Development of a high-speed bioaerosol elimination system for treatment of indoor air.

We developed a high-speed filterless airflow multistage photocatalytic elbow aerosol removal system for the treatment of bioaerosols such as severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Human-generated bioaerosols that diffuse into indoor spaces are 1-10 µm in size, and their selective and rapid treatment can reduce the risk of SARS-CoV-2 infection. A high-speed airflow is necessary to treat large volumes of indoor air over a short period. The proposed system can be used to eliminate viruses in aerosols by forcibly depositing aerosols in a high-speed airflow onto a photocatalyst placed inside the system through inertial force and turbulent diffusion. Because the main component of the deposited bioaerosol is water, it evaporates after colliding with the photocatalyst, and the nonvolatile virus remains on the photocatalytic channel wall. The residual virus on the photocatalytic channel wall is mineralized via photocatalytic oxidation with UVA-LED irradiation in the channel. When this system was operated in a 4.5 m3 aerosol chamber, over 99.8% aerosols in the size range of 1-10 µm were removed within 15 min. The system continued delivering such performance with the continuous introduction of aerosols. Because this system exhibits excellent aerosol removal ability at a flow velocity of 5 m/s or higher, it is more suitable than other reactive air purification systems for treating large-volume spaces.

Photocatalytic solar tower reactor for the elimination of a low concentration of VOCs.

We developed a photocatalytic solar tower reactor for the elimination of low concentrations of volatile organic compounds (VOCs) typically emitted from small industrial establishments. The photocatalytic system can be installed in a narrow space, as the reactor is cylindrical-shaped. The photocatalytic reactor was placed vertically in the center of a cylindrical scattering mirror, and this vertical reactor was irradiated with scattered sunlight generated by the scattering mirror. About 5 ppm toluene vapor, used as representative VOC, was continuously photodegraded and converted to CO2 almost stoichiometrically under sunny conditions. Toluene removal depended only on the intensity of sunlight. The performance of the solar tower reactor did not decrease with half a year of operation, and the average toluene removal was 36% within this period.

Aqueous mechano-bactericidal action of acicular aragonite crystals.

Nanoneedle structures on dragonfly and cicada wing surfaces or black silicon nanoneedles demonstrate antibacterial phenomena, namely mechano-bactericidal action. These air-exposed, mechano-bactericidal surfaces serve to destroy adherent bacteria, but their bactericidal action in the water is no precedent to report. Calcium carbonate easily accumulates on solid surfaces during long-term exposure to hard water. We expect that aragonite nanoneedles, in particular, which grow on TiO2 during the photocatalytic treatment of calcium-rich groundwater, exhibit mechano-bactericidal action against bacteria in water. Here, we showed that acicular aragonite modified on TiO2 ceramics prepared from calcium bicarbonate in mineral water by photocatalysis exhibits mechanical bactericidal activity against E. coli in water. Unmodified, calcite-modified and aragonite-modified TiO2 ceramics were exposed to water containing E. coli (in a petri dish), and their bactericidal action over time was investigated under static and agitated conditions. The surfaces of the materials were observed by scanning electron microscopy, and the live/dead bacterial cells were observed by confocal laser scanning microscopy. As a result, the synergistic bactericidal performance achieved by mechano-bactericidal action and photocatalysis was demonstrated. Aragonite itself has a high biological affinity for the human body different from the other whisker-sharpen nanomaterials, therefore, the mechano-bactericidal action of acicular aragonite in water is expected to inform the development of safe water purification systems for use in developing countries.

[Decontamination of chemical warfare agents by photocatalysis].

Photocatalysis has been widely applied to solar-energy conversion and environmental purification. Photocatalyst, typically titanium dioxide (TiO(2)), produces active oxygen species under irradiation of ultraviolet light, and can decompose not only conventional pollutants but also different types of hazardous substances at mild conditions. We have recently started the study of photocatalytic decontamination of chemical warfare agents (CWAs) under collaboration with the National Research Institute of Police Science. This article reviews environmental applications of semiconductor photocatalysis, decontamination methods for CWAs, and previous photocatalytic studies applied to CWA degradation, together with some of our results obtained with CWAs and their simulant compounds. The data indicate that photocatalysis, which may not always give a striking power, certainly helps detoxification of such hazardous compounds. Unfortunately, there are not enough data obtained with real CWAs due to the difficulty in handling. We will add more scientific data using CWAs in the near future to develop useful decontamination systems that can reduce the damage caused by possible terrorism.

Effect of dissolved silica on photocatalytic water purification with a TiO2 ceramic catalyst.

If photocatalytic water purification technologies will find practical applications, the impact of total dissolved solids in the source water on the activity of the photocatalyst must be evaluated. In this study, we evaluated the effects of SiO32- in water on a TiO2 ceramic photocatalyst; specifically, we determined the effects of SiO32- on the rate of photocatalytic degradation of formic acid (as a model contaminant) and on the rate of photocatalytic inactivation of Escherichia coli in an aqueous solution. Both the rate of formic acid degradation and the sterilization rate decreased with increasing SiO32- concentration. On the other hand, at a given SiO32- concentration, the activity of the photocatalyst did not decrease over the course of 120 h, and the surface structure of the photocatalyst did not change (i.e., no precipitate formed on the surface). The decreases in photocatalytic activity due to the presence of SiO32- could be recovered by flushing the experimental apparatus with distilled water. These results show that the reason for the lower photocatalytic activity in the presence of SiO32- than in its absence was due to adsorption of SiO32- onto the surface of the TiO2 photocatalyst and that SiO32- adsorption was an equilibrium process in water.

Superior disinfection effect of Escherichia coli by hydrothermal synthesized TiO2-based composite photocatalyst under LED irradiation: Influence of environmental factors and disinfection mechanism.

The photocatalytic inactivation of Escherichia coli (E. coli) under light-emitting diode (LED) light irradiation was performed with P/Ag/Ag2O/Ag3PO4/TiO2 photocatalyst to investigate the photocatalytic bactericidal activity. Our work showed that this composite photocatalyst possessed remarkable bacterial disinfection ability and could completely inactivate 108 cfu/mL of E. coli within just 40 min under the optimum catalyst loading of 0.5 g/L. The effects of different environmental factors, including light wavelength, light intensity, temperature, solution pH and inorganic ions, on the inactivation efficiency were evaluated. The results showed that bacteria inactivation by P/Ag/Ag2O/Ag3PO4/TiO2 was more favorable with blue colored LED irradiation, light intensity at 750 W/m2, temperature in the range of 30-37 °C and pH values at natural or slightly alkaline condition. The existence of different inorganic ions under normal environmental level had no significant impact on the bactericidal performance. In addition, during the inactivation process, the morphology changes of E. coli cells were directly observed by scanning electron microscope (SEM) and further proved by the measurement of K+ leakage from the inactivated E. coli. The results demonstrated that the photocatalytic inactivation caused drastic damage on bacterial cells membrane. Furthermore, the mechanisms of photocatalytic bacterial inactivation were also systemically studied and the results confirmed that the excellent disinfection activity of P/Ag/Ag2O/Ag3PO4/TiO2 resulted from the major reactive species: h+ and ·O2- from photocatalytic process instead of the leakage of Ag+ (≤0.085 ±â€¯0.005 mg/L) from photocatalyst. These results indicate that P/Ag/Ag2O/Ag3PO4/TiO2 photocatalyst has promising potential for real water sterilization application.

Photocatalytic degradation of the antiviral drug Tamiflu by UV-A/TiO2: Kinetics and mechanisms.

The photocatalytic degradation of the antiviral drug Tamiflu (oseltamivir phosphate, OP) by TiO2 - P25, ST-01 and ATO was investigated in aqueous solution under ultraviolet (UV-A) irradiation. The photocatalysis of OP is well described by pseudo-first-order kinetics with r2>98.0% for all cases. The kinetic constant of P25 with 80% anatase and 20% rutile (0.040 min(-1)) is 4 and 10 times higher than that of ATO and ST-01 with 100% purity of anatase, respectively. We examined the effects of the catalyst loading and initial OP concentration on the photodegradation of OP, and used potassium iodine, isopropanol, and calcium fluorine as radical quenchers to evaluate the contributions of the hydroxyl radical (OH) and photo hole (h+) in the photodegradation. Results confirmed that 80% of the contribution came from the OH species. Although more than 95% of the OP (21 µM) was removed after 80 min of UV-A irradiation with 20 and 100 mg L(-1) P25, the removal efficiencies of total organic carbon (TOC) were only 45.6% and 67.0%, respectively, after 360 min UV-A irradiation. Based on an intermediate analysis by HPLC coupled with a triple quadrupole spectrometer and an ion trap mass spectrometer, typical intermediate species such as hydration derivatives, hydroxyl substitutes and keto-derivatives were identified and possible degradation pathways of OP by P25 were proposed.

Differences in elimination efficiencies of Escherichia coli in freshwater and seawater as a result of TiO2 photocatalysis.

The effects of UV irradiation on the respiration and survival of Escherichia coli in various concentrations of aqueous NaCl were investigated in the presence of a photocatalyst. In this study, we anticipated that the photocatalysis of residual chlorine generated in a solution containing Cl(-) would result in bacterial elimination. Our results indicated a gradual reduction in the E. coli survival ratio in freshwater; however, no decrease in total abundance was observed during 8 h of photocatalysis with UV irradiation. Conversely, the survival ratio of E. coli in the artificial seawater decreased drastically as a consequence of photocatalysis, with a concomitant decrease in total abundance. These results revealed that the chlorinated active species that formed on the photocatalyst surface influenced the observed inactivation.

Removal of high concentration dimethyl methylphosphonate in the gas phase by repeated-batch reactions using TiO2.

The aim of our study is to develop apparatuses that use TiO(2) for effective decontamination of air contaminated by Sarin gas. We performed photocatalytic decomposition of gaseous dimethyl methylphosphonate (DMMP) by TiO(2) and identified the oxidization products. The high activity of TiO(2) (0.01 g) was observed under UV-light irradiation and high concentration DMMP (33.5 microM) was removed rapidly. On the other hand, DMMP was not decreased under UV-light irradiation without TiO(2). This indicates that photocatalytic treatment is very effective for the removal of DMMP. Methanol, formaldehyde, formic acid, methyl formate, CO, CO(2) and H(2)O were detected as the primary products. In the gas phase, no highly poisonous substances were detected. In order to examine the performance of photocatalytic activity during long-term reactions, we performed photocatalytic decomposition by repeated-batch reactions using TiO(2). High photocatalytic activities decreased gradually. Meanwhile, the strong adsorption of TiO(2) against DMMP was observed as photocatalytic activities decreased. During the repeated-batch reactions with the sample scaled up (TiO(2): 0.1g), the total amount of removed DMMP reached 968.5 microM by both photocatalytic decomposition and the strong adsorption of TiO(2). These results suggest the possibility of removing large amounts of DMMP.

Photocatalytic degradation of organophosphate and phosphonoglycine pesticides using TiO2 immobilized on silica gel.

The photocatalytic degradation of the three pesticides acephate, dimethoate, and glyphosate in water has been investigated using UV light and TiO2 immobilized on silica gel as photocatalyst. Results show that the pesticides can be efficiently degraded by the UV/TiO2 system used in the study. Complete (100%) decomposition of dimethoate and glyphosate was attained within 60 min of irradiation, while total degradation of acephate occurred after 105 min of photocatalytic treatment. Acephate and dimethoate decomposition followed the Langmuir-Hinshelwood apparent first-order degradation kinetics, suggesting the photocatalytic nature of pesticide disappearance, whereas glyphosate decomposition was governed by both adsorption and photocatalytic reactions. Evolution of heteroatoms at their highest oxidized states such as SO(4)(2-), NO(3)(-), and PO(4)(3-) ions provides evidence that pesticide degradation occurred primarily through photocatalytic oxidation reactions. Non-detection of toxic intermediates such as methamidophos and omethoate that have been reported in other studies demonstrates rapid destruction of the pesticides into harmless byproducts using the system.

Prevention of Phormidium tenue Biofilm Formation by TiO(2) Photocatalysis.

We showed that the photocatalytic effect of a coating of TiO(2) greatly reduces the formation of a biofilm by Phormidium tenue (P. tenue), a filamentous cyanobacterium, on glass plates. Sample plates were immersed in P. tenue culture solution (OD(730)=0.3) under concurrent illumination with white fluorescent (WF) and UV light (0.3 mW cm(-2), each) for 11 days. TiO(2)-coated glass plates showed greatly reduced adhesion of P. tenue over 11 days compared to bare plates. The number of P. tenue adhering to bare glass plates increased to over 10(6) cells cm(-2) in 6 days. The photocatalytic anti-biofilm effect was also observed under WF light, although it was small and lasted only a few days. The addition of 1 mM mannitol, a scavenger for the hydroxyl radical (·OH), suppressed the effect. The surface of TiO(2)-coated plates was maintained in a highly hydrophilic state for 11 days, regardless of the addition of mannitol. Therefore, we conclude that the photocatalytic oxidation of P. tenue is effective in preventing the formation of a biofilm.

Adjacent- versus remote-site electron injection in TiO2 surfaces modified with binuclear ruthenium complexes.

Nanocrystalline thin films of TiO2 cast on an optically transparent indium tin oxide glass were sensitized with ruthenium homo- and heterobinuclear complexes, [LL'Ru(BL)RuLL']n+ (n = 2, 3), where L and L' are 4,4'-dicarboxy-2,2'-bipyridine (dcb) and/or 2,2'-bipyridine (bpy) and BL is a rigid and linear heteroaromatic entity (tetrapyrido[3,2-a:2',3'-c:3",2"-h:2'",3'"-j]phenazine (tpphz) or 1,4-bis([1,10]phenanthroline[5,6-d]imidazol-2-yl)benzene (bfimbz)). The photophysical behavior of the RuII-RuII diads in solution indicated the occurrence of intercomponent energy transfer from the upper-lying Ru --> bpy charge-transfer (CT) excited state of the Ru(bpy)(2) moiety to the lower-lying Ru --> dcb CT excited state of the Ru(bpy)(dcb) (or Ru(dcb)(2)) subunit in the heterobinuclear complexes. These sensitizer diads adsorbed on nanostructured TiO2 surfaces in a perpendicular or parallel attachment mode. Adsorption was through the dcb ligands on one or both chromophoric subunits. The behavior of the adsorbed species was studied by nanosecond time-resolved transient absorption and emission spectroscopy, as well as by photocurrent measurements. In the TiO2-adsorbed samples where BL was bfimbz, the electron injection kinetics was very fast and could not be resolved because an electron is promoted from the metal center to the dcb ligand directly linked to the semiconductor. In the TiO2-adsorbed samples where BL was tpphz, for which, in the excited state, a BL localization of the lowest-lying metal-to-ligand charge transfer (MLCT) is observed, slower injection rates (9.5 x 10(7) s(-1) in [(bpy)(2)Ru(tpphz)Ru(bpy)(dcb(-))](3+)/TiO2 and 5.5 x 10(7) s(-1) in [(bpy)(dcb)Ru(tpphz)Ru(bpy)(dcb(-))](3+)/TiO2) were obtained. Among the systems, the heterotriad assembly [(bpy)(2)Ru(bfimbz)Ru(bpy)(dcb(2-))](2+)/TiO2 gave the best photovoltaic performance. In the first case, this was attributed to a fast electron injection initiated from a dcb-localized MLCT; in the second case, this is attributed to improved molecular orientation on the surface, which was due to rigidity and, at the same time, linearity of the heterotriad system, resulting in a slower charge recombination between the injected electron and the hole.