Novel GdTaO4 phase for efficient photocatalytic degradation of organic dye under visible light irradiation: An X-ray spectroscopic investigation.

The novel GdTaO4 phase exhibits good photocatalytic activity under visible light irradiation and holds great promise for the removal of organic dyes from industrial wastes. The GdTaO4 samples were synthesized using the hydrothermal and calcination process with different weight ratios of gadolinium nitrate hydrate (G) and tantalum pentachloride (T), and their structural studies confirmed the formation of the GdTaO4 (GT) phase. Among the samples, GT-4 (with a weight ratio of 4:1) exhibited the highest photocatalytic activity for the degradation of Methyl Orange (MO) dye under visible light irradiation. To enhance the photocatalytic performance, H2O2 was used as a green additive, and the photocatalytic abilities were examined by varying dye types and concentrations. X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) revealed the local atomic and electronic structures around Ta and Gd and highlighted the contribution of Gd3+ to the GT system, which is a crucial factor in supporting the enhanced photocatalytic performance. Moreover, in-situ XAS at Gd M5-edge and O K-edge were examined under illumination/dark conditions to explore the electronic structures of photo-excited electron transition in the photocatalytic process. The analytical results provided strong evidence correlating the electronic structure and photocatalytic property of the GT. This study demonstrates that GdTaO4 exhibits good photocatalytic activity under visible light irradiation, making it a promising new Ta-based photocatalyst for the effective removal of organic dyes from industrial wastes.

Synthesis and characterization of visible-light-driven novel CuTa2O6 as a promising practical photocatalyst.

In this work, the novel CuTa2O6 phase was successfully synthesized by the hydrothermal and followed by the calcination process. The X-ray diffraction pattern confirms the formation of different phases. At a low temperature, CuTa2O6 exhibits the orthorhombic phase, whereas, at a higher temperature, it underwent a phase transition to a cubic crystal structure. X-ray photoelectron spectroscopic results suggest the presence of all the elements (Cu, Ta, and O). The optical studies were carried out using a UV-Vis DRS spectrophotometer. FESEM images confirm the spherical-shaped particles for the sample annealed at a high temperature. The local atomic and electronic structures around Cu and the contribution of the Cu oxidation state in the CuTa2O6 system were determined by X-ray absorption spectroscopy. To investigate the effective usage of CuTa2O6 in treating wastewater, its photocatalytic activity was investigated by evaluating its use in the photodegradation of MO dye under visible light irradiation. Moreover, the prepared CuTa2O6 photocatalyst exhibits significant photocatalytic activity in the degradation of MO dye and shows excellent stability; it is therefore a promising material for potential use in a practical photocatalyst. The CuTa2O6 photocatalyst suggests an alternative avenue of research into effective photo-catalysts for solar hydrogen water splitting.

Large-lateral-area SnO2 nanosheets with a loose structure for high-performance acetone sensor at the ppt level.

Gas sensors with high sensitivity and high selectivity are required in practical applications to distinguish between target molecules in the detection of volatile organic compounds, real-time security alerts, and clinical diagnostics. Semiconducting tin oxide (SnO2) is highly regarded as a gas-sensing material due to its exceptional responsiveness to changes in gaseous environments and outstanding chemical stability. Herein, we successfully synthesized a large-lateral-area SnO2 nanosheet with a loose structure as a gas sensing material by a one-step facile aqueous solution process without a surfactant or template. The SnO2 sensor exhibited a remarkable sensitivity (Ra/Rg = 1.33) at 40 ppt for acetone, with a theoretical limit of detection of 1.37 ppt, which is the lowest among metal oxide semiconductor-based gas sensors. The anti-interference ability of acetone was higher than those of pristine SnO2 and commercial sensors. These sensors also demonstrated perfect reproducibility and long-term stability of 100 days. The ultrasensitive response of the SnO2 nanosheets toward acetone was attributed to the specific loose large lateral area structure, small grain size, and metastable (101) crystal facets. Considering these advantages, SnO2 nanosheets with larger lateral area sensors have great potential for the detection and monitoring of acetone.

Facet-Controlled Synthesis of CeO2 Nanoparticles for High-Performance CeO2 Nanoparticle/SnO2 Nanosheet Hybrid Gas Sensors.

CeO2 nanocubes with metastable {100} facets and CeO2 nanooctahedrons with the most stable {111} facets are herein fabricated by controlling the morphology and facets of CeO2 nanoparticles. SnO2 nanosheet-based assembled films coated with these CeO2 nanocubes or CeO2 nanooctahedrons yield {100} CeO2 nanocubes/SnO2 nanosheets and {111} CeO2 nanooctahedron/SnO2 nanosheet hybrid gas sensors, respectively. The hybrid sensors with CeO2 nanoparticles exhibited enhanced sensing responses to numerous chemical species relative to a pristine SnO2 nanosheet gas sensor, including acetone, hydrogen, ethanol, ammonia, acetaldehyde, and allyl mercaptan. In particular, the responses of {100} CeO2 nanocubes/SnO2 nanosheets and {111} CeO2 nanooctahedron/SnO2 nanosheet gas sensors to acetone or allyl mercaptan were 6.8 and 10.3 times higher, respectively, than that of the pristine SnO2 nanosheet gas sensor. Furthermore, the sensor response to ammonia was 2.5 times higher than that of a commercial volatile organic compound (VOC) gas sensor (TGS2602, Figaro Engineering Inc.). The CeO2 nanocube-based sensor with exposed metastable {100} facets promotes the adsorption and oxidation of VOCs owing to the higher surface energy of the metastable {100} facets and therefore exhibits a higher sensing performance than the CeO2 nanooctahedron-based sensor with an exposed {111} facet. The developed sensors show excellent potential for the detection of gas markers in human breath and perspiration for disease diagnosis.

Nanosheet-type tin oxide gas sensor array for mental stress monitoring.

Mental stress management has become significantly important because excessive and sustained mental stress can damage human health. In recent years, various biomarkers associated with mental stress have been identified. One such biomarker is allyl mercaptan. A nanosheet-type tin oxide exhibited high gas selectivity for allyl mercaptan; thus, in this study, a sensor array comprising nanosheet-type tin oxide gas sensors was fabricated to detecting allyl mercaptan. Supervised learning algorithms were use to build gas classification models based on the principal component analysis of the sensor signal responses from the sensor array. The comprehensive data provided by the classification models can be used to forecast allyl mercaptan with high accuracy.

Highly Sensitive and Selective Gas Sensors Based on NiO/MnO2 @NiO Nanosheets to Detect Allyl Mercaptan Gas Released by Humans under Psychological Stress.

NiO nanosheets are synthesized in situ on gas sensor chips using a facile solvothermal method. These NiO nanosheets are then used as gas sensors to analyze allyl mercaptan (AM) gas, an exhaled biomarker of psychological stress. Additionally, MnO2 nanosheets are synthesized onto the surfaces of the NiO nanosheets to enhance the gas-sensing performance. The gas-sensing response of the NiO nanosheet sensor is higher than that of the MnO2 @NiO nanosheet sensor. The response value can reach 56.69, when the NiO nanosheet sensor detects 40 ppm AM gas. Interestingly, a faster response time (115 s) is obtained when the MnO2 @NiO nanosheet sensor is exposed to 40 ppm of AM gas. Moreover, the selectivity toward AM gas is about 17-37 times greater than those toward confounders. The mechanism of gas sensing and the factors contributing to the enhance gas response of the NiO and MnO2 @NiO nanosheets are discussed. The products of AM gas oxidized by the gas sensor are identified by gas chromatography-mass spectrometry (GC/MS). AM gas detection is an unprecedented application for semiconductor metal oxides. From a broader perspective, the developed sensors represent a new platform for the identification and monitoring of gases released by humans under psychological stress, which is increasing in modern life.

Examination of VOC Concentration of Aroma Essential Oils and Their Major VOCs Diffused in Room Air.

This study analyzed temporal variation of the composition of volatile organic compounds (VOCs) at different diffusion time of gaseous phase of aroma compounds of four essential oils, lavender, tea tree, eucalyptus, and melissa. GC/MS methodology with the trace gas sampling by a thermal desorption tube is used to quantitatively determine the concentration of the corresponding 14 kinds of major and original VOCs in four essential oils. This study revealed for the first time that the concentration level of gaseous phase composition is varied, with a diffusion time from that of the liquid phase at equilibrium with it and the VOCs in the essential oils are classified into two groups, depending on whether their concentration with the time. It is verified that the total concentration of VOCs of these essential oils in the room air diffused by the ultrasonic diffuser is as low as 0.6 ppb and decreased soon below 0.1 ppb.

Self-Adaptive Gas Sensor System Based on Operating Conditions Using Data Prediction.

Through the improvement of nanomaterial technologies, a gas sensor was developed for detecting ppm or ppb levels of gas. Our SnO2 nanosheet gas sensor can detect 50 ppb of acetone without the requirement of a novel metal catalyst by exposing the (101) facet containing the Sn2+ state. Despite the high performance, the fluctuation of the gas response value based on operating conditions, even at the same concentration, is a critical problem in gas sensors. Thus, the alarm criteria of the sensor are typically determined by a safety factor. However, this method is not suitable for application in ultrasensitive sensors that require distinguishing minute differences in extremely low concentrations for medical examination or odor analysis. Therefore, we suggest a self-adaptive system that is based on operating conditions in collaboration with the data prediction model. The sensor system is based on a predictive model obtained by the response surface methodology. When the system detects a change in conditions, the alarm criteria are changed appropriately through the calculated values from the predictive model. To prepare a database for an effective predictive model, the gas responses of the SnO2 nanosheet sensor were measured with 20 treatments with 3 independent variables, namely, the temperature, flow rate, and concentration. Our prediction model achieved its best performance on training data with R2 = 0.9299 and less than 5% error in the prediction of unseen data.

Facet controlled growth mechanism of SnO2 (101) nanosheet assembled film via cold crystallization.

Cold crystallization of SnO2 was realized in aqueous solutions, where crystal growth was controlled to form SnO2 (101) nanosheet assembled films for devices such as chemical sensors. The nanosheets grew directly on a fluorine-doped tin oxide substrate without a seed layer or a buffer layer. The nanosheets had a thickness of 5-10 nm and an in-plane size of 100-1600 nm. Moreover, the large flat surface of the (101) facet was metastable. The thickness of the SnO2 (101) nanosheet assembled film was approximately 800 nm, and the film had a gradient structure that contained many connected nanosheets. TEM results revealed that the predominate branch angles between any two connected nanosheets were 90° and 46.48°, corresponding to type I and type II connections, respectively. These connections were consistent with the calculations based on crystallography. Crystallographic analysis clarified the characteristic crystal growth of the SnO2 (101) nanosheet assembled film in the aqueous solution. Furthermore, we demonstrate that the metastable (101) facet can be exploited to control the rate of crystal growth by adjusting the etching condition.

Facile synthesis of ZnO nanobullets by solution plasma without chemical additives.

ZnO nano-bullets were synthesized using solution plasma from only Zn electrode in water without any chemical agents. In this sustainable synthesis system, the rapid quenching reaction at the interface between the plasma/liquid phases facilitates the fast formation of nano-sized materials. The coil-to-pin type electrode geometry, which overcomes the discharge interruption owing to the electrode gap broadening of the typical pin-to-pin type enables the synthesis of numerous nanomaterials through a stable discharge for 1 h. The as-prepared samples exhibited a high crystalline ZnO structure without post calcination, and the length and width were 71.8 and 29.1 nm, respectively. The main exposed facet of ZnO nano-bullets was the (100) crystal facet, but interestingly, the (101) facet was confirmed at the inclined surfaces in the edges. The (101) crystal facet has an asymmetric Zn and O atom arrangement, and it could result in a focused electron density area with relatively high reactivity. Therefore, ZnO nano-bullets are promising materials for applications in advanced technologies.

Catalyst-free Highly Sensitive SnO2 Nanosheet Gas Sensors for Parts per Billion-Level Detection of Acetone.

The development of a facile gas sensor for the ppb-level detection of acetone is required for realizing health diagnosis systems that utilize human breath. Controlling the crystal facet of a nanomaterial is an effective strategy to fabricate a high-response gas sensor without a novel metal catalyst. Herein, we successfully synthesized a SnO2 nanosheet structure, with mainly exposed (101) crystal facets, using a SnF2 aqueous solution at 90 °C. The SnO2 nanosheets obtained after various synthesis durations (2, 6, and 24 h) were investigated. The sample synthesized for 6 h (NS-6) exhibited a 10-fold higher response (Ra/Rg = 10.4) for 1 ppm of acetone compared to the other samples, where Ra and Rg are the electrical resistances under air and the target gas. Furthermore, NS-6 detected up to 200 ppb of acetone (response = 3). In this study, we attributed the high response (of low concentrations of acetone) to the (101) crystal facet, which is the main reaction surface. The (101) crystal facet allows the facile formation of a depletion layer due to the highly reactive Sn2+. Additionally, the acetone adsorption energy of the (101) crystal facet is relatively lower than that of other crystal facets. Owing to these factors, our pristine SnO2 nanosheet gas sensor exhibited significantly high sensitivity to ppb levels of acetone.

Bio-inspired mineralization of nanostructured TiO2 on PET and FTO films with high surface area and high photocatalytic activity.

Nanostructured TiO2 coatings were successfully formed on polyethylene terephthalate (PET) films and fluorine-doped tin oxide (FTO) films in aqueous solutions. They contained an assembly of nanoneedles that grow perpendicular to the films. The surface area of the coatings on PET films reached around 284 times that of a bare PET film. Micro-, nano-, or subnanosized surface roughness and inside pores contributed to the high nitrogen adsorption. The coatings on FTO films showed an acetaldehyde removal rate of 2.80 µmol/h; this value is similar to those of commercial products certified by the Photocatalysis Industry Association of Japan. The rate increased greatly to 10.16 µmol/h upon annealing in air at 500 °C for 4 h; this value exceeded those of commercial products. Further, the coatings showed a NOx removal rate of 1.04 µmol/h; this value is similar to those of commercial products. The rate decreased to 0.42 µmol/h upon annealing. NOx removal was affected by the photocatalyst's surface area rather than its crystallinity.

Development of Na0.5CoO2 Thick Film Prepared by Screen-Printing Process.

The Na0.5Co0.9Cu0.1O2 thick film with the same thermoelectric performance as a Na0.5CoO2 bulk was formed on an alumina substrate by the screen-printing process. The power factor exceeded 0.3 mW/K2m, with the resistivity of 3.8 mΩcm and the thermopower of 108 µV/K. The thick film without any cracks strongly adhered to the substrate. The high-quality thick film had been realized through the carefully designed and improved process, mixing NaCl to promote the anisotropic sintering of Na0.5Co0.9Cu0.1O2, inserting a CuO interlayer to adhere the film and substrate, and Co-Cu substituting Cu for Co to control the sintering temperature.

Selective Detection of Target Volatile Organic Compounds in Contaminated Air Using Sensor Array with Machine Learning: Aging Notes and Mold Smells in Simulated Automobile Interior Contaminant Gases.

We investigated the selective detection of target volatile organic compounds (VOCs) which are age-related body odors (namely, 2-nonenal, pelargonic acid, and diacetyl) and a fungal odor (namely, acetic acid) in the presence of interference VOCs from car interiors (namely, n-decane, and butyl acetate). We used eight semiconductive gas sensors as a sensor array; analyzing their signals using machine learning; principal-component analysis (PCA), and linear-discriminant analysis (LDA) as dimensionality-reduction methods; k-nearest-neighbor (kNN) classification to evaluate the accuracy of target-gas determination; and random forest and ReliefF feature selections to choose appropriate sensors from our sensor array. PCA and LDA scores from the sensor responses to each target gas with contaminant gases were generally within the area of each target gas; hence; discrimination between each target gas was nearly achieved. Random forest and ReliefF efficiently reduced the required number of sensors, and kNN verified the quality of target-gas discrimination by each sensor set.

Co-Substitution Effect in Room-Temperature Ferromagnetic Oxide Sr3.1Y0.9Co4O10.5.

We investigated the Co substitution effect for the magnetic properties in room-temperature ferromagnetic oxide Sr3.1Y0.9Co4O10.5. The substituted element (Al and Ga) and low-spin state Co3+, which was changed from a high-spin or intermediate-spin state by Al or Ga substitution, reduced the Curie temperature to even 1.5 times lower than the temperature estimated from a simple dilution effect. Al3+ preferentially substituted for intermediate-spin-state Co3+ in the ferrimagnetic CoO6 layer and deteriorated the saturation magnetization of Sr3.1Y0.9Co4O10.5. By contrast, Ga3+ substituted for high-spin-state Co3+ in the CoO6 layer and/or the antiferromagnetic CoO4.25 layer and enhanced the saturation magnetization per Co ion. These results indicate that the magnetic properties of Sr3.1Y0.9Co4O10.5 can be controlled by selectively substituting for Co3+ with different spin states.

Effect of Crystal Defect on Gas Sensing Properties of Co3O4 Nanoparticles.

Crystal growth-controlled Co3O4 nanoparticles were prepared to examine gas sensing properties. A cube-like, an irregular shaped, and three kinds of raspberry-type structures were observed by morphology analysis. The raspberry-type structures have an expanded lattice volume with a large oxygen deficiency area, and the cube-like structure has a contracted lattice volume as compared to the irregular shaped structure. The raspberry-type structures exhibited a higher sensor signal response than the others. A relationship between sensor properties and crystal defect was investigated, and it was revealed that the gas selectivity to a high dipole moment value of a reducing gas molecule increased with increasing oxygen deficiency area of the Co3O4 nanoparticle. It was considered that the oxygen deficiency area acted as an important reaction site, which can be attributed to the selective reaction of the Co3O4 nanoparticle with gas molecules.

Emerging Atomic Energy Levels in Zero-Dimensional Silicon Quantum Dots.

Driven by the emergence of colloidal semiconductor quantum dots (QDs) of tunable emission wavelengths, characteristic of exciton absorption peaks, outstanding photostability and solution processability in device fabrication have become a key tool in the development of nanomedicine and optoelectronics. Diamond cubic crystalline silicon (Si) QDs, with a diameter larger than 2 nm, terminated with hydrogen atoms are known to exhibit bulk-inherited spin and valley properties. Herein, we demonstrate a newly discovered size region of Si QDs, in which a fast radiative recombination on the order of hundreds of picoseconds is responsible for photoluminescence (PL). Despite retaining a crystallographic structure like the bulk, controlling their diameters in the 1.1-1.7 nm range realizes the strong PL with continuous spectral tunability in the 530-580 nm window, the narrow spectral line widths without emission tails, and the fast relaxation of photogenerated carriers. In contrast, QDs with diameters greater than 1.8 nm display the decay times on the microsecond order as well as the previous Si QDs. In addition to the five-orders-of-magnitude variation in the PL decay time, a systematic study on the temperature dependence of PL properties suggests that the energy structure of the smaller QDs does not retain an indirect band gap character. It is discussed that a 1.7 nm diameter is critical to undergo changes in energy structure from bulky to molecular configurations.

Nanoarchitectonics of Acicular Nanocrystal Assembly and Nanosheet Assembly for Lithium-Ion Batteries.

Nanoarchitectonics of metal oxide nanocrystal electrodes were developed for lithium-ion batteries. The electrodes included copper nanoparticles and doped fluorine. For the acicular nanocrystals, charge-discharge reactions progressed at 1.8 V over 100 cycles at 100 and 10 µA. A 15-mmdiameter battery containing acicular nanocrystals showed capacity, coulomb efficiency, and specific capacity, respectively of 20 µAh, 98%, and ~242 mAh/g at 100 µA and 40 µAh, 99%, and 484 mAh/g at 10 µA. The TiO2/SnO2 electrode consisted of a SnO2 sheet-assembled structure with surface layers of anatase TiO2. The TiO2/SnO2 battery operated at 1.3 (100 cycles) and 1.2 (50 cycles) V at 100 and 10 µA, respectively; its capacity, coulomb efficiency, and specific capacity, respectively were 50 µAh, 98%, and 161 mAh/g at 100 µA and 200 µAh, 97-98%, and 643 mAh/g at 10 µA. The characteristic microstructure, chemical composition, and crystal faces of both materials contributed to battery performance.

Synthesis, Characterization, Photocatalytic and Sensing Properties of Mn-Doped ZnO Nanoparticles.

In this paper, Mn-doped ZnO nanoparticles (0 to 10 mol% Mn) were synthesized by facile low-temperature aqueous solution process and characterized by several techniques such as field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-visible and Raman-scattering spectroscopy. The SEM studies confirmed that the synthesized nanoparticles are grown in high density and increase in Mn content was found to have a significant effect on the morphologies of ZnO nanoparticles. The XPS studies established the structural variation of the samples with the change in dopant concentration and its oxidation state. XPS probe the existence of impurity phases in the as-synthesized samples. The results indicate further that hexagonal wurtzite structure of ZnO undergoes distortion with the increase in the dopant concentration. Also, with the increase in the dopant concentration, the blue-shift was observed in the UV-vis. spectra. Photocatalytic and chemicals sensing performances of these nanomaterials have been investigated by subjecting them to photocatalytic degradation of methyl orange (MO) under UV irradiation and for the detection of picric acid (PA) in aqueous solutions. Mn doped ZnO samples were found to be more efficient in catalyzing the MO degradation than pure ZnO. 5 mol% Mn doped ZnO nanomaterials were studied to use as fluorescence sensor for the detection of PA and the observed detection limit was found to be 2.5 µM.

Self-assembly patterning of ultrafine zirconia nanocrystal films fabricated on chemically patterned templates.

Ultra-thin zirconia (ZrO2) nanocrystal films were fabricated by using a controlled dip-coating process. ZrO2 nanocrystals possess a cubic crystalline phase and large surface-to-volume area. The film composite with only several layers of nanocrystals were obtained by controlling the withdrawal speed and mass concentration of the colloidal solution. The optical properties of ZrO2 nanocrystal films were accessed by UV-vis spectroscopy, which indicated the dense and uniform structure of the nanocrystal films. The high reflection index suggested that the films could be used in the reflection coating industry. Furthermore, a micro-pattern of self-assembled monolayers of silane molecular was used as a chemical mold for selective deposition of ZrO2 nanocrystals. As a result, a self-assembly patterning of ZrO2 nanocrystals with a neat edge was fabricated on silicon substrate. The low-cost fabricating method is compatible with conventional very-large-scale integration processes and can be extended to other kinds of nanocrystals.