Insight into Key Parameters for Fabricating Stable Single-Atom Pt-Nix Alloy by Reduction Environment-Induced Anti-Ostwald Effects.

Developing single-atom catalysts with superior stability under reduction conditions is essential for hydrogenation/dehydrogenation catalysis and green hydrogen generation. In this contribution, single-atom Pt catalysts were achieved via a reduction environment-induced anti-Ostwald approach in the highly confined Ni species (Pt-Nix ) on nonreducible Al2 O3 matrix. In-situ X-ray absorption spectroscopy indicated that the isolated Pt-Nix metallic bonds, generated at high reduction temperature, dominated the formation of single Pt atoms. A relatively large cluster of metallic Ni would benefit the stabilization of Pt single atom as observed via high-angle annular dark-field scanning transmission electron microscopy and validated by density functional theory simulation. Excellent performance on cellulose hydrogenolysis was demonstrated under harsh reductive and hydrothermal conditions, potentially expandable to other hydrogen involved reactions like CO2 hydrogenation, green hydrogen production from different hydrogen carriers, and beyond.

SiC Monolayers as Promising Substrates for the Development of Highly Stable Palladium Single Atom Catalysts: A Density Functional Theory Study.

Single-atom catalysts have been touted as highly efficient catalysts, but the catalytic single-atom sites are unstable and tend to aggregate into nanoparticles during chemical reactions. In this study, we show that SiC monolayers are promising substrates for the development of highly stable single-atom catalysts (Pd1 /SiC) within the density functional theory. In presence of a Si-vacancy, the diffusion barrier energy of a Pd1 atom embedded in the SiC monolayer is substantially enhanced from 2.3 to 7.8 eV, which is much higher than the reported diffusion barrier energies of graphene, boron nitride and defective MgO of the same catalytic system. Ab initio molecular dynamic calculations at 500 K also confirm the enhanced stability of Pd1 /SiC monolayer (Si-vacancy) such that the Pd1 atom remains embedded in the vacancy. Additionally, the Pd1 /SiC monolayer (Si-vacancy) catalysts show a ∼34 % reduction of activation barrier energy for CO oxidation as compared to pristine catalysts. This work implies that nanostructured SiC materials are promising substrates for the synthesis of highly stable single-atom catalysts.

Efficient growth of horizontally aligned single-walled carbon nanotubes by chemical vapor deposition over MgO-supported bimetallic co-based catalysts.

A series of supported cobalt-based catalysts (Co-X, where X = Mn, V, W, Gd, Mo) has been investigated for the growth of single-walled carbon nanotubes via catalytic decomposition of CH4. At 850 degrees C, Mn, W and Gd promoted Co-catalysts produce SWNTs while Mo and V do not yield any SWNTs. Furthermore, Co-Gd catalysts produce high quality SWNTs with very few defects, and also narrow diameter and chirality distributions (approximately 1 nm). The growth of horizontally aligned SWNTs (approximately 1 mm long) using the Co-Gd catalyst is also demonstrated.

Plasma-Assisted Synthesis of Carbon Nanotubes.

The application of plasma-enhanced chemical vapour deposition (PECVD) in the production and modification of carbon nanotubes (CNTs) will be reviewed. The challenges of PECVD methods to grow CNTs include low temperature synthesis, ion bombardment effects and directional growth of CNT within the plasma sheath. New strategies have been developed for low temperature synthesis of single-walled CNTs based the understanding of plasma chemistry and modelling. The modification of CNT surface properties and synthesis of CNT hybrid materials are possible with the utilization of plasma.

First-principles study of carbon nanotubes with bamboo-shape and pentagon-pentagon fusion defects.

A first-principles study of single-walled carbon nanotubes with bamboo-shape (BS) and pentagon-pentagon fusion defects was conducted. Sharp resonances occur on the BS-nanotubes as strong density of electronic states (DOS) localized at carbon atoms adjacent to the partitions, while at the partition the localized DOS was greatly depleted. A strong defect state at -0.1 eV below the Fermi level was generated and the band gap was narrowed for BS-(10, 0) nanotube. Sharp resonant states are observed in the valence and conduction bands of BS-(12, 0) nanotube. The resonant states are attributed to the pentagon defects as exemplified by the study of a (5, 5) nanotube with pentagon-pentagon fusion ring. The high chemical reactivity of the topological defects of the BS-nanotubes is correlated to the presence of localized resonant states.

Controlling the synthetic pathways of TiO2-derived nanostructured materials.

A comprehensive study of the hydrothermal synthesis of TiO2-derived nanostructured materials, including layered protonic trititanate (H2Ti3O7), metal-ion exchangeable titanate (Na(x)H(2-x)Ti3O7), TiO2(B) and anatase nanotubes and TiO2-anatase nanowires, was conducted. Nanoscaled tubular structures were found to be already present in the samples derived from prolonged hydrothermal process of bulk anatase TiO2 and could be converted to various types of nanotubes, nanowires or nanorodes by post-synthesis treatments. 0.1 M HCI acid wash and air annealing were the two key parameters to select the types of nanotubes/nanowires as the final products. XRD, Raman, TG, and XPS core level and valence band studies were carried out to elucidate our proposed synthetic pathways.

Photoluminescence and optical limiting properties of silicon nanowires.

Si nanowires (SiNWs) have been produced by thermal vaporization on Si(111) substrate without catalysts added. The grown SiNWs have been characterized by Raman scattering, SEM, XRD, and electron diffraction and shown to be highly crystalline with only little impurities such as amorphous Si and silicon oxides. Photoluminescence (PL) study has illustrated that the Si band-to-band gap increases from 1.1 eV for bulk Si to 1.56 eV for the as-grown SiNWs due to quantum confinement effect. A strong PL peak at 521 nm (2.37 eV) is attributed to the relaxation of the photon-induced self-trapped state in the form of surface Si-Si dimers, which may also play an important role in optical limiting of SiNWs with 532-nm nanosecond laser pulses. With the observation of optical limiting at 1064 nm, nonlinear scattering is believed to make a dominant contribution to the nonlinear response of SiNWs.

Room-temperature hydrogen uptake by TiO(2) nanotubes.

TiO(2) nanotubes can reproducibly store up to approximately 2 wt % H(2) at room temperature and 6 MPa. However, only about 75% of this stored hydrogen can be released when the hydrogen pressure is lowered to ambient conditions, suggesting that both physisorption and chemisorption are responsible for the hydrogen uptake. FTIR spectroscopy, temperature-programmed desorption (TPD), and pressure-composition (P-C) isotherms suggest that 75% of the H(2) is physisorbed and can be reversibly released upon pressure reduction. Approximately 13% is weakly chemisorbed and can be released at 70 degrees C as H(2), and approximately 12% is bonded to oxide ions and released only at temperatures above 120 degrees C as H(2)O.

A glucose biosensor based on electrodeposition of palladium nanoparticles and glucose oxidase onto Nafion-solubilized carbon nanotube electrode.

Electrodeposition was used for the co-deposition of glucose oxidase (GOx) enzymes and palladium nanoparticles onto a Nafion-solubilized carbon nanotube (CNT) film. The co-deposited Pd-GOx-Nafion CNT bioelectrode retains its biocatalytic activity and offers an efficient oxidation and reduction of the enzymatically liberated H2O2, allowing for fast and sensitive glucose quantification. The combination of Pd-GOx electrodeposition with Nafion-solubilized CNTs enhances the storage time and performance of the sensor. An extra Nafion coating was used to eliminate common interferents such as uric and ascorbic acids. The fabricated Pd-GOx-Nafion CNT glucose biosensor exhibits a linear response up to 12 mM glucose and a detection limit of 0.15 mM (S/N = 3).