Electrocatalytically switchable CO2 capture : first principle computational exploration of carbon nanotubes with pyridinic nitrogen

Carbon nanotubes with specific nitrogen doping are proposed for controllable, highly selective, and reversible CO2 capture. Using density functional theory incorporating long-range dispersion corrections, we investigated the adsorption behavior of CO2 on (7,7) single-walled carbon nanotubes (CNTs) with several nitrogen doping configurations and varying charge states. Pyridinic-nitrogen incorporation in CNTs is found to induce an increasing CO2 adsorption strength with electron injecting, leading to a highly selective CO2 adsorption in comparison with N2. This functionality could induce intrinsically reversible CO2 adsorption as capture/release can be controlled by switching the charge carrying state of the system on/off. This phenomenon is verified for a number of different models and theoretical methods, with clear ramifications for the possibility of implementation with a broader class of graphene-based materials. A scheme for the implementation of this remarkable reversible electrocatalytic CO2-capture phenomenon is considered.

Tuning the surface structure of nitrogen-doped TiO2Nanofibres : an effective method to rnhance photocatalytic activities of visible-light-driven green synthesis and degradation

Nitrogen-doped TiO2 nanofibres of anatase and TiO2(B) phases were synthesised by a reaction between titanate nanofibres of a layered structure and gaseous NH3 at 400–700 °C, following a different mechanism than that for the direct nitrogen doping from TiO2. The surface of the N-doped TiO2 nanofibres can be tuned by facial calcination in air to remove the surface-bonded N species, whereas the core remains N doped. N-Doped TiO2 nanofibres, only after calcination in air, became effective photocatalysts for the decomposition of sulforhodamine B under visible-light irradiation. The surface-oxidised surface layer was proven to be very effective for organic molecule adsorption, and the activation of oxygen molecules, whereas the remaining N-doped interior of the fibres strongly absorbed visible light, resulting in the generation of electrons and holes. The N-doped nanofibres were also used as supports of gold nanoparticle (Au NP) photocatalysts for visible-light-driven hydroamination of phenylacetylene with aniline. Phenylacetylene was activated on the N-doped surface of the nanofibres and aniline on the Au NPs. The Au NPs adsorbed on N-doped TiO2(B) nanofibres exhibited much better conversion (80 % of phenylacetylene) than when adsorbed on undoped fibres (46 %) at 40 °C and 95 % of the product is the desired imine. The surface N species can prevent the adsorption of O2 that is unfavourable for the hydroamination reaction, and thus, improve the photocatalytic activity. Removal of the surface N species resulted in a sharp decrease of the photocatalytic activity. These photocatalysts are feasible for practical applications, because they can be easily dispersed into solution and separated from a liquid by filtration, sedimentation or centrifugation due to their fibril morphology.

Tensile properties of a boron/nitrogen-doped carbon nanotube–graphene hybrid structure

Doping is an effective approach that allows for the intrinsic modification of the electrical and chemical properties of nanomaterials. Recently, a graphene and carbon nanotube hybrid structure (GNHS) has been reported, which extends the excellent properties of carbon-based materials to three dimensions. In this paper, we carried out a first-time investigation on the tensile properties of the hybrid structures with different dopants. It is found that with the presence of dopants, the hybrid structures usually exhibit lower yield strength, Young’s modulus, and earlier yielding compared to that of a pristine hybrid structure. For dopant concentrations below 2.5% no significant reduction of Young’s modulus or yield strength could be observed. For all considered samples, the failure is found to initiate at the region where the nanotubes and graphene sheets are connected. After failure, monatomic chains are normally observed around the failure region. Dangling graphene layers without the separation of a residual CNT wall are found to adhere to each other after failure with a distance of about 3.4 Å. This study provides a fundamental understanding of the tensile properties of the doped graphene–nanotube hybrid structures, which will benefit the design and also the applications of graphene-based hybrid materials.

Neutral and charged boron-doped fullerenes for CO2 adsorption

Recently, the capture and storage of CO2 have attracted research interest as a strategy to reduce the global emissions of greenhouse gases. It is crucial to find suitable materials to achieve an efficient CO2 capture. Here we report our study of CO2 adsorption on boron-doped C60 fullerene in the neutral state and in the 1e−-charged state. We use first principle density functional calculations to simulate the CO2 adsorption. The results show that CO2 can form weak interactions with the BC59 cage in its neutral state and the interactions can be enhanced significantly by introducing an extra electron to the system.

Resonance of graphene nanoribbons doped with nitrogen and boron : a molecular dynamics study

Based on its enticing properties, graphene has been envisioned with applications in the area of electronics, photonics, sensors, bioapplications and others. To facilitate various applications, doping has been frequently used to manipulate the properties of graphene. Despite a number of studies conducted on doped graphene regarding its electrical and chemical properties, the impact of doping on the mechanical properties of graphene has been rarely discussed. A systematic study of the vibrational properties of graphene doped with nitrogen and boron is performed by means of a molecular dynamics simulation. The influence from different density or species of dopants has been assessed. It is found that the impacts on the quality factor, Q, resulting from different densities of dopants vary greatly, while the influence on the resonance frequency is insignificant. The reduction of the resonance frequency caused by doping with boron only is larger than the reduction caused by doping with both boron and nitrogen. This study gives a fundamental understanding of the resonance of graphene with different dopants, which may benefit their application as resonators.

Tuneable resonance properties of graphene by nitrogen-dopant

Doping as one of the popular methods to manipulate the properties of nanomaterials has received extensive application in deriving different types of graphene derivates, while the understanding of the resonance properties of dopant graphene is still lacking in literature. Based on the large-scale molecular dynamics simulation, reactive empirical bond order potential, as well as the tersoff potential, the resonance properties of N-doped graphene were studied. The studied samples were established according to previous experiments with the N atom’s percentage ranging from 0.43%-2.98%, including three types of N dopant locations, i.e., graphitic N, pyrrolic N and pyridinic N. It is found that different percentages of N-dopant exert different influence to the resonance properties of the graphene, while the amount of N-dopant is not the only factor that determines its impact. For all the considered cases, a relative large percentage of N-dopant (2.98% graphitic N-dopant) is observed to introduce significant influence to the profile of the external energy, and thus lead to an extremely low Q-factor comparing with that of the pristine graphene. The most striking finding is that, the natural frequency of the defective graphene with N-dopant appears uniformly larger than that of the pristine defective graphene. While for the perfect graphene, the N-dopant shows less influence to its natural frequency. This study will enrich the current understanding of the influence of dopants on graphene, which will eventually shed lights on the design of different molecules-doped graphene sheet.

A novel identification method for ultra trace detection of biomolecules using functionalised Surface Enhanced Raman Spectroscopy (SERS)

This thesis developed a new method for measuring extremely low amounts of organic and biological molecules, using Surface enhanced Raman Spectroscopy. This method has many potential applications, e.g. medical diagnosis, public health, food provenance, antidoping, forensics and homeland security. The method development used caffeine as the small molecule example, and erythropoietin (EPO) as the large molecule. This method is much more sensitive and specific than currently used methods; rapid, simple and cost effective. The method can be used to detect target molecules in beverages and biological fluids without the usual preparation steps.

Lanthanum oxide nanostructured films synthesized using hot dense and extremely non-equilibrium plasma for nanoelectronic device applications

Lanthanum oxide (La2O3) nanostructured films are synthesized on a p-type silicon wafer by ablation of La2O3 pellet due to interaction with hot dense argon plasmas in a modified dense plasma focus (DPF) device. The nanostructured films are investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray diffraction (XRD) spectra. SEM study shows the formation of nano-films having nano-size structures with the average nanostructures size ~25, ~53, and ~45 nm for one, two, and three DPF shots, respectively. The nanostructures sizes and morphology of nano-films are consistent between the AFM and SEM analyses. XRD spectra confirms nano-sized La2O3 with an average grain size ~34, ~51, and ~42 nm for one, two, and three DPF shots, respectively. The electrical properties such as current-voltage and capacitance-voltage (C-V) characteristics of the Al-La2O3-Si metal-oxide- semiconductor (MOS) capacitor structure are measured. The current conduction mechanism of the MOS capacitors is also demonstrated. The C-V characteristics are further used to obtain the electrical parameters such as the dielectric constant, oxide thickness, flat-band capacitance, and flat-band voltage of the MOS capacitors. These measurements demonstrate significantly lower leakage currents without any commonly used annealing or doping, thereby revealing a significant improvement of the MOS nanoelectronic device performance due to the incorporation of the DPF-produced La2O3 nano-films.

Harnessing the influence of reactive edges and defects of graphene substrates for achieving complete cycle of room-temperature molecular sensing

Molecular doping and detection are at the forefront of graphene research, a topic of great interest in physical and materials science. Molecules adsorb strongly on graphene, leading to a change in electrical conductivity at room temperature. However, a common impediment for practical applications reported by all studies to date is the excessively slow rate of desorption of important reactive gases such as ammonia and nitrogen dioxide. Annealing at high temperatures, or exposure to strong ultraviolet light under vacuum, is employed to facilitate desorption of these gases. In this article, the molecules adsorbed on graphene nanoflakes and on chemically derived graphene-nanomesh flakes are displaced rapidly at room temperature in air by the use of gaseous polar molecules such as water and ethanol. The mechanism for desorption is proposed to arise from the electrostatic forces exerted by the polar molecules, which decouples the overlap between substrate defect states, molecule states, and graphene states near the Fermi level. Using chemiresistors prepared from water-based dispersions of single-layer graphene on mesoporous alumina membranes, the study further shows that the edges of the graphene flakes (showing p-type responses to NO2 and NH3) and the edges of graphene nanomesh structures (showing n-type responses to NO2 and NH3) have enhanced sensitivity. The measured responses towards gases are comparable to or better than those which have been obtained using devices that are more sophisticated. The higher sensitivity and rapid regeneration of the sensor at room temperature provides a clear advancement towards practical molecule detection using graphene-based materials.

Highly NO2 sensitive caesium doped graphene oxide conductometric sensors

Here we report on the synthesis of caesium doped graphene oxide (GO-Cs) and its application to the development of a novel NO2 gas sensor. The GO, synthesized by oxidation of graphite through chemical treatment, was doped with Cs by thermal solid-state reaction. The samples, dispersed in DI water by sonication, have been drop-casted on standard interdigitated Pt electrodes. The response of both pristine and Cs doped GO to NO2 at room temperature is studied by varying the gas concentration. The developed GO-Cs sensor shows a higher response to NO2 than the pristine GO based sensor due to the oxygen functional groups. The detection limit measured with GO-Cs sensor is ≈90 ppb.

Inductively coupled plasma-assisted RF magnetron sputtering deposition of boron-doped microcrystalline Si films

An innovative custom-designed inductively coupled plasma-assisted RF magnetron sputtering deposition system has been developed to synthesize B-doped microcrystalline silicon thin films using a pure boron sputtering target in a reactive silane and argon gas mixture. Films were deposited using different boron target powers ranging from 0 to 350 W at a substrate temperature of 250 °C. The effect of the boron target power on the structural and electrical properties of the synthesized films was extensively investigated using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and Hall-effect system. It is shown that, with an initial increase of the boron target power from 0 to 300 W, the structural and electrical properties of the B-doped microcrystalline films are improved. However, when the target power is increased too much (e.g. to 350 W), these properties become slightly worse. The variation of the structural and electrical properties of the synthesized B-doped microcrystalline thin films is related to the incorporation of boron atoms during the crystallization and doping of silicon in the inductively coupled plasma-based process. This work is particularly relevant to the microcrystalline silicon-based p-i-n junction solar cells.

High-rate, room temperature plasma-enhanced deposition of aluminum-doped zinc oxide nanofilms for solar cell applications

A custom-designed inductively coupled plasma (ICP)-assisted radio-frequency magnetron sputtering deposition system has been employed to synthesize aluminium-doped zinc oxide (ZnO:Al) nanofilms on glass substrates at room temperature. The effects of film thickness and ZnO target (partially covered by Al chips) power on the structural, electrical and optical properties of the ZnO:Al nanofilms are studied. A high growth rate (∼41 nm/min), low electrical sheet resistance (as low as 30 Ω/□) and high optical transparency (>80%) over the visible spectrum has been achieved at a film thickness of ∼615 nm and ZnO target power of 150 W. The synthesis of ZnO:Al nanofilms at room temperature and with high growth rates is attributed to the unique features of the ICP-assisted radio-frequency magnetron sputtering deposition approach. The results are relevant to the development of photovoltaic thin-film solar cells and flat panel displays.

Electron-conduction mechanism and specific heat above transition temperature in LaFeAsO and BaFe2As2 superconductors

The ionization energy theory is used to calculate the evolution of the resistivity and specific heat curves with respect to different doping elements in the recently discovered superconducting pnictide materials. Electron-conduction mechanism in the pnictides above the structural transition temperature is explained unambiguously, which is also consistent with other strongly correlated materials, such as cuprates, manganites, titanates and magnetic semiconductors.

Nanoscale surface and interface engineering : why plasma-aided?

This contribution provides arguments why and in which cases low-temperature plasmas should be used for nanoscale surface and interface engineering and discusses several advantages offered by plasma-based processes and tools compared to neutral gas fabrication routes. Relevant processes involve nanotexturing (etching, sputtering, nanostructuring, pre-patterning, etc.) and composition/structure control at nanoscales (phases, layering, elemental presence, doping, functionalization, etc.) and complex combinations thereof. A case study in p-Si/n-Si solar cell junction exemplifies a successful use of inductively coupled plasma-assisted RF magnetron sputtering for nanoscale fabrication of a bi-layered stack of unconventionally doped highly-crystalline silicon nanofilms with engineered high-quality interfaces.

ZnO layers for opto-electronic applications from solution-based and low-temperature processing of an organometallic precursor

As printed and flexible plastic electronic gadgets become increasingly viable today, there is a need to develop materials that suit the fabrication processes involved. Two desirable requirements are solution-processable active materials or precursors and low-temperature processability. In this article, we describe a straightforward method of depositing ZnO films by simple spin coating of an organometallic diethylzinc precursor solution and annealing the resulting film at low temperatures (≤200 °C) without involving any synthetic steps. By controlling the humidity in which annealing is conducted, we are able to adjust the intrinsic doping level and carrier concentration in diethylzinc-derived ZnO. Doped or conducting transport layers are greatly preferable to undoped layers as they enable low-resistance contacts and minimize the potential drops. This ability to controllably realize doped ZnO is a key feature of the fabrication process that we describe in this article. We employ field-effect measurements as a diagnostic tool to measure doping levels and mobilities in ZnO and demonstrate that doped ZnO with high charge carrier concentration is ideal for solar cell applications. Respectable power conversion efficiencies (up to 4.5%) are achieved in inverted solar cells that incorporate diethylzinc-derived ZnO films as the electron transport layer and organic blends as the active material. Extensions of this approach to grow ternary and quaternary films with organometallic precursor chemicals will enable solution based growth of a number of semiconductor films as well as a method to dope them.