Hierarchically three-dimensional (3D) nanotubular sea urchin-shaped iron oxide and its application in heavy metal removal and solar-induced photocatalytic degradation.

In this study, hierarchically three-dimensional (3D) nanotubular sea urchin-shaped iron oxide nanostructures (3D-Fe2O3) were synthesized by a facile and rapid ultrasound irradiation method. Additives, templates, inert gas atmosphere, pH regulation, and other complicated procedures were not required. Dense 3D-Fe2O3 with a relatively large Brunauer-Emmett-Teller (BET) surface area of 129.4 m2/g was synthesized within 23 min, and the BET surface area was further improved to 282.7 m2/g by a post heat-treatment process. In addition, this post processing led to phase changes from maghemite (γ phase) to hematite (α phase) Fe2O3. Subsequent characterization suggested that the growth mechanism of the 3D-Fe2O3 follows self-assembly and oriented attachment. The prepared 3D-Fe2O3 was applied to wastewater purification. Ultrasound-irradiated 3D-Fe2O3 can eliminate a As(V) and Cr(VI) from water with 25 times faster removal rate by using a one third smaller amount than commercial α-Fe2O3. This was attributed to the inter-particle pores and relatively positively charged surface of the nanostructure. In addition, post heat treatment on ultrasound-irradiated 3D-Fe2O3 significantly influenced the photocatalytic degradation of methylene blue and phenol, with a 25 times higher removal efficiency than that of commercial α-Fe2O3, because of both high BET surface area and good crystallization of the prepared samples.

Advanced nanoporous TiO2 photocatalysts by hydrogen plasma for efficient solar-light photocatalytic application.

We report an effect involving hydrogen (H2)-plasma-treated nanoporous TiO2(H-TiO2) photocatalysts that improve photocatalytic performance under solar-light illumination. H-TiO2 photocatalysts were prepared by application of hydrogen plasma of assynthesized TiO2(a-TiO2) without annealing process. Compared with the a-TiO2, the H-TiO2 exhibited high anatase/brookite bicrystallinity and a porous structure. Our study demonstrated that H2 plasma is a simple strategy to fabricate H-TiO2 covering a large surface area that offers many active sites for the extension of the adsorption spectra from ultraviolet (UV) to visible range. Notably, the H-TiO2 showed strong ·OH free-radical generation on the TiO2 surface under both UV- and visible-light irradiation with a large responsive surface area, which enhanced photocatalytic efficiency. Under solar-light irradiation, the optimized H-TiO2 120(H2-plasma treatment time: 120 min) photocatalysts showed unprecedentedly excellent removal capability for phenol (Ph), reactive black 5(RB 5), rhodamine B (Rho B) and methylene blue (MB) - approximately four-times higher than those of the other photocatalysts (a-TiO2 and P25) - resulting in complete purification of the water. Such well-purified water (>90%) can utilize culturing of cervical cancer cells (HeLa), breast cancer cells (MCF-7), and keratinocyte cells (HaCaT) while showing minimal cytotoxicity. Significantly, H-TiO2 photocatalysts can be mass-produced and easily processed at room temperature. We believe this novel method can find important environmental and biomedical applications.

Triangular Black Phosphorus Atomic Layers by Liquid Exfoliation.

Few-layer black phosphorus (BP) is the most promising material among the two-dimensional materials due to its layered structure and the excellent semiconductor properties. Currently, thin BP atomic layers are obtained mostly by mechanical exfoliation of bulk BP, which limits applications in thin-film based electronics due to a scaling process. Here we report highly crystalline few-layer black phosphorus thin films produced by liquid exfoliation. We demonstrate that the liquid-exfoliated BP forms a triangular crystalline structure on SiO2/Si (001) and amorphous carbon. The highly crystalline BP layers are faceted with a preferred orientation of the (010) plane on the sharp edge, which is an energetically most favorable facet according to the density functional theory calculations. Our results can be useful in understanding the triangular BP structure for large-area applications in electronic devices using two-dimensional materials. The sensitivity and selectivity of liquid-exfoliated BP to gas vapor demonstrate great potential for practical applications as sensors.

Black Phosphorus (BP) Nanodots for Potential Biomedical Applications.

Recently, the appeal of 2D black phosphorus (BP) has been rising due to its unique optical and electronic properties with a tunable band gap (≈0.3-1.5 eV). While numerous research efforts have recently been devoted to nano- and optoelectronic applications of BP, no attention has been paid to promising medical applications. In this article, the preparation of BP-nanodots of a few nm to <20 nm with an average diameter of ≈10 nm and height of ≈8.7 nm is reported by a modified ultrasonication-assisted solution method. Stable formation of nontoxic phosphates and phosphonates from BP crystals with exposure in water or air is observed. As for the BP-nanodot crystals' stability (ionization and persistence of fluorescent intensity) in aqueous solution, after 10 d, ≈80% at 1.5 mg mL(-1) are degraded (i.e., ionized) in phosphate buffered saline. They showed no or little cytotoxic cell-viability effects in vitro involving blue- and green-fluorescence cell imaging. Thus, BP-nanodots can be considered a promising agent for drug delivery or cellular tracking systems.

Eco-friendly carbon-nanodot-based fluorescent paints for advanced photocatalytic systems.

Fluorescent carbon nanomaterials, especially zero-dimensional (0D) carbon nanodots (CDs), are widely used in broad biological and optoelectronic applications. CDs have unique characteristics such as strong fluorescence, biocompatibility, sun-light response, and capability of mass-production. Beyond the previous green CD obtained from harmful natural substances, we report a new type of fluid-based fluorescent CD paints (C-paints) derived from polyethylene glycol (PEG; via simple ultrasound irradiation at room temperatures) and produced in quantum yields of up to ~14%. Additionally, C-paints possess a strong, UV- and visible-light-responsive photoluminescent (PL) property. Most especially, C-paints, by incorporation into a photocatalytic system, show additional roles in the emission of fluorescent light for activation of TiO2 nanoparticles (NPs) and the resultant detoxification of most organic dyes, thus further enabling embarkation in advanced water purification.

Stable semiconductor black phosphorus (BP)@titanium dioxide (TiO2) hybrid photocatalysts.

Over the past few decades, two-dimensional (2D) and layered materials have emerged as new fields. Due to the zero-band-gap nature of graphene and the low photocatalytic performance of MoS2, more advanced semiconducting 2D materials have been prompted. As a result, semiconductor black phosphorus (BP) is a derived cutting-edge post-graphene contender for nanoelectrical application, because of its direct-band-gap nature. For the first time, we report on robust BP@TiO2 hybrid photocatalysts offering enhanced photocatalytic performance under light irradiation in environmental and biomedical fields, with negligible affected on temperature and pH conditions, as compared with MoS2@TiO2 prepared by the identical synthesis method. Remarkably, in contrast to pure few layered BP, which, due to its intrinsic sensitivity to oxygen and humidity was readily dissolved after just several uses, the BP@TiO2 hybrid photocatalysts showed a ~92% photocatalytic activity after 15 runs. Thus, metal-oxide-stabilized BP photocatalysts can be practically applied as a promising alternative to graphene and MoS2.

Innovative three-dimensional (3D) eco-TiO2 photocatalysts for practical environmental and bio-medical applications.

It is known that water purified by conventional TiO2 photocatalysts may not be safe enough for drinking, due to the toxicity by tiny existence of TiO2 nanoparticles after water treatment. We herein demonstrate a facile design of a three-dimensional (3D) TiO2 photocatalyst structure with which both the efficiency of purification and the safety level of the final purified water can be improved and ensured, respectively. The structure, consisting of 3D sulfur-doped TiO2 microtubes in nanotubes (eco-TiO2), is suitable for both environmental and bio-medical applications. Investigation of its formation mechanism reveals that anodic aluminum oxide (AAO), owing to a spatial constraint, causes a simple, nanoparticles-to-nanotubes structural rearrangement as a template for nanotube growth. It is found that eco-TiO2 can be activated under visible-light irradiation by non-metal (sulfur; S) doping, after which it shows visible-light photocatalytic activities over a range of solar energy. Importantly, an in vitro cytotoxicity test of well-purified water by eco-TiO2 confirms that eco-TiO2 satisfies the key human safety conditions.

Photoluminescent carbon nanotags from harmful cyanobacteria for drug delivery and imaging in cancer cells.

Using a simple method of mass production of green carbon nanotags (G-tags) from harmful cyanobacteria, we developed an advanced and efficient imaging platform for the purpose of anticancer therapy. Approximately 100 grams of G-tags per 100 kilograms of harmful cyanobacteria were prepared using our eco-friendly approach. The G-tags possess high solubility, excellent photostability, and low cytotoxicity (<1.5 mg/mL for 24 h). Moreover, doxorubicin-conjugated G-tags (T-tags; >0.1 mg/mL) induced death in cancer cells (HepG2 and MCF-7) in-vitro at a higher rate than that of only G-tags while in-vivo mice experiment showed enhanced anticancer efficacy by T-tags at 0.01 mg/mL, indicating that the loaded doxorubicin retains its pharmaceutical activity. The cancer cell uptake and intracellular location of the G- and T-tags were observed. The results indicate that these multifunctional T-tags can deliver doxorubicin to the targeted cancer cells and sense the delivery of doxorubicin by activating the fluorescence of G-tags.

Photoluminescent green carbon nanodots from food-waste-derived sources: large-scale synthesis, properties, and biomedical applications.

We have developed a simple approach for the large-scale synthesis of water-soluble green carbon nanodots (G-dots) from many kinds of large food waste-derived sources. About 120 g of G-dots per 100 kg of food waste can be synthesized using our simple and environmentally friendly synthesis approach. The G-dots exhibit a high degree of solubility in water because of the abundant oxygen-containing functional groups around their surface. The narrow band of photoluminescence emission (400-470 nm) confirms that the size of the G-dots (∼4 nm) is small because of a similar quantum effects and emission traps on the surfaces. The G-dots have excellent photostability; their photoluminescence intensity decreases slowly (∼8%) under continuous excitation with a Xe lamp for 10 days. We carried out cell viability assay to assess the effect of cytotoxicity by introducing G-dots in cells such as Chinese hamster ovary cells (CHO-K1), mouse muscle cells (C2C12), and African green monkey kidney cells (COS-7), up to a concentration of 2 mg mL(-1) for 24 h. Due to their high photostability and low cytotoxicity, these G-dots are excellent probes for in vitro bioimaging. Moreover, the byproducts (not including G-dots) of G-dot synthesis from large food-waste derived sources promoted the growth and development of seedlings germinated on 3DW-supplemented gauze. Because of the combined advantages of green synthesis, high aqueous stability, high photostability, and low cytotoxicity, the G-dots show considerable promise in various areas, including biomedical imaging, solution state optoelectronics, and plant seed germination and/or growth.

Sea-urchin-like iron oxide nanostructures for water treatment.

To obtain adsorbents with high capacities for removing heavy metals and organic pollutants capable of quick magnetic separation, we fabricated unique sea-urchin-like magnetic iron oxide (mixed γ-Fe2O3/Fe3O4 phase) nanostructures (called u-MFN) with large surface areas (94.1m(2) g(-1)) and strong magnetic properties (57.9 emu g(-1)) using a simple growth process and investigated their potential applications in water treatment. The u-MFN had excellent removal capabilities for the heavy metals As(V) (39.6 mg g(-1)) and Cr(VI) (35.0 mg g(-1)) and the organic pollutant Congo red (109.2 mg g(-1)). The u-MFN also displays excellent adsorption of Congo red after recycling. Because of its high adsorption capacity, fast adsorption rate, and quick magnetic separation from treated water, the u-MFN developed in the present study is expected to be an efficient magnetic adsorbent for heavy metals and organic pollutants in aqueous solutions.

Hierarchical hollow spheres of Fe2O3 @polyaniline for lithium ion battery anodes.

Hierarchical hollow spheres of Fe2 O3 @polyaniline are fabricated by template-free synthesis of iron oxides followed by a post in- and exterior construction. A combination of large surface area with porous structure, fast ion/electron transport, and mechanical integrity renders this material attractive as a lithium-ion anode, showing superior rate capability and cycling performance.

Influence of visible-light irradiation on physicochemical and photocatalytic properties of nitrogen-doped three-dimensional (3D) titanium dioxide.

We report highly active visible-light driven nitrogen-doped three-dimensional polycrystalline anatase TiO2 photocatalysts (N-3D TiO2) for environmental and biomedical applications. N-3D TiO2 is synthesized at a low temperature (<90°C) without thermal treatment via a modified hydrothermal process (HP) and ultrasound irradiation (UI). The N-3D TiO2 is additionally irradiated with visible-light to improve the hydroxylation of its surface. Under visible-light irradiation, the photocatalytic activity of visible-light irradiated N-3D TiO2 (*N-3D TiO2; [k]=1.435 h(-1)) is 26.1 times higher than that of 3D TiO2 ([k]=0.055 h(-1)). The *N-3D TiO2 is highly recyclable and retained 91.8% of the initial decolorization rate after fifteen cycles. Interestingly, the *N-3D TiO2 shows very strong antibacterial properties against both Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) after exposure to visible-light for 3h. The antibacterial properties of *N-3D TiO2 are more effective than those of TiO2, 3D TiO2, and N-3D TiO2. More than 91.3% of the E. coli is sterilized after ten cycles. There are a large increase in the photocatalytic and antibacterial activity of *N-3D TiO2 relative to that of N-3D TiO2 owing to the hydroxylation of the N-3D TiO2 surface as a result of the visible-light irradiation. These results indicate that *N-3D TiO2 might have utility in several promising applications such as highly efficient water/air treatment, inactivation of pathogenic microorganisms, and solar-energy conversion.

H2 uptake and synthesis of the Li-dispersed manganese oxide nanotubes.

Well aligned Li-dispersed manganese oxide nanotubes were prepared using LiNO3, Mn(NO3)2 x xH2O and an anodic aluminum oxide template by solvent-free method for potential applications in H2 storage. The obtained nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The analyses revealed the Mn2O3 nanotubes to have a cubic structure with a uniform length, 40-50 nm in wall thickness and 250 +/- 10 nm in the outer diameter. The level of H2 adsorption was determined using the gravimetric method. The Li-dispersed manganese oxide nanotubes showed a 0.26 wt% for the amount of hydrogen adsorption at 77 K under 4.5 MPa.