Dehydration of fatty alcohols on zirconia supported tungstate catalysts
Zirconia supported tungstates catalyze octadecanol dehydration, an important step in the carbon preserving conversion of triglycerides to fuels.
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Zirconia supported tungstates catalyze octadecanol dehydration, an important step in the carbon preserving conversion of triglycerides to fuels.
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Atomic layer deposition (ALD) was used to prepare ZrO 2 films on the surface of the mesoporous silica, SBA-15, and to modify the surface of these films with WO 3 in order to form tungstated zirconia. Adsorption-desorption isotherms, pore size distributions, and transmission electron microscopy demonstrated that the ALD synthesis produced zirconia films that were conformal to the SBA-15 pores. DRIFT spectroscopy of pyridine adsorbed on the tungstated-zirconia SBA-15 samples showed adsorbed pyridinium ions, confirming the presence of Brønsted-acid sites on this material, consistent with what has been reported for bulk tungstated zirconia. Here, the ALD-synthesized, tungstated-zirconia SBA-15 was also shown to be active in the acid-catalyzed H-D exchange between toluene and D 2 O.
Zinc tungstate is a semiconductor known for its favorable photocatalytic, photoluminescence, and scintillation properties, coupled with its relatively low cost, reduced toxicity, and high stability in biological and catalytic environments. In particular, zinc tungstate evinces scintillation properties, namely the ability to emit visible light upon absorption of energetic radiation such as x rays, which has led to applications not only as radiation detectors but also for biomedical applications involving the delivery of optical light to deep tissue, such as photodynamic therapy and optogenetics. Here, we report on the synthesis of zinc tungstate nanorods generated via an optimized but facile method, which allows for synthetic control over the aspect ratio of the as-synthesized anisotropic motifs via rational variation of the solution pH. Additionally, we investigate the effect of aspect ratio on their resulting photoluminescent and radioluminescent properties. We further demonstrate the potential of these zinc tungstate nanorods for biomedical applications, such as photodynamic therapy for cancer treatment, by analyzing their toxicological profile within cell lines and neurons.
Utilization of crystal-chemical criteria has suggested three structure types in which alkali ions may be mobile: (1)hollandites K(x)Mg(x/2)Ti(8-x/2)O16 and K(x)Al(x)Ti(8-x)O16 for 1.6 less than or equal to x less than or equal to 2.0 tungstate K2W4013; and (3) sodium hexatitante Na2Ti6O13. Each is a tunnel structure. An electrical screening procedure, previously tested on beta-alumina, has indicated high K(+) ion mobility in the hollandites and in the tungstate, but not in the hexatitanate. Specimens were polycrystalline disks near 90 percent of theoretical density. The ac conductivity calculated from dielectric and capacitance measurements has been attributed to ion mobility. This ac conductivity was up to 0.01/ohm-cm for hollandites and about 0.0001/ohm-cm for the tungstate, with approximate activation energies of 21 to 25 and 16 kJ/mole (5 to 6 and 4 kcal/mole), respectively. Electronic conduction and chemical reactivity have eliminated the tungstate from further consideration. The hollandites have been considered worthy of further development and evaluation.
Lithiation-assisted epitaxy offers a flexible and robust approach for synthesizing high-quality Li-containing materials and interfaces with precise control. Here, in this study, we use lithium tungstate (Li x WO 3+x/2 , where x = 0 to 2) as a model system to investigate the intertwined effects of Li out-diffusion-induced compositional changes and surface-diffusion-induced morphological changes. By systematically varying synthesis and processing conditions, we uncover their impact on lithium tungstate film formation. Comprehensive characterizations, including X-ray diffraction, atomic force microscopy, X-ray photoemission spectroscopy and time-of-flight secondary ion mass spectrometry, reveal that low-temperature growth (< 300 °C) followed by high-temperature annealing yields continuous lithium tungstate films with significantly reduced surface roughness. In contrast, high-temperature deposition (≥ 300 °C) accelerates surface diffusion and Li out-diffusion, leading to island formation. Furthermore, in situ scanning transmission electron microscopy demonstrates the beam sensitivity of Li 2 WO 4 and reveals a phase transition from Li 2 WO 4 to LiWO 3.5 under prolonged electron beam exposure. These findings deepen our understanding of how to control composition and morphology of Li-containing films, providing valuable insights for the design and integration of energy materials.
Electromagnetic calorimeters based on PbWO4 scintillating crystals have a widespread applica- tion in experiments at different accelerator facilities such as CERN, FNAL, GSI, and Jefferson Lab. The unique properties of PbWO4 crystals, including a small radiation length and Molire radius, make them ideal for building high-granularity, radiation-hard detectors. This enables excellent spa- tial separation and energy resolution of reconstructed electromagnetic showers, making PbWO4 crystals the material of choice for numerous experiments. Lead tungstate calorimeters have been successfully used in several experiments at Jefferson Lab. Two large-scale detectors have been re- cently fabricated for future experiments : the Neutral Particle Spectrometer and the lead tungstate calorimeter of the GlueX detector. The future application of PbWO4 crystals in the ElectronIon Collider further highlights their ongoing importance in advancing experimental capabilities. In planning new experiments, the development of calorimeter instrumentation technologies becomes paramount. The integration of modern photodetectors, such as Silicon photomultipliers that are capable of operating in strong magnetic fields, and the implementation of streaming readout data acquisition systems, sophisticated shower reconstruction algorithms, and real-time data analysis are some examples of the continuously growing requirements of experimental setups. I will give an overview of the lead tungstate scintillating calorimeters and discuss some recent advancement in the calorimeter instrumentation.
A new electromagnetic calorimeter consisting of 140 lead tungstate (PbWO 4 ) scintillating crystals was constructed for the PrimEx- η experiment at Jefferson lab. The calorimeter was integrated into the data acquisition and trigger systems of the GlueX detector and used in the experiment to reconstruct Compton scattering events. The experiment started collecting data in the spring of 2019 and acquired about 30% of the required statistics. The calorimeter is a prototype for two PbWO 4 -based detectors: the Neutral Particle Spectrometer (NPS) and the lead tungstate insert of the Forward CALorimeter (FCAL) of the GlueX detector. The article presents the design and performance of the Compton calorimeter and gives a brief overview of the FCAL and NPS projects.
Hydrocracking is an insufficiently explored route for chemical recycling of plastics waste. Platinum tungstated zirconia (Pt-WZr) was used in a batch reactor at low temperatures of 250 °C and 30 bar H 2 pressure for 1-24 h reaction times using low-density polyethylene (LDPE, M w ~76 kDa). We find Pt-WZr is a bifunctional catalyst for LDPE hydrocracking leading to higher value branched fuel- and lubricant-ranged alkanes. Here we demonstrate that the catalyst metal-to-acid site molar ratio (MAB) shifts the product distribution to larger cracked products and increases the isomerization degree in the residual polymer. We propose a new adhesive isomerization mechanism between the metal and Brønsted acid sites in parallel with slow polymer chain cracking, caused by competitive adsorption of the polymer over the liquid products and stereochemical hindrance of methines. This study provides a blueprint on how to engineer effective catalysts for hydrocracking polyolefin plastic wastes using the MAB as a catalyst descriptor.
A new electromagnetic calorimeter composed of 1596 lead tungstate (PbWO 4 ) scintillating crystals has been constructed for the GlueX detector in Hall D at Jefferson Lab. The calorimeter is equipped with a light monitoring system that uses light-emitting diodes. The light monitoring system was fabricated, installed, and integrated into the GlueX trigger system. It was successfully operated during detector commissioning and data collection, providing monitoring of the detector response and verification of the calibration with a precision better than 1%. In conclusion, the paper describes the design, installation, and performance of the light monitoring system.
Here, we report on the installation and initial commissioning of a large-scale lead tungstate (PbWO4) scintillating crystal calorimeter developed for high-rate photon detection and precise energy measurement. The calorimeter comprises 1596 high-granularity, high-resolution scintillating crystals optimized for electromagnetic-shower detection over a wide energy range. Scintillation light from each crystal is read out by Hamamatsu R4125 photomultiplier tubes equipped with a custom voltage divider and front-end amplifier to ensure stable gain at high rates. All calorimeter modules were fabricated and characterized using a light-emitting diode–based optical test system prior to installation to verify uniformity and photodetector performance. After installation, the electromagnetic calorimeter was fully integrated into the experiment data acquisition and energy-based trigger systems. The optical response of the modules was equalized using the light-monitoring system, cosmic-ray muons, and photons from Compton-scattering events. Commissioning results demonstrate a reliably calibrated optical response and stable detector performance during the first run. These results validate the calorimeter design and commissioning methodology for large-scale scintillator-based photonic instrumentation.
Measurement of optical constants of magnesium oxide and calcium tungstate
Luminescence of calcium tungstate with lead in far ultraviolet region
Layered materials are particularly attractive for supercapacitors because of their unique physical, electrical and chemical properties. In this work, we demonstrate a facile and scalable electrochemical deposition method for wafer-scale synthesis of quasi-layered tungstate-doped polypyrrole films (named TALPy) with controllable thickness and size. The as-prepared TALPy film exhibits a high gravimetric density and excellent volumetric capacitance, exceeding many high-performing carbon- and polymer-based film electrodes. Based on combined results of ex-situ X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS), it is determined that TALPy stores charge through an ion intercalation process accompanied by change in oxidation states of polypyrrole backbone, which is referred as intercalation pseudocapacitance. All these results suggest the great promise of electrochemical deposition as a scalable and controllable bottom-up approach for synthesizing quasi-layered conductive organic-inorganic hybrid films for electrochemical energy storage applications with high volumetric performance.
The temperature stability window of mesoporous niobium tungstates is improved by 500 °C using pore backfilling strategies with carbon precursors.
A new electromagnetic calorimeter (ECAL) consisting of 1596 lead tungstate PbWO 4 scintillating crystals has been fabricated and installed in the experimental Hall D at Jefferson Lab (JLab). The highgranularity, high-resolution calorimeter is required by the JLab Eta Factory experiment, whose main physics goal is to study rare decays of eta mesons. The ECAL replaced the inner part of the forward lead glass calorimeter of the GlueX detector. Signals from the detector will be digitized using twelve-bit flash analog-to-digital converters operated at a sampling rate of 250 MHz. The ECAL is integrated into the trigger system of the GlueX detector using electronics modules designed at JLab. The ECAL is currently at the commissioning stage and should be ready for the physics run in January 2025. We will give an overview of the JEF experiment, the design and construction of the ECAL, and the integration of the detector and its infrastructure into the Hall D experimental setup.
The lead tungstate crystals (PWO4) are a well-known radiator material for precise homogeneous electromagnetic calorimetry. In nuclear physics experiments, the typical way to read out the crystals is using conventional photomultiplier tubes (PMTs). In the case of the presence of a magnetic field, such a method has some complications and requires a passive PMT shielding design. The recent development of Silicon Photomultipliers (SiPMs) with small pixel pitch sizes and relatively small noise levels opens an opportunity avenue to use such a device as an alternative to conventional PMTs. The SiPM readout method may be beneficial for future nuclear physics and collider experiments. We are presenting the beam test results of the calorimeter prototype instrumented with SiPM readout performed at Jefferson Lab. The SiPM readout performance was compared with PMT readout measured at the same experimental conditions. The prototype was successfully tested using beam of photons in the energy range between 3 GeV and 11 GeV in experimental Hall D. The detector performance was also studied using a secondary beam of positrons provided by Hall D pair spectrometer.
Oxygen vacancies caused by fast neutrons in calcium tungstate single crystals measured by electron spin resonance