with specific affinity towards acceptor molecules. Phosphorus-nitrogen co-dopants within the tubes have a similar effect for acceptor molecules, but the P-N bond can also accept charge, resulting in affinity towards donor molecules. This molecular selectivity is illustrated in CO and NH3 adsorbed on PN-doped nanotubes, O2 on P-doped nanotubes, and NO2 and SO2 on both P- and PN-doped nanotubes. The adsorption of different chemical species onto the doped nanotubes modifies the dopant-induced localized states, which subsequently alter the electronic conductance. Although SO2 and CO adsorptions cause minor shifts in electronic conductance, NH3, NO2, and O2 adsorptions induce the suppression of a conductance dip. Conversely, the adsorption of NO2 on PN-doped nanotubes is accompanied with the appearance of an additional dip in conductance, correlated with a shift of the existing ones. Overall these changes in electric conductance provide an efficient way to detect selectively the presence of specific molecules. Additionally, the high oxidation potential of the P-doped nanotubes makes them good candidates for electrode materials in hydrogen fuel cells.

Efficient vapor sensors using foils of dispersed nitrogen-doped and pure carbon multiwalled nanotubes.

We fabricated vapor sensors using nitrogen-doped (CNx) and pure multi-walled carbon nanotubes (MWNTs), and compared their performance. The sensors were constructed by dispersing the nanotube materials in methanol so as to form millimeter-long foils (nanotube paper), consisting of compact arrays of crisscrossing nanotubes. The devices were characterized by electrical resistance measurements and SEM studies. For CNx-based sensors, we observed that low concentrations of vapors such an acetone, ethanol, and chloroform were efficiently detected within 0.1-0.3 seconds via a physisorption mechanism. This physisorption is explained in terms of a weak interaction of the vapor molecules with the pyridinic sites (N bonded to two carbon atoms) present in the doped tubes. We believe that the methanol used for preparing the foils has a strong effect in saturating substitutional N atoms (N atoms bonded to three carbon atoms) that are also located in the CNx tubes. However, when pure carbon MWNTs were tested as sensors, we witnessed chemisorption of these vapors. First-principles density functional calculations confirmed that the gaseous molecules are able to interact with N-doped carbon nanotubes, via a physisorption mechanism, in which pyridine sites play a crucial role.

Longitudinal cutting of pure and doped carbon nanotubes to form graphitic nanoribbons using metal clusters as nanoscalpels.

We report the use of transition metal nanoparticles (Ni or Co) to longitudinally cut open multiwalled carbon nanotubes in order to create graphitic nanoribbons. The process consists of catalytic hydrogenation of carbon, in which the metal particles cut sp(2) hybridized carbon atoms along nanotubes that results in the liberation of hydrocarbon species. Observations reveal the presence of unzipped nanotubes that were cut by the nanoparticles. We also report the presence of partially open carbon nanotubes, which have been predicted to have novel magnetoresistance properties.(1) The nanoribbons produced are typically 15-40 nm wide and 100-500 nm long. This method offers an alternative approach for making graphene nanoribbons, compared to the chemical methods reported recently in the literature.

Electronic transport and mechanical properties of phosphorus- and phosphorus-nitrogen-doped carbon nanotubes.

We present a density functional theory study of the electronic structure, quantum transport and mechanical properties of recently synthesized phosphorus (P) and phosphorus-nitrogen (PN) doped single-walled carbon nanotubes. The results demonstrate that substitutional P and PN doping creates localized electronic states that modify the electron transport properties by acting as scattering centers. Nonetheless, for low doping concentrations (1 doping site per ∼200 atoms), the quantum conductance for metallic nanotubes is found to be only slightly reduced. The substitutional doping also alters the mechanical strength, leading to a 50% reduction in the elongation upon fracture, while Young's modulus remains approximately unchanged. Overall, the PN- and P-doped nanotubes display promising properties for components in composite materials and, in particular, for fast response and ultra sensitive sensors operating at the molecular level.

Production and detailed characterization of bean husk-based carbon: efficient cadmium (II) removal from aqueous solutions.

We report the production of a modified carbon by heat treating bean husk (Phaseolus vulgaris) at 270 degrees C in Ar, followed by chemical activation using HNO(3). The material was studied using thermogravimetric analysis (TGA), infrared spectroscopy (IRS), high-resolution transmission electron microscopy (HRTEM), elemental mapping, energy dispersive X-ray spectroscopy (EDX), X-ray powder diffraction and scanning electron microscopy (SEM). Cd(2+) sorption studies with this material were carried out at different concentrations. It was found that cadmium (II) is effectively removed by the modified material obtained from bean husk (180 mg/g). The sorption mechanism is discussed in terms of the activated surface properties. A relationship between the oxygen content and sorption was found in this novel material. Commercial activated carbon (AC) (F400) was used for comparison.

Heterodoped nanotubes: theory, synthesis, and characterization of phosphorus-nitrogen doped multiwalled carbon nanotubes.

Arrays of multiwalled carbon nanotubes doped with phosphorus (P) and nitrogen (N) are synthesized using a solution of ferrocene, triphenyl-phosphine, and benzylamine in conjunction with spray pyrolysis. We demonstrate that iron phosphide (Fe(3)P) nanoparticles act as catalysts during nanotube growth, leading to the formation of novel PN-doped multiwalled carbon nanotubes. The samples were examined by high resolution electron microscopy and microanalysis techniques, and their chemical stability was explored by means of thermogravimetric analysis in the presence of oxygen. The PN-doped structures reveal important morphology and chemical changes when compared to N-doped nanotubes. These types of heterodoped nanotubes are predicted to offer many new opportunities in the fabrication of fast-response chemical sensors.