Efficient plasmonic water splitting by heteroepitaxial junction-induced faceting of gold nanoparticles on an anatase titanium(IV) oxide nanoplate array electrode.

Plasmonic photocatalysts represented by gold nanoparticle (NP)-loaded titanium(IV) oxide (Au/TiO2) can be promising solar-to-fuel converters by virtue of their response to visible-to-near infrared light. Hitherto, Au/rutile (R)-TiO2 has been recognized as exhibiting photocatalytic activity higher than that of Au/anatase (A)-TiO2. Herein, we demonstrate that the high potential of A-TiO2 as the Au NP support can be brought out through atomic level interface control. Faceting of Au NPs is induced by a heteroepitaxial junction on an A-TiO2(001) nanoplate array (Au/A-TiO2 NPLA). Photoexcitation towards the Au/A-TiO2 NPLA electrode generates current for the water oxidation reaction at λ < 900 nm with a maximum efficiency of 0.39% at λ = 600 nm, which is much larger than the values reported so far for the usual electrodes. The striking activity of the Au/A-TiO2 NPLA electrode was rationalized using a potential-dependent Fowler model. This study presented a novel approach for developing solar-driven electrodes for green and sustainable fuel production.

Near Infrared Light-to-Heat Conversion for Liquid-Phase Oxidation Reactions by Antimony-Doped Tin Oxide Nanocrystals.

Effective utilization of the sunlight for chemical reactions is pivotal for dealing with the growing energy and environmental issues. So far, much effort has been focused on the development of semiconductor photocatalysts responsive to UV and visible light. However, the near infrared and infrared (NIR-IR) light occupying ∼50 % of the solar energy has usually been wasted because of the low photon energy insufficient for the band gap excitation. Antimony doping into SnO2 (ATO) induces strong absorption due to the conduction band electrons in the NIR region. The absorbed light energy is eventually converted to heat via the interaction between hot electrons and phonons. This Concept highlights the photothermal effect of ATO nanocrystals (NCs) on liquid-phase oxidation reactions through the NIR light-to-heat conversion. Under NIR illumination even at an intensity of ∼0.5 sun, the reaction field temperature on the catalyst surface is raised 20-30 K above the bulk solution temperature, while the latter is maintained near the ambient temperature. In some reactions, this photothermal local heating engenders the enhancement of not only the catalytic activity and selectivity but also the regeneration of catalytically active sites. Further, the photocatalytic activity of semiconductors can be promoted. Finally, the conclusions and possible subjects in the future are summarized.

Photothermal Oxidation of Cinnamyl Alcohol with Hydrogen Peroxide Catalyzed by Gold Nanoparticle/Antimony-Doped Tin Oxide Nanocrystals.

Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (dAu ) at 5.3 nm≤dAu ≤8.2 nm. Light irradiation (λex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs.

Noble Metal-Free Inorganic Photocatalyst Consisting of Antimony-Doped Tin Oxide Nanorod and Titanium oxide for Two-Electron Oxygen Reduction Reaction.

This study reports a noble metal-free robust inorganic photocatalyst for H2 O2 synthesis via two-electron oxygen reduction reaction (ORR). Antimony-doped tin oxide nanorods were heteroepitaxially grown from rutile TiO2 seed crystals with an orientation of (001)ATO //(001)TiO2 (ATO-NR//TiO2 ,//denotes heteroepitaxial junction) by a hydrothermal method. UV-light irradiation of ATO-NR//TiO2 particles stably and continuously produces H2 O2 from aerated aqueous solution of ethanol. Electrochemical measurements using rotating electrodes show that Sb-doping into SnO2 greatly enhances the electrocatalytic activity for two-electron ORR. The striking photocatalytic activity of ATO-NR//TiO2 stems from the effective charge separation, electrocatalytic activity for two-electron ORR, low catalytic activity for H2 O2 decomposition, and extraordinary robustness.

Switching of Electron Transport Direction from the Long Axis to Short Axis in a Radial SnO2(Head)-Rutile TiO2 Nanorod(Tail) Heteromesocrystal Photocatalyst.

Heteroepitaxial growth of rutile TiO2 nanorods from SnO2 seeds yielded radial heteromesocrystals consisting of SnO2(head) and rutile TiO2 nanorod(tail) with the SnO2(head) oriented toward the center (TiO2-NR//SnO2 HEMCs). Iron oxide clusters were formed on the surface by the chemisorption-calcination technique. The FeOx-surface modification gives rise to drastic increases in the photocatalytic activity for aerobic oxidation of 2-naphthol under irradiation of UV and visible light. As a 2D-model for 3D-TiO2-NR//SnO2 HEMC, electrochemical measurements were performed for the rutile TiO2-NR array formed on a fluorine-doped tin oxide (SnO2:F) electrode. The results showed that the FeOx clusters possess electrocatalytic activity for a multielectron oxygen reduction reaction, and the high photocurrent of the electrode is remarkably reduced by the FeOx-surface modification. Consequently, the striking photocatalytic activity of FeOx/TiO2-NR//SnO2 HEMCs was ascribable to the switching of the electron transport direction necessary for the charge separation from the long axis of the TiO2 NR to the short axis.

Ultrafast Growth of a Cu(OH)2-CuO Nanoneedle Array on Cu Foil for Methanol Oxidation Electrocatalysis.

A swift potentiostatic anodization method for growing a 5-7 µm tall nanoneedle array of Cu(OH)2-CuO on Cu foil within 100 s has been developed. This catalytic electrode when screened for methanol oxidation electrocatalysis in 1 M KOH with 0.5 M methanol, delivered a current density as high as 70 ± 10 mA cm-2 at 0.65 V versus Hg/HgO which is superior to the performance of many related catalysts reported earlier. The observed activity enhancement is attributed to the formation of both Cu(OH)2-CuO nanoneedle arrays of high active surface area over the metallic Cu foil. In addition, the Cu(OH)2-CuO/Cu electrode had also exhibited excellent stability upon prolonged potentiostatic electrocatalytic oxidation of methanol while retaining the charge-transfer characteristics. Growth of such highly ordered assembly of Cu(OH)2-CuO nanoneedles within a minute has never been achieved before. When compared to its oxygen evolution reaction activity, the addition of 0.5 M methanol has lowered the overpotential at 10 mA cm-2 by 334 mV, which is significant. This encourages the use of methanol as a sacrificial anolyte for energy-saving production of H2 from water electrolysis.

Gd-Enhanced Growth of Multi-Millimeter-Tall Forests of Single-Wall Carbon Nanotubes.

Multi-millimeter-tall vertically aligned single-wall carbon nanotube (VA-SWCNT) forests were grown using Fe/Gd/Al2Ox catalyst with high initial growth rate of ∼2 µm s-1 and long catalyst lifetime of ∼70 min at 800 °C. The addition of Gd with a nominal thickness of 0.3 nm drastically prolonged the catalyst lifetime. The analysis of the VA-SWCNT forests by a transmission electron microscope showed that the average diameter of the SWCNTs grown with Gd is constant from the top to the bottom of the forests, while it monotonically increased without Gd. This indicated that Gd suppresses the structure change of the Fe nanoparticles in the lateral direction during the CNT growth. By X-ray photoelectron spectroscopy, it was found that the longer catalyst lifetime with Gd stems from the suppression of the interaction between Fe and C resulting in the smaller structure change of the Fe nanoparticles.

Enhancing the photovoltaic performance of hybrid heterojunction solar cells by passivation of silicon surface via a simple 1-min annealing process.

Solution-based heterojunction technology is emerging for facile fabrication of silicon (Si)-based solar cells. Surface passivation of Si substrate has been well established to improve the photovoltaic (PV) performance for the conventional bulk Si cells. However, the impact is still not seen for the heterojunction cells. Here, we developed a facile and repeatable method to passivate the Si surface by a simple 1-min annealing process in vacuum, and integrated it into the heterojunction cells with poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) or carbon nanotube (CNT). A thin and dense oxide layer was introduced on the Si surface to provide a high-quality hole transport layer and passivation layer. The layer enhanced the power conversion efficiency from 9.34% to 12.87% (1.38-times enhancement) for the PEDOT:PSS/n-Si cells and from 6.61% to 8.52% (1.29-times enhancement) for the CNT/n-Si cells. The simple passivation is a promising way to enhance the PV performance of the Si cells with various solution-based heterojunctions.

An interdigitated electrode with dense carbon nanotube forests on conductive supports for electrochemical biosensors.

A highly sensitive interdigitated electrode (IDE) with vertically aligned dense carbon nanotube forests directly grown on conductive supports was demonstrated by combining UV lithography and a low temperature chemical vapor deposition process (470 °C). The cyclic voltammetry (CV) measurements of K4[Fe(CN)6] showed that the redox current of the IDE with CNT forests (CNTF-IDE) reached the steady state much more quickly compared to that of conventional gold IDE (Au-IDE). The performance of the CNTF-IDE largely depended on the geometry of the electrodes (e.g. width and gap). With the optimum three-dimensional electrode structure, the anodic current was amplified by a factor of ∼18 and ∼67 in the CV and the chronoamperometry measurements, respectively. The collection efficiency, defined as the ratio of the cathodic current to the anodic current at steady state, was improved up to 97.3%. The selective detection of dopamine (DA) under the coexistence of l-ascorbic acid with high concentration (100 µM) was achieved with a linear range of 100 nM-100 µM, a sensitivity of 14.3 mA mol-1 L, and a limit of detection (LOD, S/N = 3) of 42 nM. Compared to the conventional carbon electrodes, the CNTF-IDE showed superior anti-fouling property, which is of significant importance for practical applications, with a negligible shift of the half-wave potential (ΔE1/2 < 1.4 mV) for repeated CV measurements of DA at high concentration (100 µM).

Low temperature growth of fully covered single-layer graphene using a CoCu catalyst.

A bimetallic CoCu alloy thin-film catalyst is developed that enables the growth of uniform, high-quality graphene at 750 °C in 3 min by chemical vapour deposition. The growth outcome is found to vary significantly as the Cu concentration is varied, with ∼1 at% Cu added to Co yielding complete coverage single-layer graphene growth for the conditions used. The suppression of multilayer formation is attributable to Cu decoration of high reactivity sites on the Co surface which otherwise serve as preferential nucleation sites for multilayer graphene. X-ray photoemission spectroscopy shows that Co and Cu form an alloy at high temperatures, which has a drastically lower carbon solubility, as determined by using the calculated Co-Cu-C ternary phase diagram. Raman spectroscopy confirms the high quality (ID/IG < 0.05) and spatial uniformity of the single-layer graphene. The rational design of a bimetallic catalyst highlights the potential of catalyst alloying for producing two-dimensional materials with tailored properties.

From Growth Surface to Device Interface: Preserving Metallic Fe under Monolayer Hexagonal Boron Nitride.

We investigate the interfacial chemistry between Fe catalyst foils and monolayer hexagonal boron nitride (h-BN) following chemical vapor deposition and during subsequent atmospheric exposure, using scanning electron microscopy, X-ray photoemission spectroscopy, and scanning photoelectron microscopy. We show that regions of the Fe surface covered by h-BN remain in a metallic state during exposure to moist air for ∼40 h at room temperature. This protection is attributed to the strong interfacial interaction between h-BN and Fe, which prevents the rapid intercalation of oxidizing species. Local Fe oxidation is observed on bare Fe regions and close to defects in the h-BN film (e.g., domain boundaries, wrinkles, and edges), which over the longer-term provide pathways for slow bulk oxidation of Fe. We further confirm that the interface between h-BN and metallic Fe can be recovered by vacuum annealing at ∼600 °C, although this is accompanied by the creation of defects within the h-BN film. We discuss the importance of these findings in the context of integrated manufacturing and transfer-free device integration of h-BN, particularly for technologically important applications where h-BN has potential as a tunnel barrier such as magnetic tunnel junctions.

Ten-Second Epitaxy of Cu on Repeatedly Used Sapphire for Practical Production of High-Quality Graphene.

Epitaxial copper (Cu) films yield graphene with superior quality but at high cost. We report 1-3 µm thick epitaxial Cu films prepared on c plane sapphire substrates in 10-30 s, which is much faster than that of the typical sputtering method. Such rapid deposition is realized by vapor deposition using a Cu source heated to 1700-1800 °C, which is much higher than its melting point of 1085 °C. Continuous graphene films, either bilayer or single-layer, are obtained on the epitaxial Cu by chemical vapor deposition and transferred to carrier substrates. The sapphire substrates can be reused five to six times maintaining the quality of the epitaxial Cu films and graphene. The mechanisms and requirements are discussed for such quick epitaxy of Cu on reused sapphire, which will enable high-quality graphene production at lower cost.

Growth of Continuous Monolayer Graphene with Millimeter-sized Domains Using Industrially Safe Conditions.

We demonstrate the growth of continuous monolayer graphene films with millimeter-sized domains on Cu foils under intrinsically safe, atmospheric pressure growth conditions, suitable for application in roll-to-roll reactors. Previous attempts to grow large domains in graphene have been limited to isolated graphene single crystals rather than as part of an industrially useable continuous film. With both appropriate pre-treatment of the Cu and optimization of the CH4 supply, we show that it is possible to grow continuous films of monolayer graphene with millimeter scale domains within 80 min by chemical vapour deposition. The films are grown under industrially safe conditions, i.e., the flammable gases (H2 and CH4) are diluted to well below their lower explosive limit. The high quality, spatial uniformity, and low density of domain boundaries are demonstrated by charge carrier mobility measurements, scanning electron microscope, electron diffraction study, and Raman mapping. The hole mobility reaches as high as ~5,7002 m(2) V(-1) s(-1) in ambient conditions. The growth process of such high-quality graphene with a low H2 concentration and short growth times widens the possibility of industrial mass production.

Efficient Transfer Doping of Carbon Nanotube Forests by MoO3.

We dope nanotube forests using evaporated MoO3 and observe the forest resistivity to decrease by 2 orders of magnitude, reaching values as low as ∼5 × 10(-5) Ωcm, thus approaching that of copper. Using in situ photoemission spectroscopy, we determine the minimum necessary MoO3 thickness to dope a forest and study the underlying doping mechanism. Homogenous coating and tube compaction emerge as key factors for decreasing the forest resistivity. When all nanotubes are fully coated with MoO3 and packed, conduction channels are created both inside the nanotubes and on the outside oxide layer. This is supported by density functional theory calculations, which show a shift of the Fermi energy of the nanotubes and the conversion of the oxide into a layer of metallic character. MoO3 doping removes the need for chirality control during nanotube growth and represents a step forward toward the use of forests in next-generation electronics and in power cables or conductive polymers.

Low-Temperature Growth of Carbon Nanotube Forests Consisting of Tubes with Narrow Inner Spacing Using Co/Al/Mo Catalyst on Conductive Supports.

We grow dense carbon nanotube forests at 450 °C on Cu support using Co/Al/Mo multilayer catalyst. As a partial barrier layer for the diffusion of Co into Mo, we apply very thin Al layer with the nominal thickness of 0.50 nm between Co and Mo. This Al layer plays an important role in the growth of dense CNT forests, partially preventing the Co-Mo interaction. The forests have an average height of ∼300 nm and a mass density of 1.2 g cm(-3) with tubes exhibiting extremely narrow inner spacing. An ohmic behavior is confirmed between the forest and Cu support with the lowest resistance of ∼8 kΩ. The forest shows a high thermal effusivity of 1840 J s(-0.5) m(-2) K(-1), and a thermal conductivity of 4.0 J s(-1) m(-1) K(-1), suggesting that these forests are useful for heat dissipation devices.

Growth kinetics and growth mechanism of ultrahigh mass density carbon nanotube forests on conductive Ti/Cu supports.

We evaluate the growth kinetics and growth mechanism of ultrahigh mass density carbon nanotube forests. They are synthesized by chemical vapor deposition at 450 °C using a conductive Ti/Cu support and Co-Mo catalyst system. We find that Mo stabilizes Co particles preventing lift off during the initial growth stage, thus promoting the growth of ultrahigh mass density nanotube forests by the base growth mechanism. The morphology of the forest gradually changes with growth time, mostly because of a structural change of the catalyst particles. After 100 min growth, toward the bottom of the forest, the area density decreases from ∼ 3-6 × 10(11) cm(-2) to ∼ 5 × 10(10) cm(-2) and the mass density decreases from 1.6 to 0.38 g cm(-3). We also observe part of catalyst particles detached and embedded within nanotubes. The progressive detachment of catalyst particles results in the depletion of the catalyst metals on the substrate surfaces. This is one of the crucial reasons for growth termination and may apply to other catalyst systems where the same features are observed. Using the packed forest morphology, we demonstrate patterned forest growth with a pitch of ∼ 300 nm and a line width of ∼ 150 nm. This is one of the smallest patterning of the carbon nanotube forests to date.

Hybrids of carbon nanotube forests and gold nanoparticles for improved surface plasmon manipulation.

We report the fabrication and characterization of hybrids of vertically-aligned carbon nanotube forests and gold nanoparticles for improved manipulation of their plasmonic properties. Raman spectroscopy of nanotube forests performed at the separation area of nanotube-nanoparticles shows a scattering enhancement factor of the order of 1 × 10(6). The enhancement is related to the plasmonic coupling of the nanoparticles and is potentially applicable in high-resolution scanning near-field optical microscopy, plasmonics, and photovoltaics.

Co-catalytic absorption layers for controlled laser-induced chemical vapor deposition of carbon nanotubes.

The concept of co-catalytic layer structures for controlled laser-induced chemical vapor deposition of carbon nanotubes is established, in which a thin Ta support layer chemically aids the initial Fe catalyst reduction. This enables a significant reduction in laser power, preventing detrimental positive optical feedback and allowing improved growth control. Systematic study of experimental parameters combined with simple thermostatic modeling establishes general guidelines for the effective design of such catalyst/absorption layer combinations. Local growth of vertically aligned carbon nanotube forests directly on flexible polyimide substrates is demonstrated, opening up new routes for nanodevice design and fabrication.

Efficient field emission from triode-type 1D arrays of carbon nanotubes.

Carbon nanotube (CNT) emitters were formed on line-patterned cathodes in microtrenches through a thermal CVD process. Single-walled carbon nanotubes (SWCNTs) self-organized along the trench lines with a submicron inter-CNT spacing. Excellent field emission (FE) properties were obtained: current densities at the anode (J(a)) of 1 microA cm(-2), 10 mA cm(-2) and 100 mA cm(-2) were recorded at gate voltages (V(g)) of 16, 25 and 36 V, respectively. The required voltage difference to gain a 1:10 000 contrast of the anode current was as low as 9 V, indicating that a very low operating voltage is possible for these devices. Not only a large number of emission sites but also the optimal combination of trench structure and emitter morphology are crucial to achieve the full FE potential of thin CNTs with a practical lifetime. The FE properties of 1D arrays of CNT emitters and their optimal design are discussed. Self-organization of thin CNTs is an attractive prospect to tailor preferable emitter designs in FE devices.

Growth window and possible mechanism of millimeter-thick single-walled carbon nanotube forests.

Our group recently reproduced the water-assisted growth method, so-called "SuperGrowth", of millimeter-thick single-walled carbon nanotube (SWNT) forests by using C2H4/H2/H2O/Ar reactant gas and Fe/Al2O3, catalyst. In this current work, a parametric study was carried out on both reaction and catalyst conditions. Results revealed that a thin Fe catalyst layer (about 0.5 nm) yielded rapid growth of SWNTs only when supported on Al2O3, and that Al2O3 support enhanced the activity of Fe, Co, and Ni catalysts. The growth window for the rapid SWNT growth was narrow, however. Optimum amount of added H2O increased the SWNT growth rate but further addition of H2O degraded both the SWNT growth rate and quality. Addition of H2 was also essential for rapid SWNT growth, but again, further addition decreased both the SWNT growth rate and quality. Because Al2O3 catalyzes hydrocarbon reforming, Al2O3 support possibly enhances the SWNT growth rate by supplying the carbon source to the catalyst nanoparticles. The origin of the narrow window for rapid SWNT growth is also discussed.