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We present the design of a three-dimensional Pt/mesoporous TiO 2 Schottky nanodiode that can capture hot electrons more effectively, compared with a typical two-dimensional Schottky diode. Both chemically induced and photon-induced hot electrons were measured on the three-dimensional Pt/mesoporous TiO 2 Schottky nanodiode. An increase in the number of interfacial sites between the platinum and support oxide affects the collection of hot electrons generated by both the catalytic reaction and light injection. We show that hot electrons flowing 2.5 times higher are detected as the current in the mesoporous system, compared with typical two-dimensional nanodiode systems that have a planar Schottky junction. Identical trends for the chemicurrent and photocurrent in the mesoporous system demonstrate that the enhanced hot electrons are attributed to the larger interface area between the metal and the mesoporous TiO 2 support fabricated by the anodization process. This three-dimensional Schottky nanodiode can provide insights into hot electron generation on a practical catalytic device.

A novel three-dimensional catalytic nanodiode composed of a Pt thin film on TiO 2 nanotubes was designed for the efficient detection of the flux of hot electrons, or chemicurrent, under hydrogen oxidation. We verify a significant increase in the chemicurrent from the fast transport of electrons across the ordered supporting oxide layer. This study demonstrates the direct detection of hot electrons on well-ordered TiO 2 nanotubes during the catalytic reaction.

Titanium dioxide (TiO 2 ) nanotubes with vertically aligned array structures show substantial advantages in solar cells as an electron transport material that offers a large surface area where charges travel linearly along the nanotubes. Integrating this one-dimensional semiconductor material with plasmonic metals to create a three-dimensional plasmonic nanodiode can influence solar energy conversion by utilizing the generated hot electrons. Here, we devised plasmonic Au/TiO 2 and Ag/TiO 2 nanodiode architectures composed of TiO 2 nanotube arrays for enhanced photon absorption, and for the subsequent generation and capture of hot carriers. The photocurrents and incident photon to current conversion efficiencies (IPCE) were obtained as a function of photon energy for hot electron detection. We observed enhanced photocurrents and IPCE using the Ag/TiO 2 nanodiode. The strong plasmonic peaks of the Au and Ag from the IPCE clearly indicate an enhancement of the hot electron flux resulting from the presence of surface plasmons. The calculated electric fields and the corresponding absorbances of the nanodiode using finite-difference time-domain simulation methods are also in good agreement with the experimental results. These results show a unique strategy of combining a hot electron photovoltaic device with a three-dimensional architecture, which has the clear advantages of maximizing light absorption and a metal-semiconductor interface area.

The smart design of plasmonic nanostructures offers a unique capability for the efficient conversion of solar energy into chemical energy by strong interactions with resonant photons through the excitation of surface plasmon resonance, which increases the prospect of using sunlight in environmental and energy applications. Here, we show that the catalytic activity of CO oxidation can be tuned by using new model systems: two-dimensional (2D) arrays of metal-insulator-metal (MIM) plasmonic nanoislands designed to efficiently shuttle hot plasmonic electrons. Hot plasmonic electrons are generated upon the absorption of photons on noble metals, followed by the injection of these hot electrons into the Pt nanoparticles through tunneling or Schottky emission mechanisms, depending on the energy of the hot electrons. We found that these MIM nanostructures exhibit higher catalytic activity (i.e. by 40-110%) under light irradiation, revealing a significant impact on the catalytic activity for CO oxidation. The thickness dependence of the enhancement of catalytic activity on the oxide layers is consistent with the tunneling mechanism of hot electron flows. The results imply that surface plasmon-induced hot electron flows by light absorption significantly influence the catalytic activity of CO oxidation.

Due to the tunability of the physical, electrical, and optical characteristics of graphene, precisely controlling graphene oxidation is of great importance for potential applications of graphene-based electronics. Here, we demonstrate a facile and precise way for graphene oxidation controlled by photoexcited charge transfer depending on the substrate and bias voltage. It is observed that graphene on TiO2 is easily oxidized under UV-ozone treatment, while graphene on SiO2 remains unchanged. The mechanism for the selective oxidation of graphene on TiO2 is associated with charge transfer from the TiO2 to the graphene. Raman spectra were used to investigate the graphene following applied bias voltages on the graphene/TiO2 diode under UV-ozone exposure. We found that under a reverse bias of 0.6 V on the graphene/TiO2 diode, graphene oxidation was accelerated under UV-ozone exposure, thus confirming the role of charge transfer between the graphene and the TiO2 that results in the selective oxidation of the graphene. The selective oxidation of graphene can be utilized for the precise, nanoscale patterning of the graphene oxide and locally patterned chemical doping, finally leading to the feasibility and expansion of a variety of graphene-based applications.

We investigated the subdomain structures of single-layer graphene oxide (GO) by characterizing local friction and conductance using conductive atomic force microscopy. Friction and conductance mapping showed that a single-layer GO flake has subdomains several tens to a few hundreds of nanometers in lateral size. The GO subdomains exhibited low friction (high conductance) in the sp(2)-rich phase and high friction (low conductance) in the sp(3)-rich phase. Current-voltage spectroscopy revealed that the local current flow in single-layer GO depends on the quantity of hydroxyl and carboxyl groups, and epoxy bridges within the 2-dimensional carbon layer. The presence of subdomains with different sp(2)/sp(3) carbon ratios on a GO flake was also confirmed by chemical mapping using scanning transmission X-ray microscopy. These results suggest that spatial mapping of the friction and conductance can be used to rapidly identify the composition of heterogeneous single-layer GO at nanometer scale, which is essential for understanding charge transport in nanoelectronic devices.

Nanostructured carbon materials doped with a variety of heteroatoms have shown promising electrocatalytic activity in the oxygen reduction reaction (ORR). However, understanding of the working principles that underpin the superior ORR activity observed with doped nanocarbons is still limited to predictions based on theoretical calculations. Herein, we demonstrate, for the first time, that the enhanced ORR activity in doped nanocarbons can be correlated with the variation in their nanoscale work function. A series of doped ordered mesoporous carbons (OMCs) were prepared using N, S, and O as dopants; the triple-doped, N,S,O-OMC displayed superior ORR activity and four-electron selectivity compared to the dual-doped (N,O-OMC and S,O-OMC) and the monodoped (O-OMC) OMCs. Significantly, the work functions of these heteroatom-doped OMCs, measured by Kelvin probe force microscopy, display a strong correlation with the activity and reaction kinetics for the ORR. This unprecedented experimental insight can be used to provide an explanation for the enhanced ORR activity of heteroatom-doped carbon materials.