Carbon Dioxide Pressure and Catalyst Quantity Dependencies in Artificial Photosynthesis of Hydrocarbon Chains on Nanostructured Co/CoO Surfaces.

In this study, we investigated the influence of pressure and the quantity of Co/CoO catalyst on an artificial photosynthesis process that converts CO2 and H2O into hydrocarbons (CnH2n+2, where n ≤ 18). The adsorption of CO2 and H2O on Co/CoO surfaces proved to be pivotal in this photo-catalytic reaction. Photoexcited carbon dioxide and water molecules ((CO2)* and (H2O)*) generated by illuminating the catalyst surface led to the formation of alkene hydrocarbon molecules with carbon numbers following an approximate Poisson distribution. The optimal pressure was found to be 0.40 MPa. Pressure less than 0.40 MPa resulted in low CO2 adsorption, impeding excitation for photosynthesis. At greater pressure, oil/wax accumulation on Co/CoO surfaces hindered CO2 adsorption, limiting further photosynthesis reactions. The average number of carbon atoms in the hydrocarbons and hydrocarbon yield were correlated. The amount of Co/CoO was also found to affect the hydrocarbon yield. Our study contributes to the understanding of Co/CoO-catalyzed photosynthesis and suggests that an open-flow system could potentially enhance the productivity of long-chain hydrocarbons.

Habitual feeding patterns impact polystyrene microplastic abundance and potential toxicity in edible benthic mollusks.

That increasing microplastics (MPs, <5 mm) eventually end up in the sediment which may become a growing menace to diverse benthic lives is worthy of attention. In this experiment, three edible mollusks including one deposit-feeding gastropod (Bullacta exarate) and two filter-feeding bivalves (Cyclina sinensis and Mactra veneriformis) were exposed to polystyrene microplastic (PS-MP) for 7 days and depurated for 3 days. PS-MP numbers in the digestive system and non-digestive system, digestive enzymes, oxidative stress indexes, and a neurotoxicity index of three mollusks were determined at day 0, 3, 7, 8 and 10. After seven-day exposure, the PS-MP were found in all three mollusks' digestive and non-digestive systems. And PS-MP in M. veneriformis (9.57 ± 2.19 items/individual) was significantly higher than those in C. sinensis (3.00 ± 2.16 items/individual) and B. exarate (0.83 ± 1.07 items/individual) at day 7. Three-day depuration could remove most of the PS-MP in the mollusks, and higher PS-MP clearance rates were found in filter-feeding C. sinensis (77.78 %) and M. veneriformis (82.59 %) compared to surface deposit-feeding B. exarate (50.00 %). The digestive enzymes of B. exarate significantly reacted to PS-MP exposure, while oxidative responses were found in C. sinensis. After three-day depuration, the changes of digestive enzymes and the oxidative states were fixed, but neurotoxicity induced by PS-MP was not recoverable. Besides, it is noteworthy that changes of digestive enzymes and acetylcholinesterase are related to feeding patterns.

Electroplating Cobalt Films on Silicon Nanostructures for Sensing Molecules.

In this study, we electroplated Co and Cu on nano-spiked silicon substrates that were treated with femtosecond laser irradiations. With energy-dispersive X-ray (EDX) analysis by a scanning electron microscope (SEM), it was found that both Co and Cu are primarily coated on the spike surfaces without changing the morphology of the nanospikes. We also found that nanoscale bridges were formed, connecting the Co-coated silicon spikes. The formation of these bridges was studied and optimized through a series of time-controlled electroplating and oxidizing processes. The bridges are related to the oxidation of Co in the air. When it is irradiated with visible light, this special structure has shown a capability of interactions with carbon monoxide and carbon dioxide molecules. The electroplated cobalt may be used for gas sensors.

Study the plasmonic property of gold nanorods highly above damage threshold via single-pulse spectral hole-burning experiments.

Intense femtosecond laser irradiation reshapes gold nanorods, resulting in a persistent hole in the optical absorption spectrum of the nanorods at the wavelength of the laser. Single-pulse hole-burning experiments were performed in a mixture of nanorods with a broad absorption around 800 nm with a 35-fs laser with 800 nm wavelength and 6 mJ/pulse. A significant increase in hole burning width at an average fluence of 106 J/m2 has been found, suggesting a tripled damping coefficient of plasmon. This shows that the surface plasmonic effect still occurs at extremely high femtosecond laser fluences just before the nanorods are damaged and the remaining 10% plasmonic enhancement of light is at the fluence of 106 J/m2, which is several orders of magnitude higher than the damage threshold of the gold nanorods. Plasmon-photon interactions may also cause an increase in the damping coefficient.

Highly In-Plane Anisotropic Two-Dimensional Ternary Ta2NiSe5 for Polarization-Sensitive Photodetectors.

Intriguing anisotropic electrical and optoelectrical properties in two-dimensional (2D) materials are currently gaining increasing interest both for fundamental research and emerging optoelectronic devices. Identifying promising new 2D materials with low-symmetry structures will be rewarding in the development of polarization-integrated nanodevices. In this work, the anisotropic electron transport and optoelectrical properties of multilayer 2D ternary Ta2NiSe5 were systematically researched. The polarization-sensitive Ta2NiSe5 photodetector shows a linearly anisotropy ratio of ≈3.24 with 1064 nm illumination. The multilayer Ta2NiSe5-based field-effective transistors exhibit an excellent field-effective mobility of 161.25 cm2·V-1·s-1 along the a axis (armchair direction) as well as a great current saturation characteristic at room temperature. These results will promote a better understanding of the optoelectrical properties and applications in new categories of the in-plane anisotropic 2D materials.

Temperature Dependence of the Artificial Photosynthesis Reactions Catalyzed by Nanostructured Co/CoO.

Carbon dioxide (CO2) and water (H2O) have been converted into hydrocarbons at temperature ranging from 58 to 242 °C through an artificial photosynthesis reaction catalyzed by nanostructured Co/CoO. The experimental results show that chain hydrocarbons (alkane hydrocarbons) (C n H2n+2, where 3 ≤ n ≤ 16) mainly form at a temperature higher than about 60 °C, the production rate reaches a maximum at 130 °C, and abruptly decreases above 130 °C, and then gradually increases until 220 °C. While the temperature is higher than 220 °C, benzene (C6H6) and its derivatives such as toluene (C7H8), p-xylene (C8H10), and C9H12 form. The modeling of temperature dependence of the reaction rate reveals that the vaporization of the adsorbed water contributes to the sharp peak; the activation energy is estimated as about 1 eV, which is in agreement with the reaction of CO and H2 to synthesize chain hydrocarbons. The experimental results support the mechanism that the chemisorbed CO2 and physisorbed H2O on the CoO surface are disassociated or excited with light, and the disassociated or excited molecules then synthesize hydrocarbons. When most of the water molecules leave from the CoO at temperature higher than 220 °C, the hydrogen source is of very low concentration while the carbon source remain the same because of the chemisorption, and thus benzene and its derivatives with low hydrogen atom number form.

Femtosecond Laser-Induced Thermal Transport in Silicon with Liquid Cooling Bath.

Nanostructured regular patterns on silicon surface are made by using femtosecond laser irradiations. This is a novel method that can modify the surface morphology of any large material in an easy, fast, and low-cost way. We irradiate a solid surface with a 400-nm double frequency beam from an 800-nm femtosecond laser, while the solid surface is submerged in a liquid or exposed in air. From the study of multiple-pulses and single-pulse irradiations on silicon, we find the morphologies of nanospikes and capillary waves to follow the same distribution and periodicity. Thermal transport near the solid surface plays an important role in the formation of patterns; a simulation was done to fully understand the mechanism of the pattern formation in single pulse irradiation. The theoretical models include a femtosecond laser pulse function, a two-temperature model (2-T model), and an estimation of interface thermal coupling. The evolution of lattice temperature over time will be calculated first without liquid cooling and then with liquid cooling, which has not been well considered in previous theoretical papers. The lifetime of the capillary wave is found to be longer than the solidification time of the molten silicon only when water cooling is introduced. This allows the capillary wave to be frozen and leaves interesting concentric rings on the silicon surface. The regular nanospikes generated on the silicon surface result from the overlapping capillary waves.

Detection of Liquid Penetration of a Micropillar Surface Using the Quartz Crystal Microbalance.

A quantitative characterization of the wetting states of droplets on hydrophobic textured surfaces requires direct measurement of the liquid penetration into surface cavities, which is challenging. Here, the use of quartz crystal microbalance (QCM) technology is reported for the characterization of the liquid penetration depth on a micropillar-patterned surface. The actual liquid-air interface of the droplet was established by freezing the droplet and characterizing it using a cryogenically focused ion beam/scanning electron microscope (cryo FIB-SEM) technique. It was found that a direct correlation exists between the liquid penetration depth and the responses of the QCM. A very small frequency shift of the QCM (1.5%) was recorded when the droplet was in the Cassie state, whereas a significant frequency shift was observed when the wetting state changed to the Wenzel state (where full liquid penetration occurs). Furthermore, a transition from the Cassie to the Wenzel state can be captured by the QCM technique. An acoustic-structure-interaction based numerical model was developed to further understand the effect of penetration. The numerical model was validated by experimentally measured responses of micropillar-patterned QCMs. The results also show a nonlinear response of the QCM to the increasing liquid penetration depth. This research provides a solid foundation for utilizing QCM sensors for liquid penetration and surface wettability characterization.

Surface-assisted laser desorption and ionization mass spectrometry using low-cost matrix-free substrates.

Surface-assisted laser desorption/ionization (SALDI) substrates have been fabricated using nanospiked polyurethane (PU) substrates that are replicated by a low-cost soft nanolithography method from silicon nanospike structures formed with femtosecond laser irradiations. The strongest mass spectrometry (MS) signal of Angiotensin II was obtained on 45-nm Au-coated nanospiked PU substrates. The effective ionization appears to be due to surface plasmon excitation. Such low-cost and identical SALDI substrates can be used for MS analysis of various molecules with high reproducibility.

The thresholds of surface nano-/micro-morphology modifications with femtosecond laser pulse irradiations.

We studied the pulse energy threshold of surface nano-/micro-morphology modifications by irradiating Si, GaAs, GaP, InP, Cu and Ti surfaces with 100 fs laser pulses at a wavelength of 800 nm in air and in water. We found that the laser pulse energy thresholds required for the permanent modification in water are up to 30% lower than those in air. Different non-equilibrium dynamics processes of the surface melting layer cause the different thresholds in water and in air.

Surface-enhanced Raman scattering sensor on an optical fiber probe fabricated with a femtosecond laser.

A novel fabrication method for surface-enhanced Raman scattering (SERS) sensors that used a fast femtosecond (fs) laser scanning process to etch uniform patterns and structures on the endface of a fused silica optical fiber, which is then coated with a thin layer of silver through thermal evaporation is presented. A high quality SERS signal was detected on the patterned surface using a Rhodamine 6G (Rh6G) solution. The uniform SERS sensor built on the tip of the optical fiber tip was small, light weight, and could be especially useful in remote sensing applications.

High-density regular arrays of nanometer-scale rods formed on silicon surfaces via femtosecond laser irradiation in water.

We report on the formation of high-density regular arrays of nanometer-scale rods using femtosecond laser irradiation of a silicon surface immersed in water. The resulting surface exhibits both micrometer-scale and nanometer-scale structures. The micrometer-scale structure consists of spikes of 5-10 mum width, which are entirely covered by nanometer-scale rods that are roughly 50 nm wide and normal to the surface of the micrometer-scale spikes. The formation of the nanometer-scale rods involves several processes: refraction of laser light in highly excited silicon, interference of scattered and refracted light, rapid cooling in water, roughness-enhanced optical absorptance, and capillary instabilities.

Nanostructured magnetizable materials that switch cells between life and death.

Development of biochips containing living cells for biodetection, drug screening and tissue engineering applications is limited by a lack of reconfigurable material interfaces and actuators. Here we describe a new class of nanostructured magnetizable materials created with a femtosecond laser surface etching technique that function as multiplexed magnetic field gradient concentrators. When combined with magnetic microbeads coated with cell adhesion ligands, these materials form microarrays of 'virtual' adhesive islands that can support cell attachment, resist cell traction forces and maintain cell viability. A cell death (apoptosis) response can then be actuated on command by removing the applied magnetic field, thereby causing cell retraction, rounding and detachment. This simple technology may be used to create reconfigurable interfaces that allow users to selectively discard contaminated or exhausted cellular sensor elements, and to replace them with new living cellular components for continued operation in future biomedical microdevices and biodetectors.

Visible and near-infrared responsivity of femtosecond-laser microstructured silicon photodiodes.

We investigated the current-voltage characteristics and responsivity of photodiodes fabricated with silicon that was microstructured by use of femtosecond-laser pulses in a sulfur-containing atmosphere. The photodiodes that we fabricated have a broad spectral response ranging from the visible to the near infrared (400-1600 nm). The responsivity depends on substrate doping, microstructuring fluence, and annealing temperature. We obtained room-temperature responsivities as high as 100 A/W at 1064 nm, 2 orders of magnitude higher than for standard silicon photodiodes. For wavelengths below the bandgap we obtained responsivities as high as 50 mA/W at 1330 nm and 35 mA/W at 1550 nm.

Subwavelength-diameter silica wires for low-loss optical wave guiding.

Silica waveguides with diameters larger than the wavelength of transmitted light are widely used in optical communications, sensors and other applications. Minimizing the width of the waveguides is desirable for photonic device applications, but the fabrication of low-loss optical waveguides with subwavelength diameters remains challenging because of strict requirements on surface roughness and diameter uniformity. Here we report the fabrication of subwavelength-diameter silica 'wires' for use as low-loss optical waveguides within the visible to near-infrared spectral range. We use a two-step drawing process to fabricate long free-standing silica wires with diameters down to 50 nm that show surface smoothness at the atomic level together with uniformity of diameter. Light can be launched into these wires by optical evanescent coupling. The wires allow single-mode operation, and have an optical loss of less than 0.1 dB mm(-1). We believe that these wires provide promising building blocks for future microphotonic devices with subwavelength-width structures.