Understanding the Activation Mechanism of RhCrOx Cocatalysts for Hydrogen Evolution with Nanoparticulate Electrodes.

Mixed oxides of Rh-Cr (RhCrOx), containing Rh3+ and Cr3+ cations, are commonly used as cocatalysts for the hydrogen evolution reaction (HER) on particulate photocatalysts. The precise physicochemical mechanisms of the HER at the catalytic sites of these oxides are not well understood. In this study, model cocatalyst electrodes, composed of nanoparticulate RhCrOx, were fabricated to investigate the physicochemical mechanisms of the HER. Electroanalytical and X-ray photoelectron spectroscopic measurements revealed that nanoparticulate RhCrOx produces reduced Rh (Rh0) species by maintaining an electrode potential more negative than 0.03 V versus the reversible hydrogen electrode (VRHE). This results in significant enhancement of the HER activity. The catalytic activity for the HER stems from the reduced Rh species, and the inclusion of Cr3+ (CrOx) aided in the electron transfer process at the solid/liquid interface, resulting in a higher current density during the HER. To achieve a solar-to-hydrogen efficiency of over 3%, the conduction band minimum of the particulate photocatalyst should be positioned more negatively than -0.10 VRHE. Moreover, the formation of electron trap states at potentials more positive than 0.03 VRHE should be avoided. This study highlights the importance of understanding the catalytic sites on metal oxide cocatalysts. Moreover, it offers a design strategy for enhancing the efficiency of photocatalytic water splitting.

Efficient and stable visible-light-driven Z-scheme overall water splitting using an oxysulfide H2 evolution photocatalyst.

So-called Z-scheme systems permit overall water splitting using narrow-bandgap photocatalysts. To boost the performance of such systems, it is necessary to enhance the intrinsic activities of the hydrogen evolution photocatalyst and oxygen evolution photocatalyst, promote electron transfer from the oxygen evolution photocatalyst to the hydrogen evolution photocatalyst, and suppress back reactions. The present work develop a high-performance oxysulfide photocatalyst, Sm2Ti2O5S2, as an hydrogen evolution photocatalyst for use in a Z-scheme overall water splitting system in combination with BiVO4 as the oxygen evolution photocatalyst and reduced graphene oxide as the solid-state electron mediator. After surface modifications of the photocatalysts to promote charge separation and redox reactions, this system is able to split water into hydrogen and oxygen for more than 100 hours with a solar-to-hydrogen energy conversion efficiency of 0.22%. In contrast to many existing photocatalytic systems, the water splitting activity of the present system is only minimally reduced by increasing the background pressure to 90 kPa. These results suggest characteristics suitable for applications under practical operating conditions.

Physicochemical insights into semiconductor properties of a semitransparent tantalum nitride photoanode for solar water splitting.

The self-conductivity of tantalum nitride (Ta3N5) thin film-based semitransparent photoanodes was found to promote the current originating from the photoelectrochemical oxygen evolution reaction (PEC OER) without a conducting substrate. With surface modification by the NiFeOx-electrocatalyst, an optimized Ta3N5 thin film fabricated directly on a transparent insulating quartz substrate generated a photocurrent density of ∼5.9 ± 0.1 mA cm-2 at 1.23 V vs. the reversible hydrogen electrode under simulated AM 1.5G solar illumination. The correlation between the PEC OER performance of NiFeOx-modified Ta3N5 photoanodes and the electrical properties of Ta3N5 thin films was investigated based on the Hall effect measurements. By changing the nitridation conditions, these properties can be tuned so that the higher the Hall mobility (0.2 to 1.7 cm2 V-1 s-1) and the lower the carrier concentration (1020 to 1019 cm-3). The surface chemical states of Ta3N5 thin films were investigated using X-ray photoelectron spectroscopy as a means of evaluating surface oxygen impurities and nitrogen vacancies, which may correlate with the PEC OER performance and the electrical properties of the material.

Mechanistic Insights into Enhanced Hydrogen Evolution of CrOx /Rh Nanoparticles for Photocatalytic Water Splitting.

The hydrogen evolution reaction (HER) of Rh nanoparticles (RhNP) coated with an ultrathin layer of Cr-oxides (CrOx ) was investigated as a model electrode for the Cr2 O3 /Rh-metal core-shell-type cocatalyst system for photocatalytic water splitting. The CrOx layer was electrodeposited over RhNP on a transparent conductive fluorine-doped tin oxide (FTO) substrate. The CrOx layer on RhNP facilitates the electron transfer process at the CrOx /RhNP interface, leading to the increased current density for the HER. Impedance spectroscopic analysis revealed that the CrOx layer transferred protons via the hopping mechanism to the RhNP surface for HER. In addition, CrOx restricted electron transfer from the FTO to the electrolyte and/or RhNP and suppressed the backward reaction by limiting oxygen migration. This study clarifies the crucial role of the ultrathin CrOx layer on nanoparticulate cocatalysts and provides a cocatalyst design strategy for realizing efficient photocatalytic water splitting.

Advanced Top-Down Fabrication for a Fused Silica Nanofluidic Device.

Nanofluidics have recently attracted significant attention with regard to the development of new functionalities and applications, and producing new functional devices utilizing nanofluidics will require the fabrication of nanochannels. Fused silica nanofluidic devices fabricated by top-down methods are a promising approach to realizing this goal. Our group previously demonstrated the analysis of a living single cell using such a device, incorporating nanochannels having different sizes (102-103 nm) and with branched and confluent structures and surface patterning. However, fabrication of geometrically-controlled nanochannels on the 101 nm size scale by top-down methods on a fused silica substrate, and the fabrication of micro-nano interfaces on a single substrate, remain challenging. In the present study, the smallest-ever square nanochannels (with a size of 50 nm) were fabricated on fused silica substrates by optimizing the electron beam exposure time, and the absence of channel breaks was confirmed by streaming current measurements. In addition, micro-nano interfaces between 103 nm nanochannels and 101 µm microchannels were fabricated on a single substrate by controlling the hydrophobicity of the nanochannel surfaces. A micro-nano interface for a single cell analysis device, in which a nanochannel was connected to a 101 µm single cell chamber, was also fabricated. These new fabrication procedures are expected to advance the basic technologies employed in the field of nanofluidics.

Femtoliter nanofluidic valve utilizing glass deformation.

In the field of micro/nanofluidics, the channel open/close valves are among the most important technologies for switching and partitioning actions and integration of various operations into fluidic circuits. While several types of valves have been developed in microfluidics, few are capable in nanofluidics. In this study, we proposed a femtoliter (fL) volume nanochannel open/close valve fabricated in glass substrates. The valve consists of a shallow, circular and stepped-bottom valve chamber connected to nanochannels and an actuator. Even with tiny deformation occurring at the nanolevel in glass, an open/closed state of a nanochannel (10-1000 nm) can be achieved. We designed a fL-valve based on an analytical material deformation model, and developed a valve fabrication process. We then verified the open/closed state of the valve using a 308 fL-valve chamber with a four-stepped nanostructure fitting an arc-shape of deflected glass, confirmed its stability and durability over 50 open/close operations, and succeeded in stopping/flowing an aqueous solution at 209 fL s-1 under a 100 kPa pressure in a 900 nm nanochannel with a fast response of ∼0.65 s. A leak flow from the closed valve was sufficiently small even at a 490 kPa pressure-driven flow. Since the developed fL-valve can be applied to various nanofluidic devices made of glass and other rigid materials such as plastic, it is expected that this work will contribute significantly to the development of novel integrated micro/nanofluidics chemical systems for use in various applications, such as single cell/single molecule analysis.

From Extended Nanofluidics to an Autonomous Solar-Light-Driven Micro Fuel-Cell Device.

Autonomous micro/nano mechanical, chemical, and biomedical sensors require persistent power sources scaled to their size. Realization of autonomous micro-power sources is a challenging task, as it requires combination of wireless energy supply, conversion, storage, and delivery to the sensor. Herein, we realized a solar-light-driven power source that consists of a micro fuel cell (µFC) and a photocatalytic micro fuel generator (µFG) integrated on a single microfluidic chip. The µFG produces hydrogen by photocatalytic water splitting under solar light. The hydrogen fuel is then consumed by the µFC to generate electricity. Importantly, the by-product water returns back to the photocatalytic µFG via recirculation loop without losses. Both devices rely on novel phenomena in extended-nano-fluidic channels that ensure ultra-fast proton transport. As a proof of concept, we demonstrate that µFG/µFC source achieves remarkable energy density of ca. 17.2 mWh cm-2 at room temperature.

On-Chip Step-Mixing in a T-Nanomixer for Liquid Chromatography in Extended-Nanochannels.

Miniaturization of liquid chromatography separation columns is a key trend in chemical and biochemical areas, particularly in genomics, proteomics, and single-cell analysis. The work at this level relies upon a novel analytical platform that can deal with sample volumes that are much smaller than a cell. An extended-nanospace is within a scale of 101-103 nm and defines the space between a single molecule and normal liquid. Our group has realized high-performance liquid chromatography (HPLC) separation in extended-nanospace with sample injections of hundreds of attoliters and a separation efficiency of hundreds of thousands of plates/m that can overcome the limitations of a conventional packed column by a magnitude of several orders. However, gradient flow is needed to improve the separation performance, and in this work we present reversed-phase chromatography with step-mixing in extended-nanospace and describe its application. Six fluorescently labeled amino acids were separated in 16 s, followed by separation of 17 labeled amino acids in only 50 s with a plate height for most of the peaks of less than 1 µm.

Photocatalytic generation of hydrogen by core-shell WO3/BiVO4 nanorods with ultimate water splitting efficiency.

Efficient photocatalytic water splitting requires effective generation, separation and transfer of photo-induced charge carriers that can hardly be achieved simultaneously in a single material. Here we show that the effectiveness of each process can be separately maximized in a nanostructured heterojunction with extremely thin absorber layer. We demonstrate this concept on WO3/BiVO4+CoPi core-shell nanostructured photoanode that achieves near theoretical water splitting efficiency. BiVO4 is characterized by a high recombination rate of photogenerated carriers that have much shorter diffusion length than the thickness required for sufficient light absorption. This issue can be resolved by the combination of BiVO4 with more conductive WO3 nanorods in a form of core-shell heterojunction, where the BiVO4 absorber layer is thinner than the carrier diffusion length while it's optical thickness is reestablished by light trapping in high aspect ratio nanostructures. Our photoanode demonstrates ultimate water splitting photocurrent of 6.72 mA cm(-2) under 1 sun illumination at 1.23 V(RHE) that corresponds to ~90% of the theoretically possible value for BiVO4. We also demonstrate a self-biased operation of the photoanode in tandem with a double-junction GaAs/InGaAsP photovoltaic cell with stable water splitting photocurrent of 6.56 mA cm(-2) that corresponds to the solar to hydrogen generation efficiency of 8.1%.

Ubiquitous element approach to plasmonic enhanced photocatalytic water splitting: the case of Ti@TiO2 core-shell nanostructure.

We demonstrate a new approach to plasmonic enhanced photocatalytic water splitting by developing a novel core-shell Ti@TiO2 brush nanostructure where an elongated Ti nanorod forms a plasmonic core that concentrates light inside of a nanotubular anodic TiO2 shell. Following the ubiquitous element approach aimed at providing an enhanced device functionality without the usage of noble or rare earth elements, we utilized only inexpensive Ti to create a complex Ti@TiO2 nanostructure with an enhanced UV and Vis photocatalytic activity that emerges from the interplay between the surface plasmon resonance in the Ti core, Vis light absorption in the Ti-rich oxide layer at the Ti/TiO2 interface and UV light absorption in the nanotubular TiO2 shell.

Nanostructured WO3 /BiVO4 photoanodes for efficient photoelectrochemical water splitting.

Nanostructured photoanodes based on well-separated and vertically oriented WO3 nanorods capped with extremely thin BiVO4 absorber layers are fabricated by the combination of Glancing Angle Deposition and normal physical sputtering techniques. The optimized WO3 -NRs/BiVO4 photoanode modified with Co-Pi oxygen evolution co-catalyst shows remarkably stable photocurrents of 3.2 and 5.1 mA/cm(2) at 1.23 V versus a reversible hydrogen electrode in a stable Na2 SO4 electrolyte under simulated solar light at the standard 1 Sun and concentrated 2 Suns illumination, respectively. The photocurrent enhancement is attributed to the faster charge separation in the electronically thin BiVO4 layer and significantly reduced charge recombination. The enhanced light trapping in the nanostructured WO3 -NRs/BiVO4 photoanode effectively increases the optical thickness of the BiVO4 layer and results in efficient absorption of the incident light.

Extended-nanofluidics: fundamental technologies, unique liquid properties, and application in chemical and bio analysis methods and devices.

Engineering using liquids confined in channels 10-1000 nm in dimension, or "extended-nanofluidics," is the next target of microfluidic science. Liquid properties at this scale were unrevealed until recently because of the lack of fundamental technologies for investigating these ultrasmall spaces. In this article, the fundamental technologies are reviewed, and the emerging science and technology in the extended-nanospace are discussed.

Nanocomposite Ti/hydrocarbon plasma polymer films from reactive magnetron sputtering as growth support for osteoblast-like and endothelial cells.

Nanocomposite Ti/hydrocarbon plasma polymer (Ti/ppCH) films were deposited by DC magnetron sputtering of titanium target in n-hexane, argon, or a mixture of these two gases. The resultant films were heterogeneous, with inorganic regions of nanometer scale distributed within a plasma polymer matrix. The titanium content was controlled by adjusting the argon/n-hexane ratio in the working gas. In the pure n-hexane atmosphere, the Ti concentration was found to be below 1 at %, whereas in pure argon it reached 20 at %, as measured by Rutherford backscattering spectroscopy and elastic recoil detection analysis (RBS/ERDA). A high level of titanium oxidation is detected with TiO(2), substoichiometric titania, and titanium carbide, composing an inorganic phase of the composite films. In addition, high hydrogen content is detected in films rich with titanium. Ti-deficient and Ti-rich films proved equally good substrates for adhesion and growth of cultured human osteoblast-like MG 63 cells. In these cells, the population densities on days 1, 3, and 7 after seeding, spreading area on day 1, formation of talin-containing focal adhesion plaques as well as concentrations of talin and osteocalcin (per mg of protein) were comparable to the values obtained in cells on the reference cell culture materials, represented by microscopic glass coverslips or a polystyrene dish. An interesting finding was made when the Ti/ppCH films were seeded with calf pulmonary artery endothelial cells of the line CPAE. The cell population densities, the spreading area and also the concentration of von Willebrand factor, a marker of endothelial cell maturation, were significantly higher on Ti-rich than on Ti-deficient films. On Ti-rich films, these parameters were also higher or similar in comparison with the reference cell culture materials. Thus, both types of films could be used for coating bone implants, of which the Ti-rich film remains effective in enhancing the endothelialization of blood contacting artificial materials.