Electronic functionality in graphene-based nanoarchitectures : discovery and design via first-principles modeling

Graphene has promised many novel applications in nanoscale electronics and sustainable energy due to its novel electronic properties. Computational exploration of electronic functionality and how it varies with architecture and doping presently runs ahead of experimental synthesis yet provides insights into types of structures that may prove profitable for targeted experimental synthesis and characterization. We present here a summary of our understanding on the important aspects of dimension, band gap, defect, and interfacial engineering of graphene based on state-of-the-art ab initio approaches. Some most recent experimental achievements relevant for future theoretical exploration are also covered.

Hybrid graphene/titania nanocomposite : interface charge transfer, hole doping, and sensitization for visible light response

We demonstrated for the first time by large-scale ab initio calculations that a graphene/titania interface in the ground electronic state forms a charge-transfer complex due to the large difference of work functions between graphene and titania, leading to substantial hole doping in graphene. Interestingly, electrons in the upper valence band can be directly excited from graphene to the conduction band, that is, the 3d orbitals of titania, under visible light irradiation. This should yield well-separated electron−hole pairs, with potentially high photocatalytic or photovoltaic performance in hybrid graphene and titania nanocomposites. Experimental wavelength-dependent photocurrent generation of the graphene/titania photoanode demonstrated noticeable visible light response and evidently verified our ab initio prediction.

Enhanced hydrogen separation by vertically-aligned carbon nanotube membranes with zeolite imidazolate frameworks as a selective layer

Vertically-aligned carbon nanotube (VACNT) membranes show very high permeation fluxes due to the inherent smooth and frictionless nature of the interior of the nanotubes. However, the hydrogen selectivities are all in the Knudsen range and are quite low. In this study we grew molecular sieve zeolite imidazolate frameworks (ZIFs) via secondary seeded growth on the VACNT membranes as a gas selective layer. The ZIF layer has a thickness of 5–6 μm and shows good contact with the VACNT membrane surface. The VACNT supported ZIF membrane shows much higher H2 selectivity than Ar (7.0); O2 (13.6); N2 (15.1) and CH4 (9.8). We conclude that tailoring metal–organic frameworks on the membrane surface can be an effective route to improve the gas separation performance of the VACNT membrane.

Dermal fibroblast infiltration of poly(ε-caprolactone) scaffolds fabricated by melt electrospinning in a direct writing mode

Melt electrospinning in a direct writing mode is a recent additive manufacturing approach to fabricate porous scaffolds for tissue engineering applications. In this study, we describe porous and cell-invasive poly (ε-caprolactone) scaffolds fabricated by combining melt electrospinning and a programmable x–y stage. Fibers were 7.5 ± 1.6 µm in diameter and separated by interfiber distances ranging from 8 to 133 µm, with an average of 46 ± 22 µm. Micro-computed tomography revealed that the resulting scaffolds had a highly porous (87%), three-dimensional structure. Due to the high porosity and interconnectivity of the scaffolds, a top-seeding method was adequate to achieve fibroblast penetration, with cells present throughout and underneath the scaffold. This was confirmed histologically, whereby a 3D fibroblast-scaffold construct with full cellular penetration was produced after 14 days in vitro. Immunohistochemistry was used to confirm the presence and even distribution of the key dermal extracellular matrix proteins, collagen type I and fibronectin. These results show that melt electrospinning in a direct writing mode can produce cell invasive scaffolds, using simple top-seeding approaches.

Interaction of water with the fluorine-covered anatase TiO2(001) surface

The interaction of water with the fluorine-covered (001) surface of anatase titanium dioxide (TiO2) has been studied within the framework of density functional theory (DFT). Our results show that water dissociation is unfavorable due to repulsive interactions between surface fluorine and oxygen. We also found that the reaction of hydrofluoric acid with a surface hydroxyl group to form a surface Ti–F bond is exothermic, while the removal of fluorine from the surface needs additional energy of about half an eV. Therefore, water molecules are predicted to remain intact at the interface with the F-terminated anatase (001).

Adsorption and dissociation of ammonia borane outside and inside single-walled carbon nanotubes : A density functional theory study

Amonia borane (AB) has been identified as a potential candidate highcapacity hydrogen storage material. This work probes the adsorption and dissociation of AB inside and outside single-walled carbon nanotubes (SWCNTs) within the framework of density functional theory. The dissociation barriers of AB have been calculated and compared with that of the isolated AB molecule. On the basis of the present calculations, no notable improvement results from SWCNT confinement; on the contrary, the dissociation barrier slightly increases with respect to isolated AB.

Understanding the enhancement in photoelectrochemical properties of photocatalytically prepared TiO2-reduced graphene oxide composite

Solution-phase photocatalytic reduction of graphene oxide to reduced graphene oxide (RGO) by titanium dioxide (TiO2) nanoparticles produces an RGO-TiO2 composite that possesses enhanced charge transport properties beyond those of pure TiO2 nanoparticle films. These composite films exhibit electron lifetimes up to four times longer than that of intrinsic TiO2 films due to RGO acting as a highly conducting intraparticle charge transport network within the film. The intrinsic UV-active charge generation (photocurrent) of pure TiO2 was enhanced by a factor of 10 by incorporating RGO; we attribute this to both the highly conductive nature of the RGO and to improved charge collection facilitated by the intimate contact between RGO and the TiO2, uniquely afforded by the solution-phase photocatalytic reduction method. Integrating RGO into nanoparticle films using this technique should improve the performance of photovoltaic devices that utilize nanoparticle films, such as dye-sensitized and quantum-dot-sensitized solar cells.

Adsorption of carbon dioxide and nitrogen on single-layer aluminum nitride nanostructures studied by density functional theory

The adsorption of carbon dioxide and nitrogen molecules on aluminum nitride (AlN) nanostructures has been explored using first-principle computational methods. Optimized configurations corresponding to physisorption and, subsequentially, chemisorption of CO2 are identified, in contrast to N2, for which only a physisorption structure is found. Transition-state searches imply a low energy barrier between the physisorption and chemisorption states for CO2 such that the latter is accessible and thermodynamically favored at room temperature. The effective binding energy of the optimized chemisorption structure is apparently larger than those for other CO2 adsorptive materials, suggesting the potential for application of aluminum nitride nanostructures for carbon dioxide capture and storage.

Role of lithium vacancies in accelerating the dehydrogenation kinetics on a LiBH4(010) surface : an Ab initio study

In this work, ab initio density functional calculations were performed to explore the effect of surface lithium vacancies on the initial dehydrogenation kinetics of lithium borohydride. We found that some B−H bonds in neighboring BH4-1 complexes around the vacancy became elongated (weakened). The activation barriers for the recombination of H atoms to form H2 were decreased from 3.64 eV for the stoichiometrically complete LiBH4(010) surface to 1.53 and 0.23 eV in the presence of mono- and di-vacancies, respectively. Our results indicate that the creation of Li vacancies may play a critical role in accelerating the dehydrogenation kinetics of LiBH4.

First-principle studies of the formation and diffusion of hydrogen vacancies in magnesium hydride

Ab initio density functional theory (DFT) calculations are performed to study the formation and diffusion of hydrogen vacancies on MgH2(110) surface and in bulk. We find that the formation energies for a single H-vacancy increase slightly from the surface to deep layers. The energies for creating adjacent surface divancacies at two inplane sites and at an inplane and a bridge site are even smaller than that for the formation of a single H-vacancy, a fact that is attributed to the strong vacancy−vacancy interactions. The diffusion of an H-vacancy from an in-plane site to a bridge site on the surface has the smallest activation barrier calculated at 0.15 eV and should be fast at room temperature. The activation barriers computed for H-vacancy diffusion from the surface into sublayers are all less than 0.70 eV, which is much smaller than the activation energy for desorption of hydrogen on the MgH2(110) surface (1.78−2.80 eV/H2). This suggests that surface desorption is more likely than vacancy diffusion to be rate determining, such that finding effective catalyst on the MgH2 surface to facilitate desorption will be very important for improving overall dehydrogenation performance.

First-principle study of adsorption of hydrogen on ti-doped Mg(0001) surface

Ab initio density functional theory (DFT) calculations are performed to study the adsorption of H2 molecules on a Ti-doped Mg(0001) surface. We find that two hydrogen molecules are able to dissociate on top of the Ti atom with very small activation barriers (0.103 and 0.145 eV for the first and second H2 molecules, respectively). Additionally, a molecular adsorption state of H2 above the Ti atom is observed for the first time and is attributed to the polarization of the H2 molecule by the Ti cation. Our results parallel recent findings for H2 adsorption on Ti-doped carbon nanotubes or fullerenes. They provide new insight into the preliminary stages of hydrogen adsorption onto Ti-incorporated Mg surfaces.

Mg-based nanocomposites with high capacity and fast kinetics for hydrogen storage

Magnesium and its alloys have shown a great potential in effective hydrogen storage due to their advantages of high volumetric/gravimetric hydrogen storage capacity and low cost. However, the use of these materials in fuel cells for automotive applications at the present time is limited by high hydrogenation temperature and sluggish sorption kinetics. This paper presents the recent results of design and development of magnesium-based nanocomposites demonstrating the catalytic effects of carbon nanotubes and transition metals on hydrogen adsorption in these materials. The results are promising for the application of magnesium materials for hydrogen storage, with significantly reduced absorption temperatures and enhanced ab/desorption kinetics. High level Density Functional Theory calculations support the analysis of the hydrogenation mechanisms by revealing the detailed atomic and molecular interactions that underpin the catalytic roles of incorporated carbon and titanium, providing clear guidance for further design and development of such materials with better hydrogen storage properties.

Catalytic effects of subsurface carbon in the chemisorption of hydrogen on a Mg(0001) surface: an ab-initio study

Ab initio density functional theory (DFT) calculations are performed to explore possible catalytic effects on the dissociative chemisorption of hydrogen on a Mg(0001) surface when carbon is incorporated into Mg materials. The computational results imply that a C atom located initially on a Mg(0001) surface can migrate into the subsurface and occupy an fcc interstitial site, with charge transfer to the C atom from neighboring Mg atoms. The effect of subsurface C on the dissociation of H2 on the Mg(0001) surface is found to be relatively marginal: a perfect sublayer of interstitial C is calculated to lower the barrier by 0.16 eV compared with that on a pure Mg(0001) surface. Further calculations reveal, however, that sublayer C may have a significant effect in enhancing the diffusion of atomic hydrogen into the sublayers through fcc channels. This contributes new physical understanding toward rationalizing the experimentally observed improvement in absorption kinetics of H2 when graphite or single walled carbon nanotubes (SWCNT) are introduced into the Mg powder during ball milling.

The role of Ti as a catalyst for the dissociation of hydrogen on a Mg(0001) surface

In this paper, the dissociative chemisorption of hydrogen on both pure and Ti-incorporated Mg(0001) surfaces are studied by ab initio density functional theory (DFT) calculations. The calculated dissociation barrier of hydrogen molecule on a pure Mg(0001) surface (1.05 eV) is in good agreement with comparable theoretical studies. For the Ti-incorporated Mg(0001) surface, the activated barrier decreases to 0.103 eV due to the strong interaction between the molecular orbital of hydrogen and the d metal state of Ti. This could explain the experimentally observed improvement in absorption kinetics of hydrogen when transition metals have been introduced into the magnesium materials.

Influence of synthesis route on the catalytic properties of La1−xSrxMnO3

Lanthanum Strontium Manganate (LSM) powders were synthesized by six different routes, namely solid state reaction, drip pyrolysis, citrate, sol-gel, carbonate and oxalate co-precipitation. The LSM samples, produced by firing to 1000 °C for 5 h were then characterized by way of XRD, TPD's of oxygen, TPR and catalytic activity for a simple oxidation reaction, that of carbon monoxide to carbon dioxide. It was found that although the six samples had similar compositions and surface areas they performed quite differently during catalytic characterization. These observed differences correlated more closely to the mode of synthesis, than to the physical properties of the powders, or their impurity levels, indicating that the surface structures created by the different syntheses perform very differently under catalysis conditions. Co-precipitation and drip pyrolysis produced structures that were most efficient at facilitating oxidation type reactions.