Enhancing Long-Term Durability of Electrochemical Reactors Producing Formate from CO2 and Water Designed for Integration with Solar Cells.

Artificial photosynthetic cells producing organic matter from CO2 and water have been extensively studied for carbon neutrality, and the research trend is currently transitioning from proof of concept using small-sized cells to large-scale demonstrations for practical applications. We previously demonstrated a 1 m2 size cell in which an electrochemical (EC) reactor featuring a ruthenium (Ru)-complex polymer (RuCP) cathode catalyst was integrated with photovoltaic cells. In this study, we tackled the remaining issue to improve the long-term durability of cathode electrodes used in the EC reactors, demonstrating high Faradaic efficiencies exceeding 80% and around 60% electricity-to-chemical energy-conversion efficiencies of a 75 cm2 sized EC reactor after continuous operation for 3000 h under practical conditions. Introduction of a pyrrole derivative containing an amino group in the RuCP coupled with UV-ozone treatment to create carboxyl groups on the carbon supports effectively reduced the detachment of the RuCP catalyst by forming a strong amide linkage. A newly developed chemically resistant graphite adhesive prevented the carbon supports from peeling off of the conductive substrates. In addition, highly durable anodes composed of IrOx-TaOy/Pt-metal oxide/Ti were adopted. Even though the EC reactor was installed at an inclined angle of 30°, which is approximately the optimal angle for receiving more solar energy, the crossover reactions were sufficiently suppressed because the porous separator film impeded the transfer of oxygen gas bubbles from the anode to the cathode. The intermittent operation improved the energy-conversion efficiency because the accumulated bubbles were removed at night.

Scalable Thermochromic Composite Based on a Ternary Polymer Blend for Temperature-Adaptive Solar Heat Management.

A scalable and durable thermochromic composite is developed for temperature-adaptive solar heat management using a carbon absorber and a thermoresponsive polymer blend consisting of an isolated polycaprolactone phase (PCL) and a continuous phase of miscible poly(methyl methacrylate) and polyvinylidene fluoride. The ternary blend exhibits reversible haze transition originating from the melting and crystallization of PCL. The refractive index matching between the molten PCL and surrounding miscible blend contributes to high-contrast haze switching in the range of 14-91% across the melting temperature of PCL (ca. 55 °C). The solar-absorption-switching properties of the composite are due to the spontaneous light-scattering switching in the polymer blend and the presence of a small amount of carbon black. Spectral measurements indicate that the solar reflectance of the composite sheet varies by 20% between 20 and 60 °C upon lamination with a Ag mirror. Solar heat management using the thermochromic composite is successfully demonstrated under natural sunlight, thereby realizing a temperature-adaptive thermal management system.

Hot-carrier photocatalysts for artificial photosynthesis.

We applied hot-carrier extraction to particulate photocatalysts for artificial photosynthetic reactions including water splitting for H2 production and CO2 reduction to CO and HCOOH, and elucidated promising features of hot-carrier photocatalysts (HC-PCs). We designed a specific structure of the HC-PC; a semiconductor core in which thermalization of photo-generated carriers is significantly suppressed is surrounded by a shell whose bandgap is wider than that of the core. Among the photo-generated hot carriers in the core, only carriers whose energies are larger than the shell bandgap are extracted passing through the shell to the active sites on the shell surface. Thus, the shell functions as an energy-selective contact. We calculated the upper bounds of the rates of the carrier supply from the core to the active sites using a newly constructed detailed-balance model including partial thermalization and nonradiative recombination of the carriers. It has been revealed that the HC-PCs can yield higher carrier-supply rates and thus potentially higher solar-to-chemical energy conversion efficiencies for H2 and CO production than those of conventional photocatalysts with the assistance of intraband transition and Auger recombination/impact ionization. It should be noted, however, that one of the necessary conditions for efficient hot-carrier extraction is sufficiently large carrier density in the core, which, in turn, requires concentrated solar illumination by several hundreds. This would raise rate-limiting problems of activities of the chemical reactions induced by the photo-generated carriers and material-transfer properties.

Particulate photocatalytic reactors with spectrum-splitting function for artificial photosynthesis.

We have applied spectrum splitting, which is the most reliable way for highly efficient solar energy utilization, to particulate photocatalytic reactors. We have elucidated that the spectrum splitting is feasible using plural cells/compartments, in which photocatalyst particles of different bandgaps are suspended respectively, arranged optically in series. When the particles are sufficiently small (≤20 nm in diameter), high-energy photons are absorbed in the wide-gap cell/compartment on the solar illumination side while low-energy photons reach the backside narrow-gap cell/compartment with being scarcely diffuse-reflected. We have proposed two concrete configurations of the reactors: wide-gap cell/narrow-gap Z-scheme cell (WG/Z), and wide-gap cell/two-compartment cell of middle-gap and narrow-gap (WG/MG-NG), based on the previous configuration of a two-compartment cell of wide-gap and narrow-gap (WG-NG). We have constructed a new model of the carrier supply process from the semiconductor photocatalysts to the active sites, and calculated the practical upper limits of the carrier supply rates and solar-to-chemical conversion efficiencies. The spectrum-splitting reactors can yield higher efficiencies of artificial photosynthetic H2 and CO production by up to 1.5-1.6 times than the conventional Z-scheme reactors. The newly proposed WG/Z reactor widens the room of the material developments and improves the robustness against solar spectrum variation, and hence would be a promising practical solution, although the efficiency is slightly lower than that for the ideal WG-NG reactor. The WG/MG-NG reactor yields the highest efficiency among the three configurations, with high spectral robustness.

Absorptive angular-selective filters consisting of dielectric multilayers combined with thin absorbing layers.

We propose a concept of angular-selective filters (ASFs) that transmit the incident light in the transmitting angular ranges and mostly absorb in the blocking ranges. The absorptive ASF consists of a transparent dielectric multilayer combined with a thin absorbing layer, utilizing the change in the fringe pattern of the light intensity in the filter dependent on the incident angle. We clarified the design guide to select the suitable multilayer structure and absorbing material. Concrete structures of three types were designed using Cr for the absorbing material on the basis of ${\text{SiO}_2}/{\text{TiO}_2}$SiO2/TiO2 bandpass, shortpass, and longpass filters, exhibiting the absorptive ASF functions with the transmitting/blocking ranges of 0-10°/10-30°, 0-30°/30-60°, and 10-60°/0-10°, respectively. The present multilayered structures provide a great advantage for practical use: no need for two- or three-dimensional patterning using lithographic techniques.

Light trapping for photovoltaic cells using polarization-insensitive angle-selective filters under monochromatic illumination.

We have proposed a light-trapping concept for photovoltaic (PV) cells under monochromatic illumination with restricted incident angles. We employed a configuration consisting of a shortpass filter (SPF) on the front surface and a diffuse reflector on the rear surface of the cell. The SPF was designed so that it functioned as a polarization-insensitive angle-selective filter. We fabricated 30-80-µm-thick crystalline silicon samples for incident angles changing within 30°, and analyzed the measured results using a ray-trace simulation with the Monte Carlo method. The ratio of the absorbed intensity to the 1064 nm illumination intensity was 0.69-0.85, which was higher than those equipped with antireflection coatings instead of the SPFs by 0.19-0.13. Thus, we have proven the light-trapping concept of the SPF/diffuse reflector configuration for monochromatic illumination. The PV cells could be applied to wireless power supply, in particular from solar-pumped lasers.

Energy transfer efficiency from Cr(3+) to Nd(3+) in solar-pumped laser using transparent Nd/Cr:Y(3)Al(5)O(12) ceramics.

We report energy transfer efficiency from Cr3+ to Nd3+ in Nd (1.0 at.%)/Cr (0.4 at.%) co-doped Y3Al5O12 (YAG) transparent ceramics in the laser oscillation states. The laser oscillation has performed using two pumping lasers operating at 808 nm and 561 nm; the former pumps Nd3+ directly to create the 1064 nm laser oscillation, whereas the latter assists the performance via Cr3+ absorption and sequential energy transfer to Nd3+. From the laser output power properties and laser mode analysis, the energy transfer efficiency was determined to be around 65%, which is close to that obtained from the spontaneous Nd3+ emission.

Role of propagating modes in a double-groove grating with a +1st-order diffraction angle larger than the substrate-air critical angle.

Here we show, analytically and numerically, that in a TiO(2) double-groove grating with two different groove widths per period attached on the SiO(2) substrate, the normally incident light couples to the +1st-order transmission with 96.9% efficiency and with a 50° diffraction angle that is larger than the SiO(2)-air interface critical angle. Modal analysis reveals that three propagating modes for the +1st diffraction order reach the grating back end in phase, while the corresponding propagating modes for the -1st and zeroth orders are added destructively at the grating end. Four optical devices based on this grating characteristic are numerically demonstrated.

Purification, characterization, and molecular cloning of organic-solvent-tolerant cholesterol esterase from cyclohexane-tolerant Burkholderia cepacia strain ST-200.

Extracellular cholesterol esterase of Burkholderia cepacia strain ST-200 was purified from the culture supernatant. Its molecular mass was 37 kDa. The enzyme was stable at pH 5.5-12 and active at pH 5.5-6, showing optimal activity at pH 7.0 at 45 degrees C. Relative to the commercially available cholesterol esterases, the purified enzyme was highly stable in the presence of various water-miscible organic solvents. The enzyme preferentially hydrolyzed long-chain fatty acid esters of cholesterol, except for that of cholesteryl palmitate. The enzyme exhibited lipolytic activity toward various p-nitrophenyl esters. The hydrolysis rate of p-nitrophenyl caprylate was enhanced 3.5- to 7.2-fold in the presence of 5-20% (vol/vol) water-miscible organic solvents relative to that in the absence of organic solvents. The structural gene encoding the cholesterol esterase was cloned and sequenced. The primary translation product was predicted to be 365 amino acid residues. The mature product is composed of 325 amino acid residues. The amino acid sequence of the product showed the highest similarity to the lipase LipA (87%) from B. cepacia DSM3959.