Carbon-Based Ternary Nanocomposite: Bullet Type ZnO-SWCNT-CuO for Substantial Solar-Driven Photocatalytic Decomposition of Aqueous Organic Contaminants.

A facile two-step synthesis of ternary hetero-composites of ZnO, CuO, and single-walled carbon nanotubes (SWCNTs) was developed through a recrystallization process followed by annealing. A series of nanocomposites were prepared by varying the weight ratio of copper(II) acetate hydrate and zinc(II) acetate dihydrate and keeping the weight ratio of SWCNTs constant. The results revealed the formation of heterojunctions (ZnO-SWCNT-CuO, ZSC) of three crystal structures adjacent to each other, forming a ternary wurtzite-structured nanoparticles along with defects. Enhanced charge separation (electron-hole pairs), reduced band gap, defect-enhanced specific surface area, and promoted oxidation potential were key factors for the enhanced photocatalytic activity of the ternary nanocomposites. OH• radicals were the main active species during dye degradation, and O2-• and h+ were also involved to a lesser extent. A type II heterojunction mechanism approach is proposed based on the charge carrier migration pattern. Among the synthesized nanocomposites, the sample prepared using copper(II) acetate hydrate and zinc(II) acetate dihydrate in a 1: 9 ratio (designated a ZSC3) showed the highest photocatalytic activity. ZSC3 achieved 99.2% photodecomposition of methylene blue in 20 min, 94.1% photodecomposition of Congo red in 60 min, and 99.6% photodecomposition of Rhodamine B in 40 min under simulated sunlight. Additionally, ZSC3 showed excellent reusability and stability, maintaining 96.7% of its activity even after five successive uses. Based on overall results, the ZSC sample was proposed as an excellent candidate for water purification applications.

Facile Preparation of a Bispherical Silver-Carbon Photocatalyst and Its Enhanced Degradation Efficiency of Methylene Blue, Rhodamine B, and Methyl Orange under UV Light.

The combination of organic and inorganic materials is attracting attention as a photocatalyst that promotes the decomposition of organic dyes. A facile thermal procedure has been proposed to produce spherical silver nanoparticles (AgNPs), carbon nanospheres (CNSs), and a bispherical AgNP-CNS nanocomposite. The AgNPs and CNSs were each synthesized from silver acetate and glucose via single- and two-step annealing processes under sealed conditions, respectively. The AgNP-CNS nanocomposite was synthesized by the thermolysis of a mixture of silver acetate and a mesophase, where the mesophase was formed by annealing glucose in a sealed vessel at 190 °C. The physicochemical features of the as-prepared nanoparticles and composite were evaluated using several analytical techniques, revealing (i) increased light absorption, (ii) a reduced bandgap, (iii) the presence of chemical interfacial heterojunctions, (iv) an increased specific surface area, and (v) favorable band-edge positions of the AgNP-CNS nanocomposite compared with those of the individual AgNP and CNS components. These characteristics led to the excellent photocatalytic efficacy of the AgNP-CNS nanocomposite for the decomposition of three pollutant dyes under ultraviolet (UV) radiation. In the AgNP-CNS nanocomposite, the light absorption and UV utilization capacity increased at more active sites. In addition, effective electron-hole separation at the heterojunction between the AgNPs and CNSs was possible under favorable band-edge conditions, resulting in the creation of reactive oxygen species. The decomposition rates of methylene blue were 95.2, 80.2, and 73.2% after 60 min in the presence of the AgNP-CNS nanocomposite, AgNPs, and CNSs, respectively. We also evaluated the photocatalytic degradation efficiency at various pH values and loadings (catalysts and dyes) with the AgNP-CNS nanocomposite. The AgNP-CNS nanocomposite was structurally rigid, resulting in 93.2% degradation of MB after five cycles of photocatalytic degradation.

Structural Effect of Polyimide Precursors on Highly Thermally Conductive Graphite Films.

In this study, polyimide (PI) with high carbonization yield was used as a precursor to prepare graphite films with high thermal conductivity. The crystallinity, grain size, and thermal conductivity of the graphite films were characterized and found to vary according to the chemical structure of the PI precursor. Aromatic PIs containing ortho-substituted hydroxyl groups in the PI main chain (DHB-BPDA) were synthesized by the polycondensation reaction of 3,3'-dihydroxybenzidine (DHB) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA). The DHB-BPDA is converted to a polybenzoxazole (PBO) structure through thermolysis reaction during carbonization. The PBO containing a benzene ring and a heterocycle group can provide a strong main chain and high thermal stability due to its resonant structure. The graphite film prepared from DHB-BPDA exhibited a large grain size (63.727 nm) and a high thermal conductivity of 916 W/(mK).

Selective growth of Ti3+/TiO2/CNT and Ti3+/TiO2/C nanocomposite for enhanced visible-light utilization to degrade organic pollutants by lowering TiO2-bandgap.

A convenient route was developed for the selective preparation of two stable nanocomposites, Ti3+/TiO2/CNT (labeled as TTOC-1 and TTOC-3) and Ti3+/TiO2/carbon layer (labeled as TTOC-2), from the same precursor by varying the amount of single-walled carbon nanotubes used in the synthesis. TiO2 is an effective photocatalyst; however, its wide bandgap limits its usefulness to the UV region. As a solution to this problem, our prepared nanocomposites exhibit a small bandgap and wide visible-light (VL) absorption because of the introduction of carbonaceous species and Ti3+ vacancies. The photocatalytic efficiency of the nanocomposites was examined via the degradation of methylene blue dye under VL. Excellent photocatalytic activity of 83%, 98%, and 93% was observed for TTOC-1, TTOC-2, and TTOC-3 nanocomposites within 25 min. In addition, the photocatalytic degradation efficiency of TTOC-2 toward methyl orange, phenol, rhodamine B, and congo red was 28%, 69%, 71%, and 91%, respectively, under similar experimental conditions after 25 min. Higher reusability and structural integrity of the as-synthesized photocatalyst were confirmed within five consecutive runs by photocatalytic test and X-ray diffraction analysis, respectively. The resulting nanocomposites provide new insights into the development of VL-active and stable photocatalysts with high efficiencies.

Hierarchical Nanocauliflower Chemical Assembly Composed of Copper Oxide and Single-Walled Carbon Nanotubes for Enhanced Photocatalytic Dye Degradation.

We present the fabrication and proficient photocatalytic performance of a series of heterojunction nanocomposites with cauliflower-like architecture synthesized from copper(II) oxide (CuO) nanocrystals and carbon nanotubes with single walls (SWCNTs). These unique photocatalysts were constructed via simplistic recrystallization succeeded by calcination and were labeled as CuOSC-1, CuOSC-2, and CuOSC-3 (representing the components; CuO and SC for SWCNTs, and the calcination time in hours). The photocatalytic potency of the fabricated nanocomposites was investigated on the basis of their capability to decompose methylene blue (MB) dye under visible-light irradiation. Every as-synthesized nanocomposite was effective photocatalyst for the photodecomposition of an MB solution. Moreover, CuOSC-3 exhibited the best photocatalytic activity, with 96% degradation of the visible-light irradiated MB solution in 2 h. Pure CuO nanocrystals generated through the same route and pure SWCNTs were used as controls, where the photocatalytic actions of the nanocomposite samples were found to be remarkably better than that of either the pure CuO or the pure SWCNTs. The recycling proficiency of the photocatalysts was also explored; the results disclosed that the samples could be applied for five cycles without exhibiting a notable change in photocatalytic performance or morphology.

Heterojunction formation between copper(II) oxide nanoparticles and single-walled carbon nanotubes to enhance antibacterial performance.

We delineate the excellent bactericidal efficacy of stable heterojunction nanocomposites composed of single-walled carbon nanotubes (SWCNTs) and copper(II) oxide (CuO) synthesized via facile recrystallization and calcination. The bactericidal effectiveness of the fabricated nanocomposites was examined using the standard broth-dilution method and the growth-inhibition-zone analysis method, in which bacteria cultured in an incubator in tryptic soy broth medium were subjected to the prepared samples. The bactericidal activity of all of the as-synthesized samples is evident in both methods, displaying a substantial decrease in bacterial colonies and resulting in clear inhibition zones, respectively. Among the CuO-SWCNT nanocomposites, the sample subjected to calcination at 500 °C for 5 h was found to exhibit the best performance against Staphylococcus aureus and Escherichia coli, forming inhibition zones 182% and 162% larger than those formed by pure CuO, respectively.

Effect of Polymeric In Situ Stabilizers on Dispersion Homogeneity of Nanofillers and Thermal Conductivity Enhancement of Composites.

Boron nitride (BN) nanofiller-based polymer composites have been considered promising candidates for efficient heat-dissipating packaging materials because of their superior thermal conductivity, mechanical strength, and chemical resistance. However, strong aggregation of the BN nanofillers in the composite matrix as well as the difficulty in the modification of the chemically inert surface prevents their effective use in polymer composites. Herein, we report an effective method by using in situ stabilizers to achieve homogeneous dispersion of boron nitride (BN) nanofillers in an epoxy-based polymeric matrix and demonstrate their use as efficient heat-dissipating materials. Poly(4-vinylpyridine) (P4VP) is designed and added into the epoxy resin to produce in situ stabilizers during preparation of hexagonal BNs (h-BNs) and BN nanotubes (BNNTs) dispersion. In-depth experimental and theoretical studies indicated that the homogeneous distribution of BN nanofillers in epoxy composites achieved by using the in situ stabilizer enhanced the thermal conductivity of the composite by ∼27% at the same concentration of the BN nanofillers. In addition, the thermal conductivity of the h-BN/epoxy composite (∼3.3 W/mK) was dramatically improved by ∼48% (4.9 W/mK) when the homogeneously dispersed BNNTs (∼1.8 vol %) were added. The concept of the proposed in situ stabilizer can be further utilized to prepare the epoxy composites with the homogeneous distribution of BN nanofillers, which is critical for reproducible and position-independent composite properties.

Enhanced Thermal Conductivity of Liquid Crystalline Epoxy Resin using Controlled Linear Polymerization.

A powerful strategy to enhance the thermal conductivity of liquid crystalline epoxy resin (LCER) by simply replacing the conventional amine cross-linker with a cationic initiator was developed. The cationic initiator linearly wove the epoxy groups tethered on the microscopically aligned liquid crystal mesogens, resulting in freezing of the ordered LC microstructures even after curing. Owing to the reduced phonon scattering during heat transport through the ordered LC structure, a dramatic improvement in the thermal conductivity of neat cation-cured LCER was achieved to give a value ∼141% (i.e., 0.48 W/mK) higher than that of the amorphous amine-cured LCER. In addition, at the same composite volume fraction in the presence of a 2-D boron nitride filler, an approximately 130% higher thermal conductivity (maximum ∼23 W/mK at 60 vol %) was observed. The nanoarchitecture effect of the ordered LCER on the thermal conductivity was then examined by a systematic investigation using differential scanning calorimetry, polarized optical microscopy, X-ray diffraction, and thermal conductivity measurements. The linear polymerization of LCER can therefore be considered a practical strategy to enable the cost-efficient mass production of heat-dissipating materials, due to its high efficiency and simple process without the requirement for complex equipment.

Influence of the molecular-scale structures of 1-dodecanethiol and 4-methylbenzenethiol self-assembled monolayers on gold nanoparticles adsorption pattern.

In an effort to understand the effects of the molecular structures of self-assembled monolayers on the patterns formed by immobilized Au nanoparticles (AuNPs), we characterized and compared the morphologies and properties of AuNPs adsorbed onto self-assembled monolayers formed by 1-dodecanethiol (DDT-SAM) or 4-methylbenzenethiol (MBT-SAM) assembled on Au(111) surfaces. The AuNP adsorption pattern on the MBT-SAM surface was well-dispersed and characterized by a low degree of corrugation. By contrast, an aggregated and highly corrugated AuNP pattern was observed on the surface of the DDT-SAM. This difference was attributed to the retention or removal of citrate anions present on the AuNPs during adsorption onto the SAM surface. Direct interactions between the AuNPs and the highly corrugated hydrophobic surfaces of the DDT-SAMs could strip the citrate layers from the AuNP surfaces, leading to aggregated adsorption. The water molecules appeared to mediate the adsorption of the AuNPs by reducing the hydrophobicity of the MBT-SAM surface and promoting a more dispersed adsorption configuration.

Hot carrier-selective chemical reactions on Ag(110).

Here, we show that the pathways, products, and efficiencies of reactions occurring on a metal surface can be spatially modulated by varying the type and energy of hot carriers produced by injecting tunneling electrons or holes from a scanning tunneling microscope tip into the metal surface. Control over the metal surface reactions was demonstrated for the large-scale dissociation reaction of O2 molecules on a Ag(110) surface. Hot electrons (or holes) transported through the metal surface to chemisorbed O2 selectively dissociated the molecule into two oxygen atoms separated along the [110] (or [001]) lattice direction. The reaction selectivity was enhanced compared to the selectivity of a direct reaction involving tunneling carriers.

Adsorption and thermal decomposition of 2-octylthieno[3,4-b]thiophene on Au(111).

The adsorption and thermal stability of 2-octylthieno[3,4-b]thiophene (OTTP) on the Au(111) surfaces have been studied using scanning tunneling microscopy (STM), temperature programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). UHV-STM studies revealed that the vapor-deposited OTTP on Au(111) generated disordered adlayers with monolayer thickness even at saturation coverage. XPS and TPD studies indicated that OTTP molecules on Au(111) are stable up to 450 K and further heating of the sample resulted in thermal decomposition to produce H(2) and H(2)S via C-S bond scission in the thieno-thiophene rings. Dehydrogenation continues to occur above 600 K and the molecules were ultimately transformed to carbon clusters at 900 K. Highly resolved air-STM images showed that OTTP adlayers on Au(111) prepared from solution are composed of a well-ordered and low-coverage phase where the molecules lie flat on the surface, which can be assigned as a (9×2√33)R5° structure. Finally, based on analysis of STM, TPD, and XPS results, we propose a thermal decomposition mechanism of OTTP on Au(111) as a function of annealing temperature.

Binding structures of propylene glycol stereoisomers on the Si(001)-2×1 surface: a combined scanning tunneling microscopy and theoretical study.

The binding configuration of propylene glycol stereoisomer molecules adsorbed on the Si(001)-2×1 surface was investigated using a combination of scanning tunneling microscopy (STM) and density functional theory calculations. Propylene glycol was found to adsorb dissociatively via two hydroxyl groups exclusively as a bridge between the ends of two adjacent dimers along the dimer row. The chirality was preserved during bonding to Si atoms and was identifiable with STM imaging. The large number of propylene glycol conformers in the gas phase was reduced to a single configuration adsorbed on the surface at low molecular coverage.

The preserved aromaticity of aniline molecules adsorbed on a Si(5 5 12)-2x1 surface.

We present a scanning tunneling microscopy and first-principles calculations study of the adsorption structures of aniline on a Si(5 5 12)-2x1 surface. Dissociation from the aniline molecules of one or two H atom(s) bonded to N is favored, and then adsorption onto adatom, tetramer, and dimer rows of Si(5 5 12)-2x1 occurs in several distinct configurations. On the adatom row, aniline binds to an adatom in a tilted configuration, which is formed via a sigma bond between the adatom and N, with one dissociated H atom adsorbed on a nearby adatom. No further hydrogen dissociation occurs. On the tetramer and dimer rows, the structures with two dissociated hydrogens and upright configurations are the most stable. Aniline does not adsorb onto the honeycomb chains; this adsorption configuration has a low adsorption energy. In all the adsorption configurations of aniline on this surface, the molecule's aromaticity is preserved. Thus Si-N bonding of aromatic amine molecules provides a strategy for the homogeneous aromatic functionalization of high index Si surfaces.

Binding characteristics of pyridine on Ag(110).

A combination of low-temperature scanning tunneling microscopy and density functional theory calculations was used to determine the binding characteristics of single pyridine molecules at a low coverage on a silver surface. The results indicated that pyridine binds to silver through the nitrogen atom in either a perpendicular or a parallel configuration with the latter structure being more prevalent. Both configurations are produced predominantly through electrostatic interaction between nitrogen and silver atoms. This is induced by charge redistribution in the pyridine molecule and nearby silver atoms upon pyridine adsorption.

Electric field effect on the vibration of single CO molecules in a scanning tunneling microscope junction.

A low-temperature scanning tunneling microscope (STM) and ab initio calculations were used to study the electric field effect on the vibration of single CO molecules in an STM junction at 13 K. The vibrational energy of CO molecules adsorbed on silver atoms, measured by STM-based inelastic electron tunneling spectroscopy, depends on the direction of the electric field applied between the STM tip and the silver species. This characteristic can be explained by the charge separation model. The electric field modifies the binding characteristics of CO on silver as a result of a change in the charged states of the species, which leads to an increase (or a decrease) of the energies of the hindered rotation and the CO stretch on silver.