Correction: α-Fe2O3/TiO2 3D hierarchical nanostructures for enhanced photoelectrochemical water splitting.

Correction for 'α-Fe2O3/TiO2 3D hierarchical nanostructures for enhanced photoelectrochemical water splitting' by Hyungkyu Han et al., Nanoscale, 2017, 9, 134-142, https://doi.org/10.1039/C6NR06908H.

Achieving water-floatable photocatalyst on recycled bamboo chopsticks.

Disposable bamboo chopsticks (DBCs) are difficult to recycle, which inevitably cause secondary pollution. Based on energy and environmental issues, we propose a facile strategy to fabricate floatable photocatalyst (fPC) coated onto DBCs, which can be flexibly used in water purification. The photocatalyst of titania and titanium carbide on bamboo (TiO2/TiC@b) was successfully constructed from TiC-Ti powders and DBCs using a coating technique followed heat treatment in carbon powder, and the fPC exhibited excellent photocatalytic activity under visible light irradation. The analysis results indicate that rutile TiO2 forms on TiC during heat treatment, achieving a low-density material with an average value of approximately 0.5233 g/cm3. The coatings of TiO2/TiC on the bamboo are firm and uniform, with a particle size of about 20-50 nm. XPS results show that a large amount of oxygen vacancies is generated, due to the reaction atmosphere of more carbon and less oxygen, further favoring to narrowing the band gap of TiO2. Furthermore, TiO2 formed on residual TiC would induce the formation of a heterojunction, which effectively inhibits the photogenerated electron-hole recombination via the charge transfer effect. Notably, the degradation of dye Rhodamine B (Rh.B) is 62.4% within 3 h, while a previous adsorption of 36.0% for 1 h. The excellent photocatalytic performance of TiO2/TiC@b can be attributed to the enhanced reaction at the water/air interface due to the reduced light loss in water, improved visible-light response, increased accessible area and charge transfer effect. Our findings show that the proposed strategy achieves a simple, low-cost, and mass-producible method to fabricate fPC onto the used DBCs, which is expected to applied in multiple fields, especially in waste recycling and water treatment.

Conceptual study on extraction of formic acid from the electrolyte after electroreduction of CO2: Desalination and dehydration using a high-silica chabazite zeolite membrane.

Here, we propose a two-step pervaporation system with a high-silica CHA (chabazite) membrane, which has sufficient resistance to water and acid, to demonstrate the extraction and condensation of the formic acid formed by electroreduction of CO2. The kinetic diameters of water and formic acid are similar and smaller than the pore size of CHA, while the hydrated electrolyte ions (e.g., K+ and Cl-) are larger than the pore size of CHA. Consequently, the electrolyte ions are separated from the mixture of water and formic acid in the first desalination process, and then water molecules are easily removed from the mixture in the second dehydration process. From 300 ml of an approximately 3 wt% formic acid aqueous solution containing 0.5 M KCl, 10 ml of 18.2 wt% formic acid was obtained.

Synergistic effect of Ag decorated in-liquid plasma treated titanium dioxide catalyst for efficient electrocatalytic CO2 reduction application.

Recently, the conversion of carbon dioxide (CO2) into a useful resource and its byproducts by electrocatalytic reduction has been studied. It is well known that CO2 can be selectively reduced by gold, lead, etc. supported on conductive carbon. However, the high pH in the vicinity of the electrode raises concerns about the catalyst and catalyst support degradation. Therefore, we considered that using chemically stable TiO2 (titanium dioxide) powder as an alternative to carbon. Surface treatment using in-liquid plasma was used to improve the electrochemical properties of TiO2. TiO2 maintained its particle shape and crystalline structure after in-liquid plasma treatment. Electrochemical properties were evaluated and the disappearance of Ti4+ and Ti3+ redox peaks derived from TiO2 and a decrease in hydrogen overvoltage were observed. The hydrogen overvoltage relationship suggested that tungsten coating or doping on a portion of the reduced TiO2 surface. Electrocatalytic CO2 reduction using the silver nanoparticle-supported in-liquid plasma treated TiO2 showed increased hydrogen production. In electrocatalytic CO2 reduction, the ratio of hydrogen to carbon monoxide gas is important. Therefore, in-liquid plasma treated TiO2 is useful for the electrocatalytic CO2 reduction application.

Interfacial molecular regulation of TiO2 for enhanced and stable cocatalyst-free photocatalytic hydrogen production.

On the basis of the inherent property limitations of commercial P25-TiO2, many surface interface modification methods have attracted substantial attention for further improving the photocatalytic properties. However, current strategies for designing and modifying efficient photocatalysts (which exhibit complicated manufacturing processes and harsh conditions) are not efficient for production that is low cost, is nontoxic, and exhibits good stability; and therefore restrict practical applications. Herein, a facile and reliable method is reported for in situ amine-containing silane coupling agent functionalization of commercial P25-TiO2 by covalent surface modification for constructing a highly efficient photocatalyst. As a consequence, a high efficiency of H2 evolution was achieved for TiO2-SDA with 0.95 mmol h-1 g-1 (AQE ∼45.6 % at 365 nm) under solar light irradiation without a co-catalyst. The amination modification broadens the light absorption range of the photocatalyst, inhibits the binding of photogenerated carriers, and improves the photocatalytic efficiency; which was verified by photochemical properties and DFT theoretical calculations. This covalent modification method ensures the stability of the photocatalytic reaction. This work provides an approach for molecularly modified photocatalysts to improve photocatalytic performance by covalently modifying small molecules containing amine groups on the photocatalyst surface.

Enhanced degradation of ibuprofen using a combined treatment of plasma and Fenton reactions.

Advanced oxidation technologies (AOTs) proved to be effective in the degradation of hazardous organic impurities like acids, dyes, antibiotics etc. in the last few decades. AOTs are mainly based on the generation of reactive chemical species (RCS) such as hydroxyl, superoxide radicals etc., which plays an important role in the degradation of organiccompounds. In this work, plasma supported AOT i.e. Fenton reactions have been applied for the degradation of ibuprofen. As compared to traditional AOTs plasma assisted AOT is technologically superior due to its capability to produce RCS at a controlled rate without using chemical agents. This process work at normal room temperature and pressure. Herein, we optimized better operating conditions to generate good plasma discharge and hydroxyl radicals based on critical parameters, including frequency, pulse width and different gases like O2, Ar etc. Also, the one-pot carbonization method is used for the synthesis of Fe-based ordered mesoporous carbon (OMC) as a heterogeneous catalyst for the Fenton reactions. Using plasma-supported Fenton reactions, 88.3 % degradation efficiency is achieved using Fe-OMC catalyst for the ibuprofen degradation. Also, the mineralization of the ibuprofen is studied using total organic carbon (TOC) analysis.

Photocatalytic Inactivation of Co-Culture of E. coli and S. epidermidis Using APTES-Modified TiO2.

The presented work shows the antibacterial activity of TiO2 photocatalysts modified by 3-aminopropyltriethoxysilane (APTES). The APTES-functionalized TiO2 samples were obtained by the solvothermal process followed by calcination. The antibacterial activity of APTES/TiO2 samples was evaluated with two species of bacteria, Escherichia coli and Staphylococcus epidermidis, under artificial solar light (ASL) irradiation. The used bacteria are model organisms characterized by negative zeta potential (approx. -44.2 mV for E. coli and -42.3 mV for S. epidermidis). For the first time, the antibacterial properties of APTES-functionalized TiO2 were evaluated against mono- and co-cultured bacteria. The high antibacterial properties characterized the obtained APTES-modified nanomaterials. The best antibacterial properties were presented in the TiO2-4 h-120 °C-300 mM-Ar-300 °C sample (modified with 300 mM of APTES and calcined at 300 °C). The improvement of the antibacterial properties was attributed to a positive value of zeta potential, high surface area, and porous volume.

Enhanced Photocatalytic Degradation Activity Using the V2O5/RGO Composite.

Semiconductor-based photocatalyst materials played an important role in the degradation of organic compounds in recent years. Photocatalysis is a simple, cost-effective, and environmentally friendly process for degrading organic compounds. In this work, vanadium pentoxide (V2O5) and V2O5/RGO (reduced graphene oxide) composite were synthesized by a hydrothermal method. The prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Raman spectroscopy, and UV-Vis spectroscopic analysis, etc. Raman analysis shows the occurrence of RGO characteristic peaks in the composite and different vibrational modes of V2O5. The band gap of flake-shaped V2O5 is reduced and its light absorption capacity is enhanced by making its composite with RGO. The photocatalytic degradation of methylene blue (MB) was studied using both V2O5 and V2O5/RGO composite photocatalyst materials. The V2O5/RGO composite exhibits a superior photocatalytic performance to V2O5. Both catalyst and light play an important role in the degradation process.

High Li-Ion Selectivity of Five-Coordinate Layered Titanate K2Ti2O5.

Selectivity of ion exchangers is an important topic in adsorption science owing to its specific application in resource recovery and environmental remediation. In this study, the cation exchange property of the submillimeter-sized five-coordinate K2Ti2O5 (KTO) crystals is demonstrated. Adsorption isotherm measurements were performed on KTO crystals ion-exchanged with alkali metal cations including Li+, Na+, Rb+, and Cs+. The maximum adsorption amounts of Li+, Na+, Rb+, and Cs+ on KTO were 2.70, 1.15, 0.59, and 0.42 mmol g-1, respectively, which is contradictory to the "normal" selectivity sequence (Cs+ > Rb+ > K+ > Na+ > Li+) of conventional ion exchangers, including clays and organic resins. The Kielland plots for the Li+ and Cs+ exchange experiments showed preferential Li+ adsorption on KTO, which supports the high Li+ selectivity. The interlayer distance for M+-exchanged KTO (M = Li, Na, Rb, and Cs) was dependent on cation type. Raman and X-ray absorption near-edge structure spectroscopic analyses of the KTO samples indicated that certain Ti species in KTO underwent hydrolysis, and thereby formed hydroxyl groups on the KTO surface during ion exchange. The origin of the high Li+ selectivity of KTO is discussed herein based on experimental characterization results.

Interactions between pH, reactive species, and cells in plasma-activated water can remove algae.

Lightning strikes cause nitrogen to dissolve in water and form reactive nitrogen and oxygen species, which form natural fertilizers that can be absorbed through plant roots. Such processes during rainstorm events can be simulated by applying plasma to a solution. Plasma-activated water (PAW) has great potential as a source of various dissolved reactive chemical species. Different mixtures of species are produced using different solution compositions. Here, basil seeds were grown in PAW to prevent blooms of Chlorella vulgaris and ion chromatography and UV-vis spectroscopy were used to quantify reactive ions. NO2 -, NO3 -, and H2O2 were found to be key to the antialgal effect. Secondary reactive ions such as peroxynitrite (ONOO-, ONOOH) were also involved. The antialgal effect was strongly related to the pH around the algal cells. Acidification was predominantly caused by the generation of NO2 - and H2O2. After two weeks monitoring basil growth, the antifungal properties were preserved, few reactive oxygen species formed in the plasma zone, and only reactive nitrogen species were transformed into reactive peroxynitrite ions. The pH around the cells was determined using an iridium oxide microelectrode. The PAW antialgal mechanism depended on acidic conditions (pH 2.2, at which peroxynitrite can be generated) under which ONOOH penetrated the algal cell membranes, destroying the cells and preventing growth. This practical and sustainable PAW process allows a surprising amount of fertilizer to be generated with an antialgal effect that could be used in various eco-friendly agricultural processes under ambient conditions.

Complete decomposition of sulfamethoxazole during an advanced oxidation process in a simple water treatment system.

A simple water treatment system consisting of a deep UV light (λ = 222 nm) source, a mesoporous TiO2/boron-doped diamond (BDD) photocatalyst, and a BDD electrode was prepared and used to decompose sulfamethoxazole (SMX) in an advanced oxidation process. The mesoporous TiO2/BDD photocatalyst used with the electrochemical treatment promoted SMX decomposition, but the mesoporous TiO2/BDD photocatalyst alone had a similar ability to decompose SMX as photolysis. Fragments produced through photocatalytic treatment were decomposed during the electrochemical treatment and fragments produced during the electrochemical treatment were decomposed during the photocatalytic treatment, so performing the electrochemical and photocatalytic treatments together effectively decomposed SMX and decrease the total organic carbon concentration to a trace.

Rod-Shaped ß-FeOOH Synthesis for Hydrogen Production under Light Irradiation.

Renewable energy is spotlighted as a resource to replace fossil fuels, and among the resources, active research on hydrogen energy is ongoing. Various methods have been developed to produce hydrogen energy using photoreduction processes. In this study, we synthesized ß-phase iron oxyhydroxide (ß-FeOOH) using a hydrothermal method with an optimal synthesis time and investigated its photofunctional properties, including hydrogen production. The obtained samples were characterized and compared with reference data. X-ray powder diffraction results corresponded to the peaks of the reference data. A rod structure was confirmed by scanning electron microscopy, and no impurities were observed. The band-gap energy of ß-FeOOH was calculated as 1.8-2.6 eV. A photoreduction process was performed based on a photo-Fenton reaction to produce hydrogen by irradiating ultraviolet (UV) on ß-FeOOH. The synthesized ß-FeOOH was subjected to UV irradiation for 24 h to produce hydrogen, and we confirmed that hydrogen was successfully produced. The properties of ß-FeOOH were evaluated after UV irradiation.

Nanoflakes-like nickel cobaltite as active electrode material for 4-nitrophenol reduction and supercapacitor applications.

Catalytic reduction of nitroaromatic compounds present in wastewater by nanostructured materials is a promising process for wastewater treatment. A multifunctional electrode based on ternary spinal nickel cobalt oxide is used in the catalytic reduction of a nitroaromatic compound and supercapacitor application. In this study, we designed nanoflakes- like nickel cobaltite (NiCo2O4) using a simple, chemical, cost-effective hydrothermal method. Nanoflakes- like NiCo2O4 samples are tested as catalysts toward rapid reduction of 4-nitrophenol and as electrode materials for supercapacitors. The conversion of 4-nitrophenol into 4-aminophenol is achieved using a reducing agents like sodium borohydride and NiCo2O4 catalyst. Effect of catalyst loading, 4-nitrophenol and sodium borohydride concentrations on the catalytic performance of 4-nitrophenol is studied. As sodium borohydride concentration increases the catalytic efficiency of 4-nitrophenol increased due to more BH4- ions available which provides more electrons for catalytic reduction of 4-nitrophenol. Catalytic reduction of 4-nitrophenol using sodium borohydride as a reducing agent was based on the Langmuir-Hinshelwood mechanism. This mechanism follows the apparent pseudo first order reaction kinetics. Additionally, NiCo2O4 electrode is used for energy storage application. The nanoflakes-like NiCo2O4 electrode deposited at 120 °C shows a higher specific capacitance than samples synthesized at 100 and 140 °C. The maximum specific capacitance observed for NiCo2O4 electrode is 1505 Fg-1 at a scan rate of 5 mV s-1 with high stability of 95% for 5000 CV cycles.

Cobalt-Doped Manganese Dioxide Hierarchical Nanostructures for Enhancing Pseudocapacitive Properties.

Herein, overall improvement in the electrochemical performance of manganese dioxide is achieved through fine-tuning the microstructure of partially Co-doped manganese dioxide nanomaterial using facile hydrothermal method with precise control of preparative parameters. The structural investigation exhibits formation of a multiphase compound accompanied by controlled reflections of α-MnO2 as well as γ-MnO2 crystalline phases. The morphological examination manifests the presence of MnO2 nanowires having a width of 70-80 nm and a length of several microns. The Co-doped manganese dioxide electrode displayed a particular capacitive behavior along with a rising order of capacitance concerning with increased cobalt ion concentration suitable for certain limits. The value of specific capacitance achieved by a 5% Co-doped manganese dioxide sample was 1050 F g-1 at 0.5 A g-1, which was nearly threefold greater than that achieved by a bare manganese dioxide electrode. Furthermore, Co-doped manganese dioxide nanocomposite electrode exhibits exceptional capacitance retention (92.7%) till 10,000 cycles. It shows the good cyclability as well as stability of the material. Furthermore, we have demonstrated the solid-state supercapacitor with good energy and power density.

Indoor gas phase photoactivity of yttrium modified titanate films for fast acetaldehyde oxidation.

Photoactive materials hold structural and catalytic features that make them particularly suitable for environmental applications and in the present work, protonated H3Ti3O7-Y nanofiber-like materials were prepared via the microwave assisted hydrothermal technique. The as-prepared nanofibers exhibited high surface area with titanate structure. The nanofibers, before and after yttrium incorporation, were well-distributed and the fibrous morphology could be observed clearly; as the yttrium loading increased, ribbons and the anatase phase were formed. Practical films of these nanofibers confirmed their likely UV-photoactive properties with 200 ppm of acetaldehyde degradation within 25 min in the presence of 50% of humidity. Activity retention was achieved, keeping stability for 2 consecutive cycles at room temperature. Nowadays, the increase in home office work sets human health at risk, for the exposure to toxic volatile organic compounds and microorganisms such as viruses and bacteria is more frequent indoors. In this context, the synthesized photoactive yttrium-titanate films stand as upcoming practical UV-driven materials for cleaning pollution that concentrated urban activity and indoor environments.

Photocatalytic degradation of bisphenol A using titanium dioxide@nanodiamond composites under UV light illumination.

Different types of organic impurities such as dyes, acids, and alcohols are discharged into potable water sources. The removal of these hazardous organic pollutants from wastewater is an important task globally. However, the conventional methods used to remove organic impurities suffer from low efficiency and recycling problems. Photocatalysis is a promising advanced oxidation process for the degradation of organic compounds in aqueous solution. Titanium dioxide (TiO2) is commonly used as a photocatalyst. However, the wide bandgap of TiO2 means that it is activated by ultraviolet light, which restrains its ability to harvest solar energy. In this study, a simple water-based precipitation method was used to synthesize TiO2@nanodiamond composites. The ability of the composites to degrade bisphenol A as a model organic pollutant was investigated. It was found that 10 ppm of bisphenol A was completely degraded in 100 min by the TiO2@nanodiamond photocatalyst under ultraviolet illumination.

Flux Growth of Single-Crystalline Hollandite-Type Potassium Ferrotitanate Microrods From KCl Flux.

Hollandite-type crystals have unique and interesting physical and chemical properties. Here, we report the flux growth of hollandite-type single-crystalline potassium ferrotitanate (KFTO) with faceted surface features from a KCl flux. We varied the flux growth conditions, including the kind of flux, holding temperature, and solute concentration for growing faceted crystallites. KCl was found to be the best flux to grow the single-crystalline KFTO particles, while heating at or above 900°C was needed to yield the KFTO single crystals. The crystal growth was only weakly dependent on the solute concentration. Next, we characterized the grown single crystals and discussed the manner of their growth from the KCl flux. TEM images with clear electron diffraction spots indicated that the KFTO crystals grew along the <001> direction to form microrods ~10 µm in size. DFT calculation results indicated that the surface energy of the (100) face is lower than that of the (001) face. Based on these characterization results, we proposed a possible growth mechanism of the KFTO crystals.

One-Pot Synthesis of Anatase, Rutile-Decorated Hydrogen Titanate Nanorods by Yttrium Doping for Solar H2 Production.

We have prepared yttrium (Y)-doped hydrogen titanate nanorods (HTN) by a microwave-assisted hydrothermal method. Y-doped HTN showed much improved photocatalytic activities for both H2 evolution and dye decomposition. H2 production from a methanol-water solution under UV-visible light for 7 h was enhanced by a factor of 5.5 with 1 wt % Y-doping. Doping with Y3+ ions reduced the band gap of HTN by ∼0.28 eV and induced new phases of anatase and rutile. High photocatalysis by Y-doping was attributed to enhanced light absorption (smaller band gap) and effective charge separation (heterojunction). To optimize H2 production, a series of experiments examining effects of doping concentrations and non-noble surface metal (e.g., Ni, Cu, Co) loading were carefully performed. Y-doping in this work is a new and promising approach for synthesizing highly active HTN by producing the HTN/rutile/anatase heterostructure within the one-pot method.

Enhanced Solar Photothermal Catalysis over Solution Plasma Activated TiO2.

Colored wide-bandgap semiconductor oxides with abundant mid-gap states have long been regarded as promising visible light responsive photocatalysts. However, their catalytic activities are hampered by charge recombination at deep level defects, which constitutes the critical challenge to practical applications of these oxide photocatalysts. To address the challenge, a strategy is proposed here that includes creating shallow-level defects above the deep-level defects and thermal activating the migration of trapped electrons out of the deep-level defects via these shallow defects. A simple and scalable solution plasma processing (SPP) technique is developed to process the presynthesized yellow TiO2 with numerous oxygen vacancies (Ov), which incorporates hydrogen dopants into the TiO2 lattice and creates shallow-level defects above deep level of Ov, meanwhile retaining the original visible absorption of the colored TiO2. At elevated temperature, the SPP-treated TiO2 exhibits a 300 times higher conversion rate for CO2 reduction under solar light irradiation and a 7.5 times higher removal rate of acetaldehyde under UV light irradiation, suggesting the effectiveness of the proposed strategy to enhance the photoactivity of colored wide-bandgap oxides for energy and environmental applications.

Three-dimensional nanoflower-like hierarchical array of multifunctional copper cobaltate electrode as efficient electrocatalyst for oxygen evolution reaction and energy storage application.

The study deals with the hydrothermal growth of a CuCo2O4 hierarchical 3D nanoflower-like array on carbon cloth (CuCo2O4@CC), which is a useful multifunctional electrode. The electrocatalytic oxygen evolution reaction (OER) study of the CuCo2O4@CC electrode shows high durability and good activity in 1 M KOH. As an energy storage electrode, it shows a high specific capacitance of 1438 Fg-1 at 10 mA cm-2 in a 3 M KOH electrolyte. The electrochemical stability of the CuCo2O4@CC electrode was tested for 5000 cycles at 10 mA cm-2, and it showed 98.6% stability. This CuCo2O4@CC electrode produces a capacitance of 10 mA cm-2 at an overpotential of 288 mV for the OER, with a Tafel slope of 64.2 mV dev-1. The electrochemical stability measured at an overpotential of 292 mV for 12 h at 10 mA cm-2 shows good electronic stability in an alkaline medium. The enhanced electrochemical performance of the CuCo2O4@CC electrode may be due to the Cu and Co counterparts in addition to the high surface area. The CuCo2O4@CC electrode is a simple, flexible, and cost-effectivive electrode in both electrocatalytic OER and energy storage applications.