Oxidation behavior of P3HT layers on bare and TiO2-covered ZnO ripple structures evaluated by photoelectron spectroscopy.

P3HT layers with a thickness of ∼5 nm were deposited on bare and TiO2-covered ZnO ripple structures. The ZnO ripples were prepared wet-chemically and a TiO2 layer with a thickness less than 5 nm was prepared by atomic layer deposition. Under humid air and visible light illumination, the oxidation behaviors of P3HT on these surfaces were studied using photoelectron spectroscopy. It was found that P3HT on TiO2/ZnO oxidizes more easily than that on bare ZnO ripples. Using a model substrate of a flat ZnO surface in combination with angle-resolved photoelectron spectroscopy, we found that oxidation of P3HT occurs at the surface of the topmost layer of P3HT, not at the P3HT/oxide interfaces, even though P3HT oxidation is strongly influenced by the interface structure. It is suggested that the lifetime of electron-hole pairs can be strongly influenced by the interface structure, which can also affect the oxidation behavior of P3HT.

Thin films of size-selected Mo clusters: growth modes and structures.

Thin films of MoO3 were prepared by deposition of size-selected ligand-free Mo clusters under high vacuum conditions and subsequent exposure to air. The growth pattern is highly dependent on the cluster size. At low coverage, small clusters (Mo51) form a continuous monolayer of fused particles. On top of this monolayer, additional clusters survive as individual entities. Medium sized clusters (Mo251 and Mo1253) do not coalesce and form a monolayer of clusters. Close examination using in situ scanning tunneling microscopy reveals a local order of the particles. At higher coverage a new pattern of large 3-dimensional aggregations of clusters (pylons) appears. The pylons are not formed under high vacuum conditions. Their formation is most likely caused by the air exposure. For the largest clusters (Mo3349) studied here, no monolayer is formed. Instead, the clusters are randomly distributed as expected for particles with zero mobility. These results demonstrate the high potential of cluster deposition for the production of new types of nanostructured surfaces, thin films and nanomaterials.

Metal-organic framework@microporous organic network: hydrophobic adsorbents with a crystalline inner porosity.

This work reports the synthesis and application of metal-organic framework (MOF)@microporous organic network (MON) hybrid materials. Coating a MOF, UiO-66-NH2, with MONs forms hybrid microporous materials with hydrophobic surfaces. The original UiO-66-NH2 shows good wettability in water. In comparison, the MOF@MON hybrid materials float on water and show excellent performance for adsorption of a model organic compound, toluene, in water. Chemical etching of the MOF results in the formation of hollow MON materials.

Parallel deposition of size-selected clusters: a novel technique for studying size-selectivity on the atomic scale.

A new size-selected cluster deposition technique referred to as "parallel-deposition" is presented. An ion beam of multi-sized Aun clusters was spatially separated into individual cluster sizes by utilizing a Wien filter and the clusters spatially separated based on their atomic sizes were simultaneously deposited on a SiO2/Si(100) substrate. Parallel-deposited Aun clusters (n = 6, 7, and 8) on the SiO2/Si(100) substrate showed even-odd oxidation behaviour upon exposure to an atomic oxygen atmosphere, demonstrating the potential of this new technique to study the size-dependent properties of deposited clusters in various research fields.

CO2 reduction efficiency through electrolyte immersion in hierarchical bismuth-nickel catalysts.

Nanostructures are critical for improving the contact area with an electrolyte and catalytic efficiency for the CO2 reduction reaction (CO2RR). However, their hydrophobicity conflicts with the intended increase in the contact area and complicates the determination of the active contact area. Here, bismuth-nickel (BiNi) micro-nano hierarchical catalysts for the CO2RR were studied to understand the effects of electrolyte-catalyst contact area variation with the immersion duration in an aqueous electrolyte. The immersed BiNi samples showed about 13.4-fold higher formate production compared to the pristine BiNi sample. The 2-day pre-immersed BiNi sample exhibited faradaic efficiencies (FE%) of ∼80.1% for formate and ∼10% for H2 with a current density of 10.2 mA cm-2 at -1.5 V vs. Ag/AgCl. In contrast, the pristine BiNi catalysts exhibited an FE% of ∼12.9% for formate and ∼76.3% for H2 with a current density of 5.38 mA cm-2. Our experimental results reveal that the improved contact between the electrolyte and the catalyst surface through pre-immersion can lead to enhanced CO2RR efficiency for formate production using hierarchical BiNi catalysts.

Surface property change of C doped TiO2 nano-pillars by O2 plasma treatment.

TiO2 surface is led to super-hydrophilic surface by modifying to hydroxyl group. The super-hydrophilic surface can be applied to anti-fogging, because of preventing formation of water droplet on the surface. Super-hydrophilic coatings are made of metal oxides, polymers, or their mixtures. In this study, columnar-structured C doped TiO2 nano-pillars were grown on glass substrates by MOCVD method. For change of surface properties, grown columnar-structured C-TiO2 nano-pillars were treated by oxygen plasma. After oxygen plasma treatment, the surface property of grown columnar structured C-TiO2 nano-pillars changed from hydrophobic surface to super hydrophilic surface. For determination of this mechanism, scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), FT-IR spectroscopy, and contact angle analyzer were employed.

Growth of TiO2 nanorods on a Ta substrate by metal-organic chemical vapor deposition.

TiO2 nanorods were successfully grown on Tantalum (Ta) substrates using titanium tetra isopropoxide (TTIP) as a single precursor without any carriers or bubbling gases. For characterization of the TiO2 structures, scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were employed. For substrate temperatures below 800 degrees C, a rough film structure without nanorods could be found. However, at a sample temperature of 800 degrees C, nanorod structures with a respective diameter and length of 0.1 approximately 0.2 microm and 0.7 approximately 1.5 microm, respectively, could be synthesized. The nanorods exhibited a rutile phase with a 2:1 stoichiometry of O:Ti, identified using XRD and XPS. When the growth temperature exceeded 800 degrees C, agglomeration of the nanorods was identified.

Mesoporous SiO2 Particles Combined with Fe Oxide Nanoparticles as a Regenerative Methylene Blue Adsorbent.

Mesoporous SiO2 adsorbents were combined with Fe oxide nanoparticles (∼10 nm) that can catalyze thermal oxidation of organic compounds at low temperatures. Fe oxide nanoparticle (∼10 nm)-incorporated SiO2 adsorbents were prepared via a temperature-regulated chemical vapor deposition method followed by a thermal annealing process. The removal efficiency and reusability of Fe oxide/SiO2 particles were examined and compared to those of bare SiO2. Upon deposition of Fe oxide nanoparticles, not only the equilibrium adsorption capacity of mesoporous SiO2 for methylene blue (MB) was improved but also the reusability of SiO2 adsorbent was increased significantly. The adsorption ability of fresh Fe oxide/SiO2 particles can be almost fully recovered by simple thermal annealing at atmospheric conditions (400 °C), whereas that of bare SiO2 reduced significantly under same conditions. In addition, full recovery of initial MB adsorption ability of Fe oxide/SiO2 can be achieved by a 100 °C annealing process. Fourier transform infrared, thermogravimetric analysis, and X-ray photoelectron spectroscopy analyses indicated that Fe oxide nanoparticles catalyzed thermal degradation of adsorbed MB molecules, resulting in the improved reusability of the Fe oxide/SiO2 adsorbent. In addition to reusability, the equilibrium adsorption capacity of mesoporous SiO2 particles for various cationic dye molecules, such as MB, malachite green, and rhodamine B, can be improved by combining Fe oxide nanoparticles.

Low Temperature CO oxidation over Iron Oxide Nanoparticles Decorating Internal Structures of a Mesoporous Alumina.

Using a chemical vapor deposition method with regulated sample temperatures under ambient pressure conditions, we were able to fully decorate the internal structure of a mesoporous Al2O3 bead (~1 mm in particle diameter) with iron oxide nanoparticles (with a mean lateral size of less than 1 nm). The iron oxide-decorated Al2O3 showed a high CO oxidation reactivity, even at room temperature. Very little deactivation of the CO oxidation activity was observed with increasing reaction time at ~100 °C. Additionally, this catalyst showed high CO oxidation activity, even after annealing at ~900 °C under atmospheric conditions (i.e., the structure of the catalysts could be maintained under very harsh treatment conditions). We show that our catalysts have potential for application as oxidation catalysts in industrial processes due to the simplicity of their fabrication process as well as the high and stable catalytic performance.

Structural Effect of Thioureas on the Detection of Chemical Warfare Agent Simulants.

The ability to rapidly detect, identify, and monitor chemical warfare agents (CWAs) is imperative for both military and civilian defense. Since most CWAs and their simulants have an organophosphonate group, which is a hydrogen (H)-bond acceptor, many H-bond donors have been developed to effectively bind to the organophosphonate group. Although thioureas have been actively studied as an organocatalyst, they are relatively less investigated in CWA detection. In addition, there is a lack of studies on the structure-property relationship for gas phase detection. In this study, we synthesized various thioureas of different chemical structures, and tested them for sensing dimethylmethylphosphonate (DMMP), a CWA simulant. Molecular interaction between DMMP and thiourea was measured by 1H NMR titration and supported by density functional theory (DFT) calculations. Strong H-bond donor ability of thiourea may cause self-aggregation, and CH-π interaction can play an important role in the DMMP detection. Gas-phase adsorption of DMMP was also measured using a quartz crystal microbalance (QCM) and analyzed using the simple Langmuir isotherm, showing the importance of structure-induced morphology of thioureas on the surface.

Surface modification of a ZnO electron-collecting layer using atomic layer deposition to fabricate high-performing inverted organic photovoltaics.

A ripple-structured ZnO film as the electron-collecting layer (ECL) of an inverted organic photovoltaic (OPV) was modified by atomic layer deposition (ALD) to add a ZnO thin layer. Depositing a thin ZnO layer by ALD on wet-chemically prepared ZnO significantly increased the short-circuit current (Jsc) of the OPV. The highest power conversion efficiency (PCE) of 7.96% with Jsc of 17.9 mA/cm2 was observed in the inverted OPV with a 2-nm-thick ALD-ZnO layer, which quenched electron-hole recombination at surface defects of ZnO ripples. Moreover, an ALD-ZnO layer thinner than 2 nm made the distribution of electrical conductivity on the ZnO surface more uniform, enhancing OPV performance. In contrast, a thicker ALD-ZnO layer (5 nm) made the two-dimensional distribution of electrical conductivity on the ZnO surface more heterogeneous, reducing the PCE. In addition, depositing an ALD-ZnO thin layer enhanced OPV stability and initial performance. We suggest that the ALD-ZnO layer thickness should be precisely controlled to fabricate high-performing OPVs.

A high-performing nanostructured TiO2 filter for volatile organic compounds using atomic layer deposition.

Novel nanostructured gas filtering systems with TiO(2) thin films using atomic layer deposition (ALD) were developed for volatile organic compounds. A superior toluene adsorption efficiency was found for the nanostructured TiO(2) thin films.