Anodized nanoporous WO3 Schottky contact structure for hydrogen and ethanol sensing

This paper reports the development of nanoporous tungsten trioxide (WO3) Schottky diode-based gas sensors. Nanoporous WO3 films were prepared by anodic oxidation of tungsten foil in ethylene glycol mixed with ammonium fluoride and a small amount of water. Anodization resulted in highly ordered WO3 films with a large surface-to-volume ratio. Utilizing these nanoporous structures, Schottky diode-based gas sensors were developed by depositing a platinum (Pt) catalytic contact and tested towards hydrogen gas and ethanol vapour. Analysis of the current–voltage characteristics and dynamic responses of the sensors indicated that these devices exhibited a larger voltage shift in the presence of hydrogen gas compared to ethanol vapour at an optimum operating temperature of 200 °C. The gas sensing mechanism was discussed, associating the response to the intercalating H+ species that are generated as a result of hydrogen and ethanol molecule breakdowns onto the Pt/WO3 contact and their spill over into nanoporous WO3.

Charge mediated semiconducting-to-metallic phase transition in molybdenum disulfide monolayer and hydrogen evolution reaction in new 1T′ phase

The phase transition of single layer molybdenum disulfide (MoS2) from semiconducting 2H to metallic 1T and then to 1T′ phases, and the effect of the phase transition on hydrogen evolution reaction (HER) are investigated within this work by density functional theory. Experimentally, 2H-MoS2 has been widely used as an excellent electrode for HER and can get charged easily. Here we find that the negative charge has a significant impact on the structural phase transition in a MoS2 monolayer. The thermodynamic stability of 1T-MoS2 increases with the negative charge state, comparing with the 2H-MoS2 structure before phase transition and the kinetic energy barrier for a phase transition from 2H to 1T decreases from 1.59 to 0.27 eV when 4e– are injected per MoS2 unit. Additionally, 1T phase is found to transform into the distorted structure (1T′ phase) spontaneously. On their activity toward hydrogen evolution reaction, 1T′-MoS2 structure shows comparable hydrogen evolution reaction activity to the 2H-MoS2 structure. If the charge transfer kinetics is taken into account, the catalytic activity of 1T′-MoS2 is superior to that of 2H-MoS2. Our finding provides a possible novel method for phase transition of MoS2 and enriches understanding of the catalytic properties of MoS2 for HER.

Patenting free energy: The BlackLight litigation and the hydrogen economy

Legal Context In the wake of the Copenhagen Accord 2009 and the Cancun Agreements 2010, a number of patent offices have introduced fast-track mechanisms to encourage patent applications in relation to clean technologies - such as those pertaining to hydrogen. However, patent offices will be under increasing pressure to ensure that the granted patents satisfy the requisite patent thresholds, as well as to identify and reject cases of fraud, hoaxes, scams, and swindles. Key Points This article examines the BlackLight litigation in the United States, the United Kingdom, and the European Patent Office, and considers how patent offices and courts deal with patent applications in respect of clean energy and perpetual motion machines. Practical Significance The capacity of patent offices to grant sound and reliable patents is critical to the credibility of the patent system, particularly in the context of the current focus upon promoting clean technologies.

Pt/WO3 nanoplatelet/SiC Schottky diode based hydrogen gas sensor

This paper presents the fabrication and study of a Schottky diode based on Pt/WO3 nanoplatelet/SiC for H2 gas sensing applications. The nanostructured WO3 films were synthesized from tungsten (sputtered on SiC) via an acidetching method using a 1.5 M HNO3 solution. Scanning electron microscopy of the developed films revealed platelet crystals with thicknesses in the order of 20-60 nm and lengths between 100-700 nm. The current-voltage characteristic and dynamic response of the diodes were measured in the presence of air and 1% H2 gas balanced in air from 25 to 300°C. Upon exposure to 1% H2, voltage shifts of 0.64, 0.93 and 1.14 V were recorded at temperatures of 120, 200 and 300°C, respectively at a constant forward bias current of 500 μA.

The three-dimensional hydrogen-bonded structures in the ammonium and sodium salt hydrates of 4-aminophenylarsonic acid

The structures of two hydrated salts of 4-aminophenylarsonic acid (p-arsanilic acid), namely ammonium 4-aminophenylarsonate monohydrate, NH4(+)·C6H7AsNO3(-)·H2O, (I), and the one-dimensional coordination polymer catena-poly[[(4-aminophenylarsonato-κO)diaquasodium]-μ-aqua], [Na(C6H7AsNO3)(H2O)3]n, (II), have been determined. In the structure of the ammonium salt, (I), the ammonium cations, arsonate anions and water molecules interact through inter-species N-H...O and arsonate and water O-H...O hydrogen bonds, giving the common two-dimensional layers lying parallel to (010). These layers are extended into three dimensions through bridging hydrogen-bonding interactions involving the para-amine group acting both as a donor and an acceptor. In the structure of the sodium salt, (II), the Na(+) cation is coordinated by five O-atom donors, one from a single monodentate arsonate ligand, two from monodentate water molecules and two from bridging water molecules, giving a very distorted square-pyramidal coordination environment. The water bridges generate one-dimensional chains extending along c and extensive interchain O-H...O and N-H...O hydrogen-bonding interactions link these chains, giving an overall three-dimensional structure. The two structures reported here are the first reported examples of salts of p-arsanilic acid.

Mobile gene silencing in Arabidopsis is regulated by hydrogen peroxide

In plants and nematodes, RNAi can spread from cells from which it is initiated to other cells in the organism. The underlying mechanism controlling the mobility of RNAi signals is not known, especially in the case of plants. A genetic screen designed to recover plants impaired in the movement but not the production or effectiveness of the RNAi signal identified RCI3, which encodes a hydrogen peroxide (H2O2)-producing type III peroxidase, as a key regulator of silencing mobility in Arabidopsis thaliana. Silencing initiated in the roots of rci3 plants failed to spread into leaf tissue or floral tissue. Application of exogenous H2O2 reinstated the spread in rci3 plants and accelerated it in wild-type plants. The addition of catalase or MnO2, which breaks down H2O2, slowed the spread of silencing in wild-type plants. We propose that endogenous H2O2, under the control of peroxidases, regulates the spread of gene silencing by altering plasmodesmata permeability through remodelling of local cell wall structure, and may play a role in regulating systemic viral defence.

Ortho-Dihydroxyl-9,10-anthraquinone dyes as visible-light sensitizers that exhibit a high turnover number for hydrogen evolution

Pt/TiO2 sensitized by the cheap and organic ortho-dihydroxyl-9,10-anthraquinone dyes, such as Alizarin and Alizarin Red, achieved a TON of approximately 10 000 (TOF > 250 h−1 for the first ten hours) during >80 hours of visible light irradiation (>420 nm) for photocatalytic hydrogen evolution when triethanolamine was used as the sacrificial donor. The stability and activity enhancements can be attributed to the two highly serviceable redox reactions involving the 9,10-dicarbonyl and ortho-dihydroxyl groups of the anthracene ring, respectively

Perpendicularly oriented MoSe2/graphene nanosheets as advanced electrocatalysts for hydrogen evolution

By increasing the density of exposed active edges, the perpendicularly oriented structure of MoSe2 nanosheets facilitates ion/electrolyte transport at the electrode interface and minimizes the restacking of nanosheets, while the graphene improves the electrical contact between the catalyst and the electrode. This makes the MoSe2/graphene hybrid perfect as a catalyst in the hydrogen evolution reaction (HER). It shows a greatly improved catalytic activity compared with bare MoSe2 nanosheets.

Hydrogen-bonded supramolecular polymers as self-healing hydrogels: Effect of a bulky adamantyl substituent in the ureido-pyrimidinone monomer

In an attempt to generate supramolecular assemblies able to function as self-healing hydrogels, a novel ureido-pyrimidinone (UPy) monomer, 2-(N ′-methacryloyloxyethylureido)-6-(1-adamantyl)-4[1H]-pyrimidinone, was synthesized and then copolymerized with N,N-dimethylacrylamide at four different feed compositions, using a solution of lithium chloride in N,N-dimethylacetamide as the polymerization medium. The assembling process in the resulting copolymers is based on crosslinking through the reversible quadruple hydrogen bonding between side-chain UPy modules. The adamantyl substituent was introduced in order to create a “hydrophobic pocket” that may protect the hydrogen bonds against the disruptive effect of water molecules. Upon hydration to equilibrium, all copolymers generated typical hydrogels when their concentration in the hydrated system was at least 15%. The small-deformation rheometry showed that all hydrated copolymers were hydrogels that maintained a solid-like behavior, and that their extrusion through a syringe needle did not affect significantly this behavior, suggesting a self-healing capacity in these materials. An application as injectable substitutes for the eye's vitreous humor was proposed

Crystal structures and hydrogen bonding in the morpholinium salts of four phenoxyacetic acid analogues

The anhydrous salts morpholinium (tetrahydro-2-H-1,4-oxazine) phenxyacetate, C4H10NO+ C8H7O3- (I), (4-fluorophenoxy)acetate, C4H10NO+ C8H6FO3- (II) and isomeric morpholinium (3,5-dichlorophenoxy)acetate (3,5-D) (III) and morpholinium (2,4-dichlorophenoxy)acetate (2,4-D), C4H10NO+ C8H5Cl2O3- (IV), have been determined and their hydrogen-bonded structures are described. In the crystals of (I), (III) and (IV), one of the the aminium H atoms is involved in a three-centre asymmetric cation-anion N-H...O,O' R2/1(4) hydrogen-bonding interaction with the two carboxyl O-atom acceptors of the anion. With the structure of (II), the primary N---H...O interaction is linear. In the structures of (I), (II) and (III), the second N-H...O(carboxyl) hydrogen bond generates one-dimensional chain structures extending in all cases along [100]. With (IV), the ion pairs are linked though inversion-related N-H...O hydrogen bonds [graph set R2/4(8)], giving a cyclic heterotetrameric structure.

Substrate, molecular structure, and solvent effects in 2D self-assembly via hydrogen and halogen bonding

Recently, halogen···halogen interactions have been demonstrated to stabilize two-dimensional supramolecular assemblies at the liquid–solid interface. Here we study the effect of changing the halogen, and report on the 2D supramolecular structures obtained by the adsorption of 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (TBPT) and 2,4,6-tris(4-iodophenyl)-1,3,5-triazine (TIPT) on both highly oriented pyrolytic graphite and the (111) facet of a gold single crystal. These molecular systems were investigated by combining room-temperature scanning tunneling microscopy in ambient conditions with density functional theory, and are compared to results reported in the literature for the similar molecules 1,3,5-tri(4-bromophenyl)benzene (TBPB) and 1,3,5-tri(4-iodophenyl)benzene (TIPB). We find that the substrate exerts a much stronger effect than the nature of the halogen atoms in the molecular building blocks. Our results indicate that the triazine core, which renders TBPT and TIPT stiff and planar, leads to stronger adsorption energies and hence structures that are different from those found for TBPB and TIPB. On the reconstructed Au(111) surface we find that the TBPT network is sensitive to the fcc- and hcp-stacked regions, indicating a significant substrate effect. This makes TBPT the first molecule reported to form a continuous monolayer at room temperature in which molecular packing is altered on the differently reconstructed regions of the Au(111) surface. Solvent-dependent polymorphs with solvent coadsorption were observed for TBPT on HOPG. This is the first example of a multicomponent self-assembled molecular networks involving the rare cyclic, hydrogen-bonded hexamer of carboxylic groups, R66(24) synthon.

Metal-free graphitic carbon nitride as mechano-catalyst for hydrogen evolution reaction

Graphitic carbon nitride (g-C3N4), as a promising metal-free catalyst for photo-catalytic and electrochemical water splitting, has recently attracted tremendous research interest. However, the underlying catalytic mechanism for the hydrogen evolution reaction (HER) is not fully understood. By using density functional theory calculations, here we have established that the binding free energy of hydrogen atom (ΔGH∗0) on g-C3N4 is very sensitive to mechanical strain, leading to substantial tuning of the HER performance of g-C3N4 at different coverages. The experimentally-observed high HER activity in N-doped graphene supported g-C3N4 (Zheng et al., 2014) is actually attributed to electron-transfer induced strain. A more practical strategy to induce mechanical strain in g-C3N4 is also proposed by doping a bridge carbon atom in g-C3N4 with an isoelectronic silicon atom. The calculated ΔGH∗0 on the Si-doped g-C3N4 is ideal for HER. Our results indicate that g-C3N4 would be an excellent metal-free mechano-catalyst for HER and this finding is expected to guide future experiments to efficiently split water into hydrogen based on the g-C3N4 materials.

Unravelling the self-assembly of hydrogen bonded NDI semiconductors in 2D and 3D

Supramolecular ordering of organic semiconductors is the key factor defining their electrical characteristics. Yet, it is extremely difficult to control, particularly at the interface with metal and dielectric surfaces in semiconducting devices. We have explored the growth of n-type semiconducting films based on hydrogen-bonded monoalkylnaphthalenediimide (NDI-R) from solution and through vapor deposition on both conductive and insulating surfaces. We combined scanning tunneling and atomic force microscopies with X-ray diffraction analysis to characterize, at the submolecular level, the evolution of the NDI-R molecular packing in going from monolayers to thin films. On a conducting (graphite) surface, the first monolayer of NDI-R molecules adsorbs in a flat-lying (face-on) geometry, whereas in subsequent layers the molecules pack edge-on in islands (Stranski–Krastanov-like growth). On SiO2, the NDI-R molecules form into islands comprising edge-on packed molecules (Volmer–Weber mode). Under all the explored conditions, self-complementary H bonding of the imide groups dictates the molecular assembly. The measured electron mobility of the resulting films is similar to that of dialkylated NDI molecules without H bonding. The work emphasizes the importance of H bonding interactions for controlling the ordering of organic semiconductors, and demonstrates a connection between on-surface self-assembly and the structural parameters of thin films used in electronic devices.