Oxygen Vacancy Promoted O2 Activation over Mesoporous Ni-Co Mixed Oxides for Aromatic Hydrocarbon Oxidation.

Whether the oxygen vacancies of heterogeneous catalysts improve their catalytic activity or not has recently been the topic of intense debate in the oxidation of hydrocarbons. We designed an effective strategy to construct mesoporous Ni-Co mixed oxides via a ligand-assisted self-assembly approach. The surface oxygen vacancy concentrations of the mesoporous Ni-Co mixed oxide catalysts were regulated by changing the doping amount of Ni or the reduction method, and the relationship between oxygen vacancies and catalytic activity was studied. Controlled experiments and DFT calculations revealed that oxygen molecules were more favorably adsorbed and activated on oxygen vacancies to form active oxygen species. Increasing the oxygen vacancy concentration within a certain range can effectively enrich the active oxygen species, therefore improving the oxidation rate of ethylbenzene. The optimized mCo3O4-0.1NiO catalyst exhibited a remarkable catalytic activity for the solvent-free oxidation of ethylbenzene to acetophenone, typically including 68.0% conversion and 95.4% selectivity (20 mg mCo3O4-0.1NiO, 10 mL ethylbenzene, and 0.6 MPa O2).

Thermal Energy Transfer between Helium Gas and Graphene Surface According to Molecular Dynamics Simulations and the Monte Carlo Method.

The scattering of gases on solid surfaces plays a vital role in many advanced technologies. In this study, the scattering behavior of helium on graphene surfaces was investigated, including the thermal accommodation coefficient (TAC), outgoing zenith angle of helium, bounce number, and interaction time. First, we performed molecular dynamics simulations to describe the incident angle-resolved behaviors, and showed that the scattering is highly dependent on the zenith angle of incident helium but insensitive to the azimuthal angle. The contribution of the normal velocity component of the incident helium dominated the energy transfer. The nonlinear relationship of the parameters to the zenith angle of the incident helium could be suppressed by increasing the graphene temperature or decreasing the speed of the incident helium. Subsequently, the scattering performance considering all gas molecules in the hemispherical space was evaluated using the Monte Carlo method with angle-resolved results. The result showed that the TAC, its nominal components, and the zenith angle of the scattered helium increased with higher speeds of incident helium and lower temperatures of graphene. This study should provide a fundamental understanding of energy transfer between gas and two-dimensional materials and guidelines to tune the scattering behavior between them.

Thermal diffusivity measurement of microscale slabs by rear-surface detection thermoreflectance technique.

A new approach to measure the cross-plane thermal diffusivity of a microscale slab sample, which can be fabricated by the focused ion beam and attached to a substrate, is proposed. An intensity-modulated pump laser is applied to heat the front surface of the sample uniformly, and the thermoreflectance signal is observed at the rear surface to evaluate thermal wave transport in the material. The thermal diffusivity can be obtained by fitting the phase lags of the experimental data with a theoretical model. The model was developed for the sample with thin-film coatings and heat transfer to the substrate. Although the absorbed heat can cause a significant DC temperature increase in the microscale sample, a thin-film coating with high thermal conductivity can effectively reduce the DC temperature increase within low thermal conductivity samples. To validate the method, we conducted measurements of a fused silica sample of 2.16 µm thickness, coated with 95 nm Ti film on the front surface and 120 nm Au film on the rear surface. The measured thermal diffusivity is in good agreement with the literature value. The uncertainty analysis shows that the measurement uncertainty is within 6%. This proposed approach, designed for microscale samples, offers a unique option for thermal property measurements of special materials, such as irradiated nuclear fuel or other irradiated materials, to enable microscale property determination while minimizing sample radioactivity.

Improved Testing and Design of Intubation Boxes During the COVID-19 Pandemic.

STUDY OBJECTIVE: Throughout the coronavirus disease 2019 pandemic, many emergency departments have been using passive protective enclosures ("intubation boxes") during intubation. The effectiveness of these enclosures remains uncertain. We sought to quantify their ability to contain aerosols using industry standard test protocols. METHODS: We tested a commercially available passive protective enclosure representing the most common design and compared this with a modified enclosure that incorporated a vacuum system for active air filtration during simulated intubations and negative-pressure isolation. We evaluated the enclosures by using the same 3 tests air filtration experts use to certify class I biosafety cabinets: visual smoke pattern analysis using neutrally buoyant smoke, aerosol leak testing using a test aerosol that mimics the size of virus-containing particulates, and air velocity measurements. RESULTS: Qualitative evaluation revealed smoke escaping from all passive enclosure openings. Aerosol leak testing demonstrated elevated particle concentrations outside the enclosure during simulated intubations. In contrast, vacuum-filter-equipped enclosures fully contained the visible smoke and test aerosol to standards consistent with class I biosafety cabinet certification. CONCLUSION: Passive enclosures for intubation failed to contain aerosols, but the addition of a vacuum and active air filtration reduced aerosol spread during simulated intubation and patient isolation.

Electronic contribution in heat transfer at metal-semiconductor and metal silicide-semiconductor interfaces.

This work presents a direct measurement of the Kapitza thermal boundary resistance Rth, between platinum-silicon and platinum silicide-silicon interfaces. Experimental measurements were made using a frequency domain photothermal radiometry set up at room temperature. The studied samples consist of ≈50 nm of platinum and ≈110 nm of platinum silicide on silicon substrates with different doping levels. The substrate thermal diffusivity was found via a hybrid frequency/spatial domain thermoreflectance set up. The films and the interfaces between the two layers were characterized using scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. X-ray diffraction was also used to determine the atomic and molecular structures of the samples. The results display an effect of the annealing process on the Kapitza resistance and on the thermal diffusivities of the coatings, related to material and interface changes. The influence of the substrate doping levels on the Kapitza resistance is studied to check the correlation between the Schottky barrier and the interfacial heat conduction. It is suggested that the presence of charge carriers in silicon may create new channels for heat conduction at the interface, with an efficiency depending on the difference between the metal's and substrate's work functions.

Thermal diffusivity measurement of focused-ion-beam fabricated sample using photothermal reflectance technique.

Focused-Ion-Beam (FIB) can lift-off micrometer-sized samples from bulk materials for structural characterization and property measurement. The ability to determine thermophysical properties of such samples offers unique insight into the local microstructure-property relationship. A photothermal reflectance technique is developed to measure the thermal diffusivity of FIB-fabricated, micrometer-sized samples in this study. An analytic model is established to guide the experimental design and data analysis for the limited sample size and thickness. The thermal diffusivity of the sample can be extracted from a series of spatial-scan measurements at several modulated heating frequencies. To demonstrate the viability of the technique, a FIB-fabricated SiC plate with the size of 42 µm × 31 µm × 8 µm was used to represent high conductivity materials, which pose more challenges for the technique. The result compares favorably with literature values of SiC. The measurement uncertainty is quantified and possible experimental error sources are discussed. This technique is specially promising for thermal property measurements on nuclear fuels and materials.

Investigation of synthetic spider silk crystallinity and alignment via electrothermal, pyroelectric, literature XRD, and tensile techniques.

The processes used to create synthetic spider silk greatly affect the properties of the produced fibers. This paper investigates the effect of process variations during artificial spinning on the thermal and mechanical properties of the produced silk. Property values are also compared to the ones of the natural dragline silk of the N. clavipes spider, and to unprocessed (as-spun) synthetic silk. Structural characterization by scanning pyroelectric microscopy is employed to provide insight into the axial orientation of the crystalline regions of the fiber and is supported by XRD data. The results show that stretching and passage through liquid baths induce crystal formation and axial alignment in synthetic fibers, but with different structural organization than natural silks. Furthermore, an increase in thermal diffusivity and elastic modulus is observed with decreasing fiber diameter, trending towards properties of natural fiber. This effect seems to be related to silk fibers being subjected to a radial gradient during production.

Effects of the amino acid sequence on thermal conduction through ß-sheet crystals of natural silk protein.

Recent experiments have discovered very different thermal conductivities between the spider silk and the silkworm silk. Decoding the molecular mechanisms underpinning the distinct thermal properties may guide the rational design of synthetic silk materials and other biomaterials for multifunctionality and tunable properties. However, such an understanding is lacking, mainly due to the complex structure and phonon physics associated with the silk materials. Here, using non-equilibrium molecular dynamics, we demonstrate that the amino acid sequence plays a key role in the thermal conduction process through ß-sheets, essential building blocks of natural silks and a variety of other biomaterials. Three representative ß-sheet types, i.e. poly-A, poly-(GA), and poly-G, are shown to have distinct structural features and phonon dynamics leading to different thermal conductivities. A fundamental understanding of the sequence effects may stimulate the design and engineering of polymers and biopolymers for desired thermal properties.

The study of frequency-scan photothermal reflectance technique for thermal diffusivity measurement.

A frequency scan photothermal reflectance technique to measure thermal diffusivity of bulk samples is studied in this manuscript. Similar to general photothermal reflectance methods, an intensity-modulated heating laser and a constant intensity probe laser are used to determine the surface temperature response under sinusoidal heating. The approach involves fixing the distance between the heating and probe laser spots, recording the phase lag of reflected probe laser intensity with respect to the heating laser frequency modulation, and extracting thermal diffusivity using the phase lag-(frequency)(1/2) relation. The experimental validation is performed on three samples (SiO2, CaF2, and Ge), which have a wide range of thermal diffusivities. The measured thermal diffusivity values agree closely with the literature values. Compared to the commonly used spatial scan method, the experimental setup and operation of the frequency scan method are simplified, and the uncertainty level is equal to or smaller than that of the spatial scan method.

Hydrogen bonding-assisted thermal conduction in ß-sheet crystals of spider silk protein.

Using atomistic simulations, we demonstrate that ß-sheet, an essential component of spider silk protein, has a thermal conductivity 1-2 orders of magnitude higher than that of some other protein structures reported in the literature. In contrast to several other nanostructured materials of similar bundled/layered structures (e.g. few-layer graphene and bundled carbon nanotubes), the ß-sheet is found to uniquely feature enhanced thermal conductivity with an increased number of constituting units, i.e. ß-strands. Phonon analysis identifies inter-ß-strand hydrogen bonding as the main contributor to the intriguing phenomenon, which prominently influences the state of phonons in both low- and high-frequency regimes. A thermal resistance model further verifies the critical role of hydrogen bonding in thermal conduction through ß-sheet structures.

Effect of electrical double layer on electric conductivity and pressure drop in a pressure-driven microchannel flow.

The effect of an electrical double layer (EDL) on microchannel flow has been studied widely, and a constant bulk electric conductivity is often used in calculations of flow rate or pressure drop. In our experimental study of pressure-driven micropipette flows, the pipette diameter is on the same order of magnitude as the Debye length. The overlapping EDL resulted in a much higher electric conductivity, lower streaming potential, and lower electroviscous effect. To elucidate the effect of overlapping EDL, this paper developed a simple model for water flow without salts or dissolved gases (such as CO(2)) inside a two-dimensional microchannel. The governing equations for the flow, the Poisson, and Nernst equations for the electric potential and ion concentrations and the charge continuity equation were solved. The effects of overlapping EDL on the electric conductivity, velocity distribution, and overall pressure drop in the microchannel were quantified. The results showed that the average electric conductivity of electrolyte inside the channel increased significantly as the EDL overlaps. With the modified mean electric conductivity, the pressure drop for the pressure-driven flow was smaller than that without the influence of the EDL on conductivity. The results of this study provide a physical explanation for the observed decrease in electroviscous effect for microchannels when the EDL layers from opposing walls overlap.

A novel capacitance sensor for fireside corrosion measurement.

Fireside corrosion in coal-fired power plants is a leading mechanism for boiler tube failures. Online monitoring of fireside corrosion can provide timely data to plant operators for mitigation implementation. This paper presents a novel sensor concept for measuring metal loss based on electrical capacitance. Laboratory-scale experiments demonstrated the feasibility of design, fabrication, and operation of the sensor. The fabrication of the prototype sensor involved sputtering deposition of a thin metal coating with varying thickness on a ceramic substrate. Corrosion metal loss resulted in a proportional decrease in electrical capacitance of the sensor. Laboratory experiments using a muffle furnace with an oxidation environment demonstrated that low carbon steel coatings on ceramic substrate survived cyclic temperatures over 500 degrees C. Measured corrosion rates of sputtered coating in air had an Arrhenius exponential dependence on temperature, with metal thickness loss ranging from 2.0 nm/h at 200 degrees C to 2.0 microm/h at 400 degrees C. Uncertainty analysis indicated that the overall measurement uncertainty was within 4%. The experimental system showed high signal-to-noise ratio, and the sensor could measure submicrometer metal thickness changes. The laboratory experiments demonstrated that the sensor concept and measurement system are capable of short term, online monitoring of metal loss, indicating the potential for the sensor to be used for fireside corrosion monitoring and other metal loss measurement.

Adsorption of arsenic(V) onto fly ash: a speciation-based approach.

Arsenic (As) poses a significant water quality problem and challenge for the environmental engineers and scientists in the world. The large volume of coal fly ash produced around the world is a potentially significant anthropogenic source of arsenic. Currently the leaching behavior of arsenic from fly ash is not well understood. Batch methods were used in this study to investigate arsenic leaching using a raw ash, and arsenic adsorption using a clean, washed ash. Experimental results indicated that pH had a significant effect on arsenic leaching or adsorption. Between pH 3 and 7, less arsenic was in the dissolved phase. When pH was less than 3 or greater than 7, increasing amounts of arsenic were leached or desorbed from fly ash. The leaching and adsorption behavior of arsenic was interpreted with the speciation of surface sites and arsenic. In a new approach, a speciation-based model was developed to quantify the arsenic adsorption as a function of pH and surface acidity parameters. This work is important in offering insight into the leaching mechanism of arsenic from coal fly ash, and providing a robust model based upon specific, measurable parameters to quantify arsenic adsorption by other solid media in addition to fly ash.

The leaching characteristics of selenium from coal fly ashes.

The leaching characteristics of selenium from several bituminous and subbituminous coal fly ashes under different pH conditions were investigated using batch methods. Results indicated that pH had a significant effect on selenium leaching from bituminous coal ash. The minimum selenium leaching occurred in the pH range between 3 and 4, while the maximum selenium leaching occurred at pH 12. The release of selenium from subbituminous coal ashes was very low for the entire experimental pH range, possibly due to the high content of calcium which can form hydration or precipitation products as a sink for selenium. The adsorption results for different selenium species indicated that Se(VI) was hardly adsorbable on either bituminous coal ashes or subbituminous coal ashes at any pH. However, Se(IV) was highly adsorbed by bituminous coal ashes under acidic pH conditions and was mostly removed by subbituminous coal ashes across the entire pH range. This result suggests that the majority of selenium released from the tested fly ashes was Se(IV). A speciation-based model was developed to simulate the adsorption of Se(IV) on bituminous coal fly ash, and the pH-independent adsorption constants of HSeO3* and SeO3 2* were determined. The modeling approach is useful for understanding and predicting the release process of selenium from fly ash.

The role of ammonia on mercury leaching from coal fly ash.

The Federal Clean Air Interstate Rule issued in March 2005 will result in many power plants employing ammonia-based technologies to control NO(x) emission. The Clean Air Mercury Rule, issued at the same time, will encourage many power plants to use various technologies to remove mercury from flue gas, generating fly ashes that contain elevated concentrations of mercury. Ammonia forms relatively strong complexes with mercury compared to most other cationic elements and, therefore, may change the leaching characteristics of mercury. Understanding the impact of ammonia on the leaching of mercury from fly ash is critical in predicting the potential environmental impact of future fly ash. Batch methods were used to investigate the ammonia impact on mercury leaching from fly ash under different pH conditions. The results indicated that mercury leaching without external ammonia addition is not significant. However, ammonia addition increased mercury leaching in the alkaline pH range, due to the formation of less adsorbable mercury-ammonia complexes. Washed ash released more mercury than the raw ash if the ammonia concentration is the same, mainly due to the dissolution of some ash components during washing which exposed more mercury on ash surface. Mercury adsorption data indicated that more than 90% of available mercury was adsorbed by fly ash even in the presence of 1000 mg l(-1) ammonia addition.

Quantifying the availability and the stability of trace cationic elements in fly ash.

For adsorption-desorption controlled leaching processes, the total leachable mass and the adsorption constant are parameters representing the availability and the stability of trace elements in solid media. With these parameters, one can predict the leaching behavior of trace elements from solids under various pH and solid-to-liquid ratio conditions. An approach was developed in this paper to determine these parameters for model elements Cu(II), Cd(II), and Ni(II) in fly ash. This approach consists of a batch equilibrium titration, a batch equilibrium leaching with and without target element addition, and mathematical modeling. Results indicated that the adsorption constant of a trace element can be determined by modeling the adsorption ratio of the added element to the system as a function of pH. Results also indicated that the trace element originally present in fly ash had similar adsorption-desorption behavior as that added externally. By modeling the batch leaching data with and without external element addition, the total leachable mass and adsorption constant of the target element can be determined simultaneously. The total leachable mass is in agreement with experimental data from 50mM EDTA extraction.

Impacts of pH and ammonia on the leaching of Cu(II) and Cd(II) from coal fly ash.

Many coal-fired power plants are implementing ammonia-based technologies to reduce NO(x) emissions. Excess ammonia in the flue gas often deposits on the coal fly ash. Ammonia can form complexes with many heavy metals and change the leaching characteristics of these metals. This research tends to develop a fundamental understanding of the ammonia impact on the leaching of some heavy metals, exemplified by Cu(II) and Cd(II), under different pH conditions. Batch results indicated that the adsorption is the main mechanism controlling Cu(II) and Cd(II) leaching, and high concentrations of ammonia (>5,000 mg/l) can increase the release of Cu(II) and Cd(II) in the alkaline pH range. Based on the chemical reactions among fly ash, ammonia, and heavy metal ion, a mathematical model was developed to quantify effects of pH and ammonia on metal adsorption. The adsorption constants (logK) of Cu(2+), Cu(OH)(+), Cu(OH)(2), and Cu(NH(3))(m)(2+) for the fly ash under investigation were respectively 6.0, 7.7, 9.6, and 2.9. For Cd(II), these constants were respectively 4.3, 6.9, 8.8, and 2.6. Metal speciation calculations indicated that the formation of less adsorbable metal-ammonia complexes decreased metal adsorption, therefore enhanced metal leaching.

Characterizing the metal adsorption capability of a class F coal fly ash.

The surface physical-chemical characteristics of a class F coal fly ash were studied in an effort to establish a quantitative understanding of metal adsorption. The ash surface acidity (acid site density and acidity constant), surface electrical characteristics, and adsorption constants for selected heavy metal ions were determined using a batch titration method, an electrophoretic method, and a batch equilibrium metal adsorption method, respectively. Results showed that the fly ash has a pHzpc value of 6.2. Its surface contains three types of acid sites. The densities of these acid sites are 2.1 x 10(-4), 1.8 x 10(-5), and 5.3 x 10(-5) mol/g, with acidity constants (pK(H)) of 2.7, 7.8, and 11.0, respectively. Metal adsorption results indicated that, of the three types of acid sites on surface, only the acid site with 7.8 pK(H) is responsible for metal adsorption. The adsorption constants (log K(S)) of Cd(II), Cr(III), Cu(II), Ni(II), and Pb(II) are 4.8, 7.0, 6.4, 4.9, and 8.6, respectively. Adsorption results indicated that the metal adsorption is in the linear range of the Langmuir isotherm if the total metal in the system is less than 10% of the total metal binding site. Results also showed that the presence of anionic metal ions does not affect the adsorption of cationic metal ions by the fly ash.