New Insights on Competitive Adsorption of NO/SO2 on TiO2 Anatase for Photocatalytic NO Oxidation.

Here, we investigate competitive adsorption and photocatalytic reaction over TiO2@SiO2: NO conversion efficiency decreases by 29.1%, and the adsorption capacity decreases from 0.125 to 0.095 mmol/g due to the influence of SO2. According to identification and comparative analysis of the IR signal, SO2 has little effect on the NO conversion route and intermediates (adsorbed NO → nitrite → nitrate), but accelerates the deactivation of catalysts. The electronic interaction scheme from density functional theory (DFT) confirms that surface hydroxyls create an unsaturated coordination of neighboring Ti or O atoms, which is favorable for NO/SO2 adsorption on anatase (101). In addition, the lone pair electrons of N or S atoms prefer to be delocalized and form covalent bonds with active surface-O on the (101) facet with terminal hydroxyls. However, preadsorbed SO2 could offset the increase of hydroxyls and strongly inhibit NO adsorption, which is consistent with the result performance evaluation. A possible reaction mechanism characterized by oxygen vacancies and·O2- is proposed, while the essential reason of catalyst deactivation and regeneration is theoretically analyzed based on the experimental and DFT calculation.

Heart-rate tuned comb filters for processing photoplethysmogram (PPG) signals in pulse oximetry.

Calculation of peripheral capillary oxygen saturation [Formula: see text] levels in humans is often made with a pulse oximeter, using photoplethysmography (PPG) waveforms. However, measurements of PPG waveforms are susceptible to motion noise due to subject and sensor movements. In this study, we compare two [Formula: see text]-level calculation techniques, and measure the effect of pre-filtering by a heart-rate tuned comb peak filter on their performance. These techniques are: (1) "Red over Infrared," calculating the ratios of AC and DC components of the red and infrared PPG signals,[Formula: see text], followed by the use of a calibration curve to determine the [Formula: see text] level Webster (in: Design of pulse oximeters, CRC Press, Boca Raton, 1997); and (2) a motion-resistant algorithm which uses the Discrete Saturation Transform (DST) (Goldman in J Clin Monit Comput 16:475-83, 2000). The DST algorithm isolates individual "saturation components" in the optical pathway, which allows separation of components corresponding to the [Formula: see text] level from components corresponding to noise and interference, including motion artifacts. The comparison we provide here (employing the two techniques with and without pre-filtering) addresses two aspects: (1) accuracy of the [Formula: see text] calculations; and (2) computational complexity. We used both synthetic data and experimental data collected from human subjects. The human subjects were tested at rest and while exercising; while exercising, their measurements were subject to the impacts of motion. Our main conclusion is that if an uninterrupted high-quality heart rate measurement is available, then the "Red over Infrared" approach preceded by a heart-rate tuned comb filter provides the preferred trade-off between [Formula: see text]-level accuracy and computational complexity. A modest improvement in [Formula: see text] estimate accuracy at very low SNR environments may be achieved by switching to the pre-filtered DST-based algorithm (up to 6% improvement in [Formula: see text] level accuracy at -10 dB over unfiltered DST algorithm and the filtered "Red over Infrared" approach). However, this improvement comes at a significant computational cost.

Cobalt Nanoparticles and Atomic Sites in Nitrogen-Doped Carbon Frameworks for Highly Sensitive Sensing of Hydrogen Peroxide.

In situ monitoring of hydrogen peroxide (H2 O2 ) during its production process is needed. Here, an electrochemical H2 O2 sensor with a wide linear current response range (concentration: 5 × 10-8 to 5 × 10-2 m), a low detection limit (32.4 × 10-9 m), and a high sensitivity (568.47 µA mm-1 cm-2 ) is developed. The electrocatalyst of the sensor consists of cobalt nanoparticles and atomic Co-Nx moieties anchored on nitrogen doped carbon nanotube arrays (Co-N/CNT), which is obtained through the pyrolysis of the sandwich-like urea@ZIF-67 complex. More cobalt nanoparticles and atomic Co-Nx as active sites are exposed during pyrolysis, contributing to higher electrocatalytic activity. Moreover, a portable screen-printed electrode sensor is constructed and demonstrated for rapidly detecting (cost ≈40 s) H2 O2 produced in microbial fuel cells with only 50 µL solution. Both the synthesis strategy and sensor design can be applied to other energy and environmental fields.

Performance and Mechanism of Photocatalytic Toluene Degradation and Catalyst Regeneration by Thermal/UV Treatment.

This work presents a new strategy for industrial flue gas purification with TiO2-based photocatalysis technology, which could be achieved by a novel dual-stage circulating photocatalytic reactor. A lab-scale fixed bed reactor is utilized to investigate the performance of photocatalytic toluene degradation and inactive catalyst regeneration by thermal/UV treatment. The relationships between operational conditions and toluene oxidation are surveyed and discussed in detail. The results show that the intermediates could be further removed and decomposed by introducing UV radiation, compared with heat treatment alone. To reveal the photocatalytic mechanism and identify the accumulated intermediates over anatase TiO2, the adsorbed toluene and aromatic intermediates are identified by XPS, in situ DRIFTS, and on-line MS. The aromatic ring and other covalent bonds (C═O, C-O, and O-H) are detected during photocatalytic oxidation. The reaction pathway involving hydrogen abstraction is referred as the dominant pathway for toluene degradation, and ring opening via ·OH radicals is crucial to make aromatic intermediates change into CO2 and H2O. The results indicate that benzoic acid and benzaldehyde are the main accumulation because of their high reaction energy. A possible reaction mechanism is proposed for toluene oxidation, deactivation, and regeneration of catalysts, which has a significant value for guiding the practical applications.

Roles of Oxygen Vacancies in the Bulk and Surface of CeO2 for Toluene Catalytic Combustion.

Catalytic combustion technology is one of the effective methods to remove VOCs such as toluene from industrial emissions. The decomposition of an aromatic ring via catalyst oxygen vacancies is usually the rate-determining step of toluene oxidation into CO2. Series of CeO2 probe models were synthesized with different ratios of surface-to-bulk oxygen vacancies. Besides the devotion of the surface vacancies, a part of the bulk vacancies promotes the redox property of CeO2 in toluene catalytic combustion: surface vacancies tend to adsorb and activate gaseous O2 to form adsorbed oxygen species, whereas bulk vacancies improve the mobility and activity of lattice oxygen species via their transmission effect. Adsorbed oxygen mainly participates in the chemical adsorption and partial oxidation of toluene (mostly to phenolate). With the elevated temperatures, lattice oxygen of the catalysts facilitates the decomposition of aromatic rings and further improves the oxidation of toluene to CO2.

New Insight into SO2 Poisoning and Regeneration of CeO2-WO3/TiO2 and V2O5-WO3/TiO2 Catalysts for Low-Temperature NH3-SCR.

In this study, the poisoning effects of SO2 on the V2O5-WO3/TiO2 (1%VWTi) and CeO2-WO3/TiO2 (5%CeWTi) selective catalytic reduction (SCR) catalysts were investigated in the presence of steam, and also the regeneration of deactivated catalysts was studied. After pretreating the catalysts in a flow of NH3 + SO2 + H2O + O2 at 200 °C for 24 h, it was observed that the low-temperature SCR (LT-SCR) activity decreased significantly over the 1%VWTi and 5%CeWTi catalysts. For 1%VWTi, NH4HSO4 (ABS) was the main product detected after the poisoning process. Both of NH4HSO4 and cerium sulfate species were formed on the poisoned 5%CeWTi catalyst, indicating that SO2 reacted with Ce3+/Ce4+, even in the presence of high concentration of NH3. The decrease of BET specific surface area, NO x adsorption capacity, the ratio of chemisorbed oxygen, and reducibility were responsible for the irreversible deactivation of the poisoned 5%CeWTi catalyst. Meanwhile, the LT-SCR activity could be recovered over the poisoned 1%VWTi after regeneration at 400 °C, but not for the 5%CeWTi catalyst. For industrial application, it is suggested that the regeneration process can be utilized for 1%VWTi catalysts after a period of time after NH4HSO4 accumulated on the catalysts.

Scalable water splitting on particulate photocatalyst sheets with a solar-to-hydrogen energy conversion efficiency exceeding 1.

Photocatalytic water splitting using particulate semiconductors is a potentially scalable and economically feasible technology for converting solar energy into hydrogen. Z-scheme systems based on two-step photoexcitation of a hydrogen evolution photocatalyst (HEP) and an oxygen evolution photocatalyst (OEP) are suited to harvesting of sunlight because semiconductors with either water reduction or oxidation activity can be applied to the water splitting reaction. However, it is challenging to achieve efficient transfer of electrons between HEP and OEP particles. Here, we present photocatalyst sheets based on La- and Rh-codoped SrTiO3 (SrTiO3:La, Rh; ref. ) and Mo-doped BiVO4 (BiVO4:Mo) powders embedded into a gold (Au) layer. Enhancement of the electron relay by annealing and suppression of undesirable reactions through surface modification allow pure water (pH 6.8) splitting with a solar-to-hydrogen energy conversion efficiency of 1.1% and an apparent quantum yield of over 30% at 419 nm. The photocatalyst sheet design enables efficient and scalable water splitting using particulate semiconductors.

Impacts of Pb and SO2 Poisoning on CeO2-WO3/TiO2-SiO2 SCR Catalyst.

A CeO2-WO3/TiO2-SiO2 catalyst was employed to investigate the poisoning mechanisms of Pb and SO2 during selective catalytic reduction (SCR). The introduction of Pb and SO2 suppressed the catalytic performance by decreasing the numbers of surface acid and redox sites. Specifically, Pb preferentially bonded with amorphous WO3 species rather than with CeO2, decreasing the numbers of both Lewis and Brønsted acid sites but exerting less influence on the reducibility. SO2 preferentially bonded with CeO2 as sulfate species rather than with WO3, leading to a significant decrease in reducibility and the loss of surface active oxygen groups. Although SO2 provided additional Brønsted acid sites via the interaction of SO42- and CeO2, it had little positive effect on catalytic activity. A synergistic deactivation effect of Pb and SO42- on CeO2 was found. Pb covered portions of the weakly bonded catalyst sites poisoned by SO42-, which increased the decomposition temperature of the sulfate species on the catalyst.

Design strategies for P-containing fuels adaptable CeO2-MoO3 catalysts for DeNO(x): significance of phosphorus resistance and N2 selectivity.

Phosphorus compounds from flue gas have a significant deactivation effect on selective catalytic reduction (SCR) DeNOx catalysts. In this work, the effects of phosphorus over three catalysts (CeO2, CeO2-MoO3, and V2O5-MoO3/TiO2) for NH3-SCR were studied, and characterizations were performed aiming at a better understanding of the behavior and poisoning mechanism of phosphorus over SCR catalysts. The CeO2-MoO3 catalyst showed much better catalytic behavior with respect to resistance to phosphorus and N2 selectivity compared with V2O5-MoO3/TiO2 catalyst. With addition of 1.3 wt % P, the SCR activity of V2O5-MoO3/TiO2 decreased dramatically at low temperature due to the impairment of redox property for NO oxidation; meanwhile, the activity over CeO2 and CeO2-MoO3 catalysts was improved. The superior NO oxidation activity contributes to the activity over P-poisoned CeO2 catalyst. The increased surface area and abundant acidity sites contribute to excellent activity over CeO2-MoO3 catalyst. As the content of P increased to 3.9 wt %, the redox cycle over CeO2 catalyst (2CeO2 ↔ Ce2O3 + O*) was destroyed as phosphate accumulated, leading to the decline of SCR activity; whereas, more than 80% NOx conversion and superior N2 selectivity were obtained over CeO2-MoO3 at T > 300 °C. The effect of phosphorus was correlated with the redox properties of SCR catalyst for NH3 and NO oxidation. A spillover effect that phosphate transfers from Ce to Mo in calcination was proposed.

Improvement of activity and SO2 tolerance of Sn-modified MnOx-CeO2 catalysts for NH3-SCR at low temperatures.

The performances of fresh and sulfated MnOx-CeO2 catalysts for selective catalytic reduction of NOx by NH3 (NH3-SCR) in a low-temperature range (T < 300 °C) were investigated. Characterization of these catalysts aimed at elucidating the role of additive and the effect of sulfation. The catalyst having a Sn:Mn:Ce = 1:4:5 molar ratio showed the widest SCR activity improvement with near 100% NOx conversion at 110-230 °C. Raman and X-ray photoelectron spectroscopy (XPS) indicated that Sn modification significantly increases the concentration of oxygen vacancies that may facilitate NO oxidation to NO2. NH3-TPD characterization showed that the low-temperature NH3-SCR activity is well correlated with surface acidity for NH3 adsorption, which is also enhanced by Sn modification. Furthermore, as compared to MnOx-CeO2, Sn-modified MnOx-CeO2 showed remarkably improved tolerance to SO2 sulfation and to the combined effect of SO2 and H2O. In the presence of SO2 and H2O, the Sn-modified MnOx-CeO2 catalyst gave 62% and 94% NOx conversions as compared to 18% and 56% over MnOx-CeO2 at temperatures of 110 and 220 °C, respectively. Sulfation of SnO2-modified MnOx-CeO2 may form Ce(III) sulfate that could enhance the Lewis acidity and improve NO oxidation to NO2 during NH3-SCR at T > 200 °C.

Interaction between Nickel Oxide and Support Promotes Selective Catalytic Reduction of NOx with C3 H6.

Selective catalytic reduction of nitrogen oxides (NOx ) with C3 H6 (C3 H6 -SCR) was investigated over NiO catalysts supported on different metal-oxides. A NiAlOx mixed oxide phase was formed over NiO/γ-Al2 O3 catalyst, inducing an immediate interaction between NiOx and AlOx species. Such interaction resulted in a charge transfer from Ni to Al site and the formation of Ni species in high oxidation state. In comparison to other NiO-loaded catalysts, NiO/γ-Al2 O3 catalyst exhibited the highest NOx conversion at temperature higher than 450 °C, but a poor C3 H6 oxidation activity due to the decreased nucleophilicity for surface oxygen species. By temperature-programed NO oxidation, it is indicated that nitrate species were rapidly formed and stably maintained at high temperature over NiO/γ-Al2 O3 catalyst. In situ transient reactions further verified the Langmuir-Hinshelwood mechanism for C3 H6 -SCR, where both gaseous NO and C3 H6 were adsorbed and activated on catalyst surface and reacted to generate N2 . Due to the strong metal-support interaction over NiO/γ-Al2 O3 catalyst, both nitrate and Cx Hy Oz intermediates were well preserved to attain high C3 H6 -SCR activity.

Adaptive Doppler analysis for robust handheld optical coherence elastography.

Optical coherence tomography (OCT) allows structural and functional imaging of biological tissue with high resolution and high speed. Optical coherence elastography (OCE), a functional extension of OCT, has been used to perform mechanical characterization. A handheld fiber-optic OCE instrument allows high sensitivity virtual palpation of tissue with great convenience and flexibility and can be used in a wide range of clinical settings. Moreover, fiber-optic OCE instruments can be integrated into a needle device to access deep tissue. However, the major challenge in the development of handheld OCE instrument is non-constant motion within the tissue. In this study, a simple and effective method for temporally and spatially adaptive Doppler analysis is investigated. The adaptive Doppler analysis method strategically chooses the time interval (δt) between signals involved in Doppler analysis, to track the motion speed v(z,t) that varies as time (t) and depth (z) in a deformed sample volume under manual compression. The aim is to use an optimal time interval to achieve a large yet artifact free Doppler phase shift for motion tracking.

Iron tungsten mixed composite as a robust oxygen evolution electrocatalyst.

We report a FeW mixed composite for oxygen evolution reaction with a low overpotential and a long-term stability. A structural transformation of FeW oxide occurs during the OER process. Theoretical calculation indicates that FeOx is the OER-active site and the neighboring WOx improves the *OH to *O conversion on the Fe site.

Temporally and spatially adaptive Doppler analysis for robust handheld optical coherence elastography.

Optical coherence elastography (OCE), a functional extension of optical coherence tomography (OCT), can be used to characterize the mechanical properties of biological tissue. A handheld fiber-optic OCE instrument will allow the clinician to conveniently interrogate the localized mechanical properties of in vivo tissue, leading to better informed clinical decision making. During handheld OCE characterization, the handheld probe is used to compress the sample and the displacement of the sample is quantified by analyzing the OCT signals acquired. However, the motion within the sample inevitably varies in time due to varying hand motion. Moreover, the motion speed depends on spatial location due to the sample deformation. Hence, there is a need for a robust motion tracking method for manual OCE measurement. In this study, we investigate a temporally and spatially adaptive Doppler analysis method. The method described here strategically chooses the time interval (δt) between signals involved in Doppler analysis to track the motion speed v(z,t) that varies temporally and spatially in a deformed sample volume under manual compression. Enabled by temporally and spatially adaptive Doppler analysis, we report the first demonstration of real-time manual OCE characterization of in vivo tissue to the best of our knowledge.

Thin film transfer for the fabrication of tantalum nitride photoelectrodes with controllable layered structures for water splitting.

The fabrication of semiconductor films on conductive substrates is vital to the production of high-performance electrodes for photoelectrochemical (PEC) water splitting. In this work, a thin film transfer method was developed to produce Ta3N5 film photoanodes for PEC water oxidation. Phase-pure Ta3N5 thin films were formed on inert Si substrates via magnetron sputtering of Ta films, followed by oxidation and subsequent nitridation in a flow of gaseous NH3. The resulting porous Ta3N5 films were uniformly transferred from the Si substrates using metallic layers that allowed ohmic contact at the Ta3N5 film/metal interface. This film transfer method enables control over the film thicknesses and layered structures of the Ta3N5 photoanodes. Following modification with a Co(OH) x layer acting as an oxygen-evolution catalyst, a Ta3N5 photoanode with a NbN x interlayer exhibited a photocurrent of 3.5 mA cm-2 at 1.23 V vs. RHE under a simulated AM 1.5G light, a value 1.7 times that generated by a photoanode without interlayers. The present film transfer method is potentially applicable to the development of semiconductor thin films for efficient PEC energy conversion.